Materials Science and Engineering R 98 (2015) 1–71

Contents lists available at ScienceDirect

Materials Science and Engineering R

journal homepage: www.elsevier.com/locate/mser

A comprehensive review of Li4Ti5O12-based electrodes for lithium-ion

batteries: The latest advancements and future perspectives
Bote Zhao a,b, Ran Ran a, Meilin Liu b,*, Zongping Shao a,*
a
State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009, PR China
b
School of Materials Science and Engineering, Center for Innovative Fuel Cell and Battery Technologies, Georgia Institute of Technology, Atlanta, GA 30332-
0245, USA

A R T I C L E I N F O A B S T R A C T

Article history: Advanced electrical energy storage technology is a game changer for a clean, sustainable, and secure
Available online energy future because efficient utilization of newable energy hinges on cost-effect and efficient energy
storage. Further, the viability of many emerging technologies depends on breakthroughs in energy
Keywords: storage technologies, including electric vehicles (EVs) or hybrid electric vehicles (HEVs) and smart grids.
Lithium-ion battery Lithium-ion batteries (LIBs), a great success in the portable electronics sector, are believed also the most
Li4Ti5O12 promising power sources for emerging technologies such as EVs and smart grids. To date, however, the
Anode existing LIBs (with LiCoOx cathode and graphite anode) are still unable to meet the strict requirements
Electrode materials for safety, cycling stability, and rate capability. The development of advanced anode materials, which can
Spinel
overcome the shortcomings of graphite anode (such as formation of dendritic lithium during charge and
undesirable solid electrolyte interface), is of critical importance to enhancing the cycling stability and
operational safety of LIBs. Lithium titanate (Li4Ti5O12) has recently attracted considerable attentions as a
potential anode material of LIBs for high power applications due to several outstanding features,
including a flat charge/discharge plateaus (around 1.55 V vs. Li/Li+) because of the two-phase lithium
insertion/extraction mechanism and minimum chance for the formation of SEI and dendritic lithium,
dramatically enhance the potential for high rate capability and safety. In addition, there is almost no
volume change during the lithium insertion and extraction processes, ensuring a high cycling stability
and long operational life. However, the electronic conductivity of Li4Ti5O12 is relatively low, resulting in
large polarization lose, more so at higher cycling rates, and poor rate performance. Currently,
considerable research efforts have been devoted to improving the performance of Li4Ti5O12 at fast
charge/discharge rates, and some important progresses have been made. In this review, we first present a
general overview of the structural features, thermodynamic properties, transport properties, and the
electrochemical behavior of Li4Ti5O12 under typical battery operating conditions. We then provide a
comprehensive review of the recent advancements made in characterization, modification, and
applications of Li4Ti5O12 electrodes to LIBs, including nanostructuring, surface coating, morphological
optimization, doping, and rational design of composite electrodes. Finally, we highlight the critical
challenges facing us today and future perspectives for further development of Li4Ti5O12-based
electrodes. It is hoped that this review may provide some useful guidelines for rational design of better
electrodes for advanced LIBs.
ß 2015 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1. Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2. History. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. Fundamental properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1. Crystal structure, phase stability, and defects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2. Thermodynamic properties (including theoretical capacity) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

* Corresponding authors.
E-mail address: meilin.liu@mse.gatech.edu (M. Liu).

http://dx.doi.org/10.1016/j.mser.2015.10.001
0927-796X/ß 2015 Elsevier B.V. All rights reserved.
2 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

2.3. Transport properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

2.4. Electrochemical behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3. Tailoring the nanostructure, morphology, and defect chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1. Nanostructuring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1.1. Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.1.2. 1–3D nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.2. Morphological control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2.1. Porous electrodes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2.2. Nano/microspheres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.2.3. Thin-film electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.3. Surface coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3.3.1. Carbon coating. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.3.2. Coating/modification with other materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.3.3. Surface treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.4. Doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.5. Formation of composite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.5.1. Li4Ti5O12/graphene. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.5.2. Li4Ti5O12/carbon nanotubes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.5.3. Li4Ti5O12/SnOx . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.5.4. Li4Ti5O12/TiO2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.5.5. Li4Ti5O12/transition-metal oxides (MO, where M is Co, Ni, Cu, Fe or Zn) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4. Electrochemical behavior in different battery systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.1. Combination with different cathodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.2. Combination with different electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
4.3. Electrochemical performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
5. Critical challenges and new directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
5.1. Low theoretical capacity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
5.2. Compromise between tap density and rate capability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
5.3. Poor performance at low temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
5.4. Gassing problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
5.5. Other applications in addition to electrode for LIBs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
5.5.1. As a coating layer to enhance the performance of other electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
5.5.2. As an electrode material for rechargeable sodium-ion batteries. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5.5.3. As an electrode material for hybrid supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
6. Conclusions and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65

1. Introduction reliance on fossil fuels. The properties and performance of the

1.1. Background
During the past century, our society has relied heavily on fossil
fuels (oil, coal, and natural gas) for the development of our
industry, economy, and modern conveniences. However, the
excessive and low-efficiency use of fossil fuels, which is based
largely on traditional combustion technology, has resulted in
serious problems such as global warming and environmental
pollution. In addition, our dependence on those ever-diminishing
energy resources puts us at risk of a non-sustainable future. The
search for clean and renewable energies is our only option for a
secure and sustainable future.
Solar and wind energies are among the most abundant
renewable energies and may play important roles in future clean
energy systems. However, integration of such intermittent energy
sources challenges the existing electric power grid. Low-cost
energy storage is thus required to provide consistent renewable
energy production with the introduction of a new green, or smart,
power grids [1,2]. Among the potential methods of energy storage,
electrochemical energy storage is generally accepted as the most
promising, while secondary batteries are particularly attractive for
their high energy density and low cost. Hybrid electric vehicles
(HEVs), plug-in hybrid electric vehicles (PHEVs) and pure electric
vehicles (EVs) have also attracted considerable worldwide atten-
tion because of their potential for replacing conventional internal
combustion engines to reduce greenhouse gas emission and our
batteries used in HEVs, PHEVs and EVs determine the success of the
integration of green vehicles into daily life. The batteries for both
stationary energy storage (e.g., smart grids) and mobile applica-
tions (e.g., EVs) are required to have long cycling lifetimes, high
rate capability, safety, reliability, durability, and low cost.
Since the early 1990s, lithium ion batteries (LIBs) have been
widely used in portable electronic devices. Recently, their potential
for electrical energy storage and as power sources for HEVs, PHEVs,
and EVs have also been recognized due to their high voltage, light
weight, high power density, lack of memory effect, and environ-
mental benignness [3–6]. LIBs store electrical energy in both
electrodes, which are made of lithium intercalation (or insertion)
compounds, as schematically shown in Fig. 1. In a typical LIB, a
porous polymer membrane is usually used as the separator, and a
lithium salt (e.g., LiPF6) dissolved in a mixture of organic solvents
(e.g., ethylene carbonate and dimethyl carbonate) is used as the
electrolyte. During discharge, lithium ions move from the anode
through the electrolyte to the cathode, as electrons flow from the
anode through an external circuit to the cathode, producing
electrical power. These spontaneous processes are driven by the
difference in electrochemical potentials of the two electrode
materials. During charge, these processes are reversed under the
influence of an applied electric field (or voltage): lithium ions are
extracted from the cathode and inserted into the anode, as
electrons are pumped from the cathode through an external circuit
to the anode, consuming electric power. The electrochemical
performance of LIBs depends sensitively on the properties of
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 1. The components of a typical LIB and the corresponding electrochemical
charge/discharge processes. The cathode and anode materials shown here are
LiCoO2 and Li4Ti5O12, respectively.
electrode materials. The most advanced LIBs can exceed most other
competitive battery technologies in energy density by a factor of
2.5 [7]. The high specific energy density of LIBs is closely related
to the low molecular weight, small ionic radius, and low redox
potential of lithium.
Conventional LIBs are composed of a LiCoOx cathode and a
carbon/graphite anode. The graphite anode has a theoretical
capacity of 372 mA h g1, and the lithium insertion primarily
occurs at a voltage below 0.1 V (vs. Li/Li+), close to the lithium
electroplating potential [8]. At a high discharge rate, the carbon/
graphite electrode can be polarized to such an extent that highly
reactive dendritic lithium may form on the electrode surfaces,
which may easily penetrate through the porous separator and
cause an internal short circuit, thus posting significant safety
concern. However, as power sources for HEVs, PHEVs and EVs, the
batteries are frequently charged or discharged at a high rate over a
wide temperature range (from 30 to 60 8C). In addition, the
carbon/graphite electrodes suffer from a lack of clear end-of-
charge indicator in their voltage profiles, suggesting that the state-
of-the-art graphite anodes may not meet the strict safety and rate
performance requirements for many emerging applications.
Currently, considerable research is being conducted to develop
alternative anode materials with improved safety, cycling stability,
and rate performance.
Li4Ti5O12 is a lithium intercalation compound (or insertion
host) with a high lithium insertion/extraction voltage of approxi-
mately 1.55 V [9], well above the potential for formation of an SEI
from the reduction of the organic electrolyte and for the formation
of dendritic lithium, thus offering excellent safety. In addition to
being nontoxic and relatively inexpensive, the material experi-
ences little change in volume during the lithium insertion/
extraction processes and possesses high thermal stability, ensuring
a long cycling lifetime. Recently, Li4Ti5O12 has attracted consider-
able attention as a potential anodic material for LIBs for use in
electrochemical energy storage and electric vehicles. However,
Li4Ti5O12 exhibits low electronic conductivity (in the range of
108 to 1013 S cm1) [10–12] and low lithium-ion diffusion
3
coefficient (108 to 1013 cm2 s1) [13–17], which greatly limit
its rate performance. Recently, considerable research has been
conducted on the morphological optimization, doping, and
nanostructuring of Li4Ti5O12, or a combination of these, to improve
its capacity and rate capability.
1.2. History
Spinel Li4Ti5O12 (also reported as Li1.33Ti1.67O4, Li4/3Ti5/3O4, or
[Li]8a[Li1/3Ti5/3]16d[O4]32e) is an important member of the solid
solution family, Li3+xTi6xO12 (0  x  1) [18], which was first
reported by Jonker in 1956 [19]. Materials with a spinel structure
have a general chemical formula of AB2O4, in which the oxygen
ions (32e) form a cubic-close-packed (ccp) array with tetrahedrally
(8a, 8b, 48c) and octahedrally (16c, 16d) coordinated interstices
partially occupied by the A and B cations. Li3+xTi6xO12 initially
excited interest for its superconductivity at low temperatures. For
example, LiTi2O4, one extreme of Li3+xTi6xO12 (for x = 0), exhibits
superconductivity at temperatures below 10 K [20,21]. In contrast,
Li4Ti5O12, the other extreme of Li3+xTi6xO12 (for x = 1), is a
semiconductor down to liquid helium temperatures [22]. Murphy
et al. first reported the capability of Li4Ti5O12 for lithium
intercalation [23]. In 1989, Colbow et al. first measured the
galvanostatic charge–discharge properties of a Li/Li4Ti5O12 half-
cell and found that the material exhibited a plateau in its discharge
voltage profile and stable performance starting with the 25th cycle
during a cycling test of up to 100 iterations [24].
The relatively low lithium insertion/extraction potential
(1.55 V) prohibits the application of Li4Ti5O12 as a cathode in
LIBs; however, it can serve as a negative electrode when coupled
with high-voltage cathodic materials such as LiCoO2 and LiMn2O4
to yield safe 2.5–3.0 V lithium-ion cells with long lifetimes. Ferg
et al. may have been the first to propose Li4Ti5O12 as an anode
material for LIBs [25], but their work has been followed by
considerable research into the application of Li4Ti5O12 as a
potential anode for LIBs. Fig. 2 shows the Li4Ti5O12-related
published items in the Web of Science Core Collection for each
year from 2000 to 2014. By 2007, the number of published items
per year was over 50, which increased rapidly ever since, reaching
more than 100 in 2011 and more than 200 in 2013, suggesting
great interest in Li4Ti5O12 anodes in the past few years.
Fig. 2. Li4Ti5O12-related published items for each year in the Web of Science Core
Collection, date: January/31/2015, search strategy: TOPIC: (‘‘lithium batter*’’ OR
‘‘lithium ion batter*’’ OR ‘‘lithium cell*’’ OR ‘‘lithium ion cell*’’ OR ‘‘li-ion batter*’’ OR
‘‘Lithium-Ion Batter*’’ OR ‘‘Li rechargeable batter*’’ OR ‘‘rechargeable Li batter*’’ OR
‘‘lithium secondary batter*’’ OR ‘‘Lithium Storage’’) AND TOPIC: (Li4Ti5O12 or
Li1.33Ti1.67O4 or Li4/3Ti5/3O4 or Li[Li1/3Ti5/3]O4 or Li[Li1/3Ti5/3]O 4 or ‘‘lithium
titanate’’). Timespan: 2000–2014. Indexes: SCI-EXPANDED, SSCI, A&HCI, CPCI-S,
CPCI-SSH, BKCI-S, BKCI-SSH, CCR-EXPANDED, IC.
4 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

2. Fundamental properties

2.1. Crystal structure, phase stability, and defects

A detailed structural analysis of Li4Ti5O12 based on a single

crystal was first reported by Deschanvres et al. in 1971
[18]. Kataoka et al. determined the structure of single crystals
prepared via a LiCl flux method using a four-circle diffractometer
[26]. The basic crystal structure of Li4Ti5O12, as shown in Fig. 3 [27],
is a cubic spinel with an Fd3m space group and a unit cell
¯
parameter reported to be between a = 8.352 and 8.370 Å
[9,23,24,28–31]. At room temperature, the tetrahedral 8a sites
of the Li4Ti5O12 are believed to be occupied by Li+ ions alone, while
the octahedral 16d sites are randomly occupied by 1/6 Li+ ions and
5/6 Ti4+ ions [32]. All of the 32e sites are occupied by O atoms,
which form a ccp structure. The other half of the octahedral cation
sites in the ccp structure (16c sites) and both the tetrahedral 8b and
48f cationic sites are empty and are suitable for lithium insertion
and extraction. However, using infrared spectroscopy, Pecharro-
man et al. demonstrated that the lithium ions in the 8a tetrahedral
sites can shift to the 16c octahedral sites with increasing
temperature [33]. Based on the Rietveld refinement of X-ray and
neutron powder diffraction data, Leonidov et al. supported the
finding that the tetrahedral 8a sites in Li4Ti5O12 were occupied
solely by lithium ions at room temperature [30]. However, high-
temperature Raman spectroscopy and the electrical conductivity
data indicated that the lithium ions in the 8a sites can migrate into
16c sites at temperature above 177 8C to induce two successive
order–disorder phase transitions [30]. By applying high-tempera-
ture 6Li magic-angle spinning nuclear magnetic resonance
(MASNMR), Vijayakumar et al. also demonstrated that the lithium
ions can migrate from the tetrahedral 8a sites to the 16c octahedral
sites in Li4Ti5O12 with increasing temperature accompanied by a
progressive phase transition from a spinel to a defective NaCl-type
structure [27].
‘‘Zero-strain’’ characteristic, which is one of the most important
features of Li4Ti5O12, was first reported by Ohzuku et al. in 1995
[9]; there is almost no change in lattice dimension during lithium
ion and electron insertion into/extraction from the solid matrix
when the composition is changed between the initial state of
Li4Ti5O12 and the final state of Li7Ti5O12. Ohzuku et al. synthesized
Li4Ti5O12 samples and demonstrated that it had a defect spinel-
framework structure Li(8a)[Li1/3Ti5/3](16d)O4(32e) with a lattice
parameter a = 8.365 Å (Fd3m; oxygen positional parameter
¯ Fig. 3. Top figure: crystal structure of Li4Ti5O12 showing the three lithium sites:
u = 0.265) via XRD analysis [9]. They further found that the lattice tetrahedral 8a (yellow), octahedral 16c (green) and octahedral 16d (blue). Titanium
constant for the initial state of Li[Li1/3Ti5/3]O4 is the same as those and oxygen atoms are shown as small gray and large red balls, respectively. All three
for the other 8 different states of Li1+x[Li1/3Ti5/3]O4 (0  x  0.91) sites are shown as occupied for presentation purposes. Bottom figure: inter-atomic
distances between 16d and 16c (2.95 Å), 16c–8a (1.81 Å), and 8a–16d (3.46 Å) site
(a = 8.370  0.005 Å), indicating the zero-strain characteristic of
pairs based on the structure. [27]. (For interpretation of the references to color in
Li4Ti5O12 (Fig. 4). From then on, the ‘‘zero-strain’’ characteristic of this figure legend, the reader is referred to the web version of this article.)
Li4Ti5O12 material was further confirmed by many researchers [34–
36]. Fig. 4b shows XRD patterns of Li1+x[Li1/3Ti5/3]O4 in different
charge/discharge status (0  x  0.91). An I(5,3,3)/I(6,2,2) ratio change Li4Ti5O12 [37–41]. For the partially lithiated Li4+xTi5O12 prepared
was observed; the ratio decreased to approximately 1 when x = 0.46, by chemically inserting lithium into Li4Ti5O12, Aldon et al. used 6,7Li
and further decreased when x was increased; the ratio recovered nuclear magnetic resonance (NMR), Raman spectroscopy, X-ray
during the subsequent lithium extraction process. This result was diffraction (XRD) and neutron diffraction to demonstrate that the
explained by the inserted lithium ions occupy the octahedral 16c sites lithium ions were trapped in the 48f sites of the spinel structure and
process (Fig. 4c). During the electrochemical lithium insertion were not able to be extracted through electrochemical means; in
process, the incoming lithium ions are believed to occupy the addition, this chemical insertion process did not cause a transition in
octahedral 16c sites. The lithium ions that initially locate at the the phase structure [37]. Using a similar chemical insertion method,
tetrahedral 8a sites are simultaneously displaced into the neighbor- Wagemaker et al. were unable to observe a 48f lithium occupation
ing 16c octahedral sites due to electrostatic repulsion effects that [42]. Based on the neutron and XRD patterns of chemically lithiated
generate a rock-salt phase, [Li2]16c[Ti5/3Li1/3]16dO4, which has the Li4+xTi5O12 samples, Wagemaker et al. demonstrated that the inserted
same lattice symmetry as Li4Ti5O12 (Fd3m) [34]. Recently, various lithium could co-exist in a single phase with a mixed 8a and 16c
¯
characterization techniques including neutron diffraction, Mossbauer occupation in the lattice [42], although the co-existence of 8a and 16c
spectrometry, Raman spectroscopy, and XRD have been used to lithium ions is believed to introduce a large electrostatic repulsion
characterize the phase evolution during lithium insertion into energy due to the short lithium ion–lithium ion distance. Using
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 5

Fig. 4. (a) Records on the preparation of Li1+x[Li1/3Ti5/3]O4 for XRD examinations. Arrows directed upward indicate the locations at which XRD examinations were done for the
reduction of Li[Li1/3Ti5/3]O4, and arrows directed downward for the oxidation of the samples following 160 mA h g1 of reduction. (b) XRD patterns of Li1+x[Li1/3Ti5/3]O4 in the
status as shown in (a): (b0) x = 0, (b1) x = 0.46, (b2) x = 0.91, (b3) x = 0.46, and (b4) x = 0. XRD samples were prepared by (b0) 0, (b1) 80, and (b2) 160 mA h g1 of reduction of
Li[Li1/3Ti5/3]O4, and by (b3) 80 and (b4) 160 mA h g1 of oxidation following 160 mA h g1 of reduction. Capacity in mA h g1 is based on Li[Li1/3Ti5/3]O4 sample weight. (c) The
topotactic reaction of lithium insertion into/extraction from Li[Li1/3Ti5/3]O4 structure. [9].

difference Fourier synthesis map method, Kataoka et al. also
investigated the lithium insertion sites based on single crystals of
Li4+xTi5O12, prepared by means of an electrochemical Li-ion
intercalation technique using single parent Li4Ti5O12 crystals, and
determined that the lithium ions were inserted into both the 8a and
16c sites [43].
The insertion of lithium into Li4Ti5O12 causes the reduction of
Ti4+ to Ti3+. Because Ti3+ (0.670 Å, CN = 6) has a larger ionic radius
than Ti4+ (0.605 Å, CN = 6), an elongation of the Ti-O bond is
expected following the lithium insertion. In this case, however, a
slight dimensional shrinking was normally observed when
Li4Ti5O12 was reduced to Li7Ti5O12 following the lithium insertion
[34], although the reported values of the lattice parameters varied
somewhat among the different researchers [9,23,24,28–31]. Ronci
et al. conducted high-resolution in situ structural measurements of
Li4Ti5O12 using a high-energy (87.5 keV) synchrotron beam and
confirmed little variation in the lattice parameter of 0.07%
[35,40]. The small change in the cell volume after inserting lithium
into Li4Ti5O12 is beneficial for stable cycling. Ariyoshi et al.
provided a detailed investigation of the zero-strain mechanism of
Li4Ti5O12 by ex situ XRD [36]. After the reduction of Li4Ti5O12 to
Li7Ti5O12, the oxygen positional parameter at the 32e sites
decreased from 0.266 to 0.257. Thus, the authors suggested that
the zero strain of Li4Ti5O12 was closely related to the oxygen swing
in the lattice during the lithium insertion process.
2.2. Thermodynamic properties (including theoretical capacity)
The insertion of lithium into Li4Ti5O12 spinel is believed to
primarily follow a two-phase mechanism [9,23,24,34,44]. During
the discharge process, the incoming lithium ions insert into the 16c
octahedral sites, and the lithium ions at the 8a sites simultaneously
transfer to the 16c sites. The total number of lithium ions that can
be inserted into the 16c sites from external sources equals half the
number of empty 16c sites because the other half of the lithium
ions are transferred from the previously occupied tetrahedral 8a
sites. Thus, the insertion process can be expressed by the equation
as shown in Fig. 4c, and can be briefly expressed by the following
equation:
Li4 Ti5 O12 þ 3e þ 3Liþ ¼ Li7 Ti5 O12 (1)
The capacity, as calculated using the mass of Li4Ti5O12
according to above equation, is 175 mA h g1, which is generally
accepted as the theoretical value.
From a structural point of view, the Li7Ti5O12 could accommo-
date more lithium ions because there are empty 8a sites that can
accept lithium ions, although they are energetically less favorable
than the 16c sites. In addition, 40% of the titanium in the 16d
octahedral sites is in the Ti4+ oxidation state, which can be reduced
to Ti3+ during the accommodation of additional lithium. Because a
low discharge voltage may lead to the formation of SEI over the
Li4Ti5O12 electrode, while lithium intercalation occurs at a voltage
of approximately 1.55 V, an end of discharge voltage of 1.0 V is
often selected in the literature to investigate the charge–discharge
properties of Li4Ti5O12. However, upon closer examination of the
galvanostatic charge–discharge profiles reported by Huang et al.
(Fig. 5), who conducted discharge studies of Li4Ti5O12 down to
0.5 V [45–47], non-negligible reversible capacity is observed in the
potential range of 1.0–0.5 V, suggesting that lithium can further
insert into Li7Ti5O12 at a lower intercalation potential. Ge et al., Yao
et al. and Ahn et al. reported the discharge of Li4Ti5O12 down to a
6 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 5. Typical galvanostatic charge–discharge profiles for Li4Ti5O12 down to 0.5 V.
[45].
near zero voltage [48–50] noting a considerable capacity
contribution to the total reversible capacity of Li4Ti5O12 at
discharge voltages lower than 0.5 V. This total reversible capacity,
approaching 250 mA h g1, exceeds the generally accepted theo-
retical capacity of 175 mA h g1.
Based on the XRD and electrochemical galvanostatic charge/
discharge experiments, Ge et al. demonstrated that the tetrahedral
(8a) sites of Li7Ti5O12 can be accommodated with lithium ions at
potentials below 0.6 V vs. a Li/Li+ reference electrode [51]. The
authors further proposed the following insertion/extraction
mechanism for lithium ions into/from Li7Ti5O12:
Li6ð16cÞ ½LiTi3 3þ Ti2 4þ ð16dÞ O12ð32eÞ þ 2e þ 2Liþ
$ Li2ð8aÞ Li6ð16cÞ ½LiTi5 3þ ð16dÞ O12ð32eÞ
Ge et al. also suggested that the theoretical capacity of Li4Ti5O12
is 293 mA h g1 (2.5–0.01 V), limited by the number of tetravalent
titanium ions, not the number of octahedral or tetrahedral sites
available to accommodate the lithium ions. The final composition
following lithium intercalation was suggested to be Li9Ti5O12. The
availability of tetrahedral 8a sites for lithium-ion storage was also
supported by Borghols et al. during their investigation of size
effects on the Li4+xTi5O12 spinel [52]. By applying first-principles
calculations, Zhong et al. demonstrated that Li4Ti5O12 can be
intercalated into a final state of Li8.5Ti5O12 [53] instead of
Li9Ti5O12. Thus, the theoretical capacity of Li4Ti5O12 is calculated
to be approximately 263 mA h g1. The predicted intercalation
potentials are 1.48 and 0.05 V (vs. Li/Li+) for the Li4Ti5O12/Li7Ti5O12
and Li7Ti5O12/Li8.5Ti5O12 redox pairs, respectively. The further
insertion of lithium into the Li7Ti5O12 phase induces only a small
volumetric change. The lattice expansion of Li8.5Ti5O12 with
respect to Li4Ti5O12 was found to be only 0.4% based on the
theoretical calculations. A schematic illustration of the Li+ insertion
into and extraction from a spinel Li4Ti5O12 structure is shown in
Fig. 6 [54].
2.3. Transport properties
Since Li+ insertion into and extraction from a Li4Ti5O12 electrode
inevitably involve transport of both lithium ions and electrons, the
rate capability of the electrode depends sensitively on lithium-ion
and electronic conductivity. Because a band gap opens between the
occupied O-2p states and the empty Ti-3d states in Li4Ti5O12 [55],
the electronic conductivity is relatively low (108 to
Fig. 6. Schematic illustration for the Li+ insertion into/extraction from spinel
Li4Ti5O12 structure at (a) 3 V, (b) 1–3 V and (c) 0.01–1 V. [54].
1013 S cm1) [10–12]. After the lithium atoms are inserted into
the Li4Ti5O12 lattice, however, additional electrons are introduced
that occupy the Ti-3d states to cause a shift in the Fermi level
toward the conduction band, making the system more electroni-
cally conductive. The value of the electronic conductivity for the
Li7Ti5O12 phase was found to be in the range of 102 S cm1 [34],
much higher compared to that of the initial phase
Li4Ti5O12. Improving the electronic conductivity during the initial
discharge stage is critical to enhancing the rate capability of the
(2) Li4Ti5O12 electrode. Surface coating and doping are the two most
widely used approaches for enhancing transport properties.
Kamata et al. studied the lithium motion in Li4Ti5O12 and
determined lithium diffusion coefficient at elevated temperatures
using neutron radiography [56,57]. The transport number of the
lithium ions and the lithium diffusion coefficient in de-lithiated
Li4Ti5O12 at 900 8C were determined to be 0.99 and
1.8  106 cm2 s1, respectively. The value for lithium diffusion
coefficient is relatively high. However, for practical applications,
LIBs are typically operated at room temperature. The lithium ion
reportedly can migrate from the 8a tetrahedral sites to the
octahedral 16c sites at elevated temperatures and can induce a
progressive phase transition from a spinel to a defective rocksalt
structure, leading to an increase in lithium-ion conductivity [30]
due to increased number of vacancies at the 8a sites that facilitate
the lithium diffusion through 16c–8a–16c pathways [27]. Howev-
er, lithium diffusion coefficient drops sharply as temperature is
decreased. For example, Fehr et al. demonstrated a substantial
decrease in electrical conductivity of Li4Ti5O12 from 104 to
106 S cm1 at 500 K to only 3  1010 S cm1 at 300 K
[58]. Wilkening et al. measured the low-temperature lithium
diffusion in a phase-pure Li4Ti5O12 sample via 7Li NMR spectros-
copy [59,60] and demonstrated that the lithium diffusion rate at
low temperatures was extremely slow. For example, the Li self-
diffusion coefficients at 298 and 320 K are only 2.7(4)  1012 and
9.2(5)  1012 cm2 s1, respectively [60], which are much lower
than those reported by Esaka at 1173 K [56,57]. Chen et al. studied
the lithium-ion dynamics in Li4+xTi5O12 spinel by first-principles
calculations and demonstrated a sharp decrease in lithium
diffusion coefficient for Li4+xTi5O12 as temperature is lowered at
different states [61], suggesting that the rate capability of Li4Ti5O12
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
could be severely limited by slow lithium diffusion at low-
temperature operation. In addition, the lithium-ion diffusion
coefficient was also closely related to the degree of lithium
insertion into Li4Ti5O12. Takami evaluated the apparent lithium
diffusion coefficients in the Li7Ti5O12 and Li4Ti5O12 phases from the
results of potential step chronoamperometry with a spherical
diffusion model. The lithium diffusion coefficients were found to
be approximately 1  1012 and 1.6  1011 cm2 s1, respectively
[62], suggesting a lower lithium diffusion coefficient for Li7Ti5O12
than Li4Ti5O12.
2.4. Electrochemical behavior
Fig. 7 shows some typical galvanostatic charge–discharge
profiles for a Li4Ti5O12 anode within a potential range of 1.0–3.0
or 0.01–3.0 V. Usually, the electrochemical performance of an
anode is evaluated using lithium foil as a counter electrode (i.e., a
half-cell configuration). In this case, the Li4Ti5O12 electrode acts as
a ‘‘cathode’’ and lithium foil is the anode. Thus, the insertion of
lithium into the cathode (i.e., Li4Ti5O12) is usually named as the
discharge process (Fig. 7). However, in a full cell with Li4Ti5O12 as
the anode, the extraction of lithium from the anode is named as the
discharge process (Fig. 1). Thus, the charge curve for the anode
would be more important for real application since it determines
the output voltage of the full cell. The potential range of 1.0–3.0 V
was the most commonly studied due to the unique charateristics of
Li4Ti5O12 anode. Li4Ti5O12 features a rapid decrease in the potential
at the initial discharge (intercalation) to reach a voltage of
approximately 1.55 V [23,24]. Then, the discharge voltage remains
Fig. 7. The typical first discharge/charge profiles of Li4Ti5O12 electrode using a
current density of 175 mA g1 in the potential ranges of (a) 1.0–3.0 V and (b) 0.01–
3.0 V. Li4Ti5O12 was synthesized using a facile cellulose-assisted combustion
method [292].
7
Fig. 8. (a) A schematic illustration of two-phase mechanism for Li4Ti5O12 electrode
during the charge/discharge processes. The charge/discharge profiles were derived
from literature. [292].
nearly constant during the subsequent discharge process until
another smooth decrease in voltage occurs near the end of the
discharge to an endpoint of 1.0 V. As mentioned previously, it is
generally accepted that the lithiation/de-lithiation related to a
Li4Ti5O12 electrode involves a two-phase mechanism (Fig. 8)
[9,23,24,34,44], similar to a LiFePO4 cathode [63]. However, at the
beginning and near the end of the charge/discharge processes, the
electrode reaction could still have a single-phase mechanism. At the
beginning, the lithium insertion leads to the formation of a single
solid solution, Li4+aTi5O12 (Li4Ti5O12 + aLi+ + ae!Li4+aTi5O12),
which has identical phase structure to Li4Ti5O12. As a result, a
smooth drop in potential is observed with increasing lithium
insertion until the statured concentration of the single phase is
reached. Further increases in the degree of lithium insertion into the
Li4Ti5O12 cause the appearance of a new rock-salt-like phase,
Li7bTi5O12, via the following reaction: (spinel) Li4Ti5O12 + (3  -
b)Li+ + (3  b)e = Li7bTi5O12 (rock salt). Following that reaction,
the lithium insertion involves the Li4+aTi5O4–Li7bTi5O12 two-phase
mechanism to yield a fixed electrical potential based on the Gibbs
phase rule with a value of approximately 1.55 V. Near the end of the
discharge, a single-phase insertion reappears (Li7bTi5O12), and the
insertion is controlled by the lithium diffusion through the solid
solution. A smooth potential drop is again observed from 1.55 V until
the final insertion voltage of 1.0 V. The charge process proceeds in a
similar manner, but in the reverse direction. A core–shell mode,
which is frequently used to explain the lithium insertion/extraction
related to a LiFePO4 positive electrode [64], can also be applied to
describe the lithiation/de-lithiation process of the Li4Ti5O12 anode
[65].
The single-phase ranges at the beginning/end of charge/
discharge depend closely on the Li4Ti5O12 particle size (Fig. 9a
and b) [66,67] and the surface coating (Fig. 9c) [68]. For example,
Park et al. and Wang et al. demonstrated that the surface coating of
Ti(III)/carbon and TiN on Li4Ti5O12 (Fig. 9c) can increase the domain
of the single-phase lithium insertion/extraction [68,69]. Wage-
maker et al. assumed that the presence of a solid solution is
beneficial for Li-ion mobility [42,70]. A single phase implies
intimate mixing of the 8a and 16c occupation sites in contrast to
the two-phase region where the 8a and 16c occupation sites are
separated. The single phase is beneficial for increasing both the
apparent electronic and lithium-ion conductivity, and thus the rate
capability. Based on the neutron and X-ray diffraction of
chemically lithiated Li4+xTi5O12 at different temperatures, Wage-
maker et al. proposed that faster Li insertion leads to a kinetically
induced effective two-phase reaction, which is a non-equilibrium
8 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 9. The relationship between the single-phase range in the charge/discharge curves and properties of Li4Ti5O12 material: (a, b) particle size, and (c) surface coating. (a)
Discharge curves of the fifth discharge (1 C) of various as-prepared Li4Ti5O12 nanoparticle electrodes [66]. (b1) Calculated voltage profiles for the Li4Ti5O12-Li7Ti5O12 system.
The pink voltage curve corresponds to a composite for particles combining Li insertion into vacant 16c sites in a Li4Ti5O12 host without nearest 8a-16c neighbors at the
interface from (1 1 0) facets and Li insertion into a Li7Ti5O12 host with vacant 8a sites from (1 1 1) facets corresponding to the Wulff shape. The purple and black curves
correspond to particle sizes of 30 and 100 nm. The green-shaded area represents the region under 0 V, where no Li intercalation is feasible. The inset is Wulff shape
determined from the calculated surface energies of pure LiTi2O4 spinel, (b2) corresponding schematic illustration of lithium-ion insertion into Li 4Ti5O12[67]. (c) Charging (Li+
insertion) voltage curves of (A) pristine Li4Ti5O12 and the nitridated powders at 700 8C for (B) 10, (C) 20, (D) 30, and (E) 60 min and the corresponding two-phase equilibrium
region with different reaction time and the lattice parameters of 60 min-nitridated Li 4Ti5O12 [68]. (For interpretation of the references to color in this figure legend, the reader
is referred to the web version of this article.)

situation that will ultimately relax to a single phase at room 3.1. Nanostructuring
temperature [42,70]. The single-phase range of the curve for
Li4Ti5O12 typically appeared wider for smaller nanoparticles By reducing the particle size to the nanoscale, some unique
(Fig. 9a) than that for larger particles (Fig. 7). Similar trend was mechanical, electrical, and optical properties appear [74–
also observed for TiO2 anode, which was attributed to capacitive 77]. Nanostructuring reduces the diffusion distance for both the
lithium storage on the surface of nanosized TiO2 [71–73], lithium ions and the electrons within the bulk of the electrode
suggesting its highly related to the surface property. Using density materials. In addition, nanostructuring increases the surface area
functional theory to calculate voltage profiles, Ganapathy et al. [67] available for interfacial charge transfer and, consequently, can
revealed that the favorable lithium-ion insertion into the (1 0 0)
surfaces of the defective spinel Li4Ti5O12 contributed to the initial
capacity at high voltages due to surface storage; and the lowest
energy (1 1 0) surface was predicted to be energetically favorable
for lithium-ion insertion into the vacant 16c sites. Especially, they
found that the (1 1 1) surface allowed further lithium-ion insertion
into the Li7Ti5O12 by occupation of 8a sites in addition to the fully
occupied 16c sites via surface relaxation effects, which could
explain the slight higher capacity of nanosized Li4Ti5O12 compared
to the theoretical capacity even after initial activation. Accordingly,
the size effect on the voltage profiles was summeried as shown in
Fig. 9b. Furthermore, it is predicted that reducing the size and
tailoring the shape to increase the relative amount of (1 1 1) facets
may increase the storage capacity.

3. Tailoring the nanostructure, morphology, and defect

chemistry

Although Li4Ti5O12 is highly promising as an anode material of

LIBs, its practical application in electrochemical energy storage as
well as electric vehicles is hindered by its low electronic
conductivity and relatively poor lithium diffusion rate. Thus, a
Li4Ti5O12 electrode composed of coarse powder usually shows poor
capacity retention during cycling, more so at higher discharge/
charge rates. To achieve high specific capacity, high rate capability
and good cycling stability, several strategies have been investigat-
ed in the past decade (Fig. 10), including nanostructuring, Fig. 10. The typical strategies for improving the electrochemical performance of
morphological optimization, surface coating, doping, and forma- Li4Ti5O12 electrode. All insets are derived from the literatures
tion of composite, and significant progress has been made. [27,133,137,162,186,191,239,245,453].
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 11. The schematics of reported Li4Ti5O12 nano/microstructures (0–3D) and corresponding microscope images [133,136,137,154,159,160,245,285].
substantially improve the electrode performance. Thus, nano-
structured electrodes typically exhibit higher specific power
density than those composed of coarse powders [77,78]. To date,
various nano/microstructures of Li4Ti5O12 have been reported, as
schematically shown in Fig. 11. The details of these structures will
be discussed in the following sections.
3.1.1. Nanoparticles
Conventionally, spinel Li4T5O12 has been prepared by a solid-
state reaction using TiO2 (rutile or anatase) and Li2CO3 or LiOH as
raw materials at a calcination temperature above 800 8C over a
prolonged period of time (12–24 h to ensure high phase purity)
[34,65,79–83]. The as-synthesized powders usually have large
grains with inhomogeneous phase compositions and low specific
surface areas. Considerable efforts have been made to synthesize
nanosized Li4Ti5O12 by exploiting advanced synthetic techniques.
Soft chemical routes allow the mixing of raw materials on a
molecular level and thus may lead to significant reduction in the
synthesis temperature for the formation of phase-pure
Li4Ti5O12. Because the material sintering is thermally activated,
a reduction in synthesis temperature will effectively suppress the
grain growth, and nano Li4Ti5O12 particles may be obtained.
The sol–gel process is a well-developed soft chemical synthetic
technique that has been extensively applied to the synthesis of a
9
wide range of functional materials with better morphological
control, higher phase purity, smaller particle size and narrower
particle size distribution than solid-state reactions [84,85]. In a
typical sol–gel process, the raw materials are first dispersed in a
solvent, and the hydrolysis is conducted in a controlled manner to
produce a sol and to generate a certain spatial structure of gel via
aging. The gel is then dried and heat-treated to yield a product with
the desired composition. Because the sol–gel process allows the
reactants to be homogeneously mixed at the molecular level, the
temperature of formation for the phase-pure composite can be
significantly reduced; consequently, the product may have an
ultrafine particle size and a high surface area.
The sol–gel method has also been applied to the synthesis of
Li4Ti5O12 [86–96]. Bach et al. first applied a sol–gel process to the
preparation of Li4Ti5O12; they conducted the synthesis in a non-
aqueous medium with lithium acetate (LiAc) and titanium (IV)
isopropoxide (titanium tetraisopropoxide, TTIP) as the raw
materials [15,87]. Later, Shen et al. applied a similar process to
the synthesis of Li4Ti5O12 [88]. The sol–gel process is typically
based on inorganic polymerization from a molecular precursor,
which leads to highly dispersed colloids, or two-phase systems
with small oxide particles dispersed in a liquid medium
[84,85]. The pyrolysis speed is key to determining the particle
size of the product because rapid hydrolysis results in large
10 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 12. Field-emission SEM (FE-SEM) images of Li4Ti5O12 powders calcined at
different temperatures: (a) 800 8C, (b) 750 8C, and (c) 700 8C [93].
aggregates. To control the hydrolysis speed, Hao et al. applied
triethanolamine (TEA) and citric acid (CA) as complexing agents for
the titanium ion during the sol–gel synthesis of Li4Ti5O12 using
tetrabutyl (ortho) titanate (TBOT) as the titanium source
[89,90]. However, a calcination temperature of 800 8C (TEA) or
850 8C (CA) was still required to obtain phase-pure Li4Ti5O12. As
observed by scanning electron microscopy (SEM), the products had
relatively large grain sizes of 105–223 nm and 500 nm,
respectively, with TEA and CA as the complexing agents.
Venkateswarlu et al. successfully prepared high-purity nanosized
Li4Ti5O12 with a crystal size of 39 nm, using a sol–gel process after
further calcination at 800 8C for 12 h with TTIP and LiAc dihydrate
as the raw materials [91]. The discharge and charge capacities of
the as-synthesized electrode materials reached 255 and
142 mA h g1, respectively, in the potential range of 0.01–1.75 V
at a 0.1 C rate, while a specific charge capacity of 126 mA h g1 in
the potential range of 1.0–2.0 V was achieved at 0.2 C with good
cycling stability. Khamane et al. applied a simple cetyltrimethy-
lammonium bromide (CTAB)-assisted sol–gel technique to syn-
thesize Li4Ti5O12 [92]. The nanosized Li4Ti5O12 calcinated at 800 8C
exhibited an initial discharge capacity of 174 mA h g1 at a 0.2 C
rate. A capacity of 164 mA h g1 was maintained even after cycling
30 times at the same rate. In contrast, the sample prepared without
CTAB had an initial discharge capacity of only 140 mA h g1, which
decayed to only 110 mA h g1 after cycling 30 times at a 0.2 C rate.
In each of the above-described sol–gel processes, further
calcination at 800 8C or higher was conducted or required to
produce Li4Ti5O12 with sufficient purity; however, such high
calcination temperatures may cause serious aggregation of the
particles. For example, Wang et al. prepared nano Li4Ti5O12
powders via a gel process using acrylic acid, TBOT and lithium
nitrate as the precursors [93]. Although the samples exhibited
attractive properties, severe sintering was observed as shown in
Fig. 12, and the samples calcinated at 700, 750 and 800 8C had low
specific surface areas of only 5.8, 1.3 and 1.0 m2 g1, respectively.
Jiang et al. demonstrated that high dispersivity is important to
increasing the rate performance of a Li4Ti5O12 electrode [94]. They
applied Pluronic P123 as a surfactant to suppress particle
aggregation during the sol–gel synthesis of Li4Ti5O12. The capacity
at a discharge rate of 1 A g1 for the sample prepared without the
surfactant was only 30% of that at a rate of 0.1 A g1, while the
capacity at a rate of 1 A g1 for the sample prepared by applying
the surfactant reached approximately 88.6% of that at the 0.1 A g1
rate. Recently, Zhang et al. used a modified sol–gel method with
both ethylene diamine tetraacetic acid (EDTA) and CA as chelating
agents to prepare Li4Ti5O12 [97]. Li4Ti5O12 nanoparticles with pure
phase were obtained at 750 8C; this product delivered a capacity of
164 mA h g1 at 1 C and an outstanding capacity retention of 97%
after 1000 cycles, even though a network morphology due to the
sintering was observed.
Aggregation can be reduced by reducing the calcination
temperature and/or shortening the calcination time. For example,
Kavan et al. successfully prepared Li4Ti5O12 nanoparticles with
high surface areas of 53–183 m2 g1 and small particle sizes of 9–
19 nm using a sol–gel process employing lithium ethoxide and
Ti(V) alkoxides as the raw materials with subsequent calcination at
a low temperature of 500 8C for only 30 min [95]. The as-prepared
Li4Ti5O12, in a thin-film electrode configuration with a thickness of
2–4 mm, exhibited excellent activity toward Li insertion even at
250 C (Fig. 13). However, a small quantity of anatase phase (0.3–
0.6%) remained in the synthesized samples. Kalbac et al. further
modified the sol–gel process by controlling the hydrolysis of the
metal alkoxides by adding polyethylene glycol (PEG) and
successfully prepared phase-pure Li4Ti5O12 with a high surface
area of 183–196 m2 g1 and a crystalline size of only 9–12 nm [96].
The microemulsion method was also applied to synthesize
Li4Ti5O12 nanoparticles. Liu et al. successfully prepared pure-phase
Li4Ti5O12 nanocrystalline using a facile microemulsion method
[98]. The as-prepared Ti(OC3H7)4/n-pentanol/CTAB/cyclohexane
solution and LiOHH2O/n-pentanol/CTAB/cyclohexane solution
were mixed and aged. After washing, drying and calcining
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 13. Chronopotentiometric plot of (A) Li4Ti5O12 prepared from Ti(IV) butoxide–Li
ethoxide compared to (B) commercial Li4Ti5O12 spinel (LT-2 from Titan Kogyo
Japan). Electrolyte solution: 1 M LiN(CF3SO2)2 + EC/DME (1:1 by mass). The
charging/discharging current, i, was adjusted to charging rate of 2, 50, 100, 150,
200, and 250 C for solid curves from top to bottom. Dashed curves display the
corresponding galvanostatic discharging at the same rates. For the sake of clarity,
the time (t) is multiplied by the absolute value of i [95].
(600 8C, 2 h), pure-phase Li4Ti5O12 with sizes of 30–50 nm could be
obtained. The as-synthesized Li4Ti5O12 nanocrystalline exhibited
high capacities of 166, 136 and 130 mA h g1 at 1, 5 and 10 C after
50 cycles, respectively.
Hydrothermal/solvothermal methods are also important soft
chemical methods used for the facile preparation of nanoparticles
at controlled temperatures and pressures with versatile morphol-
ogies and properties. Nugroho et al. successfully synthesized
nanosized Li4Ti5O12 through the hydrothermal treatment of
LiOHH2O and TTIP in supercritical water at 400 8C and 300 bar
11
[99]. The powder synthesized via the supercritical hydrothermal
method after a short treatment period of 15 min and subsequent
calcination at 700 8C for 24 h is a quasi-sphere with a principal
grain size in the range of 150–200 nm. Grain sizes of 50–100 nm
can be obtained in samples synthesized via hydrothermal
treatment over 6 h without subsequent calcination. The combina-
tion of supercritical water hydrothermal treatment over a short
time with subsequent low-temperature calcination was found to
be better for achieving high performance with capacities of 193,
160 and 140 mA h g1 at 1, 10 and 20 C, respectively. Laumann
et al. developed a novel rapid, continuous flow hydrothermal
process for the synthesis of Li4Ti5O12 in sub- and supercritical
water [100]. They claimed that crystalline Li4Ti5O12 nanoparticles
of 4.5 nm with a specific surface area greater than 230 m2 g1
were successfully prepared in a single step and in less than 1 min
by the novel hydrothermal process using TTIP and lithium
dissolved in ethanol. After further calcination at approximately
600 8C, the sample delivered capacities greater than 180, 156, 143,
124, 112, and 96 mA h g1 at 0.1, 1, 2, 4, 10 and 20 C, respectively,
and a capacity of 157 mA h g1 was maintained following
50 cycles at a rate of 1 C. Zhang et al. reported a glycerol assisted
hydrothermal method to synthesize Li4Ti5O12 nanoparticles
[101]. Different initial Ti:Li molar ratios and calcining tempera-
tures were studied, and ultrafine pure Li4Ti5O12 nanoparticles with
sizes of 25 nm were successfully obtained with a Ti:Li ratio of
1:4.5125 and calcining temperature of 500 8C, which delivered a
high rate performance with a discharge capacity of 155 mA h g1
even at 20 C and stable cycling performance with a capacity
retention of 93.3% after 500 cycles at 5 C. Li et al. synthesized 70–
200 nm lump Li4Ti5O12/C using a facile hydrothermal method with
Ti(OC4H9)4 and LiAc as raw materials and CTAB as a surfactant
[102]. Super rate performance with specific capacities of 151 and
136 mA h g1 at 10 and 20 C was achieved for the lump Li4Ti5O12/C.
The authors found that the presence of CTAB is very important to
obtain a larger lithium ion diffusion coefficient and smaller charge-
transfer resistance for the Li4Ti5O12/C composite. To continuously
produce Li4Ti5O12 nanoparticles, a supercritical flow hydrothermal
reaction system was applied with appropriate Ti sources and Li/Ti
ratio [103]. Pure-phase Li4Ti5O12 with a particle size of approxi-
mately 100 nm was successfully synthesized using titanium
dioxide sols (M-6: TiO2 6%, crystallite size 5 nm, pH 3.4; A-6:
TiO2 6% pH 10) as raw materials with initial Li/Ti molar ratios >2.5
for M-6 and >2.0 for A-6. Based on the ability of continuous
synthesis, the supercritical flow hydrothermal reaction may be a
good choice for large-scale industry production of Li4Ti5O12
nanoparticles.
Solvothermal processes in polyol medium have received
attention for the synthesis of Li4Ti5O12 from a low-cost precursor
with simple processing. Kim et al. prepared Li4Ti5O12 nanoparticles
by precipitation from an ethylene glycol (EG) solution of TTIP and
Li2O2 after refluxing at 197 8C for 12 h under ambient pressure
[104]. The as-prepared sample and the products of further
calcination at 320, 500, and 800 8C for 3 h showed particle sizes
of 5, 8, 10 and 400 nm respectively, and their corresponding initial
capacities at a discharge rate of 0.05 mA cm2 reached 200, 310,
320 and 260 mA h g1, respectively, all exceeding the theoretical
value of 175 mA h g1. However, the samples showed relatively
poor cycling stability. The sample calcined at 500 8C exhibited the
best capacity retention; a value of approximately 200 mA h g1
was maintained after 60 charge–discharge cycles at rates varying
from 0.05 to 0.4 mA cm2. Lim et al. prepared nanosized Li4Ti5O12
via the solvothermal treatment of LiOH, TTIP and (HOCH2CH2)2O in
polyol medium at 235 8C for 16 h [105]. After further calcination at
500 8C for 5 h in air, the resulting powder exhibited a particle size
of 10–20 nm with initial discharge/charge capacities of 230/
179 mA h g1 at a current density of 0.1 mA cm2 in the voltage
12 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 14. (a) FE-SEM micrograph of Li4Ti5O12 powder calcined at 800 8C (b) A
magnified FE-SEM view of the selected section of (a) [111].
range of 1.0–2.5 V. In comparison, the sample prepared from a
solid-phase reaction had discharge/charge capacities of only 162/
154 mA h g1. Even at high rates of 30 and 60 C, the sample
prepared using solvothermal synthesis exhibited charge capacities
of 159 and 137 mA h g1.
In addition to soft chemical methods, combustion techniques
have been extensively investigated for the preparation of advanced
functional materials. These techniques allow the temperature to
instantly reach several thousand degrees Celsius during the
synthesis [106,107]. Such a high temperature promotes the
solid-state reaction, while the short combustion time effectively
suppresses the grain growth. As a result, high-purity products with
ultrafine particle sizes can be easily prepared. The combustion
synthesis of Li4Ti5O12 has been examined over the past several
years [108–113]. Depending on the synthetic conditions, the
resulting Li4Ti5O12 can be dense, micrometer-sized particles, sub-
micrometer-sized particles with a porous morphology, or nano-
meter-sized particles. Raja et al. applied an aqueous combustion
technique for the synthesis of Li4Ti5O12 using the amino acid
alanine as a fuel, Ti(OCH3)4 and LiNO3 as cation sources, and HNO3
as an oxidant [111]. Li4Ti5O12 nanoparticles with sizes in the range
of 40–80 nm (Fig. 14) and a phase purity of 90% were successfully
obtained after further calcination of the primary product from
direct solution combustion at 800 8C for 10 h in air.
Spray pyrolysis is a powerful technique for synthesizing a wide
range of ceramic powders with small particle sizes [114–116]. For
a typical synthesis, the raw materials are first mixed into a solution
and atomized to micrometer-sized droplets through a nozzle. The
particles are then calcined in a high-temperature furnace to
quickly form powders with the desired composition. There are
several advantages to synthesizing ceramic powders by spray
pyrolysis including a spherical particulate shape, uniform particle
size, a low degree of aggregation and high purity of the product,
continuous preparation and a short reaction time for the synthetic
process. Accordingly, spray pyrolysis was also applied to the
synthesis of Li4Ti5O12. Ernst et al. prepared a series of inorganic
composites including Li4Ti5O12 nanoparticles for LIBs via flame
spray pyrolysis; the as-prepared Li4Ti5O12 was 85% pure with a
particle size of approximately 18 nm and a specific surface area of
86 m2 g1 [117]. Doi et al. successfully prepared well-crystallized
Li4Ti5O12 nanoparticles with a fairly uniform particle size of only
approximately 12 nm via the electrospray pyrolysis of a Ti(OC3H7)4
and lithium acetonate starting solution in 2-propanol at 400 8C
[118]. Bresser et al. successfully synthesized 20–30 nm Li4Ti5O12
nanoparticles using a flame spray pyrolysis [119]. Although several
phase impurities of rutile TiO2, anatase TiO2 and Li3Ti3O7 were
observed in the as-synthesized nanoparticles, the electrode still
exhibited superior cycling performance with a stable capacity of
approximately 116 mA h g1 at 10 C through 1000 cycles. The
introduced impurities might be due to the evaporation of lithium
during the flame spray pyrolysis; increasing the amount of initial
lithium source may address this issue. Kim et al. successfully
prepared phase-pure Li4Ti5O12 nanoparticles via the flame spray
pyrolysis method with a 15% excess of lithium source and a post-
treatment at 800 8C [120]. The as-prepared nanoparticles with
sizes of 300 nm exhibited an initial capacity of 151 mA h g1 and
a high Coulombic efficiency of 99%.
The use of expensive Ti(IV) alkoxides as a raw material (TTIP or
titanium n-butoxide) makes all of the above-described processes
economically less attractive for practical applications. Therefore, the
synthesis of nano-sized Li4Ti5O12 via less complex and lower-cost
techniques has recently received attention. Although solid-phase
reactions may result in coarse particles with inhomogeneous phases,
their simplicity, low cost and mass production capability make them
highly attractive methods for powder synthesis. For many decades,
solid-state reactions were widely applied in industrial processes. In a
conventional solid-phase reaction, the product is first formed at the
reactant interface, which creates a diffusion block for further
reactions. Thus, calcination at high temperatures for a long period is
required to overcome such a diffusion block, leading to substantial
grain growth of the product. The solid-state reaction mechanism of
Li4Ti5O12 from anatase TiO2 was studied via in situ high temperature
powder X-ray diffraction and thermal gravimetry-differential
thermal analysis: in a typical reaction process, monoclinic Li2TiO3
was formed from the reaction between TiO2 and Li2CO3; it further
reacted with the remaining TiO2 to form a Li4Ti5O12 phase at a higher
temperature [121]. The authors found that decreasing crystallite
sizes could result in a reduced initial reaction temperature. During
the past several years, attempts have been made to modify solid-
phase reactions to reduce the calcination temperature and time, thus
reducing the particle size. These attempts include microwave-
assisted solid-state synthesis [122] and high-energy ball milling
(HEBM)-assisted solid-state synthesis [123–131]. Both processes
can effectively promote the solid-state reaction at a lower
temperature by providing an additional energy source. Lee et al.
introduced a novel method based on a solid-phase reaction for the
preparation of homogeneous Li4Ti5O12 nanoparticles with high
purity [132]. They first prepared 2–5-nm-thick LiOH-coated TiO2
nanoparticles via a sonochemical method. These nanoparticles were
then thermally treated at 500 8C to produce Li4Ti5O12 particles with
an average grain size of 30–40 nm.
Most of the Li4Ti5O12 nanoparticles prepared via the above-
described processes, however, had a large size distribution and
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 15. (a) TEM and (b) SEM images for nano-sized Li4Ti5O12 crystals [133].
varying degrees of aggregation. Lu et al. proposed a novel process
for the preparation of nearly uniform Li4Ti5O12 single crystals with
a size of 40 nm [133]. They first prepared a-Li2TiO3 via the
hydrothermal treatment of anatase TiO2 with a uniform particle
size of 4.5 nm in a 2 M LiOH aqueous solution, which was then
reacted with a proper amount of HCl to allow an ion exchange
between the a-Li2TiO3 and the solution leading to the formation of
(Li0.4H0.6)2TiO3 nanocrystals. Well-dispersed Li4Ti5O12 nanocrys-
tals were obtained after the further calcination of the (Li0.4H0.6)2-
TiO3 at 400 8C for 2 h. Fig. 15 provides transmission electron
microscopy (TEM) and SEM images for the as-prepared Li4Ti5O12
nano-sized single crystals. The materials demonstrated reversible
capacities of 172, 165, and 140 mA h g1 at discharge rates of 0.5, 1,
and 5 C, respectively. After 60 cycles at various rates, the capacity
at a rate of 1 C recovered to nearly the initial value, suggesting a
high cycling stability of the as-prepared electrode. Such a synthesis
13
process with as-prepared TiO2 treated in a concentrated LiOH
solution to achieve lithiation is usually named chemical lithiation.
The chemical lithiation was initially used for synthesis of
nanocrystalline Li4Ti5O12 [134], and was later expanded to
synthesize Li4Ti5O12 with various nanostructures. Fig. 16 compares
the chemical lithiation route for preparing Li4Ti5O12 with the
common synthesis route. In a common synthesis route, the initial
Li:Ti ratio of feeded raw materials is usually 4:5; some excess
lithium was used to compensate the lithium loss by evaporation
during calcination. In a chemical lithiation synthesis, however, a
concentrated LiOH solution is used as the lithium source, implying
that the initial Li:Ti ratio is much higher than 4:5. The
thermodynamically stable phase rutile TiO2 usually could not be
chemically lithiated, anatase TiO2 or amorphous TiO2 is preferred.
After proper calcination, however, a pure spinel phase could be
easily obtained. It seems that the chemical lithiation process could
result in formation of Li–Ti–O intermediate phase, which could
easily become a spinel phase. The chemical lithiation in LiOH
solution is usually carried out at low temperatures (i.e., <200 8C)
for a long period of time, and the subsequent calcination
temperature could also be relatively low when a nanosized TiO2
was used. Thus, the nanostructure of TiO2 could be retained in the
final Li4Ti5O12 phase, resulting in outstanding electrochemical
performance. To date, however, the Li–Ti–O intermediate phase
structure, the chemical lithiation mechanism, and the final Li:Ti
ratio are still not yet fully understood and could be further studied
using advanced characterization techniques.
3.1.2. 1–3D nanostructures
As previously mentioned, reducing the particle size of Li4Ti5O12
to the nanometer range can significantly reduce the diffusion
distance for both electrons and lithium ions within the electrode
bulk. The reduced particle size can also increase the specific surface
area for an interfacial reaction; as a result, the electrode may exhibit
improved performance even without surface coating and/or lattice
doping. However, some detrimental effects are introduced when
ultrafine nanoparticles are used as electrodes including an increased
difficulty in electric wiring and loss of the electrode material.
Improper wiring can render some particles electrochemically
inactive; thus, reducing the electrode performance of the nanoelec-
trodes compared to that of the micrometer-sized electrodes. In
addition, the nanoparticles released from the electrode surface may
cross the porous separator, which has a pore size in the micrometer
range, and agglomerate on the other electrode, resulting in a loss of
capacity and an internal short circuit [135]. One effective method of
solving the above-mentioned problems requires the development of
one-dimensional (1D) nanostructures such as nanotubes, nano-
wires, nanorods, and nanofibers (Fig. 11). These nanostructures
possess the properties of nanoparticles such as high surface area and
short diffusion distance of charges within the bulk. However, these
nanostructures are of the micrometer size in one dimension, which
facilitates current collection.
Nanotubes are 1D nanostructures with hollow interior chan-
nels. Because of their large surface areas, high surface-to-weight
ratios and nanosize, nanotubes are highly attractive for energy
storage applications. Lee et al. applied a two-step process for the
synthesis of Li4Ti5O12 nanotubes [136]. In this synthesis, plate-
shaped Li4Ti5O12 was first prepared via heat treatment at 500 8C of
the primary product from the reaction of a mixture of titanium n-
butoxide, cetyltrimethylammonium chloride and lithium hydrox-
ide at 120 8C for 2 h, which was then further hydrothermally
treated at 120 8C in 10 M aqueous NaOH. The as-prepared sample
exhibited a nanotube morphology with an open-ended structure
that had outer and inner diameters of 11 and 6 nm,
respectively, and a specific surface area of 53.7 m2 g1. The
product showed a reversible capacity of 156 and 145 mA h g1 at
14 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 16. Schematic illustration of the chemical lithiation synthesis route for preparing Li4Ti5O12 compared to the common synthesis route.

rates of 0.1 and 2 C, respectively. The electrode also demonstrated
good cycling stability and no obvious capacity fade after
25 charge–discharge cycles at a rate of 0.1 C.
Li et al. prepared 1D nanostructured Li4Ti5O12 from hydrogen
titanate nanotube precursors via a hydrothermal lithium ion
exchange process. The as-prepared Li4Ti5O12 had an outer
diameter of 10 nm and lengths of several hundred nanometers
to over several micrometers [137]. The hydrogen titanate
nanotube was prepared from industrial TiO2 powders via a
sonochemical–hydrothermal reaction in concentrated 10–15 M
NaOH at 120–170 8C for 24–72 h. TEM and SEM images of the
various samples at different stages are shown in Fig. 17. A higher
NaOH concentration with higher temperature and increased
reaction time resulted in hydrogen titanate nanowires, not
nanotubes. Further hydrothermal treatment of the H-TiO2
nanotube/nanowires in the aqueous LiOH solution allows an ion
exchange between H-TiO2 and the solution to form a Li4Ti5O12
precursor, which was converted to crystallized Li4Ti5O12 by further

Fig. 17. (a) TEM micrograph of hydrothermal (120 8C for 24 h) lithium ion exchanged lithium titanate nanotubes before heat treatment. (b) Sample (a) after heat treatment at
350 8C for 2 h in air atmosphere. (c) SEM micrograph of hydrothermal (120 8C for 24 h) lithium ion exchanged lithium titanate nanowires before heat treatment. (d) A single
nanowire TEM micrograph of sample (c) after heat treatment at 500 8C for 2 h in air atmosphere [137].
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 15

Fig. 18. (a) Typical SEM and (b) TEM images of LT-E6 calcined at 500 8C, (c) cycling behavior at different C rates for the LT-E6-500, LT-E6-700, LT-E8-500, and LT-E8-700
powders, respectively. LT represents Li4Ti5O12, E6 represents the solvothermal reaction in various mixed solvents including ethanol 60 vol.%, 700 represents calcination at
700 8C [141].

calcination at 300–500 8C for 2–6 h. Neither the hydrothermal ion Electrospinning has proven to be a versatile technique for the
exchange nor the subsequent calcination induced a change in fabrication of nanofibers of varied dimensions with versatile
powder’s morphology. Kim et al. prepared Li4Ti5O12 nanowires morphologies, such as hollow fibers, solid fibers and porous
with a diameter of 180 nm, a length of several micrometers and a fibers [142–146]. Such nanofibers can be easily assembled into
specific surface area of 38 m2 g1 by firing a mixture of
TiO21.25H2O nanowires and LiAc at 800 8C for 3 h [138]. The
as-prepared Li4Ti5O12 nanowires exhibited capacities of 165,
157 and 155 mA h g1 at rates of 0.1, 5 and 10 C, respectively.
No noticeable capacity decay was observed after 30 cycles at a rate
of 0.1 C. By applying a process similar to that reported by Li et al.
[137], Li et al. successfully synthesized Li4Ti5O12 nanorods with
excellent electrochemical performance [139]. They first prepared
TiO2 nanorods via the hydrothermal treatment of rutile TiO2
powder in 10 M NaOH at 180 8C. Following an acid treatment, the
resulting titanate nanorods were dispersed in an aqueous LiOH
solution for further hydrothermal treatment. The nanorods were
finally calcined at 500–800 8C to obtain well-crystallized Li4Ti5O12
nanorods. At a discharge current density of 50 mA g1, the sample
calcined at 800 8C exhibited a reversible capacity of 147.5 mA h g1
after 100 cycles, and a capacity of 133.8 mA h g1 was achieved
even at a high discharge current density of 1600 mA g1. Such high
performance was attributed to the good crystallinity, the unique
nanorod particulate morphology, and the short diffusion distances
of both the lithium ion and the electron. To further eliminate the
tedious acid-washing procedure, hydrothermally synthesized
sodium titanate (Na2Ti2O4(OH)2) nanotubes were treated in
0.8 M LiOH solution under stirring at room temperature and were
finally converted into the Li4Ti5O12 phase by calcining at 400–
700 8C [140]. The sample calcined at 500 8C exhibited the best
electrochemical performance with a specific capacity of
146 mA h g1 at 10 C and a stable capacity retention of only
0.7% decay after 200 cycles, even though the initial tubular
morphology was destroyed after calcination.
Lee et al. synthesized nanoparticle-modified Li4Ti5O12 nano-
wires through a solvothermal reaction using Li(OH)H2O and
protonated trititanate (H2Ti3O7) nanowires as the templates in an
ethanol/water mixture with subsequent heat treatment [141]. As
shown in Fig. 18, the resulting nanowires had diameters of 130 nm,
lengths in the range of 1–3 mm and high rate capacities with values
of 151, 139, 128 and 114 mA h g1 at 1, 5, 10 and 20 C, respectively.
A capacity of 125 mA h g1 was retained after 500 charge– Fig. 19. SEM images of (a) Li4Ti5O12/PVP fibers after calcining in air at 750 8C for 1 h
fabricated by electrospinning, (b) Li4Ti5O12 fibers after electrochemical reaction [147].
discharge cycles at a rate of 1 C, suggesting a high cycling stability.
16 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 20. (a, b) SEM, (c) TEM and SAED images (inset in c) of the Li4Ti5O12 nanosheet, (d) a HRTEM image of Li4Ti5O12 recorded on the corner of a sheet [158].
nonwoven nets with three-dimensional (3D) architectures to serve
as freestanding film electrodes without the need for an additional
binder or conductive additive. Lu et al. fabricated Li4Ti5O12
nanofibers via the electrospinning method with an average
diameter of 150  50 nm that were composed of small crystalline
grains with an average size of less than 100 nm [147], as shown in
Fig. 19. Such nanofibers were packed in cross-shape to form 3D
nonwoven films. When these films were applied directly as
electrodes, they exhibited high first discharge capacities of
192 and 170 mA h g1 at 0.5 and 1.5 C, respectively. However, a
relatively large capacity decay rate was observed; the capacities after
cycling at rates of 0.5 and 1.5 C reduced to 140 and 87 mA h g1,
respectively. Electrospun Li4Ti5O12 nanofibers with diameters of
230 nm were also fabricated by Wang et al. [148]. The electrodes
were prepared using a conventional coating method with 70 wt.% of
Li4Ti5O12 nanofibers, 20 wt.% carbon black and 10 wt.% binder. The
sample calcined at 700 8C exhibited good rate performance with
specific capacities of 163.3, 138.7, 123.4 and 90.4 mA h g1 at 1, 10,
20 and 60 C, respectively. Moreover, the capacity remained at
120.1 mA h g1 after 300 cycles at 20 C.
Li4Ti5O12/C composite fibers have also been fabricated via the
electrospinning method [149–155]. The introduction of carbon
into the fibers not only effectively increased the apparent
electronic conductivity, which improves the charge transfer and
current collection, but also created mesopores in the nanofibers,
facilitating the penetration of liquid electrolytes and thus
benefiting the interfacial reactions. Especially, Yang et al. observed
that the presence of carbon calcined under Ar atmosphere resulted
in the formation of a pure Li4Ti5O12 phase instead of Li4Ti5O12 and
TiO2 phases after calcination under air atmosphere [153]. There-
fore, these Li4Ti5O12/C fiber electrodes exhibited enhanced
electrochemical performance. Li et al. demonstrated that by
doping Li4Ti5O12 with Nb5+, the electrospun Li4Ti4.95Nb0.05O12/
carbon nanofibers exhibited even better rate capability with
capacities of 167.5 and 110.6 mA h g1 at 1 and 25 C, respectively,
than the electrospun Li4Ti5O12/C nanofibers (163 and 50 mA h g1
at 1 and 25 C, respectively), although both exhibited excellent
cycling stability [156]. However, most of these Li4Ti5O12/C
composite fibers did not appear to be flexible free-standing film
even though the electrospinning method is powerful for preparing
a flexible film electrode for LIBs [145]. This is mostly due to the
presence of a reaction between lithium and titanium sources for
forming the spinel phase since the flexible TiO2/C film electrode
could be easily prepared without application of lithium. The
preparation of flexible carbon fiber film and growth of Li4Ti5O12
nanostructure on it could be a good way to obtain a flexible
Li4Ti5O12/C fiber film electrode.
Beyond 1D structures, two-dimensional (2D) structures
(Fig. 11) (e.g., nanosheets and nanoplates) usually have shorter
diffusion distances for both electrons and lithium ions due to the
ultrathin thickness compared with the diameter of 1D structures
and better current collection due to the sheet morphology
compared with 1D structure and are expected to exhibit even
better electrochemical performance. Lamellar Li4Ti5O12 (called a
flower-like structure) was synthesized by a solvothermal method
with as-synthesized amorphous TiO2 spheres and LiOH as the
sources and ethanol as the solvent [157]. A pure spinel phase could
be obtained after calcination at a relatively low temperature of
600 8C for 3 h. The thickness of the as-calcined lamellar Li4Ti5O12
was only 10 nm, which is beneficial for lithium ion insertion/
extraction. As a result, superior capacities of 148, 138,
118 mA h g1 at 0.5, 5, 30 C, respectively, was demonstrated. Li
et al. prepared single-crystalline Li4Ti5O12 nanosheets with
thicknesses of 10–20 nm (Fig. 20) by the calcination of hydrother-
mally synthesized Li1.81H0.19Ti2O5xH2O nanosheets at 500 8C for
2 h [158]. A hydrolysis–Kirkendall effect–Ostwald ripening process
was proposed for the formation of lithium titanate oxide hydrate
nanosheets during the hydrothermal synthesis. The as-calcined
Li4Ti5O12 nanosheets delivered a discharge capacity of
120 mA h g1 even after 300 cycles at a 10 C rate. Recently, Sha
et al. synthesized well-crystallized Li4Ti5O12 nanoplates via
hydrothermal synthesis in a benzyl alcohol–NH3H2O solvent
using LiOHH2O and TBOT as raw materials and a subsequent
calcination at 500 8C [159]. Although the calcination temperature
is as low as 500 8C, but the as-synthesized Li4Ti5O12 nanoplates
obtained from a 6-h hydrothermal reaction exhibited a well-
crystallized nature (Fig. 21) as well as an excellent rate capability
and cycling stability with a discharge capacity of 153 mA h g1
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 17

Fig. 21. (a) TEM, (b) HR-TEM and (c) the cycling performance (10 C) of the as-prepared Li4Ti5O12 nanoplates [159].

Fig. 22. TEM image of wavelike Li4Ti5O12 nanosheet annealed at 600 8C. The inset in (c) is a corresponding schematic illustration of the wavelike nanosheet [160].

after 1000 cycles at a 10 C rate. Liu et al. prepared similar Li4Ti5O12
nanoplates via hydrothermal synthesis, in which metallic lithium
was reacted with N,N-dimethylethanolamine at first and the as-
obtained solution was mixed with tetrabutyl titanate with a Li/Ti
ratio of 4:5 followed by hydrothermal treatment and further
calcination [160]. Fig. 22 shows the typical TEM images of the
sample after calcination at 600 8C for 2 h, the microstructure of the
Li4Ti5O12 were mainly nanoplates as shown in Fig. 22a. A magnified
image (Fig. 22b) shows that the morphology of nanoplates
appeared to be similar to that reported by Sha et al. (Fig. 21a).
After careful observation, these nanoplates were wave-like
nanosheets as shown in Fig. 22c. By calcination of the sample in
the absence of oxygen, nitrogen-doped carbon derived from N,N-
dimethylethanolamine was introduced into the sample, even
though the carbon content was as low as 0.6 wt.%, excellent
electrochemical performance was achieved with capacities of
around 171, 164, 151 and 122 mA h g1, at 20, 30, 50 and 100 C,
respectively. Furthermore, the electrode exhibited outstanding
performance even at 10 C, demonstrating capacities of 172, 154,
and 135 mA h g1 at 0, 10 and 20 8C respectively.
18 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 23. Typical routes for synthesis of porous Li4Ti5O12, and the corresponding representative synthesis method.

Additionally, 2D structures can stack to form 3D structures such as-synthesized products contained impurity phases of Li2TiO3,
as flower-like microspheres composed of nanosheets or nano- rutile TiO2 and anatase TiO2 of approximately 10% of the total mass.
flakes; Li4Ti5O12 with a wide range of different 3D structures will Woo et al. prepared an 80-mm-thick 3DOM Li4Ti5O12 film via a
be discussed in the following sections. colloidal crystal (monodispersed polystyrene (PS) spheres) templat-
ing process [162] similar to that applied by Sorensen et al. [161]. A
3.2. Morphological control precursor of sol consisting of TTIP and LiAc was first impregnated
into the void space of the template. The precursor was then calcined
3.2.1. Porous electrodes at 800 8C to obtain a macroporous Li4Ti5O12 membrane with an
Incorporating pores into micrometer-sized particles is another inverse opal structure. As shown in Fig. 24, the interconnected pores
effective method for increasing the rate performance of electrode of uniform size (0.8 mm) were clearly observed with a pure Li4Ti5O12
materials. Such micrometer-sized porous electrodes have the phase composition. The 3DOM Li4Ti5O12 membrane exhibited a
advantages of easy current collection and short diffusion pathways discharge capacity of 160 mA h g1 at a rate of 0.1 C and retained a
for lithium ion. The porous structure increases the surface area, thus capacity of approximately 60 mA h g1 at a high rate of 10 C. The
producing more surface sites for lithium to insert into the electrode 3DOM Li4Ti5O12 film electrode also exhibited good cycling stability
material, while the nanometer-thick walls shorten the lithium with a discharge capacity decay rate of approximately 0.1 mA h g1
diffusion distances. Both properties are helpful for reducing the per cycle during 100 charge/discharge cycles at a rate of 1 C. Shao
electrode polarization. The micrometer-sized particles with 3D
structures also ensure inter-particle contact and increase the
electrode stability, thus suppressing capacity loss. Summarized in
Fig. 23 are three typical routes for synthesis of porous Li4Ti5O12. The
first route is using template or pore former to create pores in the
samples. The pore size and porosity could be easily controlled by
using different template or pore former. The second route is
combustion synthesis. The pores are mainly created by the diffusion
gases in the process. It is relatively simple but less controllable. The
third route is the self-assembling synthesis. The pores were from the
void space created from the special structures as well as the sites left
by removing some organic groups.
Sorensen et al. prepared three-dimensionally ordered macro-
porous (3DOM) Li4Ti5O12 using poly (methyl methacrylate) colloidal
crystal templates and metal organic aqueous precursors [161]. The
electrode performance was found to be closely related to the status
of the voids in the templates filled by the metal organic aqueous
precursors. If the voids were underfilled or perfectly filled, the rate
capability of Li4Ti5O12 was markedly improved, while the perfor-
mance was reduced with overfilled voids due to the decreased
porosity and the increased wall thickness. Unfortunately, the Fig. 24. SEM image of 3DOM Li4Ti5O12 annealed at 800 8C [162].
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 19

et al. also used monodisperse PS spheres as templates to obtain
porous Li4Ti5O12 using a sol–gel method [163]. After calcination, the
pores with an average diameter of approximately 100 nm were
created by burning of 350 nm PS sphere templates. The nanoporous
Li4Ti5O12 exhibited good cycling performance with a capacity of
170 mA h g1 after 100 cycles at 0.1 C (0.5–3.0 V).
Solid-state reactions are still the most widely used methods for
industrial powder synthesis due to their simplicity and mass
production capability. However, the products typically exhibit
large, dense grains and phase inhomogeneity. By tailoring the
synthetic parameters, solid-state reactions may also be used to
synthesize porous electrodes for LIBs. Lin et al. introduced a
modified solid-phase reaction for the synthesis of porous Li4Ti5O12
with improved electrochemical performance [164] by using LiCl
and TiCl4 as raw materials and oxalic acid as a pore former. The
initial capacities of the resulting electrode material reached
167 and 133 mA h g1 at 0.5 and 1 C charge/discharge rates,
respectively, and the capacity was maintained at 98% after
200 charge/discharge cycles at room temperature. At rates of
10 and 50 C, the electrode still delivered stable capacities of 70
and 30 mA h g1, respectively. Lv et al. synthesized porous
Li4Ti5O12 via a solid-phase reaction using phenol-formaldehyde
resin as a template [165]. The Li4Ti5O12 produced from calcination
at 800 8C for 8 h exhibited a phase-pure spinel structure, and the
sample contained mesopores primarily concentrated in the range
of 2–20 nm with discharge capacities of 167, 164, 138, 112, 71 and
62 mA h g1 at 0.2, 0.4, 1, 2, 10, and 20 C, respectively. Recently, Lai
et al. reported a mesoporous Li4Ti5O12 with a specific surface area
of 153.7 m2 g1 prepared via a ball-milling-assisted solid-state
reaction using TiOSO4xH2O and LiOHH2O as raw materials
[166]. A high specific capacity of 143.4 mA h g1 was achieved
at a 10 C rate even after 50 cycles for this mesoporous
Li4Ti5O12. The key to obtaining such a mesoporous structure could
be the calcination at a low temperature of 500 8C and the
utilization of washing of Li2SO4 impurities to generate mesopores.
Combustion synthesis is an effective fabrication technique that
has also been applied to the synthesis of porous Li4Ti5O12. In a
solution combustion process, the enormous quantity of gases
produced during the synthesis may facilitate the formation of rich
pores in the final product. Prakash et al. applied a single-step
solution combustion method for the synthesis of highly porous
spheres composed of well-crystallized Li4Ti5O12 nanoparticles with
a primary particle size between 20 and 50 nm and nano- and
micropores with sizes ranging from 0.15 to 1.5 mm (Fig. 25)
[110]. Such hierarchically nanostructured microscale materials
exhibited good rate performance (Fig. 25), achieving a

Fig. 25. (a) Digital photograph of voluminous Li4Ti5O12 formed after the combustion of corresponding metal nitrates with glycine at 800 8C, (b) corresponding SEM image, and
(c) capacity-voltage profiles for nanocrystalline Li4Ti5O12 synthesized by the combustion method at different rates. The inset shows the capacity voltage profile for bulk
Li4Ti5O12 prepared by the solid-state method [110].
20 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

near-theoretical capacity of 170 mA h g1 at a rate of 0.5 C. The
electrode continued to deliver high capacities of 105 and
70 mA h g1 even at ultrahigh discharge rates of 50 and 100 C,
respectively. In addition, the samples exhibited good cycling
stability, with a capacity retention greater than 95% after 100 cycles
at different rates. Such excellent performance was attributed to the
mesoporous powders made of fused nanoparticles. However, too
much porosity may lead to a low tap density and thus a low
volumetric energy density.
As versatile synthetic techniques, hydrothermal methods were
widely applied for the synthesis of hierarchically structured porous
Li4Ti5O12. For example, Lai et al. prepared microsized Li4Ti5O12
nanosheets via a facile hydrothermal route [167]. The microsized
grains had irregular shapes consisting of random sheet-like
Li4Ti5O12 with thicknesses of 10–16 nm. The nanosheets intro-
duced a pseudocapacitive effect, leading to improved capability at
high discharge rates. The as-prepared electrode exhibited a
capacity of 147.3 mA h g1 at 1.1 C rate and retained 128 mA h g1
1 at 11.4 C rate. Amine et al. have also developed hierarchically
structured Li4Ti5O12, micrometer-sized secondary particles (0.5–
2 mm) composed of nanometer-sized particles (<10 nm) and
nanopores, via a hydrothermal process using titanium oxy-sulfate
and lithium hydroxide precursors [168]. The electrode exhibited a
discharge capacity of up to 160 mA h g1 even at a discharge rate of
20 C. In addition, a full battery with a Li4Ti5O12 anode and a lithium
manganese oxide cathode had almost no capacity fade after
1000 charge/discharge cycles at a rate of 5 C at temperatures up to
55 8C. Chen et al. synthesized a defective mesoporous Li4Ti5O12y
(100–500 nm) by a solvothermal method with a subsequent
calcining process in N2 atmosphere [169]. The defective Li4Ti5O12y
exhibited a capacity of 139 mA h g1 at 20 C, and 91.4% of the
capacity was retained over 300 cycles. Hasegawa et al. prepared a
porous Li4Ti5O12 structure with a hierarchical architecture via
hydrothermal treatment of TiO2 wet gel in an aqueous LiOH
solution followed by calcination [170]. The typical SEM and TEM
images of the as-obtained porous Li4Ti5O12 structure calcined at
700 8C are shown in Fig. 26. It appears that the porous structure is
flower-like, composed of platy crystallites. TEM observation
further revealed that the petal of the flower-like structure was a
100–200 nm single-crystalline nanosheet (Fig. 26b). Three lattice
fringes with spacings of 0.41 nm, 0.48 nm and 0.49 nm were
observed from the HR-TEM image (Fig. 26c), which could be
assigned to the d spacings of (0 0 2), (1 1 1) and (1 1 1) planes of
Li4Ti5O12 phase, respectively. The porous Li4Ti5O12 structure with a

Fig. 26. (a) SEM image of the porous Li4Ti5O12 sample calcined at 700 8C; inset is a typical magnified image. (b) TEM image of a typical nanosheet in the sample calcined at
700 8C. (c) HR-TEM image of the nanosheet shown in (b). The inset shows a crystal structure of spinel lithium titanate viewed along [110] zone axis [170].
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 27. Specific capacity and Coulombic efficiency for the first 3000 cycles at a rate
of 64 C (184 mA/cm2) of KLE-templated Li4Ti5O12 thin film electrodes calcined at
650 8C. Cutoff voltages were set at 3.5 and 1.40 V vs. Li/Li+ [171].
Fig. 28. Schematic illustration of hollow spherical Li4Ti5O12 fabrication [173].
hierarchical architecture delivered an outstanding rate perfor-
mance with specific capacities of 165, 155, and 121 mA h g1 at 0.1,
10, and 30 C rate, respectively, and further stable cycling
performance with a capacity retention of 98% after 500 cycles at
5 C.
Haetge reported a facile polymer-directed sol–gel route via the
co-assembly of titanium(IV) n-butoxide and anhydrous LiAc
molecular inorganic precursors with the large diblock copolymer
KLE to a nanocrystalline Li4Ti5O12 thin film with a well-defined
mesoporous morphology [171]. The thin-film electrode exhibited a
capacity of 175 mA h g1 even at a rate of 2 C, which was close to
the theoretical capacity. As shown in Fig. 27, after 3000 cycles at
Fig. 29. Schematic representation of the synthesis of meso-Li4Ti5O12-C [174].
21
64 C, a capacity of 148 mA h g1 was retained with a capacity fade
rate of only 1.5  103% per cycle. These results are exciting. Such
porous Li4Ti5O12 thin films are highly promising as high-rate
anodic materials for thin-film micro-batteries. Jiang et al. prepared
porous Li4Ti5O12 with a spherical pore structure using a sol–gel
method with carbon spheres as the hard template [172]. The
porous Li4Ti5O12 had a particle size of approximately 1 mm and a
wall thickness of approximately 100 nm, which delivered a first
discharge capacity of 175 mA h g1. As a comparison, the micro-
sized and densely aggregated Li4Ti5O12 prepared without using a
carbon sphere template showed a slightly lower capacity of
160 mA h g1 at 0.57 C. However, at 5.7 C, the porous Li4Ti5O12 still
delivered a capacity of 121 mA h g1, while the densely aggregated
Li4Ti5O12 decreased sharply to only 46 mA h g1.
The emulsion method was also studied for the preparation of
porous Li4Ti5O12. Huang et al. synthesized mesoporous Li4Ti5O12
with a spherical pore structure using a macroemulsion method
[173]. As shown in Fig. 28, the authors synthesized porous
Li4Ti5O12 via macroemulsion in a two-phase solution consisting of
n-heptane and ethanol with a P123 triblock copolymer as the
emulsifier. First, a macroemulsion was formed after mixing the
ethanol solution (containing LiAc and P123) and n-heptane in
which the surface layer of the emulsion droplet consisted of P123,
while the inner phase of the droplets contained the LiAc ethanol
solution and the outer phase consisted of the Ti(OC4H9)4 n-heptane
solution. Then, water was dropped into the Ti(OC4H9)4 in the n-
heptane phase outside the emulsion droplets. With the slow
evaporation of n-heptane and ethanol, the TiO2 formed on the
emulsifier layer and the lithium salt deposited homogeneously on
the TiO2. Finally, following the complete removal of solvents, the
precursor was formed with a hollow spherical structure. After
further heat treatment, the hollow spherical Li4Ti5O12 powder was
obtained. The pores with diameters of approximately 1 mm were
formed by 100 nm nanoparticles. The samples delivered capaci-
ties of 162, 150, 128, 115 and 95 mA h g1 at 0.5, 1, 5, 10 and 20 C,
respectively. After 500 charge/discharge cycles at 2 C, a capacity of
135 mA h g1 was maintained with an average capacity loss of only
0.01% per cycle. The high capacity and good cycling stability was
attributed to the hollow morphology and the nanosized Li4Ti5O12
particles.
Kang et al. synthesized a meso-structured Li4Ti5O12-carbon
nanocomposite with uniform pores larger than 15 nm via block
copolymer self-assembly by applying polyisoprene-block-poly(-
ethylene oxide) with an sp2-hybridized carbon-containing hydro-
phobic block as a structure-directing agent [174]. After further
calcination at 700 8C, the Li4Ti5O12 phase was formed, and the
partial polyisoprene was converted to carbon, which coated the
pore walls of the mesoporous Li4Ti5O12. A schematic representa-
tion of the synthesis is shown in Fig. 29. The mesopores with sizes
of 20 nm are organized in a short-range ordered channel with
22 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 30. (a) Schematic illustration of the fabrication process of hierarchical mesoporous nest-like Li4Ti5O12. (b) SEM and (c–e) TEM images of hierarchical mesoporous nest-like
Li4Ti5O12 with different magnifications (the inset in (d) shows the SAED pattern) [175].
wormhole-like structures. The resulting mesoporous micrometer-
sized Li4Ti5O12/C particles exhibited excellent rate performance and
a capacity of 115 mA h g1 even after 500 cycles at a rate of 10 C in a
potential range of 1.0–2.5 V with a capacity retention of 89.7%. Chen
et al. prepared hierarchical mesoporous nest-like Li4Ti5O12 via a
hydrothermal method with a typical process as shown in Fig. 30
using CTAB as a surfactant and a water-soluble titanium complex,
[NH4+]4[H+]2 [Ti4(C2H2O3)4(C2H3O3)2(O2)4O2]6, as the titanium
source [175]. As shown in Fig. 30, the as-prepared Li4Ti5O12 had a
mesoporous nest-like structure composed of nanosized Li4Ti5O12
with a crystalline size of 8.2 nm, falling primarily into the ranges of
4 and 6 nm. The mesopores had wall thicknesses of 50–80 nm. Such
a unique morphological structure resulted in a large specific surface
area of 219.2 m3 g1. High and stable capacities of 135.1 and
113.6 mA h g1 at discharge current densities of 2.5 mA g1 and
10 A g1, respectively, following 200 charge/discharge cycles were
also demonstrated.
Sun et al. prepared mesoporous Li4Ti5O12 nanoclusters with
rich mesopores of 2–6 nm and a high surface area of 142 m2 g1
using a facile solution method and low-temperature calcination
[176]. Briefly, the C16H36O4Ti solution was added to a LiOH solution
under stirring at 80 8C, and the as-obtained precursor was calcined
at 400 8C to form a mesoporous structure. Although Li2CO3
impurities remained in the sample, the nanoclusters delivered a
high capacity of 162 mA h g1 after 60 cycles at 0.5 C.
The above reported porous electrodes were actually porous
active materials themselves. Recently, Singh et al. developed a
porous Li4Ti5O12 electrode by adding NH4HCO3 as a template to the
slurry before the conventional electrode coating process [177]. Brief-
ly, NH4HCO3, Li4Ti5O12/C, polyvinylidene fluoride (PVDF), and Super
P were mixed in an NMP solvent to form a slurry, which was then
coated onto a current collector. After drying at 50 8C, the electrode
was further heated at 90 8C to decompose the NH4HCO3 to form a
porous network that could act as an ionic pathway for fast lithium
storage. As a result, the porous electrode exhibited greatly enhanced
electrochemical performance, especially at high rates.
3.2.2. Nano/microspheres
Although the above-mentioned porous electrodes showed
attractive capacities, rate capabilities, and/or cycling stabilities,
they usually can not achieve high tap densities, and thus fail to meet
both the energy and power demands for practical applications.
Among the various particulate morphologies, spheres have received
particular attention as they can minimize the length of the diffusion
pathway and increase the tap efficiency of the particles. Up to now,
various Li4Ti5O12 nano/microspheres have been synthesized and
investigated as shown in Fig. 31. The Li4Ti5O12 nano/microspheres,
especially with hierarchical porous structures, have received
considerable attention for their high rate performance and high
volumetric energy density.
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 23

Fig. 31. Schematic illustration of various reported Li4Ti5O12 nano/microspheres and corresponding microscope images: dense sphere [191], porous sphere [191], hollow
sphere [204], yolk–shell sphere [183], hollow–yolk–shell sphere [379], flower-like sphere [203], hollow flower-like sphere [207].

Spray drying is a facile and universal method for mass
producing micrometer-sized spherical particles for use in a wide
range of products from medicines to ceramics. Nakahara et al. may
have been the first to apply spray drying to the preparation of
microsized spherical Li4Ti5O12 particles [178]. They obtained
spherical Li4Ti5O12 with an average particle size of 8.5 mm, by
spray drying a mixture of anatase TiO2 dispersed in a LiOHH2O
solution at 110 8C followed by calcination at 875 8C for 6 h in air.
The as-obtained spherical particles exhibited a tap density of
approximately 0.7 g mL1 and a specific surface area of
3.0 m2 g1. Although the capacity stability appears adequate, the
rate performance is not. The authors demonstrated that breaking
down the spherical particles to fine powders with sizes of
approximately 0.7 mm by milling improved the capacity at higher
discharge rates, suggesting that the microspheres likely had
insufficient current collection due to the large sizes and low
surface areas of the spherical particles, which resulted in a large
polarization resistance at high discharge rates. Han et al. prepared
Li4Ti5O12 microspheres by initial high-energy ball-milling of
Li2CO3 and anatase TiO2 and subsequent spray drying [179]. After
calcination, the microspheres exhibited porous structures and
enhanced lithium storage properties with a specific capacity of
139 mA h g1 at 10 C. Hsiao et al. demonstrated that the
introduction of pores into the microspheres prepared via the
spray drying method improved the electrode performance [80];
they prepared two types of Li4Ti5O12 spherical particles via spray
drying—one porous and the other dense. At a discharge rate of 20 C,
the electrode with porous spherical particles reached a capacity of
73 mA h g1, four times that of the electrode with dense spherical
particles (17 mA h g1).
Wen et al. applied a similar spray drying method for the
preparation of spherical Li4Ti5O12 using Li2CO3 and rutile TiO2 as
precursors and polyvinyl butyral (PVB) as a pore former [45]. The
experimental results showed that porous and spherical morphol-
ogies of the spray-dried powders were created and maintained
during the subsequent heat treatment. The Li4Ti5O12 spheres
ranged in size from several microns to 20 mm and exhibited
increased porosity compared with those prepared by Nakahara
et al. [178], likely due to the use of the PVB pore former. The first
discharge capacity reached 153 mA h g1 between 2.5 and 1.0 V at
an unknown discharge rate. However, the authors provided no rate
performance information. The relatively poor performance of the
Li4Ti5O12 microspheres may be due to their large size (several to
20 mm) and lack of surface coating. Moreover, the influence of
calcining temperature (650–800 8C) and Li/Ti atomic ratios (0.784,
0.800, 0.816 and 0.832) on the characteristic and performance of
24 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 32. SEM images of the Li4Ti5O12 powders prepared from spray solutions with different concentrations of citric acid (CA) and ethylene glycol (EG) [182].
Li4Ti5O12 by spray drying were studied by Wu et al. [180] and He
et al. [181], respectively. The results from Wu et al. [180]
demonstrated that there was no impurity phase for any of the
samples calcined at 650–800 8C, and the samples calcined at lower
temperatures of 650 and 700 8C maintained their spherical shapes
and exhibited better rate capabilities because of the higher surface
areas and lower crystallite sizes. Another Li/Ti atomic ratio study
indicated that after calcining at 700 8C for 16 h, the as-prepared
pure-phase Li4Ti5O12 with a Li/Ti ratio of 0.816 exhibited the best
performance, indicating that the Li/Ti ratio is important and that
the volatilization of lithium at high temperature should be
considered during the synthesis process.
Spray pyrolysis allows the simultaneous formation of spherical
particles and the phase structure by spraying a mixed solution
containing the reactants into a high-temperature furnace to allow
the rapid formation of the desired product via fast pyrolysis. The
large amount of gas produced may also allow the formation of
hierarchical pores within the spherical products. Ju et al.
synthesized Li4Ti5O12 microspheres via spray pyrolysis using
lithium nitrate and TTIP as reactants with dimethyl acetamide
(DMA) as a drying control chemical additive, and CA and EG
for morphology control [182]. As shown in Fig. 32, the as-prepared
Li4Ti5O12 exhibited good spherical shape with particle
diameter of 0.3–2.5 mm. At a current density of 0.17 mA g1,
the Li4Ti5O12 spheres had an initial capacity of approximately
167 mA h g1. Recently, Li4Ti5O12 microspheres with yolk–shell
structures were directly prepared by large-scale ultrasonic spray
pyrolysis using LiNO3 and TTIP as raw materials with the addition
of sucrose (Fig. 33) [183]. As observed in Fig. 33, the as-prepared
Li4Ti5O12 microspheres appeared to exhibit a unique yolk-shell
structure with outside diameters ranging from several hundreds
to approximately 2 mm. However, the microspheres prepared
under a similar process without the addition of sucrose appeared
to be dense. Because of their unique structure and higher contact
area with the electrolyte, the yolk-shell-structured Li4Ti5O12
microspheres after post-treatment at 800 8C exhibited enhanced
electrochemical performance with a discharge capacity of
172 mA h g1 even after 100 cycles compared with that of dense
microspheres.
Li4Ti5O12 is known to have poor electronic conductivity; thus, it
induces a large polarization resistance, especially at rapid discharge
rates. The microspheres prepared by spray drying or pyrolysis did
not have sufficient surface conductivity. Therefore, modification of
their surfaces with conductive agents such as porous carbon to
increase the current collection efficiency of the microspherical
Li4Ti5O12 is necessary. Improved electrochemical performance
especially for rate performance was observed by introducing carbon
into the Li4Ti5O12 prepared via spray drying [184–187]. Zhao et al.
[184] and Zhu et al. [185] prepared N-doped carbon coated porous
Li4Ti5O12 spheres and carbon-coated nanosized Li4Ti5O12 nanopor-
ous microspheres, respectively, by applying the spray drying
method. Zhao et al. first prepared Li4Ti5O12 microspheres using
the same method as Wen et al. [45] and mixed the sample with an
ionic liquid of 1-ethyl-3-methylimidazolium dicyanamide (EMIm-
dca) followed by further heat treatment at 600 8C in Ar. The obtained
Li4Ti5O12 spheres had sizes of 3–5 mm and surfaces covered with a
homogenous layer of N-doped carbon with a content of approxi-
mately 7.0 wt.%. At a low discharge rate of 0.5 C, the discharge
capacities of the carbon-coated and pristine Li4Ti5O12 reached
161 and 169 mA h g1, respectively. However, the carbon coating
significantly increased the rate performance; the coated sample
exhibited capacities of 145 and 129 mA h g1 at 5 and 10 C,
respectively, while the corresponding capacities for the pristine
samples were only 60 and 15 mA h g1. Zhu et al. applied
commercial anatase TiO2—pre-coated with a thin layer of carbon
using sugar as precursor and fired at 600 8C—and Li2CO3 as raw
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 33. (a) Schematic diagram of the large-scale ultrasonic spray pyrolysis process for preparation of Li4Ti5O12 yolk-shell powders, (b) SEM image, (c) TEM image, (d) high-
resolution TEM image, and (e) corresponding EDX elemental distribution of the Li4Ti5O12 yolk-shell powders post-treated at 800 8C [183].
materials. The spherical precursors were prepared by spray drying,
and the spherical Li4Ti5O12/C composite was finally prepared
following calcination at 800 8C under a nitrogen flow [185]. The
spherical particles had diameters of 10–20 mm, which were
constructed from nanoparticles of approximately 200 nm. The
nanoparticles packed to form nanopores with sizes between 10 and
20 nm and were distributed homogeneously from the surface to the
bulk of particles. Due to the carbon coating, the apparent electrical
conductivity of the sample increased substantially to 10 S cm1. The
as-synthesized electrodes exhibited a reversible capacity of
Fig. 34. Rate capability of carbon-free and carbon-coated (1.14 and 3.25 wt%)
Li4Ti5O12 electrodes at rates ranging from 1 C (175 mA g1) to 100 C (17.5 A g1).
The charging rate was 1 C [186].
25
160 mA h g1 at 0.2 C, and 126.4 mA h g1 at 20 C and excellent
cycling stability with a capacity retention of 95% after 1000 cycles at
a rate of 1 C. Thus, the spray drying method is promising. The results
emphasize the importance of carbon coating for the preparation of
high-performing Li4Ti5O12 microspheres for use as anodes in LIBs.
Jung et al. prepared carbon-coated Li4Ti5O12 powders by first
synthesizing carbon-free, spherical Li4Ti5O12 via a spray-drying
process followed by calcination at 900 8C in air for 20 h and
subsequent coating with pitch in combination with calcination at
750 8C for 5 h in argon [186], similar to the method applied by Zhu
et al. [185]. The carbon coating significantly increased the electronic
conductivity of the Li4Ti5O12. The as-prepared spherical Li4Ti5O12–
3.25-wt.% carbon composite had a carbon layer with thickness of
approximately 3 nm uniformly coating the primary particles. The
composite exhibited an electronic conductivity of
5.24  103 S cm1, while the pristine Li4Ti5O12 had a conductivity
of only 1.58  109 S cm1. As shown in Fig. 34, the as-prepared
Li4Ti5O12/C composite exhibited a capacity of 170.2 mA h g1 at 1 C
and 81.7 mA h g1 at 100 C. For comparison, the pristine, spherical
Li4Ti5O12 exhibited a poor rate capability, the capacity decreased
quickly to 30 mA h g1 at 100 C. The Li4Ti5O12/C composite also
showed good cycling stability; a capacity of 166 mA h g1 was
maintained after 100 cycles at 1 C.
The organic carbon source was found to have significant effect
on the microstructure and consequently the electrochemical
properties of the prepared Li4Ti5O12/C spherical particles. Lactic
acid was found to be superior to CA and malic acid as a carbon
source for improving the electrode performance of Li4Ti5O12/C
26 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
prepared by spray pyrolysis [188]. The proper selection of a carbon
source is critical to achieving high performance in the electrodes
prepared by the spray-drying/pyrolysis method.
Hydrothermal/solvothermal methods have been extensively
applied to the synthesis of micrometer-sized spherical/spheroidic
particles with different microstructures and have recently been
adopted for the preparation of spherical Li4Ti5O12 or Li4Ti5O12/C
composites [189–196]. Tang et al. successfully synthesized
nanoporous Li4Ti5O12 spheres with diameters of 200–400 nm
[189], which were constructed from nanoparticles with sizes of
approximately 20 nm to form 5–10 nm pores using a template-free
hydrothermal process in an ethanol–water mixture followed by
heat treatment. In their synthesis, the mono-dispersed, amorphous
spherical TiO2 colloids were first prepared by controlled hydrolysis
of TTIP in ethanol. Then, the hydrous titanium oxide was mixed
with LiOH ethanol–water mixtures and hydrothermally treated at
180 8C for 12 h followed by calcination at 500 8C for 1 h. The as-
fabricated mesoporous spheres had a tap density of 0.81 g cm3,
and the electrode exhibited a specific discharge capacity of
approximately 150 mA h g1 after performing 10 charge/discharge
cycles at a rate of 1 C. Even at a rate of 30 C, the specific capacity in
the 10th cycle reached 114 mA h g1, nearly 76% of the capacity at
1 C. The electrode retained a discharge capacity of 137 mA h g1
after 200 cycles, and the total capacity fade was only 5.5% during
the 10–200 cycles. After 200 cycles at a rate of 20 C, the electrode
exhibited a discharge capacity of 125.3 mA h g1 with almost no
capacity fade from the second cycle. Recently, Lin et al. also
synthesized Li4Ti5O12 submicrospheres with a high tap density via
a solvothermal method under water-ethanol solvents using sol–
gel-prepared TiO2 submicrospheres and LiOH as raw materials
[190]. Various ratios of water to ethanol in the solvents (0–
90 vol.%) and calcination temperatures (500–700 8C) were studied.
The sample prepared using a water-ethanol ratio of 60 vol.% and a
calcination temperature of 600 8C exhibited a specific surface area
of 15.5 m2 g1 and a high tap density of 1.62 g cm3. Additionally,
outstanding electrochemical performances with a high charge
capacity of 109 mA h g1 at 10 C and a capacity retention of 97.8%
over 100 cycles were achieved by this sample. Lin et al. synthesized
porous Li4Ti5O12 microspheres via hydrothermal synthesis in
combination with a high temperature calcination by combining
TTIP and a LiAc solution with acidized carbon black as pore former
[191]. As shown in Fig. 35, the as-prepared porous spherical
Fig. 35. (a, b) SEM images of (a) mesoporous and (b) non-porous Li4Ti5O12 spheres, (c) the ratio of capacity between several current rates and 0.5 C of mesoporous and non-
porous Li4Ti5O12 spheres [191].
Li4Ti5O12, which had a diameter of 2–3 mm, demonstrated stable
capacities of 140 mA h g1 at 0.5 C, and 80 mA h g1 at a rate as
high as 30 C, which was much better compared to that of dense
Li4Ti5O12 microspheres. Lin et al. further synthesized monodis-
persed mesoporous Li4Ti5O12 microspheres by a solvothermal
process with as-prepared amorphous monodispersed TiO2 spheres
as the precursor, which reacted with LiAc in an ethanol solvent
[197]. The Li4Ti5O12 microspheres delivered capacities of 147,
107 and 93 mA h g1 at 1, 3 and 5 C, respectively. Shen et al.
applied a template-free hydrothermal method using commercial
crystalline anatase titania powder and LiOH as reactants,
hydrothermally treated at 180 8C for the appropriate time to
obtain well-formed hierarchically porous microspheres with
diameters of approximately 4 mm [198]. A specific discharge
capacity of 165.8 mA h g1 was achieved at a rate of 0.5 C and was
maintained at 92.3 mA h g1 at a rate of 20 C.
Because Li4Ti5O12 has poor electronic conductivity, to further
increase the rate performance, Shen et al. prepared meso-structured
micro-sized Li4Ti5O12-C spheres with a high surface area through the
solvothermal treatment of TBOT and LiAc in the presence of furfural
allowing the formation and co-assembly of carbon and Li4Ti5O12
crystallites into an interpenetrating Li4Ti5O12-C nano-architecture
[199]. The evenly distributed carbon (5 wt.%) in the microspheres
enhanced the electronic conductivity and prevented particle
coalescence. The as-fabricated 0.2–1 mm spheres were composed
of large quantities of small crystallites with particle sizes of
approximately 11 nm. The Brunauer–Emmett–Teller (BET) specific
surface area reached 159.4 m2 g1. The pores showed a narrow pore-
size distribution with an average pore diameter of 4.3 nm. The
resulting spherical Li4Ti5O12/C composite had a capacity of
165.3 mA h g1 at a rate of 0.2 C, based on the mass of the
Li4Ti5O12/C composite. Even at a rate of 50 C, a capacity of
97.1 mA h g1 was still achieved, higher than that of the electrode
without a carbon coating. The electrode also exhibited good cycling
stability with a capacity loss of only 2.6% at 1 C and 2.5% at 50 C after
100 cycles. Jung et al. developed a facile method for the fabrication of
spherical carbon-coated Li4Ti5O12 based on a hydrothermal process
[200]. As shown in Fig. 36, first, a highly mesoporous anatase phase
TiO2 was prepared via a hydrothermal method using a high-purity
mixture of TiCl4, urea, and ammonia sulfate in a distilled water–
ethanol mixture that was heated at 120 8C for 24 h in a teflon-lined
autoclave. Then, the precipitate was further calcined at 400 8C for 5 h
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 36. (a) Schematic illustration of synthetic process of microscale, spherical,
carbon-coated Li4Ti5O12 and photographs of material formed during synthesis, (b)
rate capability of 5.2 wt% C-coated Li4Ti5O12 and (b) cyclability of 5.2 wt% C-coated
Li4Ti5O12 from 1 C-rate (0.17 A g1) to 10 C-rate (1.7 A g1) in comparison with C-
free Li4Ti5O12 cycled at 1 C-rate (0.15 A g1). Charged at 1 C-rate [200].
in air. The as-obtained mesoporous TiO2 was mixed with a
stoichiometric amount of Li2CO3 and varying quantities of pitch
as a carbon source, then calcined at 900 8C for 20 h under a flowing Ar
atmosphere. The pitch is critical to preserving the spherical
morphology of TiO2 into the Li4Ti5O12. The spherical Li4Ti5O12
particles had diameters of 1–2 mm, which were composed of the
primary particles with sizes of 10–20 nm. The external surfaces of
the particles were uniformly encapsulated in an approximately 50-
nm-thick layer of carbon to yield a carbon content of 5.25 wt.%. The
carbon layer provided an electrically conducting network improving
the electrical conductivity to 1.21  102 S cm1, more than five
orders of magnitude higher than the carbon-free Li4Ti5O12 prepared
via a similar process. Furthermore, the calcination of the pitch in the
Ar atmosphere led to the creation of Ti3+ in the oxide bulk. Both
results significantly improved the electrode performance. The
5.2 wt.% carbon-containing spherical Li4Ti5O12 delivered discharge
capacities of 165, 160 and 123 mA h g1 at 1, 10 and 100 C discharge
rates (charge rate: 1 C), respectively, without obvious capacity
fading over testing for 100 cycles (Fig. 36). The material also
exhibited high tap density of 1.31 g cm3, another highly attractive
27
property. Li et al. prepared a N-doped carbon-coated Li4Ti5O12
microspheres using polydopamine as the carbon source via chemical
lithiation of N-doped carbon-coated TiO2 microspheres under a
hydrothermal process [201]. The as-synthesized N-doped carbon-
coated Li4Ti5O12 microspheres delivered a specific capacity of
123 mA h g1 at 30 C and a good capacity retention with a capacity
of 136.5 mA h g1 after 200 cycles at 10 C.
As a versatile method, the hydrothermal/solvothermal method
can be further used to synthesize other unique Li4Ti5O12 micro-
spheres with special microstructures beyond the above micro-
spheres composed of Li4Ti5O12 nanoparticles. Tang et al.
synthesized a flower-like spherical Li4Ti5O12 composed of
nanosheets using a hydrothermal method with LiOH and TTIP
and ammonia as reactants in the presence of EG at 170 8C for 36 h
with subsequent calcination at 500 8C for 2 h [202]. The electrode
showed capacities of 167, 163 and 152 mA h g1 at rates of 0.2,
1 and 8 C, respectively, even after 100 charge/discharge cycles. By
adding H2O2 during the hydrothermal treatment, Chen et al.
demonstrated that the morphology of the Li4Ti5O12 changed
slightly [203]. Li4Ti5O12 spheres with a diameter of 0.4–0.6 mm
assembled from smooth-surfaced, sawtooth-like nanosheets were
obtained after hydrothermal treatment at 130 8C for 12 h by
applying TTIP and LiOH as reactants in the presence of H2O2 with a
subsequent thermal treatment at 550 8C for 6 h in air. The spheres
contained pores primarily with sizes of 2.5 and 8 nm and a specific
surface area of 139.4 m2 g1. Specific capacities of 177, 169, 161,
150 and 143 mA h g1 at discharge current densities of 200 mA g1
(1.1 C), 1000 mA g1 (5.5 C), 2500 mA g1 (14 C), 5000 mA g1
(28.5 C) and 1000 mA g1 (57 C), respectively, were demonstrated.
Yu et al. successfully prepared mesoporous Li4Ti5O12 hollow
spheres using silica nanospheres as templates [204]. As shown in
Fig. 37, TiO2 was first coated on the surface of silica nanospheres,
and the composite was treated with a LiOH solution to complete
the chemical lithiation. After further calcination, mesoporous
Li4Ti5O12 hollow spheres were obtained, which exhibited a BET
specific surface area of approximately 220 m2 g1 and excellent
electrochemical performance with a capacity of 104 mA h g1 even
at 20 C. Moreover, the addition of various amounts of TBOT could
easily be used to control the shell thickness, as shown in Fig. 37 b-d.
Cheng et al. prepared hierarchical hollow Li4Ti5O12 urchin-like
microspheres using silica nanospheres as templates using a
synthesis route (Fig. 38) [205] similar to that reported by Yu
et al. [204]. The differences in microstructures seem to be due
mainly to the difference in concentration of the aqueous LiOH
solution (0.4 M vs. 0.5 mM). By controlling the reaction time, Zhao
et al. developed advanced yolk-shell Li4Ti5O12 microspheres with
hierarchical macro-mesopores by the hydrothermal treatment of
TTIP, LiOH and CTAB in EG and distilled water environment at
170 8C for 48 h followed by calcination at 500 8C for 2 h, and these
researchers observed that the structure formed during the Ostwald
ripening process during the hydrothermal treatment [206]. Based
on the unique structure, an outstanding high-rate performance
with a discharge capacity of 117.9 mA h g1 at 10 C (1700 mA g1)
was achieved.
The introduction of conductive carbon into such advanced
Li4Ti5O12 microspheres with unique microstructures was also
studied to further improve their electrochemical performance.
Zhang et al. successfully synthesized hierarchical hollow Li4Ti5O12
microspheres composed of N-doped carbon-coated nanosheets
using a hydrothermal method with amorphous TiO2 microspheres
and LiOHH2O as raw materials (Fig. 39) [207]. The use of
hexadecylamine in the preparation of TiO2 microspheres intro-
duced N-doped carbon into the final Li4Ti5O12 microspheres,
resulting in excellent rate capability with a specific capacity of
140.8 mA h g1 at 20 C. A one-pot template-free solvothermal
method based on the benzyl alcohol route was studied by Yu et al.
28 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 37. (a) Schematic illustration of the formation of mesoporous Li4Ti5O12 hollow spheres through a templating approach: (I) uniform coating of an a-TiO2 shell on the silica
sphere through a sol-gel process; (II) chemical lithiation in a LiOH solution under hydrothermal environment and subsequent annealing treatment to convert the core-shell
sphere into the mesoporous Li4Ti5O12 hollow sphere, (b–d) TEM images of as-synthesized Li4Ti5O12 hollow spheres with different shell thicknesses by adding different
amounts of TBOT: (b) 1, (c) 3, and (d) 5 mL [204].

Fig. 38. (a) Schematic illustration of the synthesis procedure for the hierarchical hollow Li4Ti5O12 urchin-like microspheres. (b–d) TEM images of the hollow
(Li1.81,H0.19)Ti2O52H2O urchin-like microspheres with different hydrothermal reaction times: (b) 30 min, (c) 2 h, and (d) 24 h [205].

[208] for the synthesis of micrometer-sized Li4Ti5O12. This method
primarily involves the solvothermal treatment of lithium and
titanium alkoxide in benzyl alcohol. The as-synthesized material
consists of 1–2-mm-sized spherical particles made of 10-nm
crystalline nanoplatelets containing 2.5 wt.% carbon. The nano-
crystals are crystallographically oriented randomly with respect to
each other. The coulombic efficiency of the calcined sample
reached 94.8% for the first cycle, and the reversible capacity at a
rate of 20 C still achieved approximately 100 mA h g1, corre-
sponding to 85% of the total capacity at 1 C. After calcination, the
sample still exhibited good rate performance, although its specific
surface area was reduced to only 8 m2 g1. Recently, Li4Ti5O12/C
hollow microspheres were successfully by prepared using
solvothermally synthesized TiO2/polyfurfural hollow micro-
spheres as raw materials [209]. LiOHH2O was applied as the Li
source and mixed with the Ti source in a Li/Ti molar ratio of 4.5:5 in
methanol. After calcination at 800 8C for 10 h under Ar atmosphere,
Li4Ti5O12/C hollow microspheres were obtained, which exhibited
excellent rate capability with discharge capacities of 169, 152, 130,
116, 93, and 76 mA h g1 at 0.2, 1, 2, 5, 30 and 60 C, respectively.
Even though the above advanced Li4Ti5O12 microspheres
exhibit unique morphology and further improved electrochemical
performance compared with that composed of nanoparticles, the
large space inside the microspheres results in a low tap density and
low volumetric energy density. For the synthesis of Li4Ti5O12
microspheres as an anode for LIBs, the authors suggest that we
should simultaneously focus on the electrochemical performance
and tap density by optimizing the microstructure and coating
carbon instead of developing a unique morphology with low tap
density.
In addition to the methods described above, other techniques
have also been exploited for the synthesis of spherical Li4Ti5O12 or
Li4Ti5O12/C composite, including the emulsion gel process [210]
and supercritical alcohol route [211,212]. Gao et al. reported an
‘‘inner gel’’ method for the preparation of spherical Li4Ti5O12 or
Li4Ti5O12/C composite for use as an anode in LIBs [213,214]. In their
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 39. (a, b) SEM, (c) TEM, and (d, e) HRTEM images of hierarchical hollow Li4Ti5O12 microspheres composed of N-doped carbon coated nanosheets, (d) and (e) are from the
top view and side view of one single nanosheet, respectively [207].
processes, TiCl4 was dissolved in de-ionized water to first form a
solution, which was mixed with (CH2)6N4 and carbamide CO(NH2)2
by stirring at less than 10 8C. The mixture was dripped into coal oil
under stirring; then the mixed slurry was heated at 70 8C for
10 min to obtain the spherical gel precursor, which was mixed
uniformly with Li2CO3 and sintered at 800 8C for 16 h to form
spherical Li4Ti5O12 particles with diameters of 5–10 mm. Spherical
particles of a Li4Ti5O12/C composite were also prepared when
carbon black was introduced into the TiCl4 solution during the
preparation of the spherical gel precursor. The resulting spheres
have tap densities as high as 1.64 and 1.73 g cm3 for the Li4Ti5O12
and Li4Ti5O12/C composite, respectively, which are among the
highest reported in the literature for such electrodes. The Li4Ti5O12
spheres are relatively dense with few pores, while the spheres
created with the carbon black have more pores and smaller particle
sizes. The electrode without the carbon had a discharge capacity of
161 mA h g1 at a current density of 0.08 mA cm2 that quickly
decreased to 121.5 mA h g1 at a current density of
0.32 mA cm2. The Li4Ti5O12/C electrode exhibited discharge
capacities of 158.2, 150.6 and 132.4 mA h g1 at current densities
of 0.08, 0.32, and 3.2 mA cm2, respectively, and the carbon
coating improved the rate performance of the electrode. Recently,
Nugroho et al. successfully prepared mesoporous Li4Ti5O12
microspheres using a facile supercritical methanol route [211]. Pre-
cursor microspheres were formed during the supercritical alcohol
reaction in a high-pressure reactor in a molten salt bath at 400 8C
and were transformed into the Li4Ti5O12 phase after calcination at
500–700 8C under air. The sample obtained at 600 8C displayed the
best rate performance with capacities of 155.6, 108.5 and
79.7 mA h g1 at 4, 10 and 20 C, respectively. Nugroho et al.
further prepared mesoporous Li4Ti5O12/C microspheres using the
same supercritical alcohol (methanol, ethanol and isopropanol)
route followed by calcination under 5%H2/Ar [212]. The sample
obtained using methanol exhibited a smaller crystallite size, larger
surface area, and higher carbon and Ti3+ contents and the optimal
electrochemical performance with stable discharge capacities of
173.2, 159.1, 116.9 and 93.5 mA h g1 at 0.1, 1, 10 and 20 C,
29
respectively. Although no-structure-directing chemicals or tem-
plates were applied in the synthesis process, a high-pressure
reactor at 400 8C was needed to achieve a supercritical condition,
limiting its large-scale application.
Besides the classical sphere structure, other deuterogenic
microstructures were also studied. Recently, donut-shaped
Li4Ti5O12 structures prepared by combining sol–gel and electro-
spinning techniques were reported (Fig. 40a and b) [215]. The
unique structures were composed of well-sintered and highly
interconnected nanograins that offer shorter Li+ diffusion lengths,
and its mesoporous structure was beneficial to electrolyte
transport (Fig. 40c). The donut-shaped Li4Ti5O12 electrode deliv-
ered specific capacities of 159, 144, 131, 120, and 100 mA h g1 at
0.1, 1, 3, 5 and 10 C rates, respectively.
3.2.3. Thin-film electrodes
Thin-film batteries have been found many potential applica-
tions in microelectronic mechanical systems, smart cards, on-chip
power sources and portable electronic devices. Recently, thin-film
electrode has been a popular subject in the literatures. A thin-film
electrode can effectively reduce the electrode polarization by
reducing the lithium diffusion distance in the electrode. Brousse
et al. successfully prepared a 2-V thin-film cell with a thin-film
Li4Ti5O12 anode, a thin-film LiCoO2 cathode and a thick solid
Li0.33La0.56TiO3 electrolyte [216] in which both the Li4Ti5O12 anode
and LiCoO2 cathode were prepared via spray pyrolysis. By applying
an electrostatic spray deposition technique and using LiAc and
titanium butoxide as the starting materials, Yu et al. successfully
prepared a thin-film Li4Ti5O12 electrode without the application of
an electrically conducting additive. An initial capacity of approxi-
mately 175 mA h g1 was achieved at a C/18 rate, and the capacity
still reached approximately 155 mA h g1 after 70 cycles [208]. By
using a pulsed laser deposition technique, Deng et al. prepared a
thin-film Li4Ti5O12 electrode on Pt/Ti/SiO2/Si substrates. A high
capacity of 146 mA h g1 was achieved at a discharge rate of
approximately 3.45 C [217]. Nano-sized epitaxial Li4Ti5O12 (1 1 0)
films were also prepared using a pulsed laser deposition technique
30 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 40. (a, b) FE-SEM images of Li4Ti5O12 sub-micrometer donuts after calcination. (c) Schematic to compare the lithium ion diffusion kinetics in Li4Ti5O12 submicrometer
particles and donut shapes with nanograins [215].
[218]. The initial discharge capacity was as high as 217 mA h g1;
however, the capacity decreased in subsequent cycles. Recently,
epitaxial growth of a Li4Ti5O12 thin film was realized using a pulsed
laser deposition technique with SrTiO3 single-crystal substrates,
i.e., Li4Ti5O12 (1 1 1) on SrTiO3 (1 1 1), Li4Ti5O12 (1 1 0) on SrTiO3
(1 1 0) and Li4Ti5O12 (1 0 0) on SrTiO3 (1 0 0) [219]. Wunde et al.
fabricated Li4Ti5O12 thin films using the ion beam sputtering
method and measured the lithium diffusion coefficient
(3.27  1016 m2 s1) [220]. A Li4Ti5O12 thin film was also
successfully prepared using a PVP sol–gel coating method
[221]. At a rate of 1 C, a capacity of approximately 140 mA h g1
was achieved after 300 cycles at the 1 C rate. A thin-film Li4Ti5O12
electrode was also successfully deposited on an Au/Ti/SiO2/Si
substrate by applying a magnetron sputtering technique [222]. Zhao
et al. applied a versatile ink-jet printing technique for the
preparation of thin-film Li4Ti5O12 electrodes on Au substrates; the
film had a porous microstructure with a thickness of 1.7–1.8 mm
[223]. Under optimized fabrication conditions, the as-obtained thin-
film electrode exhibited a capacity of 153 mA h g1 even after
300 cycles at a current density of 10.4 uA cm2. Homogeneous,
crack-free Li4Ti5O12 thin films were also prepared by spin coating
using a rapid thermal annealing process [224]. Compared with
conventional furnace annealing, the rapid thermal annealing
resulted in a smaller Li4Ti5O12 grain size, higher capacity
(59.5 mAh cm2 mm1 compared with 55.9 mAh cm2 mm1) and
more stable cycling performance.
The Li4Ti5O12 thin-film electrodes prepared via the above
techniques are more suitable for basic scientific research than
practical applications because these techniques usually require
expensive equipment or complicated processes as well as special
inactive substrates and the mass loading of Li4Ti5O12 is relatively
low. Beyond these conventional techniques for the preparation of
Li4Ti5O12 thin-film electrodes, novel techniques have recently been
developed.
Printing and painting have been successfully used to fabricate
Li4Ti5O12 thin-film electrodes, such as 3D patterned Li4Ti5O12
electrodes [225] and Li4Ti5O12-entrapped cross-linked carbon
nanotube (CNT) film network film electrodes [226]. For example,
a paintable battery was developed as shown in Fig. 41, in which a
porous Li4Ti5O12 film electrode could be easily obtained using a
slurry including commercial Li4Ti5O12 powders, conductive agent
and binder [227]. This work highlighted that the battery could be
painted on any arbitrary surface. However, a liquid electrolyte was
still required, which limited its wide application. Additionally, this
Li4Ti5O12 film electrode suffers from the disadvantages of the use of
additives, as in the conventional electrode.
In the conventional slurry-coating Li4Ti5O12 electrode, additives
(a conductive agent and binder) are necessary; the conductive
agent is used to enhance the electron transformation and a binder
is used for cohering the active materials and conductive agent to
the current collector. However, these additives are usually
electrochemically inactive, which reduces the volumetric/gravi-
metric energy density of the electrode; furthermore, the binder
usually cannot store/transport lithium ions or electrons, resulting
in a negative effect on the electrochemical performance. Although
several works on the modification of the binder for Li4Ti5O12
anodes have been performed, such as introducing conductive
graphene into the conventional PVDF binder [228] and using an
alternative binder (sodium-carboxymethyl cellulose (CMC) [229],
polyacrylonitrile (PAN) [230], water soluble Acryl S020 [231],
lithium-ion-conductive PEG-based copolymer [232], polymeric
ionic liquid nanoparticles [233], etc.). However, these binders will
still reduce the volumetric/gravimetric energy density of the
Li4Ti5O12 electrode. Recently, binder-free thin films have received
increasing attention as electrodes for LIBs [73,145,234,235]. Sever-
al strategies have also been applied to develop binder-free
Li4Ti5O12 film electrodes.
A binder-free multi-layer electrode with porous Li4Ti5O12
sphere layer sandwiched between carbon nanotube and graphene
network layers was designed and prepared by Choi et al. [236] via a
multi-step spraying process as shown Fig. 42a, including air-spray
coating of graphene layer on current collector and the following
electrostatic spray (E-spray) coating of ball-milled Li4Ti5O12
nanoparticles, and subsequent air-spray coating of CNTs layer.
During the E-spray coating, the ball-milled Li4Ti5O12 aggregate
together to be porous spheres. The typical morphology of resultant
hybrid was shown in Fig. 42b. The binder-free multi-layer
electrode exhibited an outstanding rate capability with a specific
capacity of 109.3 mA h g1 at 100 C rate, much better than that of
the pristine and bead-milled Li4Ti5O12 powder electrode prepared
via a conventional slurry-coating technique (Fig. 42c). The
electrochemical performance was attractive, but the electrode
fabraction process was really complicated. Future work could focus
on the development of a simplified one-step spraying process of
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 41. (a) Schematic illustration of direct fabrication of Li-ion battery on the
surface of interest by sequentially spraying component paints stencil masks
tailored to desired geometry and surface, (b) cross-sectional SEM micrograph of a
spray painted full cell showing its multilayered structure, with interfaces between
successive layers indicated by dashed lines for clarity [227].
Li4Ti5O12, graphene sheet, and CNTs mixture ink, as well as further
improvement of Li4Ti5O12 mass loading.
Binder-free Li4Ti5O12 nanowire/nanotube/nanosheet arrays on
metal substrates have been successfully developed, as schemati-
cally summarized in Fig. 43 [237–240], where the nanostructure is
beneficial to Li+/electron diffusion, and the large open space among
the nanowires/nanotubes ensures a good contact between the
electrolyte and electrode for fast lithium storage. Because it would
be difficult to directly obtain Li4Ti5O12 nanowire/nanotube arrays,
the Ti-based (e.g., H2Ti2O5H2O or TiO2) nanowire/nanotube arrays
were usually first synthesized via hydrothermal treatment [237] or
the template method [239], and then, a chemical lithiation was
performed to transform the TiO2 phase into the spinel Li4Ti5O12
phase. To further increase the electrochemical performance of
these arrays, strategies for enhancing the electronic conductivity
were applied, for example, calcination under 5% H2/Ar to obtain
hydrogenated Li4Ti5O12 nanowire arrays (Fig. 44a) [237], which
demonstrated excellent rate performance with capacities of 173,
166, 157, 145 and 119 mA h g1 at 0.2, 1, 5, 10, 30 C rate,
respectively. Wang et al. used a similar hydrothermal route with
modification to prepare a web-like Li4Ti5O12 anode without
hydrogenation; the as-obtained nanowires had a length of about
20 mm [241]. Such a binder-free web-like Li4Ti5O12 electrode
31
exhibited an outstanding cycling stability with specific capacities
of 153 and 115 mA h g1 at 2 C and 20 C rate, respectively, even
after 5000 cycles. Other than the nanowire array structure, a
nanotube array is believed to be more beneficial to Li+/electron
diffusion. Cha et al. prepared an anodized TiO2 nanotube array;
however, the nanotube structure was not maintained after
calcination with Li2CO3 because of the solid-state reaction at such
a high temperature of 800 8C [238]. A relatively dense Li4Ti5O12
film was obtained instead of Li4Ti5O12 nanotube arrays after such
lithiation, resulting in unattractive electrochemical performance.
Recently, Liu et al. successfully prepared Li4Ti5O12 nanotube arrays
by chemical lithiation of template-synthesized TiO2 nanotube
arrays in a 3 M LiOH solution with subsequent calcination at the
low temperature of 550 8C (Fig. 44b) [239]. After carbon coating,
the as-prepared Li4Ti5O12-C nanotube arrays delivered outstand-
ing rate capability with specific capacities of 165, 154, 135, 106 and
81 mA h g1 at 1, 10, 30, 60 and 100 C, respectively, and stable
cycling performance at 10 C for 500 cycles.
In addition, Li4Ti5O12 nanosheet array was also successfully
synthesized by Chen et al. through a hydrothermal treatment of Ti
foil in LiOH solution and a subsequent calcination [240]. The
typical SEM and TEM images of the nanosheet array were shown in
Fig. 44c1 and c2, respectively, with vertically aligned rectangular
nanosheets of 14 nm in thickness. Even though an outstanding
rate capability with a specific capacity of 78 mA h g1 at 200 C rate
was reported for the Li4Ti5O12 nanosheet array (Fig. 44c3), the
mass loading of Li4Ti5O12 was too low. Gao et al. reported a porous
Li4Ti5O12–TiO2 nanosheet array by a hydrothermal synthesis [242],
even though the electrochemical performance was not as
attractive as the results reported by Chen et al. [240], the mass
loading of the active materials was increased to
0.3 mg cm2. However, this value was still too low for commer-
cial application. While such a large open space among nanowires/
nanotubes/nanosheets is definitely beneficial to the electrochemi-
cal performance, it inevitably results in low volumetric energy
density of the electrode (Fig. 43).
Direct growth of Li4Ti5O12 on a 3D conductive substrate (3D
current collector) is also an effective approach for the preparation
of a high-performance binder-free thin film Li4Ti5O12 electrode,
which could result in maximum utilization of the active material.
Shen et al. used a commercial carbon fiber cloth as a substrate and
grew TiO2 nanosheets on it via a solvothermal method with
subsequent chemical lithiation and calcination to form Li4Ti5O12
nanocrystals [243]. The as-prepared thin-film electrode with such
a 3D structure delivered excellent rate performance with specific
capacities of 177, 152, 134, 119 and 103 mA h g1 at 1, 10, 30,
60 and 90 C, respectively. Such an excellent rate capability as well
as its stable cycling performance at 10 C for 200 cycles are very
attractive; however, the large diameter of the carbon fiber
(10 mm) resulted in low mass loading of Li4Ti5O12 nanocrystals
and a low gravimetric energy density. Furthermore, the large space
between the fibers leads to a low volumetric energy density. Li
et al. reported a thin, flexible, lightweight and high-performance
LIB with graphene foam as the current collector [244]. Typically,
graphene foam was first synthesized by vapor deposition and was
then hydrothermally treated in LiOH and Ti(OC3H7)4 solution. After
calcination, the Li4Ti5O12 nanosheets formed homogeneously on
the surface of graphene foam as shown in Fig. 45. The as-prepared
Li4Ti5O12/graphene exhibited an outstanding capacity of
135 mA h g1 at high rate as high as 200 C (discharge in 18 s)
and stable cycling stability at 30 and 100 C for 500 cycles.
Importantly, the Li4Ti5O12 content in the film electrode could reach
88 wt.%, suggesting that high gravimetric energy density could
be achieved. However, achieving a high volumetric energy density
remains a major challenge because of the presence of pores on the
scale of hundreds of micrometers in the graphene foam. Li et al.
32 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 42. (a) Schematic illustration of sequential fabrication steps for the multi-stacked graphene sheets/Li4Ti5O12/CNTs electrode consisting of the self-aggregated nanoporous
Li4Ti5O12 interconnected by graphene sheets and CNTs. (b) SEM image of the self-aggregated nanoporous Li4Ti5O12 hybrid electrode interconnected by graphene sheets and
CNTs. (c) discharge (Li-insertion) capacities of graphene sheets/Li4Ti5O12/CNTs (G-LTO-C), the pristine Li4Ti5O12 electrode (P-LTO; 1.3 mg cm2), and the bead-milled
Li4Ti5O12 electrode (BM-LTO; 1.3 mg cm2) during cycling with different current densities [236].

Fig. 43. Schematic illustration of reported binder-free Li4Ti5O12 nanostructure arrays on metal substrates: (a) nanowire arrays, (b) nanotube arrays, and (c) nanosheet arrays.
The advantages and disadvantages of the Li4Ti5O12 nanostructure arrays are also given below the schematics.
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 33

Fig. 44. (a1, a2) Cross-sectional SEM images of hydrogenated Li4Ti5O12 nanowire arrays annealing at 600 8C under 5% H2/Ar; and (a3) schematic illustration of the
electrochemical reaction of hydrogenated Li4Ti5O12 nanowire arrays [237]. (b1) SEM images of Li4Ti5O12-C nanotube arrays on stainless steel foil, showing that the whole
surface of the steel foil is uniformly coated by well-aligned Li4Ti5O12-C nanotubes; (b2) TEM images of some typical Li4Ti5O12-C nanotubes exhibiting their wall thickness of
approximate 20–30 nm; (b3) HRTEM image of a well-crystallized carbon-coated Li4Ti5O12 nanotube showing its lattice planes and the amorphous carbon thin layer; and (b4)
schematic representation of diffusion of Li+ and electrons during discharge/charge processes of the self-supported electrode, which possess a large specific space that
facilitates the fast transfer of Li+, while the electronic conductivity of Li4Ti5O12 nanotubes can be significantly improved by the inner and outer surface-coated carbon layers
[239]. (c1) Cross-sectional SEM images of Li4Ti5O12 nanosheet arrays standing on Ti foil; (c2) TEM image of large Li4Ti5O12 nanosheets scratched from Ti foil; and (c3) Rate
performances of the binder-free anodes made of the self-supported arrays of Li4Ti5O12 nanosheets 14 nm in thickness (LTO-NSA-1) and thicker Li4Ti5O12 nanosheets
80 nm in thickness (LTO-NSA-2), as well as the traditional anode made of the randomly dispersed Li4Ti5O12 nanosheets (LTO-NS) [240].

further developed a flexible binder-free electrode via vacuum-
filtration of N-doped-carbon-coated Li4Ti5O12 nanosheets (Fig. 46)
[245]. This strategy is similar to the recently reported formation of
a self-standing graphene film, and the key process should be the
synthesis of appropriately sized nanosheets. The as-synthesized
N-doped-carbon-coated Li4Ti5O12 nanosheets used for vacuum
filtration appeared to be thin and transparent, as observed in
Fig. 46 a, which is similar to graphene sheet. Atomic force
microscopy (AFM) analysis revealed that the thickness of
nanosheet was approximately 2.5 nm. With the above unique

Fig. 45. (a) SEM and (b) TEM images of the Li4Ti5O12/graphene foam, (c) discharging voltage curves of the Li4Ti5O12/graphene foam with different charge/discharge rates, and
(d) capacities of the Li4Ti5O12/graphene foam charged/discharged at constant 30 and 100 C rates for 500 cycles [244].
34 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 46. (a) TEM image and (b) representative AFM image of N-doped carbon-coated Li4Ti5O12 nanosheets; (c) corresponding thickness analysis taken along the white line in
(b), which reveals a thickness of about 2.5 nm for the nanosheets; (d) digital photograph of a self-standing N-doped carbon-coated Li4Ti5O12 nanosheet film electrode being
bent, showing its good flexibility; (e) cross-section SEM image and (f) high-magnification image of the film electrode [245].

characteristics, a free-standing film (Fig. 46d–f) could be easily
obtained by vacuum filtration. Importantly, the flexible film
electrode delivered an outstanding rate performance with a
specific capacity as high as 72% of the theoretical capacity at an
ultrahigh rate of 100 C (corresponding to 36 s charge/discharge),
and the carbon content in this film electrode was only 4 wt.%;
therefore, the high gravimetric energy density could be further
improved compared with that of their graphene foam-based
electrode, and the volumetric energy density was also estimated to
be much higher because of the reduced void space in this structure
(Fig. 46e and f) relative to their graphene foam-based electrode
(Fig. 45 a). Besides, assembly of free-standing Li4Ti5O12/CNT film
via filtration was also explored [246,247], which result in
enhanced electrochemical performance.
3.3. Surface coating
Due to low electronic conductivity of Li4Ti5O12, the transfer of
electrons from Li4Ti5O12 particles in the electrode to the external
circuit is difficult, leading to high electrode polarization resistance
during the charge/discharge processes, especially at a high
discharge rate. One way to overcome this problem is to modify
the surface of Li4Ti5O12 particles with a thin layer of a conductive
material that is permeable to lithium. In addition to enhancing the
conductivity of the electrode material, the surface coatings on the
Li4Ti5O12 material may affect other properties as well, as
summarized in Fig. 47, such as suppressing the decomposition
of the electrolyte on the surface of Li4Ti5O12 and influencing the
phase structure in some cases.

Fig. 47. Schematic illustration of the effects of the surface coating on the Li4Ti5O12 materials.
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Cheng et al. prepared carbon-coated Li4Ti5O12 via thermal vapor
decomposition using toluene vapor as a carbon source [248]. The
treatment of the Li4Ti5O12 in the toluene vapor at 800 8C resulted in
a uniformly graphited carbon layer on the particle surfaces with a
thickness of approximately 5 nm. The resulting Li4Ti5O12/C
composite exhibited an electrical conductivity as high as
2.5 S cm1, while the electrical conductivity was less than
1013 S cm1 for the pristine Li4Ti5O12. At 24 C, the carbon-coated
Li4Ti5O12 retained 50% of its initial capacity at an 8 C rate. This
value was only 29% for the pristine Li4Ti5O12.
Kellerman et al. demonstrated that the surface coating also had
an effect on the structure of the Li4Ti5O12 phase [249]. First,
Li4Ti4.92(CrV)0.04O12 was prepared by calcining a mixture of TiO2
anatase, lithium carbonate (Li2CO3), Cr2O3 and vanadium oxide
(V2O5) at 800 8C in air. Then, they treated the samples under an
argon/acetylene gas mixture with a volumetric ratio of 40:1 at
800 8C. The treatment in acetylene gas not only resulted in the
formation of a carbon coating but also caused a structural
transformation in the Li4Ti5O12 by inducing a lithium transfer
from the tetrahedral 8a sites to the vacant octahedral 16c sites.
Such a phase transformation reportedly increases the electronic
conductivity [42,70], thus increasing the electrode performance.
In addition to increasing the surface conductivity and possibly
affecting the lattice structure, He et al. demonstrated that a surface
coating may also suppress the decomposition of the electrolyte on
the Li4Ti5O12 electrode [250]. Lithium batteries using Li4Ti5O12 as an
anodic material are easily inflated during the charge/discharge
processes, especially at high temperatures when reduction gases
such as hydrocarbon gases and CO are generated in the batteries. The
reduction reactivity of the electrolyte on the uncoated Li4Ti5O12
electrode differed greatly from that on the carbon-coated Li4Ti5O12
composite electrodes. The reduction decomposition reaction
appeared at 0.7 V on the uncoated Li4Ti5O12 electrode during
cycling from 2.5 to 0.0 V, whereas the same reaction occurred at the
first cycle on the carbon-coated electrode. This observation is in
agreement with the findings of Ding et al. indicating that the carbon
coating can reduce the activity of the Li4Ti5O12 surface [251].
Song et al. questioned the necessity of conductive carbon in the
Li4Ti5O12 electrode for achieving high capacities at a high rate
[252] by demonstrating that excellent electrochemical perfor-
mance can still be achieved without any carbon additive. They
prepared a carbon-free Li4Ti5O12 composite film on Al foil with
only a PVDF binder, free of any conductive agent. This electrode
had capacities at different rates between 0.1 and 10 C, nearly
identical to those of the electrode containing a 5 wt.% carbon
additive. This result suggests that the electronic conductivity of
Li4+dTi5O12 and its interphase boundary with Li7Ti5O12 is likely the
origin of its interesting electrochemical properties. However, the
low-carbon content of 5 wt.% for the carbon-containing electrode
may still be insufficient to improve the current collection
efficiency, and the higher content of PVDF in carbon-containing
electrode (5 wt.%) compared to that of carbon-free electrode
(2 wt.%) may also have a detrimental effect on the rate capability.
Moreover, for practical application, higher mass loading will be
required, thus, carbon still be required for a high current collection
efficiency since carbon has a much higher electronic conductivity
compared to that of Li4+dTi5O12/Li7Ti5O12.
3.3.1. Carbon coating
Carbon is one of the most attractive surface coating materials
due to its low cost, easy preparation and versatile origins. Carbon
coating has turned out to be highly effective in improving the rate
performance of the well-known LiFePO4 cathode [253,254], which
also has the disadvantage of low electronic conductivity. Several
materials have been exploited as carbon sources, including pitch
[186], sugar [255], CA [256], Super P [257], toluene [248], starch
35
[258], acetylene gas [249], sucrose [11], glycine [259], glucose
[260], PVB [261], acetyl glucosamine [262], amphiphilic carbona-
ceous material (from green needle coke) [263], oleic acid [264],
chitosan [265] and so forth. All investigations have demonstrated
that a carbon coating improves the electrode performance
(capacity, rate capability, or cycling stability).
The carbon source and carbon content were found to affect the
performance of Li4Ti5O12. Hu et al. systematically investigated the
effect of the carbon source and carbon content on the electrode
performance of Li4Ti5O12/C prepared by in situ carbon formation
during high temperature calcination for the Li4Ti5O12 phase
formation using PAALi + TiO2, CALi + TiO2, MALi + TiO2 and PVA + -
LiOH + TiO2 as reactants in which PAA, CA, MA and PVA represent
polyacrylate acid, CA, maleic acid and polyvinyl alcohol, respectively
[266]. PAA was found to be the best carbon source in terms of
electrochemical performance. The optimum carbon content was
found to be approximately 3.5 wt.% in the Li4Ti5O12/C composite and
exhibited capacities of 168.6, 143.5 and 132.7 mA h g1 at 0.2, 8 and
10 C, with a capacity loss of 2.8, 8.7 and 9.9% after 50 charge/
discharge cycles, respectively. Hu et al. further investigated the
synthesis of carbon-coated Li4Ti5O12 via a solid-state reaction using
LiOHH2O and TiO2 as reactants and PAA as a carbon source
[267]. They demonstrated that the properties and electrochemical
performance of the as-synthesized Li4Ti5O12/C composite was
strongly affected by the molecular weight of the polyacrylic acid,
the heating rate and the sintering time. PAA, with the molecular
weight of 10,000, heated at 20 8C min1 and sintered over 8 h was
optimal, and the resulting Li4Ti5O12/C composite exhibited a
capacity of 116.4 mA h g1 at 20 C and a capacity retention of
87.6% after 50 cycles.
There are two primary ways to introduce carbon (Fig. 48), i.e.,
introducing carbon after the synthesis of Li4Ti5O12 (Fig. 48a) and in
situ forming carbon during the phase formation of Li4Ti5O12
(Fig. 48b). Another minor way is to first coat carbon on the TiO2,
and then to carry out lithiation and calcination processes to obtain
a spinel Li4Ti5O12 phase (Fig. 48c). For the post-synthesis method,
Li4Ti5O12 crystalline phase is first prepared, and then the sample is
calcinated under an inert or reducing atmosphere at an elevated
temperature in the presence of a liquid or gaseous organic carbon
source [186,248,268]. The organic carbon source is decomposed and
Fig. 48. Schematic illustration of the ways to introduce carbon on Li4Ti5O12
materials.
36 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 49. (a, b) SEM images of (a) carbon-free and (b) 5 wt% pitch-coated Li4Ti5O12 powders, (c) HRTEM image of the 5 wt% pitch-coated Li4Ti5O12 after calcination at 750 8C [186].
deposited on the surface of the Li4Ti5O12 to form a thin carbon layer
during the calcination. H.G. Jung first prepared carbon-free spherical
Li4Ti5O12 by spray drying and subsequent solid-state calcination at
900 8C for 20 h in air. The material was then mixed with a proper
amount of pitch and calcined for 5 h at 750 8C in a furnace purged
with Ar [186]. Fig. 49a&b shows typical SEM images of carbon-free
Li4Ti5O12 spheres and a Li4Ti5O12/C composite. The sample color
darkens after the carbon coating. The carbon coating was homoge-
neous over the Li4Ti5O12 grains with a thickness of 3 nm as shown in
Fig. 49c. The electronic conductivity increased substantially from
1.58  109 S cm1 for the pristine Li4Ti5O12 to 5.24  103 S cm1
for the carbon-coated Li4Ti5O12 with a carbon content of 3.25 wt.%.
An improved rate performance was demonstrated after the carbon
coating; within the potential range of 1.0–3.0 V, the pristine
Li4Ti5O12 delivered capacities of 164, 142, 120, 90, 33, and
29 mA h g1, at 1, 5, 10, 20, 50, and 100 C rates, respectively, while
the corresponding capacities after the carbon coating were 175,
172, 171, 170, 116, and 82 mA h g1, respectively. The conversion of
conventional organic substances to solid carbon typically requires a
temperature higher than 700 8C. Such a high calcination tempera-
ture not only increases the energy consumption but also promotes
the sintering of the Li4Ti5O12 particles. Jian et al. proposed the use of
C28H16Br2 as a carbon source and successfully prepared few-layer
graphene on porous Li4Ti5O12 at a calcination temperature as low as
400 8C [269]. The as-synthesized Li4Ti5O12/C composite with
3.51 wt.% carbon exhibited capacities of 153, 134 and 104 mA h g1
1 at rates of 0.5, 5 and 10 C, respectively, and a capacity of
124.4 mA h g1 was maintained at a rate of 2 C after 2400 cycles
with capacity retention of 86%. In comparison, the pristine Li4Ti5O12
had capacities of only 61 and 30 mA h g1 at 5 and 10 C, respectively.
The in situ creation of carbon during the formation of the
Li4Ti5O12 phase has been applied more widely. The raw materials
for Li4Ti5O12 and the carbon source are mixed in the precursor
stage, which are further calcinated at elevated temperatures under
an inert or reducing atmosphere. During the calcination, the
formation of a crystalline Li4Ti5O12 phase and solid carbon happen
simultaneously. Because only one calcination step is involved, the
process is cost effective. In addition, the in situ-formed carbon acts
as a diffusion block to suppress the grain growth of the Li4Ti5O12
phase, and the particles of the as-synthesized Li4Ti5O12/C are
typically of smaller size than that of the pristine Li4Ti5O12 prepared
under the same conditions. Both carbon coating and the reduced
particle size help to improve the electrode performance, especially
at high discharge/charge rates. Yin et al. synthesized a Li4Ti5O12/
carbon composite using TiO2, LiOHH2O and PAN as starting
materials calcined at 800 8C for 12 h under a nitrogen atmosphere
[270]. The high temperature allowed the formation of a Li4Ti5O12
phase and enabled the simultaneous pyrolysis of PAN to solid
carbon. The carbon primarily coated over the Li4Ti5O12 surface as
shown by TEM and had a thickness of 1–10 nm. Using 10 wt.% PAN
during the synthesis, the surface area reached 4.42 m2 g1,
compared with 0.35 m2 g1 for the pristine Li4Ti5O12, suggesting
that the carbon suppresses the grain growth of the Li4Ti5O12 phase.
The carbon coating also resulted in an increased tap density to
1.51 g cm3 for Li4Ti5O12/C (with 10 wt.% during the synthesis)
compared with 1.13 g cm3 for pristine Li4Ti5O12. The capacities of
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
the Li4Ti5O12/C reached 158, 138, 121 and 100 mA h g1, at 1/5, 1/3,
3 and 6 C, respectively, while the corresponding values are 114,
111, 104 and 65 mA h g1 for pristine Li4Ti5O12. The improved
capacities can be explained by the increased surface electronic
conductivity and the reduced particle size. By applying thermo-
gravimetric (TG) analysis, Hu et al. further analyzed the kinetics of
the solid-state reaction for the formation of Li4Ti5O12/C using
LiOHH2O and PAALi as reactants [82]. The TG analysis revealed
two endothermic reactions, which were assigned to the thermal
decomposition of PAALi and solid-state reaction (350–550 8C) and
the Li4Ti5O12 crystal particle growth and crystalline perfection
(550–650 8C). Using the Flynn–Wall–Ozawa (FWO) and Friedman–
Reich–Levi (FRL) methods, the reaction mechanism was well
described by the Jander equation: a 3D diffusion with spherical
symmetry. The formation of the Li4Ti5O12/C composites was found
to have an entropy-driven one-step solid-state reaction mecha-
nism. Shen et al. designed and synthesized carbon-coated Li4Ti5O12
using a facile and general solid-state reaction [271]. The metal
acetylacetonate was used as titania and the single-source carbon
source. After mixing with Li2CO3 and heat treatment, nanostruc-
tured Li4Ti5O12 with a nanoscale carbon coating layer was
obtained. The as-prepared Li4Ti5O12 exhibited a superior rate
performance with discharge capacities of 153, 146, 138, and
119 mA h g1 at 1, 5, 10, and 30 C, respectively.
Wang et al. developed a facile method to prepare carbon-coated
Li4Ti5O12 nanoparticles that simultaneously achieved nanosize
structure and double surface conductive modification based on
Ti(III) and carbon [69]. In this method, the nanosized TiO2 was first
prepared with polyaniline (PANI) coatings through a concurrence of
the hydrolysis of Ti(OC3H7)4 and the polymerization of aniline. The
PANI-coated TiO2 and Li2CH3COO were then milled for 1 h and
calcined at 400 8C in 5% H2–Ar for 4 h, re-milled for 1 h, and finally
calcined again at 800 8C for 24 h under a 5% H2–Ar atmosphere. The
PANI was carbonized during the high temperature calcination with
the formation of solid carbon, which covered the particle surfaces.
The carbonization of PANI was found to effectively restrict the grain
growth of the Li4Ti5O12. Even after sintering at 800 8C for the
prolonged time of 24 h, the resulting powders had small particle
sizes of only 50–70 nm, and the surface was modified with both
carbon and Ti(III) (LiTiO2). These results suggested a unique
morphological structure that not only increased the surface
conductivity but also extended the single phase insertion/extraction
region. As a result, the material demonstrated a high rate
performance, achieving 160 mA h g1 at a current density of
0.1 A g1 and 70 mA h g1 at 3.0 A g1. However, the potential
partial reduction of Ti4+ in the bulk phase to Ti3+ cannot be excluded
due to the application of the reducing atmosphere of 5% H2–Ar
during the high temperature calcination. Cheng et al. further
modified the preparation process of Wang et al. by preparing a
carbon-coated TiO2 via chemical vapor decomposition and further
reacting the resulting TiO2/C with lithium salt at elevated
temperatures to form a Li4Ti5O12/C composite (Fig. 48c) [272]. By
selecting TiO2 with different morphologies, including nanorods,
hollow spheres and nanoparticles, the morphologies can success-
fully transfer to the as-synthesized Li4Ti5O12/C composites, thus
providing a facile way to prepare carbon-coated Li4Ti5O12 with
varying morphologies.
Beyond the traditional carbon coating, a heteroatom-doped
carbon coating on Li4Ti5O12 has also been studied for further
improving the electrode performance, such as nitrogen-doped
carbon coating [184,262,273–275], and boron-doped carbon
coating [276]. Ding et al. investigated the effects of carbon coating,
with and without nitrogen doping, on the electrochemical
performance of Li4Ti5O12 in detail [251] and found that Li4Ti5O12
coated with C-N derived from pyridine using chemical vapor
deposition exhibited a significant improvement in the rate and
37
cycling performance compared with that of Li4Ti5O12 coated via
chemical vapor deposition with normal carbon derived from
toluene. The reversible capacities of the Li4Ti5O12/C–N with
4.9 wt.% carbon are 149 and 133 mA h g1 at 5 and 10 C,
respectively, while the corresponding capacities for Li4Ti5O12/C
with similar carbon content (4.5%) are 130 and 97 mA h g1,
respectively. Based on first-principles calculations, the authors
demonstrated strong binding between the graphene coating layer
and the Ti-terminated Li4Ti5O12 surface, which greatly reduced the
surface activity of the Li4Ti5O12 due to a charge transfer between
the graphene layer and the Li4Ti5O12 substrate, thus stabilizing the
electrode/liquid electrolyte interface and improving the electrical
conductivity of the interface. The nitrogen doping further
increased the interfacial stability, the electrical conductivity, the
defect for the penetration of the liquid electrode and resulted in a
further improvement in the electrode performance.
3.3.2. Coating/modification with other materials
Metals have a very high electronic conductivity; silver and
copper are among the best electronic conductors. The modification
of Li4Ti5O12 with metals has recently received attention. Silver was
widely investigated for modification of Li4Ti5O12 [47,277–279], not
only because of its high electronic conductivity but also because of
its easy preparation by thermal decomposition from silver salt
(e.g., AgNO3) without the application of a reducing agent or
reducing atmosphere. Huang et al. prepared a Li4Ti5O12 surface
modified with silver particles via the thermal decomposition of
AgNO3 added to Li4Ti5O12 powders [47]. The Ag content and mixing
media played an important role in the electrochemical perfor-
mance of the as-prepared composite. A composite with 5 wt.% Ag
yielded the best performance. As a mixing medium, water resulted
in smaller silver particles and a more homogenous dispersion than
alcohol. The Ag/Li4Ti5O12 with 5 wt.% Ag prepared using a water
medium exhibited a reversible capacity of 184.2 mA h g1 in the
potential range of 0.5–2.5 V. After 50 charge/discharge cycles, a
capacity degradation rate of 0.067% per cycle was demonstrated.
S.H. Huang also investigated copper, which was introduced by
the thermal decomposition of a mixture of Cu(NO3)2 and the
precursor Li4Ti5O12 under an H2-N2 or air atmosphere, as an
additive to improve the conductivity of Li4Ti5O12 [280]. The
conductivities of pristine Li4Ti5O12, Li4Ti5O12/Cu prepared under a
hydrogen atmosphere and Li4Ti5O12/Cu prepared under an air
atmosphere are 2.5  107, 1.45  106 and 1.3  107 S cm1,
respectively. The improved conductivity for the sample prepared
under a hydrogen atmosphere could be attributed to the partial
reduction of Ti4+ in the Li4Ti5O12 or to the reduction of CuxO to
metallic copper in hydrogen. The composite prepared under a
hydrogen atmosphere showed a capacity of 137.6 mA h g1 after
100 cycles with a capacity loss of 5.6%, while the capacity of the
composite prepared in air decreased to only 68.8 mA h g1 with a
capacity loss of up to 13.7%. Clearly, the improved performance of
the Li4Ti5O12/Cu prepared under a hydrogen atmosphere over that
of the Li4Ti5O12/Cu prepared under an air atmosphere is closely
related with the improved electronic conductivity. Huang et al.
further prepared a Li4Ti5O12/Cu composite using an electroless
deposition of copper particles [46]. A small quantity of copper
(with a copper concentration as low as 1%) resulted in an increase
in the electronic conductivity by two orders of magnitude. The
Li4Ti5O12/Cu electrodes exhibited stable capacities of 171, 166.6,
153.6, 144.6 and 141.6 mA h g1 at 1, 2, 4, 8 and 10 C, respectively,
in a voltage range of 2.0–0.5 V. The corresponding capacities for the
pristine Li4Ti5O12 are 164.2, 155, 117.3, 72.5 and
61.2 mA h g1. Cheng et al. prepared a Li4Ti5O12/Cu composite
by calcining a mixture of Cu(NO3)23H2O and a precursor of
hydrothermal-synthesized Li4Ti5O12 under N2[281]. The as-
formed copper nanoparticles were highly dispersed on the surface
38 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
of Li4Ti5O12, and improved electrochemical performance at
different rates was observed after modification with copper
nanoparticles. Li et al. synthesized a Li4Ti5O12/Cu composite using
a one-pot solvothermal method using LiOHH2O, TTIP, and
Cu(NO3)23H2O as starting materials [282]. The effect of different
amounts of copper (0, 3.75, 7.5, 15 and 22.5 wt.%) on the
morphology and electrochemical performance was investigated.
Although the elemental mappings demonstrated that the copper
was not homogeneously distributed in the composite, enhanced
electrochemical performance for the Li4Ti5O12/Cu composite,
especially with 15 wt.% copper, was achieved with a specific
discharge capacity of 107 mA h g1 even after 1000 cycles (87%
retention). Further improvement in the rate performance may be
achieved by introducing a continuous conductive copper phase
instead of dispersed copper nanoparticles.
Other methods, such as the electroplating method [283], have
also been applied to coat copper on the Li4Ti5O12 to achieve surface
modification, resulting in improved electrochemical performance,
especially for the rate capability. Hsieh et al. deposited a thin layer of
zinc via microwave irradiation onto the surface of the Li4Ti5O12 with
a thickness of 1–10 nm by using zinc nitrate as a raw material
[284]. The Zn coating significantly improved the capacity retention
at high rates—78.1% at a 10 C rate (142.9 mA h g1) over that at a rate
of 0.2 C (183 mA h g1) with a coulombic efficiency greater than
99.9% attributed to the increased electronic conduction and reduced
cell polarization due to the zinc coating. In comparison, the
capacities of the pristine Li4Ti5O12 are 175 and 96.6 mA h g1 at
0.2 and 10 C, respectively, with capacity retention of only 55.2% at
10 C with respect to that at 0.2 C. Gold has also been studied as a
coating metal on Li4Ti5O12 nanorod aggregates using a liquid
method with Au (III) solution as the Au source [285]. After Au
coating, the Li4Ti5O12/Au composite material exhibited much higher
electronic conductivity (approximately 8.53  103 S cm1) com-
pared with that of pure Li4Ti5O12 (approximately 1013 S cm1) and
enhanced electrochemical performance, especially at high rates.
However, the high cost and scarcity of gold limits its commercial
application.
TiN is a hard refractory material and an excellent metallic-type
conductor [286]. Snyder et al. firstly applied an approximately 5.8-
nm thin layer of TiN as a coating on Li4Ti5O12 using an atomic layer
deposition technique [287]. Compared to pristine Li4Ti5O12, the TiN-
coated Li4Ti5O12 showed improved capacities in the range of 0.05–
0.2 C. Zhang et al. fabricated Li4Ti5O12/TiN composites using a facile
high-energy ball-milling method by mixing spinel Li4Ti5O12 and TiN
powder with different mass ratios [288]. The HRTEM results
indicated that TiN formed a 1.5-nm thin layer on the surface of
Li4Ti5O12 with a mass ratio of 100:2 (Li4Ti5O12:TiN). This composite
sample exhibited a high capacity of 130 mA h g1 at 20 C, which is
10 times that of pristine Li4Ti5O12. Ming et al. introduced urea into
the synthesis process of Li4Ti5O12 including hydrolysis of tetrabutyl
titanate and ball-milling with Li2CO3 and observed that N–C and TiN
were formed [289]. TiN was detected by X-ray photoelectron
microscopy (XPS) and Raman analysis. With proper amounts of urea,
the as-synthesized Li4Ti5O12 composite exhibited a smaller particle
size and enhanced electrochemical performance.
Oxides have also been used as coatings to improve the
electrochemical performance of Li4Ti5O12 anodes, e.g., CeO2 was
coated on Li4Ti5O12 to form core-shell nanospheres using a one-pot
co-precipitation method; the as-form composite nanosphere
exhibited enhanced performance with a capacity of 152 mA h g1
1 at 10 C even after 180 cycles [290]. The enhanced performance
could be mainly attributable to the unique core-shell nanosphere
microstructure compared with the irregular and aggregated
particles of pure Li4Ti5O12. SiO2 was coated on the surface of
commercial Li4Ti5O12 via a facile sol–gel method followed by
calcination, resulting in improved rate capability within a potential
range of 1.0–3.0 V [291]. Since SiO2 has poor electronic conductiv-
ity, the SiO2 coating may increase the resistance of the electrode;
however, a decrease in electrochemical polarization was reported.
Thus, the real reason for the improved electrochemical perfor-
mance was still not clear in this case. Jiang et al. systematically
studied Li4Ti5O12 and SiO2-incorporated Li4Ti5O12 as anodes under
different conditions, including discharge to an end potential of 1.0/
0.01 V at room/elevated temperature (55 8C) [292]. XRD Rietveld
refinement analysis indicated that the SiO2 was incorporated into
Li4Ti5O12 in two forms, Si-doping (53.5%) into the Li4Ti5O12 spinel
lattice and a SiO2 (46.5%) separate phase as a coating layer. The
effect of SiO2-coating on the electrochemical performance was
negligible within a potential range of 1.0–3.0 V; however, it
somewhat improved cycling stability at 55 8C compared to the
unmodified Li4Ti5O12. Within the potential range of 0.01–3.0 V,
both Li4Ti5O12 and SiO2-incorporated Li4Ti5O12 electrodes exhib-
ited a stable cycling performance at room temperature for
400 cycles at a current density of 175 mA g1 as shown in
Fig. 50a. At an elevated temperature of 55 8C, both electrodes
exhibited an interesting ‘‘decrease-increase-decrease’’ cycling
behavior (Fig. 50b), and a mechanism of ‘‘SEI film formation-SEI
dissolution/delamination-SEI reformation/consumption of elec-
trolyte’’ was proposed (Fig. 50c) and supported by EIS (Fig. 50d and
e) and TEM analysis. Importantly, the SiO2 coating layer did help to
effectively increase the cycling stability of Li4Ti5O12 at an elevated
temperature between 0.01 and 3.0 V (Fig. 50b). Coatings of other
oxides, e.g., ZnO, were also reported to improve the cycling
performance of Li4Ti5O12 electrodes [293].
Conductive polymers are also attractive coating materials. Yu
et al. prepared a Li4Ti5O12/polyacene composite via the in situ
carbonization of a phenol–formaldehyde resin to from a carbon-
based composite [294]. The electronic conductivity of the Li4Ti5O12/
polyacene is 108 times higher than that of the pristine
Li4Ti5O12. After 200 cycles, the pristine Li4Ti5O12 has capacity
retention of 57.4% at a 5 C discharge rate, while the capacity
retention is 87.6, 80 and 78.2% at discharge rates of 3, 5 and 10 C for
Li4Ti5O12/polyacene, respectively. Wang et al. successfully coated a
poly (3,4-ethylenedioxythiophene) (PEDOT) layer on spinel
Li4Ti5O12 nanorods [295]. A sample of Li4Ti5O12/C with calcination
of Li4Ti5O12/PEDOT to obtain a carbon-coating layer was also
prepared and studied. The Li4Ti5O12/PEDOT sample exhibited the
highest electronic conductivity of 0.083 S cm1 compared with that
of pure Li4Ti5O12 nanorods (109 S cm1) and Li4Ti5O12/C
(0.051 S cm1) and the best electrochemical performance. High
rate performance with a discharge capacity of 135.2 mA h g1 at
10 C and stable cycling performance with a capacity of
168.7 mA h g1 after 100 cycles at 1 C were achieved for the
PEDOT-coated sample.
3.3.3. Surface treatment
(1) N-containing environment (e.g., ammonia atmosphere, solid
nitrogen sources)
Because both TiN and TiO2 contain titanium, they can easily be
fabricated through calcination of Li4Ti5O12 in an ammonia-
containing atmosphere [68,296]. Park et al. reported the modifi-
cation of the surface structure of Li4Ti5O12 by thermal nitridation
via annealing in an ammonia atmosphere [68]. High resolution
transmission electron microscopy (HR-TEM) and XPS results
(Fig. 51a) showed that a thin TiN layer of several nanometers
formed over the Li4Ti5O12 surface to create a core-shell composite
with a Li4Ti5O12 core and a TiN + Li2CO3 shell. The white color of the
initial Li4Ti5O12 suggests its inherent low electronic conductivity.
The color of white Li4Ti5O12 became dark after thermal nitridation
under NH3 atmosphere, and it was apparently black after 1 h
(Fig. 51b). Because TiN is a metallic conductor, the apparent
conductivity of the modified Li4Ti5O12 is expected to increase
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 39

Fig. 50. (a, b) Cycling performance of the cellulose-assisted combustion-synthesized unmodified Li4Ti5O12 (CS-LTO) and SiO2-incorporated Li4Ti5O12 (CS-SiO2/LTO) electrodes
tested at (a) room temperature and (b) 55 8C between 0.01 and 3.0 V (discharge/charge current density: 175 mA g1). (c) The schematic illustration of mechanism for the
‘‘decrease-increase-decrease’’ cycling behavior of Li4Ti5O12 between 0.01 and 3.0 V at 55 8C. (d) Impedance spectra of CS-LTO at different cycle times (tested at 1.6 V after
cycling between 0.01 and 3.0 V at 55 8C); (e) equivalent circuit [292].

substantially. The capacities after nitridation were not substan-
tially different from those of pristine Li4Ti5O12 at rates below 1 C
(Fig. 51c). However, the discharge capacities of the Li4Ti5O12
treated even after 10 min of nitridation are 6 times higher than
those of pristine Li4Ti5O12 at a high discharge/charge rate of 10 C.
The treatment also resulted in an increase in the single solution
region during the lithium insertion/extraction processes, as shown
in Fig. 9c, which is believed to benefit the lithium intercalation/de-
intercalation because of an apparent increase in the electron and
lithium-ion conductivity [42,70]. Park et al. treated the 1D
electrospun nanofibers under ammonia at 700 8C to obtain TiN/
TiOxNy-coated Li4Ti5O12 nanofibers [297]. HR-TEM analysis
revealed the formation of an amorphous TiN/TiOxNy layer, which
was further confirmed by XPS. The nitridated Li4Ti5O12 nanofiber
electrode achieved a discharge capacity of approximately
1.35 times that of a pristine nanofiber electrode at 10 C rate.
However, in addition to the formation of the conductive TiN, the
partial reduction of Li4Ti5O12 by the reducing ammonia atmo-
sphere may play an important role in the improved rate
performance. Lin et al. demonstrated that ammonia was primarily
reduced to H2 and N2 at elevated temperatures [298], while the
Li4Ti5O12 can be partially reduced by H2 via a substantial increase
in the electronic conductivity, leading to an increase in the rate
performance of the Li4Ti5O12 [299]. Because TiN is inert to lithium
insertion, the coating layer thickness should be sufficiently thin;
otherwise, it may block the lithium transport into the Li4Ti5O12

Fig. 51. (a) XPS analysis of the Ti 2p3/21/2, and N 1s core peaks performed onto Li4Ti5O12 before and after nitridation: pristine Li4Ti5O12 and the nitridated powders at 700 8C
for 10, 30, 60 min. (b) Li4Ti5O12 powder color change after thermal nitridation at 700 8C with NH3 gas flow. The annealing time is indicated on each powder samples. (c)
Reversible capacities of pristine and 10 min-nitridated Li4Ti5O12 with different charge/discharge current densities during cycling [68].
40 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

phase. The coating layer thickness can be controlled by adjusting
the ammonia concentration, the calcination temperature, and the
calcination time during the thermal nitridation process. Wan et al.
reported a facile solid-state reaction method for preparing
nitrogen- and TiN-modified Li4Ti5O12 with a calcining precursor
under NH3/N2 (3, 7, 13, 20 and 100%) atmosphere [300]. Calcination
in the NH3-containing atmosphere resulted in partial reduction of
Ti4+ to Ti3+ and a TiN phase formed in a NH3/N2 7% atmosphere,
which could both improve the electronic conductivity. However,
the sample calcined at 3% NH3/N2 exhibited the best rate
performance with a specific capacity of 103 mA h g1 at 20 C rate,
which was more than three times that calcined in air. It was
suggested that sufficient electronic conductivity was already
reached from the partial reduction of Ti4+ to Ti3+ by the reducing
atmosphere, and the formed TiN layer in this situation mainly
acted as a diffusion block for lithium ions.
Although an ammonia atmosphere was effective for forming
TiN- or/and nitrogen-modified Li4Ti5O12, the toxic nature limits the
application of an ammonia atmosphere. Recently, solid nitrogen
sources were also used to achieve a nitridation process of
Li4Ti5O12. Zhao et al. used urea as a nitrogen source and mixed
it with Li4Ti5O12 for a solid-state reaction by planetary ball milling
[301]. Li4Ti5O12/TiN composites with different amounts of urea
were successfully synthesized, and the formation of TiN was
directly evidenced by Raman measurements. An improved rate
performance and much enhanced cycling stability were achieved
after the modification of TiN. The composite treated with 6% urea
exhibited the best rate performance with a specific capacity of
116.1 mA h g1 at a cycling rate of 10 C rate and enhanced cycling
performance with a capacity of 148.3 mA h g1 after 600 cycles at a
3 C rate, which was approximately 90% of the initial capacity.
Melamine was also reported as a solid nitrogen source for the
nitridation of Li4Ti5O12 [302], in which Li4Ti5O12 was synthesized
via a solid-state reaction and then was mixed with melamine
followed by a calcination at 700 8C under Ar atmosphere. XPS, TEM
and corresponding linear scanning energy-dispersive X-ray
spectroscopy (EDX) results demonstrated the formation of a
homogenous TiN layer on the surface of Li4Ti5O12. Such an as-
formed TiN layer resulted in enhancement in the electronic
conductivity, and further rate capability and cycling performance.
(2) Reducing environment (e.g., H2, solid carbon for carbothermal
reduction)
In addition to formation of a TiN coating layer by surface
treatment, partial reduction of Ti4+ to Ti3+ on the surface of Li4Ti5O12
by a thermal treatment in a reducting atmosphere (e.g., H2, H2/Ar)
was also reported to result in an enhancement in electronic
conductivity and further electrochemical performance. Industrial
grade white Li4Ti5O12 powders were treated under a 40 bar H2
atmosphere at 500 8C by Qiu et al. [303], and it was found that the
white color became blue (Fig. 52a), suggesting an enhancement in
the electronic conductivity. Such treatment did not significantly
affect the microstructure and phase structure of the Li4Ti5O12
(Fig. 52b), but dramatically altered the defect structure. Importantly,
the electrochemical performance was much improved after the
treatment under H2 atmosphere; the reversible capacities was
increased from 135 mA h g1 (before reduction) to 173.6 mA h g1
(after reduction) at a rate of 0.5 C (Fig. 52c). The rate capability was
also enhanced after reduction. Wolfenstine et al. prepared Li4Ti5O12
samples from rutile TiO2 and Li2CO3 using a solid-state method, in
which the sample was calcined at 800 8C under air or 3 vol.% H2/Ar to
understand the effect of reducing atmosphere on the electronic
conductivity and further rate performance [299]. The Li4Ti5O12
sample reduced in H2/Ar turned to gray with an electronic
conductivity of 1  105 S cm1, which is much higher than that
for the white Li4Ti5O12 sample. As expected, the Li4Ti5O12 sample
reduced in H2/Ar exhibited improved rate capability.

Fig. 52. (a) Digital photos, (b) XRD patterns, and (c) specific charge and discharge capacities at various C rates of the initial white Li4Ti5O12 and blue Li4Ti5O12 obtained at
500 8C under a 40 bar H2 atmosphere [303]. (d) Digital photos of as-prepared materials and that after storage for 5 weeks: LTO-O (undoped LTO in an oxidizing atmosphere),
LTO-R (undoped LTO in a reducing atmosphere), Mo-LTO-O (Mo-doped LTO in an oxidizing atmosphere), and Mo-LTO-R (Mo-doped LTO in a reducing atmosphere) [304]. (e)
Electron paramagnetic resonance signals, and (f) rate capability of LTO-O, LTO-R and Mo-LTO-R [304]. (For interpretation of the references to color in this figure legend, the
reader is referred to the web version of this article.)
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Even though the treatment under a reducing atmosphere is
facile and an effective way to improve the electrochemical
performance, it suffers from two shortcomings [304]. First, the
reduced state Ti3+ in the lattice is not very stable and will be re-
oxidized, resulting in gradually retrogressing of electronic
conductivity. Second, the formed oxygen vacancies may induce
lattice distortion, leading to a decrease in lithium-ion mobility in
the lattice. Accordingly, a higher valence metal cation doping may
result in stabilization of the lattice treated under a reducing
atmosphere. Song et al. selected Mo6+ as a dopant and found a
prominent stabilization of the structure of the Li4Ti5O12 after
calcination under a reducing atmosphere (10% H2 in Ar) [304]. As
shown in Fig. 52d, the undoped Li4Ti5O12 obtained under a
reducing atmosphere appeared to be blue with an electronic
conductivity of 8.1  106 S cm1, and its color changed signifi-
cantly from dark blue to light blue after 5 weeks. However, the
color of the Mo-doped Li4Ti5O12 obtained under a reducing
atmosphere was maintained after 5 weeks, and the change in
electronic conductivity was negligible, from 1.1  102 to
1.4  102 S cm1. XPS analysis indicated that the presence of
rich Ti3+ and Mo6+ in the Mo-doped Li4Ti5O12 obtained under a
reducing atmosphere, and electron paramagnetic resonance
demonstrated its signal was significantly lower than that observed
for the undoped Li4Ti5O12 obtained under a reducing atmosphere
(Fig. 52e), suggesting that fewer oxygen vacancies were present in
the lattice. These results demonstrated the successful enhance-
ment in electronic conductivity and in structure stability by Mo
doping into Li4Ti5O12 under a reducing atmosphere. Accordingly,
the Mo-doped Li4Ti5O12 obtained under a reducing atmosphere
exhibited excellent rate capability with a specific capacity of
167 mA h g1 even at a rate of 10 C (Fig. 52f), and the performance
could be maintained after 5 weeks.
As an alternative thermal reduction method, carbothermal
reduction was also used to enhance the electronic conductivity of
the Li4Ti5O12 very recently (Fig. 53) [12]. In a typical process, small
amount of acetylene black was mixed with the raw materials (i.e.,
Fig. 53. The schematic illustration of formation process of carbothermal reduction for Li4Ti5O12. The insets are the corresponding digital photos of as-prepared Li4Ti5O12
calcined under Ar and air [12].
41
Li2CO3 and TiO2) and then heat-treatmented at 850 8C under Ar
atmosphere. The as-obtained Li4Ti5O12 appeared to be blue as
shown in Fig. 53, consistent with the color of the sample obtained
under a reducing atmosphere (Fig. 52a and d). In contrast, the color
of the sample prepared under similar conditions but calcined in
ambient air was white (Fig. 53). Importantly, the carbothermally
synthesized blue Li4Ti5O12 demonstrated an enhanced electronic
conductivity of 1.34  104 S cm1 and further improved electro-
chemical performance, compared to that of sample obtained in
ambient air (4.03  108 S cm1).
(3) Other environment
Nakajima et al. investigated the effects of surface fluorination
and conductive additives on the charge/discharge properties of
Li4Ti5O12 [305,306]. The surface fluorination of Li4Ti5O12 powder
was conducted using low-pressure F2, NF3 or ClF3 as a treating
atmosphere. After fluorination by F2, a LiF film was formed on the
Li4Ti5O12 surface, while the number of small mesopores with
diameters of 2 nm increased following the fluorination with
ClF3. An improved capacity at high rate was also observed after the
fluorination of the electrode at a proper temperature. By adding
vapor-grown carbon fiber, the electrical contact between the
Li4Ti5O12 particles and the current collectors was further increased,
resulting in an improved rate performance.
Jo et al. successfully prepared phosphidated Li4Ti5O12 nano-
particles via the thermal decomposition of trioctylphosphine (TOP)
[307]. The surface layer corresponds to Li–O–P bonding with
coordinated Ti3+. The insulating character of the Li4Ti5O12 can be
attributed to the Ti–O dangling bond. The empty Ti 3d states were
reduced by the TiO–P and LiO–P bonds, thus enhancing the
electronic conductivity of the Li4Ti5O12 during the electrochemical
reaction. The phosphidation appeared to facilitate electronic or
ionic conduction through the surface of the Li4Ti5O12, as glassy
lithium phosphates are known to be stable Li+ conductors and can
be doped with transition metals to achieve good electronic
conduction. The capacity of the phosphidated Li4Ti5O12 was found
to be approximately 140 mA h g1 at a rate of 0.1 C with attractive
42 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

cycling stability within 50 cycles in comparison with a capacity
of 120 mA h g1 for pristine Li4Ti5O12 in the voltage range of
3.0–1.0 V. At a high current density of 10 C, the phosphidated
Li4Ti5O12 maintained a capacity of 100 mA h g1, which is
20 mA h g1 larger than that of the pristine Li4Ti5O12.
3.4. Doping
Doping is sometimes effective at altering the structural
properties and thus the performance of many oxides. A small
amount of aliovalent-cation doping will not cause a change in the
phase structure of the parent oxide; however, it may significantly
affect the bond strength, the local environment of the lattice, the
valence state of the compositional cations, and it may introduce a
lattice defect. As a result, the charge transport properties of the
oxides are modified. To mitigate the drawbacks of Li4Ti5O12, such
as its poor electronic conductivity and poor lithium-ion conduc-
tivity, extensive research has been conducted to increase the
transport properties, thus the performance of the Li4Ti5O12 oxide
through doping at the 8a tetrahedral Li+ site, the octahedral 16 d
Ti4+ site, the oxygen anion site, or a combination of these sites.
Currently, only doping at the tetrahedral 8a sites, octahedral 16d
sites and oxygen anion sites has been attempted, with a focus on
the octahedral sites. Dopants including Mg2+ [10,308–310], Sn2+/4+
[311,312], Mo4+ [313,314], V5+ [315–318], Ta5+ [319], Nb5+
[156,320–323], Zr4+ [324–328], Si4+ [328], Mnx+ [329–332], Fe3+
[333–336], Cr3+ [17,337–340], Ni3+/2+ [338,341], Al3+ [342–348],
La3+ [349–352], Co3+ [353], Sc3+ [354], Cu2+ [355–357], Zn2+ [358–
363], Na+ [364–366], K+ [367], Ag+ [368], Ca2+ [369,370], Sr2+ [371],
Y3+ [372], Nd3+ [373], Ru4+ [374], W6+ [375–377], F [342,378,379],
and Br [377] have been exploited. Different dopants may have
different solubilities, preferred doping sites, and varying effects on
the phase structure, and thus the conductivity and electrochemical
performance of the oxides. Table 1 lists dopants, structural formula,

Table 1
Doped Li4Ti5O12 with different dopants.

Dopant Structural formula, doping amount Phase structure Doping site Change after doping Ref.

Mg2+ Li4xMgxTi5O12 (0  x  1) Spinel 8a, 16d High conductivity (s = 102 S cm1, x = 1.0), increased rate [10]
(+Li2MgTi3O8 + capability (x = 0.25)
MgTi2O5, x > 0.75)
Li4xMgxTi5O12 (0.05  x  0.2) Spinel 8a, 16d Improved reversible capacity and cycling stability, especially [308]
for x = 0.1
Li(42x)MgxTi(5x)/3O4 (0x < 0.6) Spinel 8a, 16d Increased ionic conductivity of Li+ by the calculations, but [309]
opposite results by experimental measurements
Li20MgTi27O64 Spinel + minor 8a Smaller particle size, higher electronic conductivity, improved [310]
anatase rate performance and cycling stability
TiO2

Sn2+ Li3.9Sn0.1Ti5O12 Spinel / Coating of carbon, creation of nanopores, increased rate [311]
capability, 100% capacity retention after 100 cycles (5 C)
4+
Sn Li4Ti5xSnxO12 (x = 0, 0.05, 0.1) Spinel + SnO2 / Smaller particle size, higher DC electrical conductivity; [312]
improved electrochemical performance (0–3.0 V, x = 0.1)

Mo4+ Li4Ti5xMoxO12 (0.5  x  1.5) Spinel 16d Increased electronic conductivity (1.6, 2.8, and [313]
(+Li4Mo5O12, x = 1.5) 5.8  103 S cm1, x = 0.5, 1.0, 1.5)
Li4Ti4.95Mo0.05O12 Spinel / Enhanced electronic conductivity, increased rate capability [314]
(117.03 mA h g1 at 10 C, 94.24 mA h g1 at 30 C), only 5.8% of
capacity loss (100 cycles, 1 C)

V5+ Li4Ti5xVxO12 (0  x  0.3) Spinel (0  x  0.1), 16d Excellent cycling capability of Li4Ti4.95V0.05O12 (between [315]
appeared TiO2 1.0 and 2.0 V), Li4Ti4.9V0.1O12 (183 mA h g1 after 100 cycles
and VO2 phase between 0.5 and 2.0 V, 229 mA h g1 after 130 cycles between
(x 0.15) 0.0 and 2.0 V)
Li4Ti4.95V0.05O12 Spinel / Good cycling performance and high discharge capacity [316]
(218.4 mA h g1 after 50 cycles)
Li4Ti4.9V0.1O12 Spinel / Enhanced conductivity (e, Li+) and narrower particle size [317]
distribution, 177.5 (0.1 C), 166 (0.5 C), 142.8 (2 C), and
117.3 mA h g1 (5 C). Capacity retention is 97.9% after
1713 cycles (2 C) and 93.2% after 4374 cycles (5 C)
Li4Ti5xVxO12/C Spinel / Enhanced electron conductivity and Li diffusion coefficient, [318]
(x = 0.05, 0.1, 0.15) e.g., 5.44  106 S cm1 and 2.84  1011 cm2 s1 for
Li4Ti4.9V0.1O12/C, respectively. The composite (x = 0.1) achieves
discharge capacities of 165.59 and 76.76 mA h g1 at a 0.2/1 C
and 0.2/20 C rate (0.5–2.5 V), respectively
Ta5+ Li4Ti4.95Ta0.05O12 Spinel 16d Enhanced electronic conductivity (1  103 S cm1) [319]
synthesized under 3 vol.%H2/Ar

Nb5+ Li4Ti4.95Nb0.05O12/C Spinel / Enhanced conductivity (0.072 S cm1 of Li4Ti4.95Nb0.05O12/C [156]

compared to 0.011 S cm1 of Li4Ti5O12/C), increased rate
capability (140.0 mA h g1 at 10, 110.6 mA h g1 at 25 C)
Li4Ti4.95Nb0.05O12 Spinel / Increased capacity of 231.2 mA h g1 after 100 cycles [320]
(35 mA g1, 0–2.5 V)
Li4+xTi4.95xNb0.05O12d Spinel (700–900 8C) 16d Enhanced rate capability (140 mA h g1 at 3 C rate) [321]
(x = 0.110.13)
Li4Ti4.95Nb0.05O12 Spinel / Increased conductivity (1.127  109 S cm1 of [322]
Li4Ti4.95Nb0.05O12 compared to 6.615  1010 S cm1 of
Li4Ti5O12 is), excellent rate capability (135 mA h g1 at 10 C and
80 mA h g1 at 40 C)
Li4Ti4.995Nb0.005O12 Spinel / Slightly decreased electrical conductivities [323]
(Li4Ti4.995Nb0.005O12), but it is much enhanced after Ar
annealing
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 43

Table 1 (Continued )

Dopant Structural formula, doping amount Phase structure Doping site Change after doping Ref.

Zr4+ Li4Ti5xZrxO12 (x = 0, 0.05, 0.1, 0.2) Spinel, appeared ZrO2 / Good rate capability and cycling stability (x = 0.1, 143 mA h g1 [324]
phase (x = 0.1, 0.2) at 5 C and 118 mA h g1 at 20 C; 141 mA h g1 after 100 cycles at
5 C)
Li4Ti5xZrxO12/C (x = 0, 0.05) Spinel 16d Good cycling stability (289.03 mA h g1 after 50 cycles at 0.2 C, [325]
0–2.5 V)
Li4Ti5xZrxO12 (0  x  0.25) Spinel + ZrO2 / Improved specific capacity and rate performance (0–2.5 V, 1.0– [326]
2.5 V)
Li4Ti5xZrxO12 (x = 0, 0.05, 0.1, 0.15) Spinel, appeared / Increased Li+ diffusivity and improved specific capacity, rate [327]
ZrO2 phase capability, and cycling properties (x = 0.05)
(x = 0.1, 0.15)
Zr4+ Li4Ti5xZrxO12 (x = 0, 0.05, 0.1) Spinel + Li2TiO3 / Enhanced DC conductivity for x = 0.05, decreased conductivity [328]
(x = 0, 0.05) for y = 0.05;
(+TiO2, x = 0.1)
Si4+ Li4Ti5ySiyO12 (y = 0, 0.05, 0.1) Spinel + Li2TiO3 + Sample with x = 0.05 exhibited best electrochemical
TiO2 + Li2TiSiO5 performance
(y = 0.05, 0.1)

Mn4+ Li4Ti4.5Mn0.5O12, Li4Ti4.75V0.25O12, Spinel + Li2TiO3 8a, 16d 16d Decreased the mass capacities [329]
V4+ Li4.25Ti4.75Fe0.25O12 Spinel 8a, 16d
Fe3+ Spinel

Mn3+ Mn-doped Li4Ti5O12 Spinel (+TiO2, 8a, 16d 8a Decreased conductivity [330]
Mn2+ (Mnx+30% of Tix+) Li2TiO3, LiMn2O4)

Mn4+ Li4Ti5xMnxO12 (x = 0.0, 0.05, 0.1) Spinel (+MnO2, x = 0.1) / Reduced particle size, improved cell performance (0.01–3.0 V) [330]
Mn2+ Li4Ti5xMnxO12 Spinel + Li2TiO3 / Enhanced ionic conductivity [332]
(x = 0, 0.005, 0.025, 0.01, 0.05, (+TiO2, x = 0.005)
0.075, 0.1, 0.2)

Fe3+ Li0.5+0.5xFe2.51.5xTixO4 (0  x  1.66) Spinel with space Fd3m: 8a; P4332: / [333]
¯
group Fd3m 8c, 12d
¯
(0.4  x  1.2 and
1.57  x  1.66);
space group P4332
(0  x  0.4 and
1.2  x  1.57)
Li4/35y/3(3y)Fe5y/(3y)Ti5(1y)/(3y)O4 Spinel (y < 0.5), 8a (y = 0–0.143) Poor insertion/extraction electrochemistry (y 0.5) [334]
(0  y  1.66) inverse spinel (y 0.5) 8a, 16d (0.143–1)
1
Li1+xFe13xTi1+2xO4 (0.0  x  0.33) Spinel (non-normal) 8a Reversible capacities in excess of 150 mA h g over 20 cycles [335]
(x = 0.30, Vlimits = 0.01–2.00 V, i = 100 mA)
Li1.3Fe0.1Ti1.6O4 Spinel (Fd3m) P4332 8a, 16d Stable capacity over 100 cycles [336]
¯
Li1.25Fe0.25Ti1.5O4 8c

Cr3+ Li[Li(1x)/3CrxTi(52x)/3]O4 (0  x  1.0) Spinel (+TiO2) 16d Low area specific impedance and increased rate capability [17]
(88 mA h g1 at 2 C)
Li(4x)/3Ti(52x)/3CrxO4 (0  x  0.9) Spinel 16d Sample of x = 0.7 exhibited best electrochemical performance [337]
Li4Ti2.5Cr2.5O12 Spinel + TiO2 16c High-rate cycling stability (132 mA h g1 after 20 cycles at 5 C) [339]
Li4x/3Ti52x/3CrxO12 Spinel / Increased electronic conductivity; increased Li+ ion diffusivity [340]
(x = 0, 0.25, 1.00, 2.00, 3.00) due to decreased structural disorder
Cr3+ Li1.317Cr0.050Ti1.633O4 Spinel 16d Increased conductivity [338]
Ni3+ Li1.317Ni0.050Ti1.633O4 Spinel + TiO2 + Li2TiO3 16d Decreasd conductivity
Al3+/F Li4AlxTi5xFyO12y Spinel / Increased (Al3+)/decreased (F) reversible capacity and cycling [342]
stability

Al3+ Li4xAlxTi5O12 (x = 0, 0.05, 0.1, 0.2) Spinel / Decreased specific capacity but increased rate-capability [343]
Li4Ti4.85Al0.15O12 Spinel 8a, 16d Decreased crystallite size, increased surface area, enhanced [344]
first discharge capacity and rate performance
Li4Ti4.95Al0.05O12/C Spinel 16d Improved initial capacity and cycling performance [345]
Li4AlyTi5yO12 (y = 0.10, 0.15, 0.25) Spinel / High reversible capacity and high coulombic efficiency [346]
(+LiAlO2, y = 0.25) (y = 0.15)
Li4Ti4.95Al0.05O12 Spinel 16d Enhanced electronic conductivity, and high rate capability [347]
(1.0–2.5 or 0–2.5 V)
Li4x/3AlxTi52x/3O12 Spinel (+TiO2, x = 0.01, 8a, 16d Increased reversible capacity and cycling stability (x = 0.01, [348]
(x = 0, 0.01, 0.05, 0.1, 0.15, 0.2) 0.1, 0.15, 0.2) 0.05, 0.1)

La3+ La3+-doped Li4Ti5O12 Spinel / Improved initial discharge capacity of 161.5 mA h g1 at 0.1 C, [349]
(La/Ti = 1:100, mol/mol) 135.4 mA h g1 after 50 cycles
Li4Ti5xLaxO12 (0  x  0.2) Spinel + Li3xLa2/3xTiO3 Little Formation of Li3xLa2/3xTiO3-Li4Ti5O12 solid solution, improved [350]
La3+ enter the electronic conductivity and lithium diffusion coefficient
crystal lattice (x = 0.05)
La3+-doped Li4Ti5O12 Spinel + Li0.35La0.55TiO3 8a (part of La3+) Smaller particle size, higher surface area, and improved rate [351]
(La/Ti = 0.75:100, mol/mol) capability with reversible capacities of 156.2 and
150.8 mA h g1 at 1 and 5 C, respectively
Li3.95La0.05Ti5O12 Spinel / Improved specific capacity, cycling performance and rate [352]
capability
3+
Co Li1.33xCo22xTi1+0.67xO4 (0  x  1) Spinel (Fd3m) / Improved electrical properties of the electrode materials [353]
¯
(0  x  0.40, x = 1)
P4332 (0.50  x  0.875)
44 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Table 1 (Continued )

Dopant Structural formula, doping amount Phase structure Doping site Change after doping Ref.
3+
Sc Li4Ti4.95Sc0.05O12d Spinel 16d Smaller particle size and higher specific surface area, improved [354]
rate performance and cycling stability

Cu2+ Li4Ti5CuxO12+x Spinel (x  0.6) / Improved rate performance [355]

(x = 0, 0.075, 0.15, 0.3, 0.6, 1.20, 1.67) Spinel + TiO2 + CuO
(x = 1.20, 1.67)
Li4xCuxTi5O12 (x = 0, 0.1, 0.2) Spinel / Decreased charge transfer resistance, improved cycling [356]
stability and rate capability
Li42xCu3xTi5xO12 (0  x  0.15) Spinel 16d Enhanced electronic conductivity and Li+ diffusion coefficient [357]
by at least two orders of magnitude and four times,
respectively. After further introducing CNTs, Li3.8Cu0.3Ti4.9O12/
CNTs delivered 114 mA h g1 at 10 C, whereas that of Li4Ti5O12
is only 11 mA h g1

Zn2+ LiZn0.5Ti1.5O4 Spinel (disordered) Fd3m: 8a, 16d; / [358]

¯
P4332: 8c, 4b
Li2xZn2–3xTi1+xO4 (0.33  x  0.67) Spinel (Fd3m, P4132 8a, 16d Maximal lithium conductivity while lithium initially [359]
¯
or P4332) completely occupies 8a sites
Li4Ti5xZnxO12 (0  x  0.2) Spinel 16d Improved lithium ion diffusion coefficient, higher and more [360]
stable cycling performance at high rate of 5 C (180 mA h g1,
x = 0.2, 0–2.5 V)
Li3.95Zn0.05Ti5O12 Spinel / Thinner thickness of nanosheets, larger specific surface area [361]
(about twice compared to that of Li4Ti5O12), and enhanced rate
performance
Li4Ti4.95Zn0.05O12 Spinel / Higher capacity and improved rate performance (0–2.5 V) [362]
Li4Ti4.95Zn0.05O12 Spinel 16d Higher capacity and improved rate performance (0–2.5 V) [363]

Na+ Li4xNaxTi5O12 (0  x  0.2) Spinel / Smaller particle size, enhaced ionic and electronic conductivity, [364]
and rate capability (x = 0.1, 0.15)
NaxLi4xTi5O12 Spinel + 4.3% TiO2 8a Expanded oxygen framework and facilitated Li ion diffusion, [365]
(Na0.24Li3.93Ti5.00O12, by ICP-AES) enhanced rate capability and cycling performance
Li4xNaxTi5O12 (x = 0, 1, 2, 3, 4) Spinel + Li2TiO3 (x = 0) Substituting Low operation potential, decreased rate performance [366]
Spinel + Li2TiO3 + instead doping
NaLiTi3O7 (x = 1)
NaLiTi3O7 (x = 2)
NaLiTi3O7 + Na4Ti5O12
(x = 3)
Na4Ti5O12 (x = 4)
K+ Li4xKxTi5O12 Spinel / Good rate capability and cycling stability (x = 0.04), [367]
(x = 0.02, 0.04, 0.06) 138 mA h g1 at 3 C (138 mA h g1 after 200 cycles),
121 mA h g1 at 5 C
Ag+ Ag-Li4Ti5O12 Spinel + Ag Ag did not enter Improved electronic conductivity, high rate discharge capacity [368]
and cycling stability
Fe3+ Li1+xM13xTi1+2xO4 Spinel 8a Great capacity fade for M = Ni [380]
Ni3+ M = Fe, Ni, Cr (x = 0.30) 16d
Cr3+ 16d

Ni2+ Li(Ni1/6Li2/9Ti1/9)Ti3/2O4 Spinel 16d Enhanced rate capability and good cycling stability [381]
Li42xNi3xTi5xO12 (0  x  0.25) Spinel 16d Improved electronic conductivity (3.1  108 S cm1, x = 0.075) [341]
and rate performance

Ca2+ Li4xCaxTi5O12 Spinel 8a Improved rate capability and cycling stability, especially for [369]
(x = 0, 0.05, 0.1, 0.15, 0.2) x = 0.1
Li3.9Ca0.1Ti5O12 Spinel 8a Higher specific capacity, better cycling stability and improved [370]
rate capability (0–2.5 V)
Sr2+ Sr-doped Li4Ti5O12 (Sr/Ti = 0.01/1, Spinel + SrLi2Ti6O14 May be 8a Smaller particle size, decreased charge transfer resistance, and [371]
0.02/1, 0.03/1, mol/mol) enhanced the rate capability with a capacity of about
1.62 times that of Li4Ti5O12 at 5 C; SrLi2Ti6O14 impurity also
makes a contribution to the specific capacity
Y3+ Y-doped Li4Ti5O12 (Y/Ti = 0.004/1, Spinel / Enhanced electronic and ionic conductivities, excellent long- [372]
0.008/1, 0.012/1, 0.016/1, term cyclability (over 1000 cycles) at 10 C and outstanding rate
0.02/1, mol/mol) capabilities (especially for the sample of Y/Ti = 0.012/1)
Nd3+ Li4Ti5xNdxO12 Spinel / Improved rate capability, Li4Ti4.98Nd0.02O12 exhibited excellent [373]
(x = 0, 0.01, 0.02, 0.03) rate capability and cycling stability at 5 C even without
conductive additive
Ru4+ Li4Ti5xRuxO12 Spinel (+RuO2, / Li4Ti4.95Ru0.05O12 shows the best rate performance and cycling [374]
(x = 0, 0.05, 0.10, 0.15) x = 0.10, 0.15) stability with a capacity of 131 mA h g1 over 100 cycles even at
17,500 mA g1 (0.01–2.5 V)

W6+ Li4Ti4.95W0.05O12 Spinel / Improved cycling stability and rate performance with a [375]
capacity of 118.6 mA h g1 at 20 C compared to that
(69.2 mA h g1) of undoped Li4Ti5O12
Li4Ti5xWxO12 Spinel 16d Improved electronic conductivity (1.5  101 S cm1, x = 0.1), [376]
(x = 0.05, 0.1, 0.15, 0.2) rate capability and cycling stability
Li4Ti5xWxO12xBrx Spinel 16d Increased electrical conductivity and Li+ diffusion coefficient, [377]
(x = 0.025, 0.050, 0.100) and further electrochemical performance by W6+ and Br
co-doping
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Table 1 (Continued )
Dopant Structural formula, doping amount Phase structure

F Li4Ti5O12xFx (0  x  0.5) Spinel
Li4Ti5O12xFx (x = 0.174, by XPS) Spinel
Br Li4Ti5xWxO12xBrx Spinel
(x = 0.025, 0.050, 0.100)
doping amount, phase structure, doping site and change after
doping.
Based on the defect equilibrium, the doping of an aliovalent
cation at a higher oxidation state into the tetrahedral 8a lithium
sites or the octahedral 16d sites or an anion with a lower oxidation
state into the O2 site, such as F and Br, can promote the
formation of Ti3+ in the lattice, thus increasing the electron
concentration in the bulk. The increase in electronic conductivity
improves the electrochemical performance of the Li4Ti5O12,
especially the rate performance, if the polarization resistance of
the electrode process primarily derives from the electron charge
transfer. An Mg-substituted lithium titanate spinel provides a
typical example of the successful doping of the tetrahedral 8a site
in Li4Ti5O12 (at least partially) with a cation at a higher valence
state to increase the electronic conductivity. Chen et al. synthe-
sized Li4xMgxTiO12 (0  x  1) via a solid-state reaction at an
elevated temperature under a 3% H2–He reducing atmosphere
[10]. Powder XRD demonstrated that the substitution of Mg2+ for
Li+ in the structure did not affect the crystalline structure of the
oxide at 0  x  0.75; however, additional peaks were observed for
samples at x > 0.75, which were attributable to small concentra-
tions of Li2MgTi3O8 and MgTi2O5 in the samples. The Mg cations
were found to be distributed over both the tetrahedral (8a) sites
and the octahedral (16d) sites of the cubic spinel structure (Fd-
3 m). Rietveld refinement for the compound with a nominal
composition of Li3.5Mg0.5Ti0.5O12 showed that approximately 18%
of the tetrahedral sites were occupied by magnesium. The
conductivity increased by many orders of magnitude from
s  1013 S cm1 for the pristine Li4Ti5O12 (x = 0) to
s  102 S cm1 for Li3MgTi5O12 (x = 1.0), although the reduction
of Ti4+ in Li4xMgxTi5O12 by the reducing atmosphere during the
calcination may also contribute to the high electronic conductivity.
The improved conductivity decreased the area-specific impedance
of the Li/Li4xMgxTi5O12 cells and increased the rate capability of
the electrodes for a small value of x. For example, Li3.75Mg0.25Ti5O12
delivered a capacity of 63 mA h g1 at 17 C, which is nearly 50% of
the capacity obtained at a C/2 rate (135 mA h g1).
Dopants including Al3+, Mn4+, Fe3+, V4+ and Sn4+ were also able
to incorporate into the tetrahedral 8a sites to some extent
[311]. However, doping at the tetrahedral 8a sites is detrimental
to the lithium-ion conductivity because it can reduce the Li+
concentration in the 8a sites. If the lithium bulk diffusion is the
principal controlling step for lithium insertion into Li4Ti5O12, a
decreased rate capability is expected. The reversible capacity of
Mg-substituted Li4xMgxTi5O12 at a high Mg content was found to
be inferior to that of pristine Li4Ti5O12 [10].
To maintain a high capacity, doping of the octahedral 16d sites
is preferred. Some elements are found to preferentially dope into
the octahedral 16d sites, including Ni3+, Cr3+ and Mo4+ [313], while
many other elements are able to dope into both the tetrahedral 8a
sites and the octahedral 16d sites, such as Mg2+, Al3+, Mn4+, Fe3+,
V4+ and Sn4+. To increase the electronic conductivity by doping at
the octahedral 16d Ti4+ sites, the dopants should have a higher
valence state than Ti4+ to increase the electron concentration
45
Doping site Change after doping Ref.
32e Improved rate capability (0.01–2.5 V), the best performance [378]
was achieved when x = 0.3
32e Increased electronic conductivity through Ti3+ generation, [379]
increased the robustness of structure, improved rate capability
(144, 123, 108, 91, and 60 mA h g1 at 5, 10, 30, 60, and 140 C,
respectively) and cycling stability
32e Increased electrical conductivity and Li+ diffusion coefficient, [377]
and further electrochemical performance by W6+ and Br co-
doping
through the formation of Ti3+. Such dopants are typically +5
cations, such as V5+, Ta5+, Nb5+ and Sb5+, or even +6 cation like W6+
[376]. In real synthetic conditions, the doping of Ti4+ with a high-
valence-state cation may not necessarily lead to the formation of
Ti3+ because the charge compensation may also conduct through
the formation of a Li+ cation vacancy or a Ti4+ cation vacancy. When
the charge compensation occurs through a Li vacancy, an increase
in Li-ion conductivity, not the electronic conductivity, is expected
compared with pristine Li4Ti5O12, while no significant increase in
either the electronic conductivity or the Li-ion ionic conductivity is
likely if the defect model is in the form of a Ti vacancy. A typical
example is Ta-doped Li4Ti5O12. Wolfenstine et al. synthesized and
investigated 1% Ta-doped Li4Ti5O12 [319] and found that the
sample prepared via heat-treatment under an oxidizing atmo-
sphere had a conductivity similar to that of pristine Li4Ti5O12, with
a value of approximately 1  109 S cm1. This result implies that
the charge compensation due to the Ta5+ doping likely occurred
through the formation of a Ti vacancy. However, when calcined
under a dilute hydrogen atmosphere, the Li4Ti4.95Ta0.05O12 sample
reached a much higher conductivity of 1  103 S cm1 in
comparison with 3  105 S cm1 for the pristine Li4Ti5O12
synthesized under similar conditions, suggesting that the charge
compensation occurred primarily through the formation of Ti3+ in
the oxide lattice.
Among the various dopants, Mn2+, Al3+, Fe3+, Cr3+, Ni3+ and V5+
have been investigated most thoroughly. Based on the primary
results of XAS measurements, Kubiak et al. claimed that Mn was
located as Mn4+ in the Mn-doped Li4Ti5O12, most likely on both the
tetrahedral and octahedral sites [329]. Capsoni et al. studied the
cation distribution and valence states in the Mn-substituted
Li4Ti5O12 structure with a Mn-doping content of up to 30% of the Ti
ions using a combination of X-ray powder diffraction, electron
paramagnetic resonance (EPR), 7Li MASNMR, and impedance
spectroscopy techniques [330]. Mn was found to occupy both the
tetrahedral 8a sites and the octahedral 16d sites, and the quantity
of Mn in the tetrahedral sites increased with an increase in the Mn
dopant from 3 to 10%, then remained constant with further
increases in the Mn dopant. All Mn was in the 2+ or 3+ valence
state; no Mn4+ was detected. Based on the EPR data, Mn2+ was
found to occupy only the tetrahedral sites, until a nearly constant
value of 10% was reached for the Mn-substituted samples. The
Mn3+ ions occupied both octahedral and tetrahedral sites, with a
constant value in the tetrahedral sites (0.013), independent of the
total quantity of Mn. The differences between Kubiak’s and
Capsoni’s observations of the Mn oxidation states strongly
suggests the significant impact of the synthetic method on the
oxidation state of the multivalent dopant (Mn).
A Cr- and Ni-doped Li4Ti5O12 compound has been characterized
through the combined use of XRD, EPR, 7Li MASNMR, micro-
Raman and magnetization measurements [338]. According to the
structural refinement, supported by the neutron diffraction studies
of Cr-doped Li4Ti5O12, the Cr insertion into the spinel lattice
occurred in both the octahedral 16d Ti and Li sites. The electronic
conductivity of the Cr-doped Li4Ti5O12 was slightly higher than
46 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
that of the pristine Li4Ti5O12 because the Cr 3d bands are close to
the Ti 3d bands. The Rietveld refinement suggests that Ni also
inserted exclusively into the octahedral spinel site. The Ni-doped
Li4Ti5O12 oxides were found to have a lower electronic conductivi-
ty than the pristine Li4Ti5O12 because the Ni 3d bands are localized
and the electrons were not easily excited. Ganesan specifically
investigated the electrochemical performance of Cr-doped
Li4Ti5O12 with the nominal composition of Li4Ti2.5Cr2.5O12
[339]. CV studies showed a shift in the discharge potential by
approximately 40 mW from 1.54 V for Li4Ti5O12 to 1.50 V for
Li4Ti2.5Cr2.5O12. This shift is interesting because a reduction in the
de-lithiation voltage can increase the operation potential and thus
the energy density of a cell. Based on the impedance study, lithium
mobilities of 2.94  106 and 5.13  106 cm2 V1 s1 were found
for Li4Ti5O12 and Li4Ti2.5Cr2.5O12, respectively, implying that the
charge neutrality compensation from the Cr3+ doping likely
occurred, at least in part, through the formation of a lithium
vacancy. As a result, an improved capacity and cycling stability was
observed at higher rates after the Cr doping. Recently, Song et al.
discovered an interesting phenomenon that Cr3+-ion doping in
Li4Ti5O12 resulted in a decrease of structural disorder (Fig. 54),
which was different from the common understanding that doping
may introduce a lattice defect [340]. These researchers first
observed the decreased structural disorder upon Cr doping using
Rietveld refinement of high-resolution powder diffraction, which
demonstrated that the oxygen parameter was more reliable for Cr-
doped Li4Ti5O12. The phenomenon was then confirmed by analysis
of the Debye-Waller factor in EXAFS and absorption edge in XANES.
Moreover, the EELS results and DFT calculations revealed that the
reason for structural phenomenon was due to the charge
redistribution. Because of the increased lithium ion diffusivity
due to the decreased structural disorder upon doping and
increased electronic conductivity due to impurity band formation
upon doping, the Li4x/3Ti52x/3CrxO12 (x = 0.25) exhibited a high
discharge capacity of 125 mA h g1 at 10 C, which was approxi-
mately twice that of undoped Li4Ti5O12. Although Li1.3Ni0.1Ti1.6O4
has a higher first discharge capacity than pristine Li4Ti5O12 in the
potential range of 2.00–0.01 V, it had a higher capacity fading rate
during cycling, suggesting that Ni may be not an ideal dopant for
Li4Ti5O12 [380]. Kim et al. produced a comparative study of pristine
Li4Ti5O12 and Ni-incorporated Li(Ni1/2xLi2x/3Tix/3)Ti3/2O4 (x = 1/3)
anodes for use in rechargeable Li batteries [381]. Based on the
Rietveld refinement of the XRPD, the Ni was completely doped into
the 16d Li+ and Ti4+ sites, as expected. The Ni K-edge XANES spectra
indicated that the nickel was primarily in a 2+ oxidation state. The
Li(Ni1/6Li2/9Ti1/9)Ti3/2O4 exhibited a progressive decay in its
capacity over the first five cycles at 0.2 C; however, the capacity
was stabilized during subsequent cycling at various rates within a
potential range of 1.0–2.5 V. The improved rate capability
Fig. 54. Simulated structure of Li4x/3Ti52x/3CrxO12 in the [110] direction for (a) x = 0 and (b) x = 0.25. To more clearly demonstrate the difference, the bond angle is somewhat
exaggerated. Li is purple, Ti is gray, and O is red [340]. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
compared with that of pristine Li4Ti5O12 was attributed to the
fact that Li(Ni1/6Li2/9Ti1/9)Ti3/2O4 has an electronic conductivity of
(108 S cm1) that is three orders of magnitude higher than that
of Li(Li1/3Ti5/3)O4 (1011 S cm1). The improved cycling stability
over that reported by Robertson et al. is likely due to the increased
ending potential applied in this study (1.0 V), which may avoid the
deep reduction of Ni2+ in the lattice.
Among the various dopants, Fe3+ is of particular interest due to
its abundance and nontoxicity. Several composites with nominal
compositions of Li0.5+0.5xFe2.51.5xTixO4 (0  x  1.66) were syn-
thesized and characterized by Scharner et al. [333]. XRD and 57Fe
Mossbauer spectroscopy characterization demonstrated the ideal
spinel structure with space group Fd3m was successfully obtained
¯
for the composites in the ranges of 0.4  x  1.2 and
1.57  x  1.66, while ordered structures with the P4332 space
group were observed for the composites in the ranges of
0  x  0.4 and 1.2  x  1.57. Robertson et al. used neutron
refinement of Li1.3Fe0.1Ti1.6O4 (M = Fe, Ni, Cr) to demonstrate that
the iron occupied the tetrahedral 8a sites of the spinel structure,
while Ni and Cr occupied only the 16d octahedral sites [380], which
was in good agreement with the observations of Capsoni et al.
[338]. The structure of the iron-substituted lithium-titanium
spinels with nominal compositions of Li1.3Fe0.1Ti1.6O4 (Fd3m) and
¯
Li1.25Fe0.25Ti1.5O3 (P4332) were further investigated in detail by
Reale et al. [336]. Based on the Rietveld refinement, most of the
iron in Li1.3Fe0.1Ti1.6O4 was found to preferably occupy the
tetrahedral 8a sites, leading to a stoichiometry that can be written
as (Li0.91Fe0.09)(8a)[Li0.39Fe0.01Ti1.6](16d)O4(32e). In contrast, the
Li1.25Fe0.25Ti1.5O4 appeared isotropic to the Li0.5Fe2.5O4, indexed
in the P4332 space group with a formula written as Li0.5(4b)(Li0.75-
Fe0.25)(8c) Ti1.5(12d)O4(8c,24e). These electrodes had reversible
capacities of 160–180 mA h g1 at 0.2 C in the 2.9–0.2 V potential
range. Their electrochemical lithium insertion–extraction process-
es respond quite differently to that of a pure Li4Ti5O12 electrode—
several one-phase and two-phase steps involved the electrochem-
ical reduction/oxidation of both Ti4+ and Fe3+.
The maximum quantity of lithium that can be incorporated into
the spinel lattice is fixed, and the dopants by themselves typically do
not contribute additional lithium storage. Therefore, to increase the
gravimetric energy density, a dopant with a small weight number is
preferred. Due to its light weight and its stability in an octahedral
environmental, Al3+ has attracted attention as a dopant for
Li4Ti5O12. Huang et al. were the first to synthesize Li4Ti5O12-based
composites with the nominal composition of Li4AlyTi5yO12 (y = 0,
0.10, 0.15, 0.25) by a solid-state reaction [346]. The spinel phase with
an Fd-3 m space group was observed for all samples, although a
small quantity of LiAlO2 was detected at x = 0.25. The particle
aggregation was clearly alleviated after the Al3+ doping. The
Li4AlyTi5yO12 (y = 0.10, 0.15) exhibited improved electrochemical
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
performance over that of pristine Li4Ti5O12. Among the various
samples, Li4Al0.15Ti4.85O12 exhibited the largest reversible capacity
and the highest columbic efficiency, with a discharge capacity in the
first and second capacity of 195.6 and 173.6 mA h g1, respectively,
within a discharge potential range of 2.5–0.5 V. Zhao et al.
synthesized and investigated an Al-doped Li4Ti5O12 with the
nominal composition Li4xAlxTi5O12 as an anodic material for LIBs
[343]. The incorporation of Al into Li4Ti5O12 lattice did not affect the
phase composition and the particulate morphology at x = 0.05 but
easily resulted in a lattice distortion and thus poor crystallinity of the
oxide. The Li3.9Al0.1Ti5O12 exhibited an excellent cycling stability
compared with that of pristine Li4Ti5O12. Wang et al. synthesized a
carbon-coated Li4Ti4.95Al0.05O12/C via a solid-state reaction for use in
a lithium-ion battery with discharge voltage down to 0 V
[345]. Based on the slight shift in the diffraction peak to a lower
2u angle, the authors concluded that the Al3+ was successfully doped
into the 16d octahedral site as targeted. The pristine Li4Ti5O12,
Li4Ti5O12/C and Li4Ti4.95Al0.05O12/C have electrical conductivities of
8.2  108, 7.9  106 and 1.1  105 S cm1, respectively. The
Li4Ti4.95Al0.05O12/C has a slightly higher electrical conductivity than
the Li4Ti5O12/C. However, such a small difference likely originated
from experimental errors. The Li4Ti4.95Al0.05O12/C exhibited im-
proved initial capacity, cycling performance, and a discharge
capacity reaching 248 mA h g1 after 50 cycles. The discharge
capacity for the Li4Ti5O12/C decreased to 226 mA h g1 between
2.5 and 0.0 V. The capacity difference for the two samples was less
significant when the discharge was conducted between 2.5 and
1.0 V. Thus, the Al3+ doping seemed to improve the reversible
capacity between 1.0 and 0.0 V for the spinel lithium titanate. Cai
et al. synthesized an Al-doped Li4Ti5O12 compound with a nominal
composition of Li4Ti4.85Al0.15O12 via a cellulose-assisted glycine–
nitrate combustion method [344]. The Al3+ doping did not affect the
phase structure but increased the surface area and decreased the
crystalline size possibly due to the increased crystal face energy of
the oxide. The electrical conductivities of pristine Li4Ti5O12 and
Li4Al0.15Ti4.85O12 as measured by 4-probe DC method were
7.0  108 and 4.0  107 S cm1, suggesting that most of the
Al3+ was doped into the octahedral 16d Ti4+ site. A lithium diffusion
coefficient of 4.03  1010 cm2 s1 was observed for the Li4Al0.15-
Ti4.85O12, which is lower than the pristine Li4Ti5O12 value of
5.43  109 cm2 s1. A small quantity of Al3+ may have been
partially doped into the 8a tetrahedral Li+ site, which caused a block
against lithium diffusion within the oxide lattice. The improved
capacity and rate capability of the Li4Al0.15Ti4.85O12 over the
Li4Ti5O12 were attributed to the increased surface area of the oxide
caused by the inhibited sintering effect of the aluminum.
Vanadium has also been investigated as a dopant for Li4Ti5O12
due to its high valence state, wide availability and low weight. Yi
et al. synthesized and characterized Li4Ti5xVxO12 (0  x 0.3)
with a wide range of V content [315,316]. The XRD and Raman
spectra demonstrated that the V5+ partially substituted the Ti4+
and Li+ in the spinel. Li4Ti4.95V0.05O12 had the highest initial
discharge capacity and cycling performance among the samples
cycled between 1.0 and 2.0 V, while Li4Ti4.9V0.1O12 had the highest
initial discharge capacity and best cycling performance among the
samples cycled between 0.0 and 2.0 V or between 0.5 and 2.0 V.
Li4Ti4.95V0.05O12 exhibited excellent cycling performance between
1.0 and 2.0 V. The capacities of Li4Ti4.9V0.1O12 reached
183 mA h g1 after 100 cycles between 0.5 and 2.0 V and
229 mA h g1 after 130 cycles between 0.0 and 2.0 V. Yu et al.
synthesized Li4Ti4.9V0.1O12 nanometric powders via a facile solid-
state reaction method under an inert atmosphere [317]. The
electronic conductivity of the Li4Ti4.9V0.1O12 powders reached
2.9  101 S cm1, which could be attributed to the transformation
of some Ti4+ to Ti3+. The Li4Ti4.9V0.1O12 powders also had smaller
particles and a narrower particle size distribution than the pristine
47
Li4Ti5O12. Electrochemical impedance spectroscopy (EIS) demon-
strated that Li4Ti4.9V0.1O12 had a faster lithium-ion diffusivity than
that of Li4Ti5O12 with lithium diffusion coefficients of 6.5  1013
and 2.7  1015 cm2 s1, respectively. Between 1.0 and 2.5 V, the
discharge capacities reached 166 and 117.3 mA h g1 at 0.5 and
5 C, respectively. Li4Ti4.9V0.1O12 also exhibited a long-term
cyclability, retaining over 97.9% of its initial discharge capacity
beyond 1713 cycles at a rate of 2 C.
Wang et al. [355] investigated copper as a dopant for
Li4Ti5O12. Although copper was successfully doped into the lattice
structure by synthesis under an oxidizing atmosphere, Cu2+ was
reduced to the metallic element after the first discharge process.
Thus, it acted as a conductive modifier of the Li4Ti5O12 surface
during the subsequent cycling. Silver was also studied as a dopant
for Li4Ti5O12 [368]. However, the as-obtained sample was actually
a composite of metallic silver and the Li4Ti5O12 spinel phase, even
though the synthesis was performed under an oxidized atmo-
sphere (air). Although silver is a metal with ultrahigh electronic
conductivity, its application as a surface modifier is not practical
given its high price and heavy weight.
Although many dopants have been studied, improvements in
the electrochemical performance of Li4Ti5O12 via doping, in
particular the rate capability and cycling stability, are minor
compared with nanostructuring or surface coating. In some cases,
the doping was actually detrimental. Better dopant or doping
mechanisms must be developed. Currently, most research has
focused on single cation doping. A synergistic effect may be created
by applying two or more dopants, thus significantly improving the
electrochemical performance of the Li4Ti5O12 electrodes. Co-
doping was well exploited in ABO3 perovskite oxides to tailor
their properties over a wide range. However, co-doping with two
or more elements was seldom applied to Li4Ti5O12. This subject
may be actively researched in the future. Both nanostructuring and
surface coating change only the surface properties. Once the
surface properties were well optimized, a further increase in the
electrode performance requires the modification of the bulk
properties of the oxides. Doping is the only strategy that can
modify the bulk properties. The development of advanced
Li4Ti5O12 anode materials by combining two or three strategies
can further improve their electrochemical performance, such as
the recently reported porous Zr-doped Li4Ti5O12 microspheres
[382], 1D Na-doped Li4Ti5O12 nanorods [365], Fe2+ or Cr3+ doped
Li4Ti5O12/multi-wall carbon nanotube (MWCNT) composites
[383], and Cu-doped Li4Ti5O12–TiO2 Nanosheets [384]. Ma et al.
developed a carbon-encapsulated F-doped Li4Ti5O12 composite
with a ball-in-ball structure via a hydrothermal synthesis and
subsequent solid-state lithiation at high temperatures (Fig. 55)
[379], which delivered remarkable cycle stability with a capacity of
159 mA h g1 after 200 cycles at 1 C and outstanding rate
capability with specific capacities of 162, 144, 123, 108, 91, and
60 mA h g1 at 1, 5, 10, 30, 60, and 140 C, respectively, due to the
combined effect of fluoride doping, unique ball-in-ball microstruc-
ture, and presence of carbon. Thus, nanostructuring, surface
coating and doping could be conducted simultaneously to
significantly improve the properties and performance of Li4Ti5O12
spinel oxides, including their capacity, rate capability and cycling
stability, and to promote their practical application as power
sources for energy storage or EVs and HEVs.
3.5. Formation of composite
In addition to nanostructuring, doping, morphological optimi-
zation and surface coating, the electrode performance of Li4Ti5O12
can be improved by forming a composite with a different material
[47,257,280,385]. The second phase can be an electron conductor
such as carbon, a lithium-ion conductor, or a mixed electron and
48 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 55. (a) Schematic of the preparation of carbon-encapsulated F-doped Li4Ti5O12 composites, (b) FE-SEM image of carbon-encapsulated F-doped Li4Ti5O12 composites at
low magnification; the inset in (b) is a TEM image of a single particle, (c) cycle stability of carbon-encapsulated F-doped Li4Ti5O12 composites at different C rates [379].
lithium-ion conductor. The electrodes in conventional LIBs can also
be treated as composites because large quantities of binders and
conductive additives were added to the active material to improve
the adhesion of the electrode to the current collector and to
increase the current collection efficiency. The carbon-coated
Li4Ti5O12 may also be treated as a composite electrode, which
has a specific core-shell morphological structure with low second-
phase content (typically less than 5 wt.%). By forming a composite
electrode, the apparent electronic conductivity and lithium-ion
conductivity may both be improved. Another advantage to a
composite electrode is that the second phase may also act as a
support to improve the mechanical properties of the electrode so
that the quantity of binder may be reduced or even omitted
completely, which can improve the gravimetric energy density,
operational safety and cycling life of the electrode as side reactions
between the binder and other additives within the liquid
electrolyte can be minimized or avoided. The electrodes can also
be prepared as self-standing thin films without the application of
any additional binder or conductive additive.
Compounds with high electronic conductivity, such as amor-
phous carbon [386–390], graphene [391–393], carbon nanotubes
[394,395], ordered porous carbon (CMK-3 [396,397], and ordered
bimodal mesoporous carbon [398]) and other carbon materials
(Ketjen Black [399], Super P [400], carbon black Vulcan XC72R
[401]) are applied to form composite electrodes with Li4Ti5O12. In
addition, metals such as copper and silver have recently been
tested. Such second phases perform primarily as conductive
networks in the electrode to increase the current collection
efficiency. For example, Wang et al. reported a composite electrode
with Li4Ti5O12 nanoparticles loaded on a bicontinuous Cu scaffold
as shown in Fig. 56a and b [402]. The composite Li4Ti5O12/Cu
electrode exhibited ultrafast lithium storage properties with a
specific capacity of 127 mA h g1 at a rate of 80 C (Fig. 56c) and
excellent cycling stability at rate of 1 C for 2000 cycles (Fig. 56d).
The structure of the as-obtained Li4Ti5O12 was further analyzed
(Fig. 56e) to understand the capacity of the composite at a low rate,
which was slightly higher than the theoretical value due to the
surface effect as shown in Fig. 9b. Because these conductive phases
have negligible lithium insertion capacity at potentials approach-
ing 1.0 V, which is often selected as the end of discharge voltage for
a Li4Ti5O12 electrode, their content in the composite electrodes
should remain at a low level to minimize the detrimental effect on
the gravimetric energy density. Researchers are currently inter-
ested in composite electrodes formed with electronically conduc-
tive lithium-insertion materials as the second phase such as
metallic tin, which is a well-known lithium insertion host with a
high reversible capacity [403–405]. Sn is an attractive second
phase because it can be easily electrochemically reduced from
SnO2; thus, the synthesis can be conveniently conducted under an
oxidant atmosphere (air).
Interfacial design is a unique way to tune the electron/ion
conducting properties of materials. This method has also received
considerable attention for its ability to improve the performance of
electrodes in LIBs including Li4Ti5O12. For polycrystalline materials,
the conduction of electrons and ions involves not only the surface
and bulk diffusion but also the grain boundary diffusion. For some
materials, the diffusion rate of the charges around the grain
boundary may be higher than that of the bulk [311,406]. By
increasing the grain boundary density, the apparent conductivity of
the materials may be significantly improved. Grain boundaries have
been reported to act as either channels to allow Li+ to enter the
particles or as lithium reservoirs [407,408]. By tailoring the
properties of the grain boundaries, both the electron and lithium-
ion transport properties of the polycrystalline Li4Ti5O12 may be
improved, leading to a possible improvement in the rate perfor-
mance. By forming a composite, not only can the grain boundary
density be improved but also the grain boundary properties. In
addition, the morphological stability may be further improved if
several materials are combined in an appropriately structured
composite. For example, a binary Li4Ti5O12–TiO2 composite was
synthesized and investigated as a novel electrode for LIBs and
exhibited improved performance over pristine Li4Ti5O12 [409,410].
3.5.1. Li4Ti5O12/graphene
Graphene is a 2D one-atom-thick sheet of carbon arranged in a
honeycomb network. Since its first successful isolation in 2004
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 49

Fig. 56. (a) Schematic illustration of a new ‘one stone, two birds’ strategy to fabricate a bicontinuous Li4Ti5O12/Cu electrode via a three-dimensional nanoporous Cu scaffold
template route, where Li4Ti5O12 nanoparticles can be encapsulated into the Cu nanopores. (b) TEM image of the Li4Ti5O12/Cu sample. The inset shows the schematic drawing
of the Li4Ti5O12/Cu. (c) Rate capabilities of Li4Ti5O12/Cu electrode. (d) The cycling performance and corresponding Coulombic efficiency of Li4Ti5O12/Cu electrode at 1 C. (e) The
enlarged (FFT inverse) image of Li4Ti5O12 nanoparticles taken from Li4Ti5O12/Cu composite, where the black holes denote the 16c (vacancy) sites and Li2 represents Li1/3Ti5/3.
[402].

[411], graphene has attracted intense interest from both the
experimental and theoretical scientific communities because of its
unique properties. Due to its excellent thermal and electrical
conductivities in two dimensions, its superior mechanical
strength, its high flexibility and high specific surface area
(>2600 m2 g1), graphene’s application in energy production
and storage has received considerable attention [412]. Although
it has poor reversible capacity to perform alone as an anode in LIBs
[413], many graphene-based composites have been investigated
for use in LIBs to improve the electronic conductivities and
mechanical properties of the electrodes [414–416].
The formation of a Li4Ti5O12/graphene composite to avoid
aggregation of the Li4Ti5O12 nanoparticles and to increase the
apparent conductivity of the electrode has been recently reported
[391–393,417–420]. Apart from its excellent conductivity, the high
surface area of graphene can also improve the interfacial contact
with poorly conducting particles. The Li4Ti5O12 nanoparticles
attached to graphene also effectively prevented the aggregation
and restacking of the graphene to maintain their large active
contact area between the electrode and liquid electrolyte. As a
result, the electrode performance, especially its rate capability,
may be improved even with very a low content of graphene
[391,421]. Zhu et al. used 1 wt.% graphene as a conductive agent to
fabricate graphene-embedded Li4Ti5O12 nanofibers that exhibited
greatly improved surface conductivity and rate capability
[391]. Zhang et al. introduced 1.86 wt.% graphene into Li4Ti5O12
powders by mixing Li4Ti5O12 with graphene oxide dispersion and
further reducing, resulting in a significantly improved rate
capability with approximately twice the capacity at 20 C compared
with that without graphene, even though the effect of the possible
reduction of Ti4+ on the electrochemical performance has not been
considered [417]. Shi et al. prepared a Li4Ti5O12/graphene
composite via the ball milling of Li4Ti5O12 powders with 5 wt.%
graphene [392]. The Li4Ti5O12 particles were found to be well
dispersed among the graphene sheets, and the graphene extended
in all directions as in a stretched network, providing a conductive
connection between the Li4Ti5O12 particles. The charge transfer
resistance at the Li4Ti5O12/liquid electrolyte interface decreased
from 53.9 V for the pristine electrode to only 36.3 V after the
formation of the composite with graphene. A capacity of
132.2 mA h g1 was retained at 20 C for the first discharge and a
capacity of 124 mA h g1 was maintained after 300 cycles.
However, a trade-off exists between the improvement in electrical
conductivity and the decrease in the initial columbic efficiency.
Guo et al. synthesized a carbon-coated Li4Ti5O12/graphene
composite by the ball milling of carbon-coated TiO2, Li2CO3, and
graphene in hexamethylene [419]. The carbon pre-coated on TiO2
successfully avoided the aggregation and agglomeration of the
Li4Ti5O12 particles and optimized the combination between
Li4Ti5O12 particles and graphene sheets. The resultant composite
exhibited a greatly improved electrochemical performance with a
capacity of approximately 102 mA h g1 at 10 C compared with
that of a Li4Ti5O12/graphene composite (40 mA h g1) or pure
Li4Ti5O12 (30 mA h g1). Oh et al. successfully prepared gra-
phene-wrapped Li4Ti5O12 via a solid-state reaction between
graphene-oxide-wrapped TiO2 and Li2CO3 [420]. The graphene-
oxide-wrapped TiO2 was prepared from TiO2 and graphene oxide
solution at pH 2 via electrostatic interactions. The as-prepared
Li4Ti5O12 was wrapped with wrinkled-flexible graphene. The effect
of different amounts (1.0, 2.1, 4.5 wt.%) of graphene on the
electrochemical performance was investigated. The graphene-
wrapped Li4Ti5O12 with 2.1 wt.% graphene exhibited outstanding
performance with a specific capacity of 147 mA h g1 at 10 C after
100 cycles, which was also expected to be beneficial for the tap
density based on its stacking and relatively large particle size
(150 nm). Xiang et al. prepared a Li4Ti5O12/graphene composite
by applying graphene, obtained from the thermal expansion of
graphene oxide at elevated temperatures, as an additive to a
solution precursor for the sol–gel synthesis of Li4Ti5O12 [393]. The
presence of graphene in the sol–gel synthesis effectively sup-
pressed the grain growth of the Li4Ti5O12 phase during the
calcination. At a rate of 0.2 C and a discharge–charge potential
range of 1.0–2.5 V, both the pristine Li4Ti5O12 and its composite
with 7.5 wt.% graphene had a similar capacity of approximately
175 mA h g1; however, at a rate of 10 C, the reversible capacity of
the Li4Ti5O12/graphene (146 mA h g1) is higher than that of the
50 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
pristine Li4Ti5O12 (131 mA h g1). In addition, the cycling stability
was also improved at a rate of 10 C between 1.0 and 2.5 V. Such
improvement was attributed to the increased electronic conduc-
tivity from the introduction of graphene. When the end of
discharge potential extended to 0.0 V, the Li4Ti5O12/graphene
exhibited a reversible capacity of 228 mA h g1 compared with
185 mA h g1 for the pristine Li4Ti5O12, suggesting a contribution
to the lithium reversible storage by graphene. Ding et al.
successfully introduced 3 wt.% graphene into the hydrothermal
synthesis of Li4Ti5O12 nanosheets [422]. The as-obtained Li4Ti5O12/
graphene demonstrated enhanced electrochemical performance
with a specific capacity of more than 120 mA h g1 at 1600 mA g1
after 200 cycles compared with that of bare Li4Ti5O12 nanosheets
and Li4Ti5O12/conductive carbon black; the enhanced lithium
storage was attributed to the smaller Li4Ti5O12 nanocrystals on
graphene sheets, improved electronic conductivity, lower charge
transfer resistance, smaller diffusion impedance and especially the
stronger faradaic pseudocapacitive effect.
Instead of forming a Li4Ti5O12/graphene composite with
randomly distributed Li4Ti5O12 and graphene dual phases as
demonstrated by Shi et al. and Xiang et al. [392,393], Jian et al.
prepared a Li4Ti5O12/graphene composite with a specific morphol-
ogy of porous Li4Ti5O12 spheres and a surface modified by few-
layer graphene using C28H16Br2 as a precursor for the graphene
with a low processing temperature of approximately 400 8C
[269]. The composite containing 5.91 wt.% graphene exhibited
capacities of 134 and 104 mA h g1 at rates of 5 and 10 C,
respectively, which were improved over those of the pristine
Li4Ti5O12 spherical electrode (61 and 30 mA h g1).
Based on the high conductivity of graphene, Shen et al. directly
anchored nanocrystalline Li4Ti5O12 onto conducting graphene
nanosheets to maximize their current collection efficiency
[423]. The TiO2 nanoparticles were first anchored to the graphene
oxide and were then transformed in situ into the Li4Ti5O12 and
highly conductive graphene via a hydrothermal process with a
subsequent post-annealing treatment. The electronic conductivity
of the composite with 15.5 wt.% graphene reached
4.1  103 S cm1, which is more than 108 times higher than
that of the pristine Li4Ti5O12. The resulting composite exhibited
higher electrochemical performance, especially for the rate
capability (83 mA h g1 at 60 C), compared with that of pristine
Li4Ti5O12. Yang et al. prepared a Li4Ti5O12/graphene composite
using non-oxidative cathodically induced graphene using a similar
synthesis route as shown in Fig. 57a. An electronic conductivity of
1.2  104 S cm1 was achieved for the Li4Ti5O12/graphene com-
Fig. 57. (a) Schematic illustration for the fabrication of Li4Ti5O12/nonoxidative cathodically induced graphene (CIG) composite. (b, c) TEM images of (b) Li4Ti5O12/CIG
composite and (c) pure Li4Ti5O12 prepared in the same fashion. (d) Rate performance of Li4Ti5O12/CIG composite and pure Li4Ti5O12 [424].
posite with even a low graphene content of 3.5 wt.%. In the
presence of graphene, the particle sizes of the as-obtained
Li4Ti5O12 in the composite were 20–50 nm (Fig. 57b), which were
definitely smaller than that of pure Li4Ti5O12 (50–100 nm, Fig. 57c)
prepared in the same fashion. Accordingly, the Li4Ti5O12/graphene
composite exhibited much better rate performance compared to
that of pure Li4Ti5O12 (Fig. 57d) [424]. Chen et al. successfully
synthesized mesoporous single crystal Li4Ti5O12 on reduced
graphene oxide through a route including preparation of TiO2/
graphene using reflux reaction and hydrothermal reaction,
chemical lithiation using hydrothermal reaction with LiOH, and
final heat-treatment at 600 8C [425]. The as-synthesized composite
exhibited high specific capacities of 171 and 132 mA h g1 at a rate
of 0.5 and 40 C, respectively, and stable cycling performance at a
rate of 10 C with a 85% capacity retention after 2000 cycles. Ri et al.
reported a Li4Ti5O12/graphene composite with Li4Ti5O12 nanopar-
ticle sizes of 18 nm using a microwave-assisted hydrothermal
method using ionic liquid (C12H23ClN2) as an exfoliated agent
[426]. In the presence of ionic liquid, the resultant composite
exhibited optimized phase and pore structures, showing excellent
cycling stability (159 mA h g1 at 0.5 C after 100 cycles) and high-
rate performance (148.5 mA h g1 at 20 C). In the absence of an
ionic liquid, H.K. Kim successfully synthesized a Li4Ti5O12/
graphene composite with 7–10 nm Li4Ti5O12 nanoparticles uni-
formly supported on the graphene surface via a microwave-
assisted process [427]. The nanocomposite delivered an excellent
electrochemical performance with capacities of 168 mA h g1
(based on the weight of Li4Ti5O12, content in the composite:
83 wt.%) at 1 C and 98 mA h g1 even at 50 C. Recently, Ni et al.
developed a simple ultrasonic-assisted liquid deposition method
for the scalable synthesis of high-performance Li4Ti5O12/graphene
[428]. Briefly, a CH3COOLi solution in distilled water and ethanol
was dropped into a suspension with graphene oxide and
C16H36O4Ti ultrasonically dispersed in ethanol. After further
sonication and calcination, 100 nm Li4Ti5O12 nanoparticles on
graphene were successfully prepared. The composite delivered
outstanding rate performance with capacities of 162, 154 and
149 mA h g1 at 1, 10 and 20 C, respectively. A stable cycling
performance with high retention of 98.9% for 200 cycles at 5 C was
also achieved.
Li4Ti5O12 sphere/graphene composites were also reported to
improve the electrochemical performance of Li4Ti5O12 spheres
[429,430]. Pang et al. prepared a mesoporous Li4Ti5O12 nano-
sphere/graphene composite by electrostatic assembly of graphene
oxide and positively charged Li4Ti5O12/carbon nanospheres
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
[429]. Most of the Li4Ti5O12/carbon nanospheres were covered by
graphene sheets to form an interconnected composite, and the
composite exhibited a greatly enhanced rate capability with a
capacity of 124 mA h g1 compared with that of the initial
Li4Ti5O12/carbon nanospheres (40 mA h g1) at 20 C because of
the presence of an efficient electronic conducting network.
3.5.2. Li4Ti5O12/carbon nanotubes
Carbon nanotubes were first discovered in 1991 [431] and can
be seen as a single graphene sheet rolled on itself to form a tube.
Due to their unique structures and physical properties, both single-
wall and multi-wall carbon nanotubes have received tremendous
attention for a wide range of potential applications, such as next-
generation electronics and optoelectronics [432–434]. CNTs are
extremely strong and mechanically robust; in addition, they have
high electronic conductivity, a wide electrochemical window, a
high aspect ratio, high chemical stability and a large surface area.
Recently, their potential applications for electrochemical energy
storage have been recognized [435]. CNTs have been used as
additives to form composites with other active materials, serving
as electron conducting channels and/or a volume expansion buffer
in LIBs [436,437]. The electron conduction of the entire network is
more important than the intrinsic electron mobility of the CNTs for
this application.
Huang and Jiang are the first to report the use of Li4Ti5O12/
carbon nanotube composites as electrodes for LIBs. The composite
was prepared by applying MWCNTs as an additive during the sol–gel
synthesis of Li4Ti5O12 [438]. The CNTs suppressed the grain growth
of the Li4Ti5O12 phase. The as-prepared sample delivered excellent
rate capability and cycling performance within the potential range of
1.0–2.5 V. The reduced grain size and the improved electronic
conductivity from the addition of the CNTs accounted for the
improved electrode performance. Li et al. synthesized a Li4Ti5O12/
carbon nanotube composite using a simple physical mixing method
and ball milling [439]. The pristine Li4Ti5O12 had capacities of only
142 and 60 mA h g1 at 0.5 and 10 C, respectively. However, by
introducing only 3.04 wt.% graphitized CNTs with a diameter of
50 nm and lengths of 1–2 mm, the resulting composite showed
Fig. 58. Schematic presentation of the electrochemical reaction path on MWNT@Li4Ti5O12 coaxial nanocables (left) and three Li4Ti5O12 particles (right) [444].
51
improved capacities of 149 and 134 mA h g1 at 0.5 and 10 C,
respectively. EIS indicated that the charge transfer polarization
resistance was reduced after the introduction of the CNTs. The
formation of conductive nanotube networks likely increased the
apparent conductivity of the electrode, thus improving its current
collection efficiency. By introducing a third carbon phase with the
formation of Li4Ti5O12/C/CNTs, the rate performance was further
improved [440].
Unlike Li et al. [440], who mixed pre-synthesized Li4Ti5O12 with
CNTs by ball milling, Jhan et al. introduced the CNTs during the
solid-state synthesis of Li4Ti5O12 [441]. In addition to performing
as a support matrix to provide a 3D conductive network, the CNTs
acted as an inhibitor to suppress the aggregation of the in situ-
formed Li4Ti5O12 nanoparticles during the calcination process. As a
result, a reduction in the particle size and aggregation of the
Li4Ti5O12 was observed, ensuring a short lithium diffusion path
length. The formed composite exhibited 161 and 147 mA h g1
after 100 cycles at rates of 1 and 10 C, respectively, while the
pristine Li4Ti5O12 prepared by a similar ball milling-assisted solid-
state reaction had capacities of 112 and 68 mA h g1 after
100 cycles. A third carbon phase (acetylene black) was also
introduced during the solid-state synthesis by Fang et al. to form a
Li4Ti5O12/C/CNT composite [442], excellent rate capability and
cycling performance were achieved. Ni et al. successfully anchored
nano-Li4Ti5O12 on CNTs by a facile liquid phase deposition
[443]. The functionalized CNTs and TBOT were dispersed in
ethanol, and then, the LiAc ethanol–water solution was dropped
and aged. After calcination, the as-prepared nano-Li4Ti5O12/CNTs
exhibited high capacities of 171 and 112 mA h g1 at 1 and 20 C
rates, respectively.
Shen et al. grew a porous Li4Ti5O12 sheath on the outer surface
of multi-walled CNTs to form a novel special coaxial nanocompo-
site [444]. The resulting composite contains approximately
82.5 wt.% Li4Ti5O12 and 17.5 wt.% CNTs with a porous 25-nm-
thick Li4Ti5O12 sheath. The material exhibited much improved
cycling stability and rate capability compared to that of pristine
Li4Ti5O12. A simple model (Fig. 58) was proposed to explain this
improvement. By using the Li4Ti5O12/carbon nanotube composites
52 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
with specific co-axial morphological shapes, the effective reaction
area is greatly extended. The diffusion distance in the Li4Ti5O12 of
the composite is only 25 nm, while it is 100 nm for the pristine
Li4Ti5O12, which ensures an easier lithium intercalation in the
composite. Moreover, the higher surface area of the composite
provided a higher electrode/electrolyte contact surface area,
resulting in a lower electrochemical reaction polarization resis-
tance. Recently, Kim et al. successfully prepared a Li4Ti5O12/CNT
composite with Li4Ti5O12 nanoparticle sizes of 15–20 nm uniform-
ly decorated on the CNTs using a simple microwave-solvothermal
reaction [445]. The CNT content in the composite (20 wt.%) is
similar to that reported by Shen et al. [444]; however, the rate
capability was further improved with specific capacities of 172,
151, 140 and 104 mA h g1 at 1, 10, 20 and 60 C, respectively.
Additionally, an excellent capacity retention of 98% at 10 C over
1000 cycles was achieved. Jia et al. prepared a nanostructured
Li4Ti5O12/CNT composite via aerosol spray drying process followed
by calcination [246]. The composite was further built to be a
flexible film electrode through a vacuum filtration of the mixture
dispersion of 80 wt.% of Li4Ti5O12/CNT composite particles and
20 wt.% extra CNTs (Fig. 59a and b). The flexible Li4Ti5O12/CNT
composite film electrode delivered excellent electrochemical
performance with specific capacities of 163, 143, and 108 mA h g1
1 at 1, 10, and 100 C rates, respectively (Fig. 59c). The rate
capability of Li4Ti5O12/CNT composite in traditional electrode is
much lower, that is, 74 mA h g1 at 100 C rate. The flexible film
electrode exhibited an ultralong cycling stability at 1 A g1 with a
capacity retention of 89% even after 8000 cycles (Fig. 59d), which
was much better compared to capacity retention of Li4Ti5O12/CNT
composite electrode prepared by conventional slurry-coating
technique (75% after 6000 cycles).
3.5.3. Li4Ti5O12/SnOx
SnO2 is an anode material with a first discharge capacity as high
as 1494 mA h g1. A two-step intercalation mechanism is proposed
Fig. 59. (a) Structure and fabrication of the flexible Li4Ti5O12/CNT electrode. (b) A digital photograph of the flexible electrode. (c) Rate performance of the flexible electrode
compared with traditional electrode. (d) Cycling stability and Coulombic efficiency of flexible Li4Ti5O12/CNT electrode at a current density of 1 A g1 [246].
for lithium insertion into a SnO2 electrode, i.e., SnO2 is first reduced
to metallic tin by the insertion of lithium (SnO2 + 4-
Li+ + 4e ! Sn + 2Li2O); then, the further incoming lithium is
inserted into metallic Sn with the formation a Sn–Li alloy
(Sn + 4.4Li+ + 4.4e ! Li4.4Sn). Because only the second step is
reversible, SnO2 has a reversible capacity of 782 mA h g1 (based
on the mass of SnO2), which is two times that of graphite. However,
a large volume variation is experienced during the tin alloying and
de-alloying processes, and the volume expansion can reach up to
300% when tin alloys with lithium to form Li4.4Sn [446]. By
forming a Li4Ti5O12–SnO2 composite electrode, multiple benefits
may be derived: (i) because both Li4Ti5O12 and SnO2 are lithium-
insertion hosts, the composite may have a higher theoretical
capacity than the composites with carbon, Cu or Ag inserted as the
second phase; (ii) Li4Ti5O12 is a material with almost no volume
change during the lithium insertion/extraction processes and can
act as a buffer for the Sn phase, resulting in improved cycling
stability of the Sn phase; (iii) as a metal, tin has a high electronic
conductivity, which in turn acts as a surface modifier for Li4Ti5O12
to increase its surface electronic conductivity and improve its rate
capacity.
Lai et al. first reported Li4Ti5O12–SnO2 composites as potential
anodic materials for LIBs [447,448]. They successfully prepared
Li4Ti5O12–SnO2 composites with a core-shell structure by solution
precipitation of SnO2 onto a pre-synthesized Li4Ti5O12 core. The
composite contained 20 wt.% SnO2 and delivered capacities of
1089 and 182 mA h g1 for the first cycle and the 16th cycle,
respectively, between a potential range of 0.05–3.0 V. These
capacities are higher than those of both pure SnO2 and Li4Ti5O12
electrodes, suggesting a synergistic interaction between the
Li4Ti5O12 and SnO2. The authors proposed that SnO2 acted as a
bridge between the spinel particles to reduce the contact
resistance between the Li4Ti5O12 particles, while the aggregation
of small Sn particles was hindered by the Li4Ti5O12 phase. As a
result, the composite electrode exhibited an improved reversible
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
capacity for the Li4Ti5O12 and improved cycling stability of the
SnO2 phase. Among the various Li4Ti5O12-SnO2 composites of
varying SnO2 content, Li4Ti5O12–SnO2 (5 wt.%) demonstrated the
best cycling stability. Following 42 charge/discharge cycles at a
current rate of 0.5 mA cm2, the material maintained a capacity of
189 mA h g1.
Composites of Li4Ti5O12 nanosheets and SnO2 nanocrystals
were also fabricated by Han et al. via the crystal growth of SnO2 on
the surface of 2D Li4Ti5O12 nanosheets and were tested between
0.001 and 2.0 V [449]. However, the best sample exhibited a
discharge capacity of 150 mA h g1 after 30 cycles, which is even
lower than the theoretical capacity of Li4Ti5O12 (175 mA h g1)
between 1.0 and 3.0 V. A Li4Ti5O12/Sn composite formed by a
simple physical mixing method with the help of HEBM demon-
strated improved cycling performance compared with pristine
Li4Ti5O12 and Sn electrodes [450]. By using a cellulose-assisted
combustion technique, Cai et al. prepared ultrafine Li4Ti5O12/Sn
composites [451]. A certain chemical interaction was created
between the Li4Ti5O12 and SnO2 phases during the synthesis; as a
result, the grain growth of the SnO2 during the calcination was
successfully suppressed. However, the tin oxide acted as a
sintering aid for the Li4Ti5O12 phase, and the sintering of Li4Ti5O12
became obvious at 700 8C. The proper selection of calcination is
therefore important to achieving high performance. A calcination
temperature of 500 8C was proposed, and the as-prepared
composite electrode with a Li4Ti5O12-to-Sn weight ratio of 9:1
exhibited a capacity of 224 mA h g1 after 50 charge–discharge
cycles at a current density of 100 mA g1.
Yang et al. successfully prepared Li4Ti5O12/SnO2 hollow spheres
by a spray drying process using LiNiO3, TTIP and tin oxalate
(SnC2O4) as raw materials with 0.5 M CA as the chelating agent
[452]. These researchers further prepared and studied Li4Ti5O12/
SnO2 hollow spheres using an ultrasonic spray pyrolysis process
using the same raw materials with different Li4Ti5O12/SnO2 ratios
[453]. Li4Ti5O12 and SnO2 phases with no impurities were observed
by XRD, and the corresponding nanocrystals were observed to be
Fig. 60. TEM and dot-mapping images of the post-treated Li4Ti5O12-SnO2 (0.4/0.6) composite powders [453].
53
homogenously dispersed by TEM observation and mapping
(Fig. 60). However, the possibility of Sn-doping in the Li4Ti5O12
was not considered and studied. Nevertheless, the sample with a
Li4Ti5O12/SnO2 ratio of 0.4/0.6 exhibited the best cycling stability
with capacity retention of 70% after 60 cycles at a current density of
700 mA g1 between 0.1 and 2.5 V.
3.5.4. Li4Ti5O12/TiO2
Fig. 61 shows the pseudobinary Li2O–TiO2 phase diagram
[454]. For the synthesis of Li4Ti5O12, the impurities of Li2TiO3 or
TiO2 will be present with excess lithium or less lithium,
respectively. Historically, pure-phase Li4Ti5O12 is expected to
exhibit better electrochemical performance. Thus, researchers
always attempted to synthesize phase-pure Li4Ti5O12 to avoid the
formation of impurities. Lithium excess was frequently adopted in
the starting raw materials to compensate the potential lithium loss
by evaporation during high-temperature calcination. However,
Li4Ti5O12–TiO2 composites have been reported to demonstrate
high electrochemical performance. Rahman et al. successfully
synthesized a Li4Ti5O12-anatase TiO2 composite by applying a basic
molten salt process using LiNO3, LiOHH2O, Li2O2 and
Ti[O(CH2)3CH3]4 as raw materials. The sample, synthesized at
400 8C, showed outstanding electrochemical performance, deliv-
ering initial discharge capacities of 193, 168, 146, 135 and
117 mA h g1 at rates of 0.2, 0.5, 1, 2 and 5 C, respectively, within
the potential range of 1.0–3.0 V. A discharge capacity of
135 mA h g1 was maintained at 1 C with capacity retention of
95% after 100 cycles [409]. By introducing a third phase of
amorphous carbon with the formation of a Li4Ti5O12–TiO2–C
composite prepared via the molten salt process, the electrode
performance showed obvious improvement [410]. As shown in
Fig. 62, the composite reached initial capacities of 166 and
135 mA h g1 at 0.5 and 10 C rates, respectively, while the
corresponding values were 167 and 107 mA h g1 for a carbon-
free Li4Ti5O12–TiO2 composite and 147 and 57 for pristine
Li4Ti5O12. A capacity of 110 mA h g1 was maintained after
54 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 61. The pseudobinary Li2O–TiO2 phase diagram. [454].
100 cycles at a rate of 10 C, which is 82% of the initial capacity. In
comparison, the discharge capacities dropped to only 83 and
40 mA h g1 for the Li4Ti5O12–TiO2 and Li4Ti5O12 electrodes,
respectively.
By using a hydrothermal route in the presence of thiourea, Li
et al. successfully synthesized a Li4Ti5O12-anatase TiO2 nanocom-
posite [455]. The results of galvanostatic charge–discharge, cyclic
voltammetry and electrochemical impedance spectra indicated
that the composite presented improved electrochemical perfor-
mance over single-phase Li4Ti5O12 and anatase TiO2. After
300 cycles at a rate of 1 C, the composite electrode retained a
discharge capacity of 116 mA h g1. In addition, a pseudocapaci-
tive effect was created with the formation of the composite due to
the presence of abundant phase interfaces, which were believed to
cause the enhanced rate capability and improved cycling stability.
Liu et al. also successfully synthesized Li4Ti5O12-TiO2 nanocrys-
tallines via a hydrothermal process under an appropriate
temperature [456], and greatly enhanced electrochemical perfor-
mance, especially the rate capability, was demonstrated. However,
the actual weight ratio of the Li4Ti5O12 to TiO2 was not determined
and was difficult to control for the composite synthesized via the
hydrothermal method. Lai et al. synthesized Li4Ti5O12-TiO2
microspheres using PANI/TiO2 microspheres and LiOHH2O as
raw materials with a Ti/Li mole ratio of 5:3.13[457]. The composite
microspheres exhibited enhanced electrochemical performance
with a capacity of 156.9 mA h g1 at 1500 mA g1 compared with
that of pure Li4Ti5O12 microspheres (105.8 mA h g1). Wang et al.
introduced ammonia into a solvothermal synthesis process of
Li4Ti5O12 spheres, resulting in much smaller Li4Ti5O12–TiO2
nanoparticles and enhanced rate performance [458]. After further
carbon coating, the composite delivered a reversible capacity of
140 mA h g1 at 5 C even after 100 cycles.
Liao et al. synthesized highly mesoporous lithium titanate
hierarchical microspheres using a hydrothermal method using
hierarchical TiO2 spheres and LiOH as raw materials followed by
heat treatment [459]. A further hydrothermal treatment in glucose
solution was applied to coat the carbon to enhance electronic
conductivity. Notably, a TiO2 phase formed simultaneously, which
may be transformed from an LiTiO2 impurity or Li4Ti5O12 after
carbon coating, which was beneficial to the electrochemical
performance. The carbon-coated Li4Ti5O12–TiO2 composite micro-
sphere exhibited a high capacity of >230 mA h g1 at 0.2 C. Chen
et al. synthesized a Li4Ti5O12-anatase TiO2 nanocomposite via a
microemulsion-assisted hydrothermal method followed by calci-
nation at 550 8C using a Li/Ti molar ratio of 4:5, whereas a pure
Li4Ti5O12 phase is formed using the Li/Ti molar ratio of
4.5:5[460]. The composite exhibited much enhanced electrochem-
ical performance with a capacity of 108.9 mA h g1 even at
7 A g1. This enhancement was attributed to the high theoretical
capacity of TiO2 and improved electronic conductivity in the
presence of TiO2 by the authors. However, the abundant phase
interfaces, which were very important, were not considered and
studied. More recently, Jiang et al. successfully synthesized
hierarchical Li4Ti5O12/TiO2 tubes composed of ultrathin nanoflakes
by a hydrothermal treatment of porous amorphous TiO2 and
LiOHH2O followed by calcination at 400 8C [461]. The ordered
fringe-like crystallographic defects and rich grain boundaries
among the spinel Li4Ti5O12 and anatase TiO2 were clearly observed
via TEM and HR-TEM analysis. Combined with the hierarchical
structure, crystallographic defect and grain boundary, the as-
synthesized Li4Ti5O12/TiO2 composite delivered high initial dis-
charge capacities of 420, 225, and 160 mA h g1 at 0.01, 0.1, and
1.0 A g1, respectively, and a good capacity retention of 87% after
100 cycles at 1.0 A g1. Besides, Li4Ti5O12–TiO2 nanosheet-nano-
tube composites [462], and Li4Ti5O12–TiO2 hollow spheres
composed of nanoflakes [463] have also successfully synthesized
by solvothermal/hydrothermal process followed by a calcination
process, which also demonstrated improved electrochemical
properties. Wu et al. synthesized petal-like Li4Ti5O12–TiO2
nanosheets via a boiling treatment with further calcination using
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 55

Fig. 62. The initial galvanostatic charge-discharge profiles of (a) Li4Ti5O12, (b) Li4Ti5O12-TiO2, and (c) Li4Ti5O12-TiO2-C electrodes at different current densities from 0.5 to 10 C
between 2.5 and 1.0 V; (d) cyclic performance beyond 100 cycles at 10 C [410].

H2TiO3 and LiOHH2O as raw materials in the presence of H2O2 and
ammonia; the composite exhibited good electrochemical perfor-
mance, especially with an initial discharge capacity of
112.5 mA h g1 at 20 C [464]. Although the TiO2 phase was not
designed to be introduced, excellent electrochemical performance
was still achieved.
Liao et al. prepared a Li4Ti5O12–TiO2 nanowire array by
controlling the chemical lithiation reaction time [465]. Li4Ti5O12
and TiO2 nanowire arrays were also synthesized as a comparison.
As shown in Fig. 63a and b, the characteristic redox peaks and
discharge/charge plateaus of Li4Ti5O12 and anatase TiO2 phases
were distinctly observed in the curves of Li4Ti5O12–TiO2 nanowire
array electrode. Because of the higher theoretical capacity of TiO2,
the specific capacities at low rate (0.1–1 C) of Li4Ti5O12–TiO2
nanowire array electrode were higher compared to that of
Li4Ti5O12 nanowire array electrode and lower compared to that
of TiO2 nanowire array electrode, importantly, the superior rate
capability was achieved for Li4Ti5O12–TiO2 nanowire array
electrode (Fig. 63c). The enhanced rate performance was attributed
to the rich grain boundary interfaces in the Li4Ti5O12–TiO2
nanowires, which mainly improve lithium storage kinetics. Shao
et al. proposed a novel method based on an in situ nitriding-
oxidizing process [466]. During the synthesis, TiO2 anatase and
Li2CO3 were applied as the raw materials and were well mixed by
HEBM followed by calcination at 800 8C under an ammonia
atmosphere for 3 h to yield a primary product composed of an N-
doped Li4Ti5O12 and a TiN shell. The composite was then further
calcined under an air atmosphere at 600 8C for 3 h to allow the re-
oxidation of TiN to TiO2. Finally, a micrometer-sized Li4Ti5O12–TiO2
composite with rich two-phase boundaries, but a small specific

Fig. 63. (a) CV curves of TiO2 nanowire, Li4Ti5O12-TiO2 composite nanowire, and Li4Ti5O12 nanowire electrodes. (b) The first three charge–discharge curves at 0.1 C of
Li4Ti5O12–TiO2 composite nanowire electrode. (c) The rate performance at various current rates from 0.1 to 30 C and then back to 0.1 C (1 C = 175 mA g1) of TiO2 nanowire,
Li4Ti5O12–TiO2 composite nanowire, and Li4Ti5O12 nanowire electrodes [465].
56 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
surface area, was obtained. The sample exhibited outstanding
capacity, rate capability and cycling stability, reaching a capacity of
155 mA h g1 at 10 C with almost no capacity fade after
100 cycles. The high performance was attributed to the rich
two-phase boundaries, while the micrometer particle size with a
small surface area benefited the high cycling stability. By this facile
method, the Li4Ti5O12 to TiO2 ratio can be easily controlled. Thus,
this method provides a novel way to develop high-performance
Li4Ti5O12-TiO2 composites for LIBs.
Rutile TiO2 is thermodynamically the most stable phase among
the various TiO2 polymorphs. However, in bulk crystal form, it
usually exhibits a poor lithium intercalation capability [467]. Im-
proved electrode performance was observed for Li4Ti5O12 by
forming a composite with rutile TiO2 [54]. C.T. Hsieh prepared a
Li4Ti5O12-rutile TiO2 composite by spray drying followed by a high-
temperature solid-state reaction. The composite had superior
performance in terms of capacity, rate capability and cycling
stability compared to pristine Li4Ti5O12, suggesting the beneficial
effects of a rutile TiO2 phase on the lithium insertion behavior of
Li4Ti5O12. Such improvement likely has two causes. First, the
presence of a rutile TiO2 phase provided additional capacity;
second, the presence of a TiO2 phase effectively prevented the
occurrence of Li2O, LiOH and/or Li2CO3 impurity phases, which can
be introduced during the synthesis of Li4Ti5O12 by applying
excessive Li raw materials and are believed to deteriorate the
intercalation properties of the Li4Ti5O12 phase by blocking the
interfacial charge transfer because of their low electronic and
lithium-ion conductivities [52]. Recently, Li4Ti5O12/rutile TiO2
mesoporous microspheres were also designed and prepared using
TiO2 microspheres as a precursor [468]. An enhanced lithium ion
diffusion coefficient was obtained in the presence of the rutile TiO2
phase, which was explained by the open channels along the [0 0 1]
direction for elevated lithium ion diffusion with an appropriate
amount of the rutile TiO2 phase, resulting in improved electro-
chemical performance. Carbon was introduced to further improve
its performance, and discharge capacities of 170.9, 162.5,
147.5 and 120.6 mA h g1 at 0.5, 1, 2 and 5 C were achieved,
respectively.
3.5.5. Li4Ti5O12/transition-metal oxides (MO, where M is Co, Ni, Cu, Fe
or Zn)
Since the nano-sized transition-metal oxides (MO) were found
to demonstrate high electrochemical activity and undergo a
conversion reaction by discharging to an end potential of 0.01 V in
2000 [469], MO have attracted significant attention as promising
candidates for anodes for high-capacity LIBs.
However, MO usually suffers from large volume variation,
which results in poor current collection, finally leading to poor
cycling performance. The benefits from using a Li4Ti5O12–MO
composite as an anode are similar to those obtained for Li4Ti5O12–
SnOx: MO will contribute a higher capacity compared with
Li4Ti5O12; Li4Ti5O12 acts as a stable matrix, which could
accommodate the volume variation of MO; and MO will transform
to a metal in a specific voltage range, which could increase the
conductivity of Li4Ti5O12. The use of several MO (M is Co, Ni, Cu, Fe
or Zn) has recently been attempted to form composites with
Li4Ti5O12 to achieve improved electrochemical performance [470–
473]. Hu et al. synthesized Li4Ti5O12–MO (Fe2O3 and CuO)
composites as modified anodes with 5 wt.% MO [471]. The LTO–
CuO composite exhibited the best rate performance with a specific
capacity of 106 mA h g1 at 20 C. However, the comparison of the
electrochemical performance of the composite within a voltage
range of 0.005–3.0 V and that of Li4Ti5O12 between 1.0 and 3.0 V is
not reasonable because Li4Ti5O12 also exhibits electrochemical
activity below 1.0 V. Additionally, the preparation of the composite
with MO, butyl titanate and LiNO3 may also make the M a dopant.
ZnO was also introduced into Li4Ti5O12 to form a composite via
facile ball-milling [472], and the composite demonstrated
enhanced electrochemical performance, especially the rate capa-
bility, within potential ranges of 0.01–3.0 and 1.0–3.0 V.
By changing the end potential to 1.0 V, the capacity of MO will
be obviously reduced; however, it remains higher compared with
conductive graphite/carbon anodes. Additionally, MO has a higher
density. Li4Ti5O12/Fe2O3 was designed and prepared by dispersing
solid-state-synthesized Li4Ti5O12 powders in a Fe(OH)3 colloid
combined with further calcination, which resulted in an obviously
enhanced rate performance with a discharge capacity of
109.4 mA h g1 at 10 C compared with that of pure Li4Ti5O12 with
a capacity of only 40.5 mA h g1 [473].
4. Electrochemical behavior in different battery systems
To date, the Li4Ti5O12 anode has been combined with various
cathode materials and electrolytes to build batteries for diverse
applications, such as power sources for thin-film electronics [216],
auxiliary or main power sources for hybrid vehicles [474] including
start-stop applications [475], power systems for load leveling
application [476], and electrochemical energy storage devices
[477].
4.1. Combination with different cathodes
The replacement of a commercial graphite anode with a
Li4Ti5O12 anode in LIBs is believed to result in significantly
enhanced safety, rate capability, and cycling stability. However,
the voltage of batteries with a Li4Ti5O12 anode decreased compared
with that of conventional carbon anodes because of the higher Li+
insertion/extraction potential (approximately 1.55 V) in
Li4Ti5O12. Thus, combining a Li4Ti5O12 anode with befitting
high-voltage cathode materials raises concerns in terms of
obtaining the desired voltage output. Various cathodes have been
explored to combine with the Li4Ti5O12 anode; the corresponding
discharge/charge curves as well as operation voltage of the cells are
shown in Fig. 64.
(1) Layered oxide cathode
Layered LiCoO2, which has been the most successful cathode
over the past two decades, is usually combined with a conventional
graphite anode for commercial LIB applications. By replacing
graphite with a Li4Ti5O12 anode, the Li4Ti5O12/LiCoO2 battery
system has also been studied [216,478–480]. Brousse et al.
fabricated all-oxide solid-state LIBs using a thin-film Li4Ti5O12
anode, a Li0.33La0.56TiO3 electrolyte and a thin-film LiCoO2 cathode,
which were successfully cycled for 100 times. However, the
current density was only 50 uA cm2, which could be attributed to
the rather thick electrolyte of approximately 1 mm [216]. Gaikwad
et al. reported a high areal capacity flexible Li4Ti5O12/LiCoO2
battery with nonwoven fibrous membrane-reinforced electrodes
in which freestanding CNT film as current collectors (Fig. 65)
[481]. The reinforced electrode exhibited excellent mechanical
performance with a tensile strength of 5.5–7.0 MPa. Fig. 65d–f
shows the typical charge/discharge curves of the Li4Ti5O12/CNT
electrode, LiCoO2/CNT electrode, and full battery, respectively. The
operation voltage of the full Li4Ti5O12/LiCoO2 battery was around
2.4 V. The full battery delivered a high areal capacity of
1 mA h cm2 and a stable cycling performance with a capacity
retention of 94% after 450 cycles at a C/2 rate. Although other
researchers have attempted to understand the details for this
Li4Ti5O12/LiCoO2 battery system via EIS analysis [479], and to
improve its electrochemical performance using a novel electrolyte
[480] and adding an additive [478], the key issues are the high-cost
of the cobalt source and the oxygen release problem in LiCoO2
during the charge/discharge process [482].
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 57

terms of safety, power and cycling life [490]. Based on the

Fig. 64. The discharge/charge curves for various cathode materials including
LiNi0.5Mn1.5O4, LiMn2O4, LiCoO2, LiFePO4 (20 8C, 0.2 C rate) [500], LiCoPO4 (0.1 C
rate) [493], LiMn0.8Fe0.2PO4 (30 8C, 0.1 C rate) [496], LiMnPO4/C (0.05 C rate) [492],
and LiNi1/3Co1/3Mn1/3O2 (25 8C, 20 mA g1) [484] combined with Li4Ti5O12 anode
material [493]. All the curves are derived from the literatures with horizontally
flipping, smoothing and dyeing.
Optimized layer oxide cathodes, LiNi0.8Co0.15Al0.05O2 and LiNi1/
3Co1/3Mn1/3O2, which have received increasing attention [483–
485], have also been combined with a Li4Ti5O12 anode to deliver
improved electrochemical performance [419,486–489]. Guo et al.
combined a carbon-coated Li4Ti5O12/graphene composite anode
with a LiNi1/3Co1/3Mn1/3O2 cathode; the full cell demonstrated
excellent rate performance with a specific capacity of
116 mA h g1 and 95 mA h g1 at 1 and 8 C, respectively [419].
(2) Lithium-phosphate cathode
As a critical cathode material among the lithium-phosphate
group, olivine-structured LiFePO4, which undergoes a two-phase
mechanism with the reversible reaction during the electrochemi-
cal lithium insertion/extraction processes [64], is outstanding in
superiority of LiFePO4 and Li4Ti5O12, a full cell composed of this
anode/cathode couple could achieve high rate capability and cycling
stability [244,318,491]. Li et al. developed a flexible graphene-foam-
based Li4Ti5O12/LiFePO4 full battery, which delivered a specific
capacity of 117 mA h g1 (calculated based on the weight of the
cathode active material) even at a 10 C rate, 88% of the capacity at a
1 C rate [244]. Note that this flexible full battery device avoids the
use of conventional additional conductive carbon black, binder, and
heavy metal foil current collectors; thus, a high gravimetric energy
density of the full battery could be achieved. Moreover, a stable
cycling performance at 10 C over 100 cycles with only 4% capacity
loss was achieved for this flexible full battery device. Long-term
cycling performance could also be easily achieved for the Li4Ti5O12/
LiFePO4 battery system due to the unique characteristics of the
electrode materials; for example, a specific capacity of
130 mA h g1 (calculated based on the weight of the lower weight
electrode) was delivered even after 1200 cycles at 0.5 C for a full cell
with Ketjen-black-modified LiFePO4 as the cathode and an
unmodified Li4Ti5O12 as the anode [491]. Although a high rate
capability and stable cycling performance have been successfully
achieved using the Li4Ti5O12/LiFePO4 couple, the relatively low
discharge potential plateau of 3.4 V (vs. Li/Li+) for LiFePO4 results in
a low voltage output of approximately 1.85 V (Fig. 64).
In comparison with LiFePO4, LiMnPO4 has a much higher
operation voltage of 4.1 V (vs. Li/Li+) and offers a competitive
energy density of 701 Wh kg1 (171 mA h g1  4.1 V). To deploy
LiMnPO4 as a cathode material and address its corresponding
issues (e.g., Jahn–Teller distortion, poor electronic and ionic
conductivity, and interfacial strain between the LiMnPO4 and
MnPO4 phase, etc.), Ramar et al. prepared a mesoporous LiMnPO4/C
cathode using a high-energy ball-mill-assisted soft template
method and combined this cathode with a Li4Ti5O12/C anode
[492]. This full cell delivered an average voltage and capacity of
2.3 V and 54 mA h g1 (calculated based on the weight of the
cathode active material, the capacity was close to that at 1 C in the
half-cell configuration vs. Li foil), respectively, at a rate of 1 C.
Relatively stable cycling performance within 20 cycles was also
demonstrated. However, the capacity was relatively low, and the
end-of-charge indication in the voltage profile was not clear
compared with that of the Li4Ti5O12/LiFePO4 couple.

Fig. 65. (a) Schematic of the flexible battery laminated within aluminum-lined pouch. (b) Demonstration of the flexible lithium-ion battery connected in series with a 200 V
resistor and a green light-emitting diode (LED). (c) Areal capacity (mA h cm2) and columbic efficiency (%) of the full cell cycled between C/4 and 1 C rate. The full cell had a total
active area of 2.5  2.5 cm2 and Li4Ti5O12 and LiCoO2 loading of 13.4 and 12.5 mg cm2, respectively. (d, e) Galvanostatic charge/discharge curves for (d) Li4Ti5O12/CNT anode and
(e) LiCoO2/CNT cathode cycled between 1.0 and 2.0 V vs. Li/Li+ and 3.0–4.2 V vs. Li/Li+, respectively, at C/4 rate. (f) Galvanostatic charge/discharge curves for the full cell cycled
between C/4 and 1 C rate. The capacity at C/4, C/2 and 1 C rate was 117, 104 and 90 mA h g1, respectively. Columbic efficiency of all the batteries was above 99.5% [481].
58 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Recently, another olivine-structured candidate from the lithi-
um-phosphate group, LiCoPO4, which has a usable operation
voltage (4.8 V vs. Li/Li+), was also combined with a Li4Ti5O12 anode
to achieve a high voltage output of 3.25 V [493,494]. However, the
reported cycling performances of the Li4Ti5O12/LiCoPO4 couple
were definitely poorer compared with that of the Li4Ti5O12/LiFePO4
couple, limiting its widespread commercial application. Other
lithium-phosphate-like Li3V2(PO4)3/C composite was also com-
bined with a Li4Ti5O12 anode; the cell demonstrated three charge/
discharge plateaus at 2.56/2.46 V (50%), 2.15/2.05 V and 2.07/
1.97 V and an initial capacity of 117 mA h g1 at 0.5 C [495].
To combine the advantages of LiMnPO4 and LiFePO4 and avoid
the decomposition of electrolyte solutions based on alkyl
carbonate solvents at too high of a voltage, a promising cathode,
LiMnyFe1yPO4, has been combined with a Li4Ti5O12 anode to
obtain an improved battery system. Borgel et al. combined a
commercial carbon-coated LiMn0.8Fe0.2PO4 cathode with a
Li4Ti5O12 anode; the cell works at a main potential of 2.5 V
(80%), exhibiting good rate capability at 30 8C with discharge
capacities of 153 and 118 mA h g1 (calculated based on the
weight of the cathode active material) at 0.1 C and 5 C rates,
respectively, and a stable cycling life with 100 cycles at 0.5 C
[496]. Yang et al. used their V-doped Li4Ti5O12 (Li4Ti4.90V0.10O12/C)
prepared by a solid-state method [318] as an anode and LiFe0.5-
Mn0.5PO4/C as a cathode; the cell demonstrated specific capacities
of 161, 141, 111, and 84 mA h g1 (calculation was undefined) at
0.2, 1, 5, and 10 C, respectively, and exhibited stable cycling
performance for 100 cycles at 1 C [497]. Thus, LiMnyFe1yPO4 is
demonstrated to be a promising cathode to combine with a
Li4Ti5O12 anode for commercial application.
(3) Spinel oxide cathode
A spinel LiMn2O4 cathode has also been combined with a
Li4Ti5O12 anode, and the battery system offers a relatively high
voltage output of 2.55 V. Combining Li4Ti5O12 nanorods with a
LiMn2O4 porous sphere cathode results in a good rate capability
with discharge capacities of 44.1, 42.9, 37.4, and 34.1 mA h g1
(calculated based on the total weight of both the cathode and
anode active electrode materials) at 0.5, 1, 10 and 20 C,
respectively [498]. A 60% capacity retention after 1000 cycles
at 10 C was also achieved. Reale et al. fabricated a cell with a
Li4Ti5O12 anode and a LiMn2O4 cathode in a PVDF-based gel
electrolyte to yield operational voltages of 2.5 and 3.0 V,
respectively [499]. The Li4Ti5O12/LiMn2O4 cell delivered a capacity
of 130 mA h g1. Even under an unoptimized configuration, the cell
can be operated at rates exceeding 1.0 C with minor polarization.
For the LiMn2O4 cathode, the high content of Mn3+ usually
results in a Jahn–Teller distortion, that is, dismuting into Mn4+ and
highly soluble Mn2+. Partial substitution of Mn with Ni in the
LiMn2O4 cathode has been recognized as an effective approach to
avoid the Jahn–Teller distortion because Mn4+ will form instead of
Mn3+[500]. For instance, in ordered LiNi0.5Mn1.5O4, all the Mn
elements should be in the +4 valence state. In particular, the
LiNi0.5Mn1.5O4 cathode material is highlighted because of its high
operation voltage (4.7 V) and high energy density; thus, it has
been recognized as a promising cathode to combine with Li4Ti5O12
anodes, and many related works have been performed
[501,502]. Reale et al. further reported Li4Ti5O12/gel polymer
electrolyte (GPE)/LiNi0.5Mn1.5O4 batteries with a cell voltage of
3.1 V at room temperature [499]; the batteries were successfully
operated at rates as high as 2.5 C with a capacity decay of only
10% after 100 cycling at 0.2 C. Zheng et al. investigated the effect
of residual lattice Mn3+ on the electrochemical performance of a
Li4Ti5O12/LiNi0.5Mn1.5O4 full cell; they found that the benefit of
lattice Mn3+ is more manifest in the Li+ deficient environment of
the LiNi0.5Mn1.5O4-limited full cell, and importantly, they demon-
strated that the cycling stability in the Li4Ti5O12-limited full cell
was much improved with a stable 100 cycles at 0.2 C compared
with that in the LiNi0.5Mn1.5O4-limited full cell due to the reduced
utilization of the second two-phase transition reaction [502]. A
metal-doped LiNi0.5Mn1.5O4 cathode was also studied for combi-
nation with the Li4Ti5O12 anode [503,504]. Ding et al. synthesized a
LiNi0.473Mn1.473Al0.054O4 nanotube cathode and combined it with a
commercial Li4Ti5O12 anode, demonstrating a high rate capability
with 158 mA h g1 (calculated based on the limited Li4Ti5O12
mass) at 0.5 C and 120 mA h g1 at 10 C and a further good cycling
stability with a 87% capacity retention after 200 cycles at 1 C
charge/5 C discharge rate [504]. Because of the benefit of an
appropriate Mn3+ content in the LiNi0.5Mn1.5O4 cathode material,
where Li+ ion transport can be accelerated in the crystalline
structure [505], an optimized LiNi0.4Mn1.6O4 composition has been
developed [506]; in addition, studies in the battery system with a
Li4Ti5O12 anode have also been conducted. The output voltage of
the Li4Ti5O12/LiNi0.4Mn1.6O4 battery system is especially attractive
for commercial application; however, the selection of the
electrolyte with proper additive [505,507] is of significant
importance to prevent its degradation at high voltage and to
further achieve a real stable electrochemical performance. To
further increase the working voltage, a cathode with a higher
lithium-intercalation voltage is necessary. Panero et al. first
reported the combination of Li4Ti5O12/Li2Co0.4Fe0.4Mn3.2O8, two
high-voltage spinels, as the anode and cathode of LIBs to yield a
3.5-V cell [508].
(4) Other cathodes
As one of the high-capacity cathode materials, vanadium
pentoxide (V2O5) is widely investigated [509,510]. Researchers
have also attempted to combine it with a Li4Ti5O12 anode, however,
there is no lithium in V2O5; thus, a chemical lithiation process was
adopted. Typically, two discharge plateaus at 1.84 and 1.61 V
were observed for chemically lithiated V2O5 particles [511]. How-
ever, the cycling performance is poor even at a low current density
of 20 mA g1. Use of chemically lithiated electrospun V2O5
nanofibers resulted in enhanced cycling performance of the full
cell [512]; however, they remains unattractive for commercial
application.
4.2. Combination with different electrolytes
To date, various electrolytes have been developed and used for
LIBs [513]. The most commonly used electrolyte is a carbonate
organic liquid electrolyte containing a dissolved lithium salt such
as LiPF6, which has an ionic conductivity higher than 103 S cm1
at room temperature. The typical carbonate solvent consists of
ethylene carbonate (EC) and dimethyl carbonate (DMC, or
ethylmethyl carbonate (EMC)), in which EC allows good ionic
dissociation of lithium salt to ensure acceptable ionic conductivity,
and DMC (or EMC) acts as a thinning solvent to reduce the viscosity
[514]. Additionally, for the conventional graphite/carbon anode, a
passivating SEI layer could form from EC on the surface of graphite/
carbon as a barrier to avoid further decomposition of the
electrolyte [515,516]. For a Li4Ti5O12 anode that is usually operated
above 1.0 V, most of the papers reviewed in Section 3 for Li4Ti5O12
modification are based on the conventional carbonate organic
liquid electrolyte (e.g., LiPF6 in EC/DMC (or EMC)); stable cycling
stability and excellent rate capability can be successfully achieved
at room temperature. Stable cycling performance can also been
demonstrated even with an end potential of 0.01 V using these
conventional carbonate electrolytes [517].
The replacement of conventional LiPF6 with other unique
lithium salts (e.g., lithium difluoro(oxalato)borate (LiDFOB)) can
result in improved electrochemical performance of the Li4Ti5O12/
LiFePO4 battery system, that is, cycling stability with a capacity
retention of 90% after 100 cycles compared with that based on
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
LiPF6 (75%) at high temperature (60 8C) [518]. However, the
conventional carbonate organic liquid electrolyte still suffers from
several issues, that is, the high flammability leads to a potential
safety issue, and the high reactivity above 50 8C results in
decreased cycling performance [514]. These issues strongly limit
its practical application in the Li4Ti5O12–anode battery system.
Thus, alternative electrolytes have been developed and studied to
meet the demands of safety, thermal stability, and even high
operation voltage window to match the high operation voltage
cathode that is combined with the Li4Ti5O12 anode. Recently, most
studies on alternative electrolytes for the Li4Ti5O12–anode battery
system have focused on non-flammable electrolytes based on ionic
liquids [519–524] and sulfone solvents [514,525–527].
Ionic liquids are generally defined as salts with a melting point
below 100 8C [528]. Due to their high thermal stability, wide
potential windows and high flash points, ionic-liquid-based
electrolytes have attracted increasing attention [523]. The typical
cations for ionic liquids are imidazolium, ammonium, pyrrolidi-
nium, and pyridinium. [529]. Although the advantages of ionic
liquids are very attractive, they suffer from high intrinsic viscosity.
Alternatively, mixtures of ionic liquids and alkylcarbonates have
recently been demonstrated to have potential application for the
Li4Ti5O12–anode battery system [521–523]. Lombardo et al. used a
mixture of N-butyl-N-methylpyrrolidinium bis(trifluoromethane-
sulfonyl)imide (Py14TFSI) and 1 M LiPF6 in EC:DMC in a weight
ratio of 3:7 as a electrolyte, which demonstrated enhanced safety
compared with that of flammable alkylcarbonate electrolyte
[522]. A Li4Ti5O12/LiFePO4 battery system using this mixed
electrolyte delivered a specific capacity of approximately
150 mA h g1 (calculated based on Li4Ti5O12 mass) at a 0.2 C rate.
Sulfone-based electrolytes were demonstrated to have an
ultrahigh anodic potential above 5.0 V vs. Li/Li+ [514] but suffer
from poor cathodic stability for the conventional graphite/carbon
anode because they cannot form a stable SEI layer to prevent the
electrolyte from further consumption [530]. Thus, sulfone-based
electrolytes are ideal partners for the Li4Ti5O12–anode battery
system because Li4Ti5O12 is usually operated above 1.0 V and a
high operation potential cathode is required for combination with
Li4Ti5O12 to obtain a high voltage output. Abouimrane et al. used
the sulfone-based electrolytes for Li4Ti5O12/LiMn2O4 and
Li4Ti5O12/LiNi0.5Mn1.5O4 battery systems, which demonstrated
stable cycling performance [514]. In particular, a relatively stable
cycling performance with a capacity of 80 mA h g1 for
1000 cycles at 240 mA g1 was achieved for the Li4Ti5O12/1 M
LiPF6 in (tetramethyl sulfone (TMS)-EMC)/LiNi0.5Mn1.5O4 battery
system.
Moreover, deep eutectic solvents (generally, a eutectic mixture
composed of 2 components; through hydrogen bond interac-
tions, its corresponding melting point is lower than that of each
individual component and usually lower than 100 8C [531], e.g.,
lithium salt/N-methylacetamide) have also been used as electro-
lytes for the Li4Ti5O12/LiFePO4 battery system, which demonstrat-
ed good electrochemical performance [532]. The problem for deep
eutectic solvents is their high viscosity, which is even higher than
that of ionic liquids; thus, mixtures with low viscosity solvent may
currently be an effective selection.
Other liquid electrolytes with stability and a large window
have also been developed. Xiang et al. proposed a dimethylpho-
sphonate (DMMP)-based electrolyte of 1M LiPF6/
EC + DMC + DMMP (1:1:2 wt.) for a cell with a Li4Ti5O12 anode
and a LiNi0.5Mn1.5O4 cathode in a 3-V lithium-ion battery,
demonstrating that the nonflammable electrolyte exhibited good
compatibility with both the Li4Ti5O12 anode and the
LiNi0.5Mn1.5O4 cathode [533]. An oligo(ethylene oxide)-function-
alized organosilicon compound (i.e., [3-(2-(2-methoxyethox-
y)ethoxy)-propyl]triethoxysilane) was developed by Qin et al.
59
that exhibited a wide operation window of 5.2 V and a high ionic
conductivity of 1.14 mS cm1[534]. Combining 1 M LiPF6 in this
compound with 1 vol% vinyl carbonate as an electrolyte with a
Li4Ti5O12 anode and Li1.2Ni0.2Mn0.6O2 cathode resulted in a
battery system that demonstrated an initial capacity of
161.3 mA h g1 and 86% capacity retention after 30 cycles (0.5–
3.1 V, 18 mA g1).
In addition, solid-state electrolytes have also been combined
with a Li4Ti5O12 anode, such as the recently reported electrolytes
based on Li6PS5Cl [535], Li2SiO3 [536]; however, the electrochemi-
cal performance compared with that of conventional liquid
electrolyte is not attractive.
4.3. Electrochemical performance
Even though there have been an increasing number of research
papers published on Li4Ti5O12 as an anode in LIBs, as observed in
Fig. 2, Li4Ti5O12 is no longer a material that remains confined to the
lab; this material is now being proposed for practical applications.
Jansen et al. tested a lithium-ion battery composed of a Li4Ti5O12
anode and a LiCoO2 cathode designed for potential application as a
power assist in hybrid vehicles [474]. As demonstrated in Fig. 66, the
authors reported the successful cycling of the batteries over 117,000
times with each cycle taking 60 s, including a 9-s discharge pulse, an
18-s rest, a 10-s charge pulse, and a 23-s low current charge. Such
batteries are highly promising for use in high-power applications in
which safety is a primary concern, such as EVs and HEVs. However,
two main problems arise in these batteries—the relatively low cell
voltage and large area-specific impedance. Du Pasquier et al.
proposed a hybrid battery–super capacitor using a nanostructured
Li4Ti5O12 anode to bridge the power capacity gap between
conventional LIBs and normal supercapacitors [537]. A 40 Wh kg1
1 Li-ion battery, which can be fully charged in 3 min, was fabricated
in soft laminate packaging using a nanostructured Li4Ti5O12 anode,
activated carbon/LiCoO2 composite cathode and PVDF-hexafluor-
opropylene (HFP) binder. The specific power of the battery reached
4 kW kg1, which is comparable to that of an electrochemical
double-layer supercapacitor. As observed in Fig. 67, after 9000 cycles
at a full depth of discharge, the capacity loss is only 20%. Similarly, Hu
et al. fabricated a hybrid battery capacitor using LiFePO4-activated
carbon as a cathode and Li4Ti5O12 as an anode, which combined the
advantages of the high rate capability of an activated carbon/
Li4Ti5O12 hybrid capacitor and the high capacity of a Li4Ti5O12/
LiFePO4 battery [538].
Zaghib et al. prepared the ‘‘18650’’ battery using carbon-coated
LiFePO4 as a cathode and carbon-free Li4Ti5O12 derived from a
solid-state reaction as an anode; this battery could deliver a
capacity of 800 mA h [539]. More importantly, an outstanding
cycling stability was demonstrated, with a definitely stable
Fig. 66. Voltage profile for a Li4Ti5O12/LiCoO2 cell operated under the Partnership for
a New Generation of Vehicles (PNGV) 100-W h test profile. Data shown for every
200th cycle. [474].
60 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 67. Discharge capacity vs. cycle number for Li4Ti5O12/LiCoO2 cells made with
55% LiCoO2 and 20% activated SuperP carbon, at matching ratio of 1.67.
(Galvanostatic cycling at 20 C charge–discharge rate between 1.6 and 3.0 V.) [537].
capacity after 20,000 cycles at a charge rate of 10 C (6 min) and
discharge rate of 5 C (12 min), even a 95% capacity retention was
observed after 30,000 cycles at a charge rate of 15 C (4 min) and
discharge rate of 5 C, as shown in Fig. 68. High safety with no flame
and no smoke detected during the testing was also reported, and
the maximum temperature reached was 72 8C. This battery was
used in a real car with the charge time reduced to 5 min using three
levels charger in parallel (500 V, 125 A). Such outstanding stability
gives the battery system great potential for EV applications.
However, the low voltage of 1.9 V and correspondingly insufficient
energy density (67.5 mWh g1) are the major limitations of this
battery system.
Fig. 68. (a, b) Cycle life of a Li4Ti5O12/EC-DEC-1M LiPF6/LiFePO4 18650-cell: (a) the cycle charge rate is 10 C (6 min) at 100% SOC, the discharge rate is 5 C (12 min) at 100% DOD,
(b) the cycle charge rate is 15 C (4 min) at 100% SOC, the discharge rate is 5 C (12 min) at 100% DOD, (c) photographs of cars presented at the World Energy Council (Montréal,
September 2010), equipped with the Li4Ti5O12/LiFePO4 battery built with the same cells as described in the present work. The charging time is reduced to 5 min with three
levels charger in parallel (500 V, 125 A) [539].
Batteries with Li4Ti5O12 anodes were believed to be much safer
than batteries with conventional graphite anodes because of their
higher lithium intercalation voltage and much higher thermal
stability. Several authors have conducted safety and stability
investigations of full cells with Li4Ti5O12 anodes. Belharouak et al.
examined the operational safety of a Li4Ti5O12/LiMn2O4 lithium-
ion battery system [540] by conducting accelerated rate calori-
metric tests on 18650 cells containing Li4Ti5O12 anodes and
LiMn2O4 cathodes and observed that no thermal runaway,
explosion or fire occurred. Amine et al. also demonstrated
outstanding abuse tolerance for a battery with a Li4Ti5O12 anode
and a LiMn2O4 cathode [168]. When the 2.5-V Li4Ti5O12/LiMn2O4
cell was overcharged to 15 V, the cell temperature reached only
80 8C with no explosion or thermal runaway; in addition, the cell
exhibited no capacity fade after 1000 cycles under aggressive
charge–discharge test conditions at 5 C and a temperature of 55 8C.
Takami tested a 2-V class lithium-ion battery system using a
Li4Ti5O12 anode [541] and observed that the short-circuit reaction
on the Li4Ti5O12 was 3 orders of magnitude slower than that on the
graphite anode. Thus, the Li4Ti5O12 anode was self-protecting
against the rapid discharge reaction of an internal short circuit,
ensuring outstanding safety performance. Xiang et al. investigated
the effect of capacity matchup between a LiNi0.5Mn1.5O4 cathode
and a Li4Ti5O12 anode in the cell system [542] and observed that
the cell with its capacity limited by Li4Ti5O12 exhibited better
tolerance to high voltage and overcharging than the cell with its
capacity limited by LiNi0.5Mn1.5O4. Thus, the former is recom-
mended. All the above-mentioned tests demonstrate the out-
standing safety of LIBs with Li4Ti5O12 anodes.
The Toshiba corporation developed a super charge/discharge
ion battery (SCiB) using Li4Ti5O12 as an anode that exhibited a high
level of safety, a long life of more than 6000 charge/discharge
cycles—approximately 2.5 times more than regular LIBs, rapid
charging with 80% recharge in just 15 min, high power output
performance, and good cryogenic operation (down to 30 8C). This
type of SCiB has been applied in the i-MiEV (Mitsubishi innovative
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 69. The critical challenges for the wide application of Li4Ti5O12 as an anode for
LIBs.
electric vehicles) model by Mitsubishi Motors and used by Honda
in its EV-neo and Fit EV electric scooters [543].
5. Critical challenges and new directions
With the concerted efforts of worldwide researchers and
industry, the use of Li4Ti5O12 as an anode for LIBs has achieved
success even in practical application; however, it still faces several
critical challenges for truly wide application as shown in Fig. 69.
5.1. Low theoretical capacity
As mentioned in Section 2.2, the theoretical capacity of
Li4Ti5O12 is 175 mA h g1 with a typical end potential of 1.0 V.
As summarized in Section 3, the specific capacity of a Li4Ti5O12
anode could reach 160–170 mA h g1 and even the theoretical
capacity of 175 mA h g1 at a common rate (e.g., 1 C) by tailoring
the nanostructure, morphology, composite and defect chemistry.
However, the challenge is that the theoretical capacity of Li4Ti5O12
itself is low even compared with that of conventional graphite
anode (372 mA h g1) [8]. As mentioned in Section 2.2, a Li4Ti5O12
anode could deliver a significantly enhanced specific capacity with
an end potential lower than 0.5 V (e.g., 0.01 V). Importantly,
Li4Ti5O12 still demonstrates a near zero-strain character with a
lower end potential (i.e., 0 V) with only 0.4% lattice expansion
with 4.5 mol Li+ insertion according to theoretical calculations,
ensuring its structure stability within a potential range of 3.0–0 V.
Additionally, as summarized in Section 3.5, introducing a high
theoretical capacity anode (e.g., SnOx and MO) into Li4Ti5O12 to
form a composite anode operated within a potential range of 3.0–
0.01 V should also be an effective approach to further improve the
specific capacity; however, this approach will also cause the
problem that the added high theoretical capacity anode usually
faces, that is, large volume variation during lithium insertion/
extraction. In general, discharge to a lower end potential (e.g.,
0.01 V) results in an enhanced specific capacity for the Li4Ti5O12
anode that still demonstrates near zero-strain character; however,
this approach also causes other problems: (1) an SEI layer will form
on the surface of the Li4Ti5O12 anode due to electrolyte
decomposition; because SEI is an electronic insulator, this will
lead to a negative effect on the electrochemical performance; (2)
the electrolyte selection will become a problem again for
combination with a high operation potential cathode because
such an electrolyte usually appears to be unstable under 1.0 V; (3)
the advantage of flat charge/discharge plateaus will disappear
because the charge/discharge curves between 0.5 and 0.01 V
appear to be slope-shaped.
61
The above conventional approach focused on the Li4Ti5O12
material itself to improve its specific capacity. Changing the
thinking patterns to pay attention to the electrode design instead
of the material itself will be a novel research direction, that is,
improvement of the total electrode capacity instead of the specific
capacity of Li4Ti5O12 itself. For example, in a typical commercial
anode electrode, there is usually 20 mg cm2 of active material,
(15 wt.%/85 wt.%)  20 mg cm2 of conductive agent and binder,
and 10 mg cm2 of current collector (i.e., copper foil) [437]. The
capacity based on the total electrode weight will only be
104 mA h g1 calculated from the theoretical capacity of Li4Ti5O12
(175 mA h g1). By designing a novel additive-free electrode with a
lightweight current collector (e.g., 2 mg cm2), the total electrode
capacity could increase to 152% compared with that of the
conventional electrode. Additionally, using a 3D current collector
to replace the conventional 2D current collector could effectively
improve the current collection (Fig. 70) as well as the rate
capability and cycling performance. Several works are, or are
partially, consistent with this concept, such as Li4Ti5O12/graphene
foam electrode [244], flexible thin film electrode from Li4Ti5O12
nanosheets [245] as presented in Section 3.2.3 (thin-film electro-
des), and Li4Ti5O12/CNT film electrode with an areal mass density
of 0.3 mg cm2 for its CNT current collector [544]. These
electrodes demonstrated excellent electrochemical performance;
more importantly, these designs would significantly improve the
capacity of the total electrode as well as the gravimetric energy
density of the battery system. However, there are still several
challenges for their commercial application, such as large open
spaces inside the Li4Ti5O12/graphene foam electrode [244] that will
result in a low volumetric energy density, time-consuming
preparation process of flexible Li4Ti5O12 nanosheet film electrode
[245], and high cost for the methanol mediated floating catalyst
chemical vapor deposition of CNTs [544]. Thus, future work to
overcome the low theoretical capacity of Li4Ti5O12 could be
performed to focus on the novel electrode design instead of
discharge to lower potential. Furthermore, the film-related
properties (e.g., strength, repeated bendability, etc.), and prepara-
tion cost should also be evaluated.
5.2. Compromise between tap density and rate capability
The tap density is significant when an electrode material moves
from the lab to industry because it is directly related to the
volumetric energy density. The theoretical density of Li4Ti5O12 is
3.5 g cm3 [31,80,96,100]; a tap density of approximately half of
the theoretical density (i.e., 1.8 g cm3) remains very attractive for
commercial applications. As discussed in Section 3, Li4Ti5O12
materials with various nanostructures from 0D to 3D have been
designed and successfully synthesized. These advanced nanos-
tructures resulted in greatly enhanced electrochemical perfor-
mance compared with that of the conventional coarse particles.
Additionally, in the formation of a composite with a conductive
carbon substrate such as graphene, CNTs could also result in
improvement of the electrochemical performance of the Li4Ti5O12
anode. However, the above strategy usually introduces space (e.g.,
larger mesopores, micropores, and space between particles) into
the Li4Ti5O12 electrode material, leading to low tap density and
energy density. Thus, there is a compromise between the tap
density and rate capability (or power density). Alternatively, the
synthesis of microspheres or doping could achieve a high tap
density as well as high power density. For microspheres, good
control of the inner porosity is required to obtain a high tap
density. As mentioned in Section 3.2.2, a high tap density of
1.62 g cm3 with a surface area of 15.5 m2 g1 as well as
outstanding rate capability could be achieved for mesoporous
Li4Ti5O12 submicrospheres [190]. Compared with the formation of
62 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Fig. 70. Schematic description of paths for electron transport in the conventional Li4Ti5O12 + additive electrode and the novel Li4Ti5O12/3D carbon current collector electrode
[601].
microspheres, doping could be achieved using a facile solid-state
method, which remains most preferred for commercial applica-
tion. Importantly, the use of a solid-state method could easily
achieve a high tap density, and appropriate doping could improve
the electrochemical performance. For doping, a better understand-
ing of the mechanisms should be obtained; thus, researchers could
design and dope the proper element for required properties
instead of trying every element from the periodic table.
Additionally, co-doping is suggested based on its success in
ABO3 perovskite oxides. Treatment under a reducing atmosphere
during/after phase formation is also an affective approach to
achieve a high tap density and rate capability because it can also be
processed using a solid-state method.
Briefly, to achieve a high tap density for a wide range of
commercial applications of Li4Ti5O12 anodes, it is suggested that
future research should focus on the facile preparation of micro-
spheres and the mechanisms of doping, co-doping, and treatment
under reducing atmosphere as well as their effects on structural
stability instead of the development of hollow structures, high
porosity and nanostructures with high specific surface area to
improve the rate capability.
5.3. Poor performance at low temperatures
The ability to adapt to a wide range of operating temperatures is
significantly important for the practical application of Li4Ti5O12
anodes. As summarized in Section 2.3, lithium diffusion increases
with increasing temperature. The enhanced kinetic performance of
Li4Ti5O12 anodes at higher temperature [545] could result in
improved electrochemical performance compared with that at
room temperature. For the electrochemical performance of
Li4Ti5O12 anodes at elevated temperature, the problem should
be the stability of the electrolyte instead of the Li4Ti5O12 anode
itself. Thus, the low kinetic performance of the Li4Ti5O12 anode at
low temperature becomes a challenge for its commercial applica-
tion. Although numerous studies on the modification of Li4Ti5O12
anode have been performed, as described in Section 3, there are
relatively few reports on its low-temperature performance
[11,31,160,419,546–552]. Such kinetic performance at low tem-
perature is highly related to the lithium ion and electron transfer in
the electrode; enhancement of the lithium ion and/or electron
transfer could effectively result in enhanced low-temperature
performance. For instance, a smaller particle size could shorten the
diffusion length and offer more lithium insertion sites, which has
demonstrated improved low-temperature performance compared
with that of a Li4Ti5O12 anode with larger particle size
[31,546,552]. Approaches for enhancing electron transfer in the
electrode have also been reported to result in improved low-
temperature performance, such as the formation of Li4Ti5O12/
carbon [11,547], and carbon-coated Li4Ti5O12/graphene compo-
sites [419] and the use of a Cu/carbon composite as an conductive
additive instead of common carbon (i.e., Super P) [548]. Doped
Li4Ti5O12 (La0.06Li3.94Ti5O12) has also been reported to result in
good low-temperature performance with a reversible capacity of
118.3 mA h g1 at 0.1 C at a low temperature of 40 8C
[549]. Moreover, an impedance study suggested that the modifi-
cation of electrolyte-active material interfaces (e.g., optimization
of the electrolyte composition) may also result in enhancement of
the low-temperature performance because there is obvious
lithium ion transfer in the interface limiting process at lower
temperature [550].
There are few reports on the low-temperature performance of
battery systems based on Li4Ti5O12 anodes [475,552–554]. Recent-
ly, the low-temperature performance of a 18650 cell based on a
LiFePO4/carbon cathode and Li4Ti5O12/carbon anode was studied
[554]; even the electrochemical performance at 10 8C was
improved by using a low temperature electrolyte but it is still
not very attractive. Thus, further research on the low-temperature
performance of Li4Ti5O12 should be performed, such as a detailed
study of the mechanism and development of an effective approach
for improvement of the low-temperature performance. Impor-
tantly, when researchers attempt to improve the specific capacity
and tap density of the Li4Ti5O12 anode, the low-temperature
performance should also be considered simultaneously because
Li4Ti5O12 is no longer only a material studied only in the lab but a
material that is moving toward commercial application.
5.4. Gassing problem
For Li4Ti5O12 anode-based LIBs, gases (e.g., CO2, H2, CO) will
form during charge/discharge cycles and even during the storage
process, which lead to serious swelling and further safety issues
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
[555,556]. Thus, the gassing problem (especially at elevated
temperatures) is also a main obstacle for wide commercial
application of Li4Ti5O12 anodes. He et al. observed that the
formation of gases was mainly due to the reaction between
Li4Ti5O12 and the electrolyte; CO2 will be generated even by simply
soaking the electrode in electrolyte-free solvents, and H2 and CO
(with minor gaseous hydrocarbon, e.g., CH4, C2H4 and C2H6, etc.)
will further form during the charge/discharge cycles [556]. Wu
et al. tested the cycling performance of a () Li4Ti5O12-C j
electrolyte j LiNi1/3Co1/3Mn1/3O2 (+) soft-packed battery with 1 M
LiPF6 in EC, DMC and EMC (1:1:1 in wt.% ratio) as the electrolyte
and observed stable performance at 10 C with only 11% capacity
loss after 5000 cycles at 25 8C [557]. The graphite anode cells
exhibited inferior performance with 20% capacity loss after
1000 cycles at 25 8C. However, the Li4Ti5O12 anode cells exhibited
poor cycling performance at a high temperature of 55 8C because of
the gas generation (dominant gas: H2). These researchers further
studied the mechanism of swelling of the Li4Ti5O12 anode-based
battery system at elevated temperature and observed that the
gassing problem was mainly attributable to the high electrochem-
ical redox potential compared with graphite [489]. They indicated
that the H2 and soluble species should originate mainly from linear
carbonates; however, the gaseous alkylene and insoluble salts
were derived from cyclic carbonates. Guo et al. found that the
generated H2 and CO on the Li4Ti5O12 electrode might be highly
related to the (1 1 1) facet of Li4Ti5O12 phase based on comparative
experiments of XRD analysis, electrochemical testing and gas
chromatography [558]. Belharouak et al. proposed another
mechanism for H2 evolution in the Li4Ti5O12 anode-based battery
system, that is, H2 originated from moisture, whereas CO2 and CO
were suggested to be derived from the decomposition of the
electrolyte solution initiated by a strong Lewis acid (i.e., PF5)
[555]. Recently, on-line electrochemical mass spectrometry was
performed to investigate the gassing behavior to understand the
mechanism by Bernhard et al. [559], which supported Belharouak’s
hypothesis for H2 evolution. It was suggested that CO2 evolution
was due to a ring-opening reaction of alkyl carbonate caused by
OH from H2O. However, the effect of the addition of water (200,
1000 and 2000 ppm) to the electrolyte (1 M LiPF6 in EC: EMC) on
the Li4Ti5O12/LiCoO2 battery system was recently investigated by
Burns et al. [560]. These researchers concluded that no major
detrimental effects on the electrochemical performance were
observed in the presence of such amounts of water, suggesting
relaxed requirements on the stringent control of water in the
Li4Ti5O12/LiCoO2 battery system, which could further decrease the
cost of this system. Thus, the real mechanism for the gassing
problem remains unclear. Based on the above discussion, the main
reason for the gassing problem could be the reaction of the
electrolyte on the surface of Li4Ti5O12 or the presence of moisture.
Accordingly, the key to solving the gassing problem should be
avoiding the reaction between Li4Ti5O12 and the electrolyte (e.g.,
surface coating [556,561,562]), or maintaining low moisture
content in the battery system. He et al. observed that a suitable
nanoscale carbon coating along with a stable SEI film around
Li4Ti5O12 could effectively prevent the interfacial gassing reaction
[556]. Selecting a stable electrolyte is also important to obtain good
and stable performance for the Li4Ti5O12 anode, especially at
elevated temperatures. Zaghib et al. assembled and tested
Li4Ti5O12-C/LiFePO4-C batteries with different electrolytes
[563]. It was concluded that the cell with 0.5 M lithium
bis(trifluoromethanesulfonyl)imide (LiTFSI) + 1 M LiBF4 in an EC-
g-butyrolactone electrolyte could operate at least up to 60 8C, even
at a high rate (>10 C).
Along with the gassing problem, another topic of interest is
whether significant SEI formation occurs on a Li4Ti5O12 anode
when operated above 1.0 V. It is generally accepted that no SEI
63
layer will form on the surface of a Li4Ti5O12 anode operated above
1.0 V because the operation potential is above the reduction-
reaction/decomposition of the electrolyte solution. However, He
et al. observed an SEI layer on the surface of Li4Ti5O12 via ex situ
TEM and indicated that the formation mechanism for Li4Ti5O12 was
different from that for graphite [556]. The formation of the SEI
layer on the surface of Li4Ti5O12 was mainly due to the interfacial
reactions between the electrolyte solution and Li4Ti5O12 instead of
a reduction reaction of the electrolyte solution. Song et al. also
observed an SEI layer on the surface of Li4Ti5O12 with an operation
potential above 1.0 V via TEM as well as XPS analysis [564]. These
researchers further indicated that the conductive carbon in the
electrode aids in the formation of the SEI layer on Li4Ti5O12 and acts
as active sites for the SEI formation. These results suggest that an
SEI layer may form on the surface of Li4Ti5O12 with an operation
potential above 1.0 V beyond the general understanding. However,
these studies were based on ex situ methods; future works using in
situ characterization as well as powerful EIS analysis should be
performed to further understand whether an SEI layer exists as
well as the formation mechanism.
In summary, the mechanism involved in the gassing problem
remains unclear, and more detailed works should be performed to
understand the reason for the gassing problem and enable the
discovery of an effective strategy to address this issue.
5.5. Other applications in addition to electrode for LIBs
Because of the unique characteristics (e.g., zero-strain during
charge/discharge cycling), Li4Ti5O12 has also been used for other
purposes: as a coating layer to enhance the stability and
performance of other electrodes, as an electrode material for
rechargeable sodium-ion batteries, and as an electrode material for
hybrid supercapacitors.
5.5.1. As a coating layer to enhance the performance of other
electrodes
The use of Li4Ti5O12 in other anode materials to improve the
electrochemical performance has been discussed in Sections
3.5.3 and 3.5.5. In this section, we will briefly review the use of
Li4Ti5O12 as a coating layer to enhance the stability and
performance of other cathode materials.
Many cathode materials, especially Mn-containing cathode
materials, suffer from poor cycling performance, more so at elevated
temperatures. Take LiMn2O4 as an example, the poor cycling
performance is originated from the dissolution of Mn ions by as-
fromed HF acid, Jahn–Teller distortion, and decomposition of
electrolyte on the surface of the electrode [565]. Surface coating of
a proper material has been recognized as an effective approach to
improve the cycling performance of the cathode materials. Various
oxides, such as SiO2, Al2O3, and ZnO, have been studied as a coating
layer due to their easy preparation. In addition, lithium-containing
Li4Ti5O12 has been reported as a promising coating material for
cathodes, due to its zero-strain characteristic, and higher ion
conductivity compared to that of the conventional coating oxides.
Especially for a spinel cathode, a Li4Ti5O12 coating layer and cathode
could share the same spinel structure. Li4Ti5O12 has been reported as a
coating layer for LiCoO2 [566–568], LiMn2O4 [565,569,570], LiMn1.4-
Ni0.4Cr0.2O4 [571], LiNi0.5Mn1.5O4 [572,573], Li1.5Ni0.25Mn0.75O2.5
[574], LiNi1/3Co1/3Mn1/3O2 [575], and Li[Li0.2Mn0.54Ni0.13Co0.13]O2
[576] cathode materials to improve their electrochemical
performance. For example, with a 3 wt.% Li4Ti5O12 coating layer,
Li[Li0.2Mn0.54Ni0.13Co0.13]O2 electrode exhibited a stable cycling
performance with a specific capacity of 245 mA h g1 after 50
cycles at 25 mA g1 (capacity retention: 95%) compared to that of
uncoated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 electrode (specific capacity:
191 mA h g1 after 50 cycles; capacity retention: 74%) [576].
64 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Usually, Li4Ti5O12 coating is applied using a traditional sol–gel
process; however, it is difficult to produce a thin, uniform, robust,
and conformal coating layer. To further optimize the coating layer
to achieve a satisfactory electrochemical performance, other
techniques for synthesis of Li4Ti5O12 shown in Section 3 could
be adopted, such as solvothermal-assisted processing [570] etc.
Even though a Li4Ti5O12 coating is superior to a conventional oxide
coating, Li4Ti5O12 still suffer from its low electronic conductivity.
Thus, it may be necessary to enhance the electronic conductivity
and lithium-ion diffusivity of Li4Ti5O12, such as doping (Section
3.4), or surface treatment under a reducing environment (Section
3.3.3, part (2)) by a controllable process. A more ‘‘conductive’’
Li4Ti5O12 coating would be more effective in improving the cycling
stability and rate capability of the cathode materials.
5.5.2. As an electrode material for rechargeable sodium-ion batteries
Since the physical and chemical properties of sodium are
similar to those of lithium while sodium salts are less expensive than
lithium salts, rechargeable sodium-ion batteries have received
extensive attention for various applications. Many electrode
materials for LIBs have been modified for use in sodium-ion
batteries, including Li4Ti5O12. By using Li4Ti5O12 as an anode for
sodium-ion batteries, charge/discharge potential plateaus between
0.7 and 1.0 V vs. Na/Na+ was demonstrated and a reversible specific
capacity of 145–155 mA h g1 could be achieved [577–580]. The
potential plateaus are lower and the reversible specific capacity is
comparable to that of Li4Ti5O12 anode in a LIB. Even though it was
reported that 3 mol Na+ could be inserted into a Li4Ti5O12 unit, the
mechanism was very different from that in LIBs; a three-phase
separation mechanism has been proposed with formation of
Li7Ti5O12 and Na6LiTi5O12 after Na-ion insertion, which has been
confirmed by density functional theory calculations, in situ
synchrotron X-ray diffraction, and scanning transmission electron
microscope imaging techniques [578,579]. It was further proposed
that during the Na+ insertion process, the inserted Na+ will occupy
the vacancy of 16c site and Li+ at 8a site will be driven into 16c site; a
lattice volume expansion of 12.5% was found for the formation of
Na6LiTi5O12 phase and the lattice volume expansion should be 6.3%
based on the Li7Ti5O12 and Na6LiTi5O12 two phases since the process
from Li4Ti5O12 to Li7Ti5O12 is zero-strain [578]. Thus, in the case for
sodium-ion batteries, Li4Ti5O12 is no longer a zero-strain material
but is still attractive due to its low volume expansion during Na+
insertion/extraction.
To date, several strategies have been adopt to improve the
electrochemical performance, such as synthesis of Li4Ti5O12
nanorods [581], hierarchically porous Li4Ti5O12 [170], Li4Ti5O12
nanoparticles embedded in carbon nanofibers [152], carbon-
coated Li4Ti5O12 nanowires [582], carbon-nanotube decorated
Li4Ti5O12 nanoparticles embedded in carbon nanofibers [583], and
copper-doped Li4Ti5O12/carbon nanofiber [584]. Even though an
improved electrochemical performance was demonstrated, the
rate capability is still unsatisfactory compared to that in LIBs.
Typically, the specific capacity will decrease to <120 mA h g1 at
1 C rate as an anode for sodium-ion batteries, and even
<50 mA h g1 at 10 C rate [170]. Thus, future work could focus
on using a combination of several effective strategies (as discussed
in Section 3) to improve the electrochemical performance of
Li4Ti5O12 as an anode for sodium-ion batteries based on further
understanding of the insertion/extraction mechanism.
5.5.3. As an electrode material for hybrid supercapacitors
In a typical hybrid supercapacitor, a non-faradaic capacitive
storage material (e.g., activated carbon) is used as an electrode to
combined with a faradaic intercalation material electrode
[477,585]. Because of the stable structure during insertion/
extraction processes, good rate capability, and low voltage with
respect to standard hydrogen electrode (1 V vs. SHE), nanostruc-
tured Li4Ti5O12 is considered an ideal material as the negative
electrode for hybrid supercapacitors [477,586]. For example, a
Li4Ti5O12/activated carbon couple with a typical nonaqueous
electrolyte (e.g., LiPF6 in EC/DMC) could exhibit a sloping voltage
profile from 3.0 to 1.5 V, 90% capacity utilization at 10 C rates, and
85–90% capacity retention after 5000 cycles [477]. The widened
operation voltage window has been reported to be 3.0–1.0 V [587],
and even 3.0–0.0 V [588]. The energy density of such a hybrid
supercapacitor depends sensitively on the property of the carbon
positive electrode material and cell operation voltage, whereas the
power density is determined primarily by the properties of
Li4Ti5O12. As reported by Amatucci et al. in 2001, such a hybrid
supercapacitor based on the Li4Ti5O12/carbon couple is no longer a
novel research topic, but it could bridge the gap in energy and
power densities between electrical double-layer capacitors and
LIBs, which has attracted more interest during the past five years.
Besides the development of novel positive electrodes and
electrolytes, various Li4Ti5O12-based materials have been reported
for superior hybrid supercapacitor with improved properties, such
as Li4Ti5O12 nanoparticles [589], doped Li4Ti5O12 [590], Li4Ti5O12
spheres [591], Li4Ti5O12 nanowire array [592], Li4Ti5O12/carbon
nanofibers [150,155,593], Li4Ti5O12/carbon composite [594–596],
Li4Ti5O12/carbon hybrid nanotubes [597] and Li4Ti5O12/graphene
[588,598,599]. However, the combination of more than one
strategies to enhance the performance of Li4Ti5O12 is yet rarely
reported, such as doped Li4Ti5O12 on a carbon substrate. In fact, all
the strategies as summarized in Section 3 could applied to further
improve the property of Li4Ti5O12 in a hybrid supercapacitor.
6. Conclusions and perspectives
Carbon/graphite is the state-of-the-art anodic material for LIBs
and has had great success in the portable electronics sector. For
two newly emerging fields, electrochemical energy storage and
electric vehicles (including pure EVs, HEVs, and PHEVs), the
carbon/graphite anode does not meet the safety and rate
performance requirements. Spinel Li4Ti5O12 is a promising
alternative to the carbon/graphite anode given its outstanding
safety originating from its high lithium intercalation voltage and
potentially long cycling stability, its zero-strain character and its
high thermal stability. However, the poor electronic conductivity
of Li4Ti5O12 limits its rate capability. To overcome this problem,
many strategies have been developed and some progress has been
made. To realize large-scale commercial application of Li4Ti5O12 in
LIBs, however, significant scientific and technological advances
must still be made.
During the past several years, considerable attention has been
devoted to improving the rate capability and cycling stability of
Li4Ti5O12. However, many of the technologies developed are too
complicated to be cost-effective. Nanostructuring is widely applied
and highly effective at improving the rate performance; however,
it may increase the reactivity with liquid electrolytes and adversely
affect the cycling stability. In commercial LIBs, the electrodes are
on the micrometer scale. Recently, we proposed a new concept for
the development of a Li4Ti5O12-based electrode by forming a
composite with a solid lithium-ion conductor, lithium lanthanum
titanate perovskite [600]. By introducing a lithium-ion conducting
electrolyte as the second phase to form a composite electrode, the
apparent lithium-ion conductivity of the electrode is substantially
improved. In addition, rich two-phase boundaries are created,
resulting in high electrode performance, in particular improved
rate performance, even for micrometer-sized electrodes that are
dense in nature, which ensures a low electrode–liquid electrolyte
interface area for reducing side reactions and ensuring high
cycling stability. This method provides a new way to develop a
 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71
Li4Ti5O12-based electrode for high power batteries; thus, it is worth
further investigation. Historically, researchers have attempted to
synthesize phase-pure Li4Ti5O12 by applying excessive lithium to
compensate for the lithium loss during the high-temperature
calcination. Recently, the presence of TiO2 as an impurity phase
was found to be beneficial for improving the capacity and rate
performance. The individual phase also performs as a diffusion
block for the other phase, thus increasing its thermal stability. The
rutile TiO2 phase become electrochemically active in the compos-
ite, and the discharge platform of rutile TiO2 and Li4Ti5O12 merged
to extend the platform capacity. Therefore, Li4Ti5O12-based
composite electrodes are of great interest and require future
research. For future work on the Li4Ti5O12 anodes, a combination of
two or more effective strategies (e.g., nanostructuring, carbon-
coating, doping, and electrode designing etc.) is suggested to
address the critical challenges simultaneously.
Since energy density of a battery is directly proportional to its
cell voltage, research continues to develop a cathode with high
lithium intercalation potential (e.g., 5 V Li2Co0.4Fe0.4Mn3.2O8) to
match the high potential of Li4Ti5O12 anode. However, such a high
voltage introduces a great challenge for developing a proper
electrolyte solution with sufficiently wide potential window. On
the other hand, if the intercalation potential of the Li4Ti5O12 could
be lowered, it would effectively improve the energy density of the
batteries. For example, Cr-doping was reported to reduce the
platform voltage of Li4Ti5O12 by approximately 50 mV. However,
little research has been conducted on this subject to date. Most
doping has been conducted using a single dopant. Co-doping is
seldomly investigated, which may yield a synergistic effect on the
cell performance and the lithium intercalation voltage; thus, it is
worthy of future research.
Because of the high intercalation voltage of Li4Ti5O12, a cathode
with a high intercalation voltage should be developed for
application as a power source in pure electric vehicles to ensure
sufficiently high energy and power densities. However, for
applications where rate capability and cycling lifetime are more
important than energy density such as power sources for hybrid
vehicles or energy storage devices for load-leveling in smart grids,
batteries consisting of Li4Ti5O12 combined with a normal cathode
may still be one of the best options.
Acknowledgements
This work was partially supported by US National Science
Foundation under award number DMR-1410320, National Science
Foundation for Distinguished Young Scholars of China under
contract No. 51025209, Outstanding Young Scholar Grant at
Jiangsu Province under contract No. 2008023, National Natural
Science Foundation of China under contract No. 21103089, and the
Key Projects in Nature Science Foundation of Jiangsu Province
under contract No. BK2011030. Dr. Zongping Shao also acknowl-
edges ARC future fellowship.
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Bote Zhao is currently a postdoctoral fellow at the
School of Materials Science and Engineering at Georgia
Institute of Technology, USA. He received his B.S. and
Ph.D. from Nanjing Tech University, China. His research
Glossary
experiences include work with binder-free films,
Acronyms nanostructured materials and graphene-based materi-
als for lithium-ion batteries and supercapacitors as well
as the electrospinning synthesis of fibers, fabrication
1D: one-dimensional and water management of proton exchange membrane
2D: two-dimensional fuel cells, and hydrogen production from hydrous
3D: three-dimensional hydrazine. He is currently focusing on the synthesis
3DOM: three-dimensionally ordered macroporous and characterization of novel materials for batteries,
AFM: atomic force microscopy fuel cells, and supercapacitors.
BET: Brunauer–Emmett–Teller
CA: citric acid
CNTs: carbon nanotubes
CTAB: cetyltrimethylammonium bromide Ran Ran is an associate professor of Nanjing Tech
DMC: dimethyl carbonate University. She received her Ph.D. from Dalian Institute
DMA: dimethyl acetamide of Chemical Physics, Chinese Academy of Sciences, in
DMMP: dimethylphosphonate 2003. She was a visiting scholar of Petroleum Institute
EC: ethylene carbonate of Catalysis Madrid, Spain. She joined the college of
EDX: energy-dispersive X-ray spectroscopy chemistry and chemical engineering in Nanjing Tech
EG: ethylene glycol University in 2005. The main research fields: electrode
EIS: electrochemical impedance spectroscopy materials of lithium-ion batteries, hydrogen production
EMC: ethylmethyl carbonate process from hydrocarbon, anode coating catalyst of
EMIm-dca: 1-ethyl-3-methylimidazolium dicyanamide solid oxide fuel cells.
EPR: electron paramagnetic resonance
EVs: electric vehicles
FE-SEM: field-emission SEM
FRL: Friedman–Reich–Levi
FWO: Flynn–Wall–Ozawa Meilin Liu is a Regents’ Professor of Materials Science
GPE: gel polymer electrolyte and Engineering and Co-Director of the Center for
HEBM: high energy ball milling Innovative Fuel Cell and Battery Technologies at Georgia
HEVs: hybrid electric vehicles Institute of Technology, Atlanta, Georgia, USA. He
HFP: hexafluoropropylene received his BS from South China University of Technol-
HR-TEM: high resolution transmission electron microscopy ogy and both MS and Ph.D. from University of California
ICP-AES: Inductively coupled plasma atomic emission spectrometry at Berkeley. His research interests include in situ/
LiAc: lithium acetate operando characterization and multi-scale modeling of
LIBs: lithium-ion batteries charge and mass transfer along surfaces, across inter-
LiDFOB: lithium difluoro(oxalato)borate faces, and in membranes, thin films, and nanostructured
LiTFSI: lithium bis(trifluoromethanesulfonyl)imide electrodes, aiming at achieving rational design of
MA: maleic acid materials and structures with unique functionalities
MASNMR: magic-angle spinning nuclear magnetic resonance for efficient energy storage and conversion.
MiEV: Mitsubishi innovative electric vehicles
MWCNTs: multi-wall carbon nanotubes
NMR: nuclear magnetic resonance
P123: HO(CH2CH2O)20(CH2CH(CH3)O)70(CH2CH2O)20H Zongping Shao earned his Ph.D. from Dalian Institute
PAA: polyacrylate acid of Chemical Physics, Chinese Academy of Sciences, in
PAN: polyacrylonitrile 2000. He worked as a postdoc from 2002 to 2005 in
PANI: polyaniline California Institute of Technology, USA. He joined the
PEDOT: poly (3,4-ethylenedioxythiophene) college of chemistry and chemical engineering in
PEG: polyethylene glycol Nanjing Tech University in 2005, where he was
PHEVs: plug-in hybrid electric vehicles promoted to professor. Since then he is the director
PS: polystyrene of institute of new energy materials and technology. His
PVA: polyvinyl alcohol research interests include lithium-ion batteries, super-
PVB: polyvinyl butyral capacitors, solid oxide fuel cells, oxygen permeable
PVDF: polyvinylidene fluoride membranes and polymer electrolyte membrane fuel
SCiB: super charge/discharge ion battery cells. He has published over 300 international journal
SEI: solid electrolyte interface papers with a total citation of >9000.