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Environmental Science
Cite this: Energy Environ. Sci., 2011, 4, 56
www.rsc.org/ees REVIEW
Nanostructured silicon for high capacity lithium battery anodes
Jeannine R. Szczech* and Song Jin*
Received 19th July 2010, Accepted 21st October 2010
DOI: 10.1039/c0ee00281j

Nanostructured silicon is promising for high capacity anodes in lithium batteries. The specific capacity of
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silicon is an order of magnitude higher than that of conventional graphite anodes, but the large volume
change of silicon during lithiation and delithiation and the resulting poor cyclability has prevented its
commercial application. This challenge could potentially be overcome by silicon nanostructures that can
provide facile strain relaxation to prevent electrode pulverization, maintain effective electrical contact,
and have the additional benefits of short lithium diffusion distances and enhanced mass transport. In this
review, we present an overview of rechargeable lithium batteries and the challenges and opportunities for
silicon anodes, then survey the performance of various morphologies of nanostructured silicon (thin film,
nanowires/nanotubes, nanoparticles, and mesoporous materials) and their nanocomposites. Other
factors that affect the performance of nanostructured silicon anodes, including solvent composition,
additives, binders, and substrates, are also examined. Finally, we summarize the key lessons from the
successes so far and offer perspectives and future challenges to enable the applications of silicon
nanoanodes in practical lithium batteries at large scale.

1. Introduction vehicles and power storage to accommodate the intermittent

Lithium ion secondary batteries are attractive energy storage
devices with high gravimetric and volumetric capacity and the
ability to deliver high rates of power.19 They have become
ubiquitous power sources for mobile applications such as
personal electronics and laptop computers, but current lithium
battery technology cannot meet the ever increasing power
requirements for applications such as electric and hybrid electric
Department of Chemistry, University of WisconsinMadison, 1101
University Avenue, Madison, Wisconsin, 53706, USA. Web: jin.chem.
wisc.edu. E-mail: szczech@chem.wisc.edu; jin@chem.wisc.edu
Electronic supplementary information (ESI) available: Data Tables
summarizing the morphology, composition, and method of preparation
of those nanoscale and nanostructured silicon anodes reported in the
recent literature, along with their electrochemical performance. See
DOI: 10.1039/c0ee00281j
nature of certain renewable energy sources. This has spurred
intense interest in developing high gravimetric and volumetric
capacity battery electrodes to surpass the energy density of the
current generation of lithium batteries. Significant research
challenges and opportunities exist for all aspects of battery
materials:2,5 cathode, anode, electrolyte, and separators. We will
focus on the anode materials in this discussion.
Based on energy density considerations, lithium metal is the
best anode material. However, the electroplating of dendritic
lithium during charging can lead to short circuit, posing severe
safety concerns for lithium metal anodes. The most frequently
used material for commercial secondary lithium ion battery
anodes is graphite, in which a maximum of one lithium can
intercalate for every six carbon atoms.10 The volumetric expan-
sion during lithium intercalation between the planar graphite
layers is just over 10%, resulting in high reversibility and stable

Broader context
Rechargeable lithium batteries have become the ubiquitous power source for portable electronics such as cell phones and laptop
computers. They may soon find widespread usage in hybrid and electric vehicles and become an important part of the energy storage
solutions in renewable energy technologies. To meet the ever increasing power requirements of these applications, new electrode
materials are needed to increase the energy density beyond currently available lithium batteries. Although silicon anode materials are
known to have high lithium storage capacity, they cannot be used in their bulk form due to the extreme structural degradation that
occurs during use. This challenge may be overcome by utilizing nanostructures, such as thin films, nanowires or nanotubes, and
nanoparticles, which are more resistant to structural degradation by virtue of their small nanoscale sizes. In this review, we survey the
impressive progresses recently made in this active research area, describe the pressing issues currently facing nanostructured silicon
electrodes, and discuss how these challenges may be overcome.

56 | Energy Environ. Sci., 2011, 4, 5672 This journal is The Royal Society of Chemistry 2011

capacity over repeated cycling.11 Nonetheless, the theoretical
capacity of graphite (372 mAhg1) is low compared to other
possible anode materials, such as the lithium alloys of silicon or
tin, limiting the power density. Development of high capacity
anodes capable of sustaining high power rates is therefore
necessary.
Silicon is a promising high capacity alternative to graphite
anodes. It has a low discharge potential ( 370 mV vs. Li/Li+),12
which makes it suitable for high-power applications when paired
with common cathode materials such as LiCoO2 or LiMn2O4. It
is abundant and non-toxic, and can be alloyed with up to 4.4
lithium atoms per silicon atom to create an alloy with high
electrochemical capacity.13 The theoretical capacity of the fully
lithiated alloy Li4.4Si is 4212 mAhg1, an order of magnitude
higher than graphite. Similar to graphite, silicon exhibits a long
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plateau over much of its discharge curve, providing a stable
voltage during cycling, and silicon does not suffer from solvent
co-intercalation, presenting an additional advantage over
graphite.14
However, the commercial use of silicon in lithium cells has
been limited by the low cycling stability of bulk silicon. The large
volume change (> 300%)15 during lithiation leads to high internal
stress, electrode pulverization and subsequent loss of electrical
contact between the active material and current collector, leading
to poor reversibility and rapidly declining capacity. Moving from
bulk to nanoscale morphologies has the potential to solve this
limitation by managing the large stresses associated with the
expansion and contraction of alloy anodes during electro-
chemical alloying. This potential is being explored by academic
and commercial researchers alike; in recent years, the number of
patents granted for Si or Si-based composite electrodes with
nanostructured morphologies has increased markedly.1629
A number of nanoscale morphologies have been investigated
to minimize electrode pulverization and capacity loss in silicon
anodes, including thin films,13,3053 nanowires and nanotubes,5467
and nanoparticles.61,68114 These morphologies improve cycling
stability by minimizing the total volumetric expansion, incor-
porating pores or voids to accommodate expansion, or by
exploiting high surface-to-volume ratios to manage material
stress.57 Nanostructured materials also offer other benefits,
Jeannine Szczech studied chem-
istry at the University of WI
Madison, graduating with a B.S.
degree in 2005. She remained at
the UWMadison to continue
her studies in the Song Jin
research group, earning a Ph.D.
in Materials Chemistry in 2010.
Her research interests include
nanoscale materials with appli-
cations in thermoelectric and
electrochemical devices.
Jeannine R: Szczech
This journal is The Royal Society of Chemistry 2011
View Article Online
including short lithium diffusion distances within the electrode,
high rate capability due to the large surface area, and enhanced
diffusion along surfaces and grain boundaries.
Nanostructured silicon anodes face some important challenges
as well. High surface-to-volume ratios can facilitate efficient
transfer of lithium from the solvent to the active material to
achieve high rates, but the potential for uncontrolled reaction
and thermal runaway is greater for high surface area electrodes.
Although there have not yet been reports in the literature to
suggest thermal runaway in nanostructured silicon anodes poses
a serious problem, morphological optimization to achieve
a balance between high rates and safety is needed. The high
surface area of nanostructured electrodes may also present
a challenge for limiting irreversible capacity (the difference
between the charge and discharge capacity) caused by formation
of a passivation layer, or solid electrolyte interface (SEI) layer,
on the electrode surface. High irreversible capacities have been
reported for silicon anodes, thus the formation of a stable self-
limiting SEI layer is expected to be a formidable challenge.
In this review, we will first present a broad overview of
secondary (rechargeable) lithium batteries and explain the basic
operation of a secondary lithium battery. Then we will detail
the advantages of using nanostructured silicon as the anode and
the challenges that must be overcome before it can be used as the
anode in a practical cell. A survey of recent work in this area will
follow, and additional factors that can negatively impact elec-
trode performance will be presented. Unless otherwise noted, all
cycling capacities discussed herein are reported as the specific
delithiation capacity of the active material (either pure Si or a Si-
based nanocomposite).
2. Lithium battery operation and challenges for
silicon anodes
Lithium batteries consist of one or more electrochemical cells
connected in parallel or in series to obtain the desired current and
voltage characteristics, comprised of a positive electrode (the
cathode) and a negative electrode (the anode), which are sepa-
rated from one another by a lithium ion permeable membrane,
and an electrolyte that conducts lithium ions. Fig. 1 shows
Song Jin received his B.S. from
Peking University in 1997 and his
Ph.D. from Cornell University in
2002. He has been at the Univer-
sity of Wisconsin-Madison since
2004 and is currently an associate
professor of chemistry. He is
interested in the chemistry and
physics of nanomaterials. Dr Jin
studies the fundamental formation
mechanisms of nanowires, their
novel physical properties, and
applications in renewable energy
Song Jin such as photovoltaic and thermo-
electric energy conversion, and
energy storage.
Energy Environ. Sci., 2011, 4, 5672 | 57

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Fig. 1 Schematic of a lithium battery containing a silicon anode and
lithium metal oxide cathode during a) charging and b) discharging.
a schematic of a lithium battery with a silicon anode and
a lithium metal oxide (LiMxOy) intercalation cathode. The anode
and cathode are connected through an external circuit. During
charging (Fig. 1a), electrons driven by an external power source
flow from the cathode (LiMxOy) through the external circuit to
the anode (silicon), while lithium ions deintercalate from the
cathode and move through the electrolyte to the anode to
maintain charge neutrality. As lithium ions are alloyed with
silicon, the anode expands until it has reached the desired state of
charge. Discharging is simply the reverse of this process (Fig. 1b).
The anode undergoes volume contraction as lithium ions are
liberated. The ions shuttle back through the electrolyte and
undergo insertion at the cathode, while electrons move towards
the cathode through the external circuit, performing useful work
in the process.
The open circuit voltage (VOC) represents the voltage between
the two terminals when a load is not connected and is propor-
tional to the difference between the cathode and anode electro-
 m  manode 
chemical potentials VOC cathode , where F is the
F
Faraday constant. VOC is typically close to 34 V in lithium cells.
2.1 Electrolytes and SEI formation
A mixture of aprotic organic solvents is typically used in
commercial lithium batteries, including cyclic and linear alkyl
carbonates such as ethylene carbonate (EC), dimethyl carbonate
(DMC), diethyl carbonate (DEC), ethyl methyl carbonate
(EMC), and propylene carbonate (PC). The solvent composition
is chosen to achieve a balance between viscosity, the ability of the
solvent to form a stable passivation layer, and sufficiently high
58 | Energy Environ. Sci., 2011, 4, 5672
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dielectric constant to dissolve lithium salts such as lithium hex-
afluorophosphate (LiPF6) or lithium perchlorate (LiClO4). The
operating potential of the anode in lithium cells is close to the
potential of metallic lithium, which lies outside of the thermo-
dynamic stability region of organic electrolytes. Hence, the
electrolyte solution undergoes electrochemical decomposition
resulting in the formation of a passivating SEI layer, which
inhibits electron transfer between the electrolyte and electrode,
and provides kinetic stability outside of the solvent potential
window.115
Well-formed SEI layers are impermeable to the solvent, but
allow migration of lithium ions between the solvent and active
material. The SEI layer is thus self-limiting when electrode
expansion is minimized. Nonetheless, exposure of fresh active
material from electrode expansion during cycling encourages
continual SEI growth and irreversible capacity loss. This is
a difficult challenge to overcome in intermetallic alloy anodes,
because the SEI layer does not undergo a similar expansion and
cracking of the SEI layer can be severe.97 To minimize capacity
loss, a uniform SEI layer should form during the first charge
cycle and heal quickly from any cracking that may occur from
expansion mismatches during lithiation/delithiation.116
The composition of the SEI layer, which contains electrolyte
decomposition products in addition to products from side reac-
tions between the electrolyte and active material, is important
because it influences the kinetics of lithium ion transfer between
the electrolyte and the electrode and thus the achievable rate of
charge and discharge. If the SEI layer hinders mass transport,
electrode polarization will increase, lowering the power density.
The SEI layer on silicon electrodes in alkyl carbonate electrolytes
typically consists of a heterogeneous mosaic of compounds
including poly(ethylene) oxides (-[CH2-CH2-O]n-) (PEO), lithium
alkyl carbonates (ROCO2Li), lithium alkoxides (ROLi), lithium
carbonate (Li2CO3), lithium oxide (Li2O), and lithium fluoride
(LiF), in addition to fluorinated carbon or silicon
species.50,78,117,118 The composition differs slightly on silicon
electrodes coated with carbon, to instead contain primarily
siloxanes (-[SiORR0 ]n-), PEOs, ROCO2Li, ROLi, Li2CO3, and
LiF.78
2.2 Challenges for silicon anodes
Unlike intercalation electrodes, such as graphite anodes and
LiMxOy cathodes, intermetallic alloy electrodes experience large
volume changes during lithiation and delithiation and may go
through multiple crystallographic phase transitions, which
shortens the cycle life and contributes to cell failure. According
to the Li-Si phase diagram, four crystalline Li-Si phases exist:
Li12Si7, Li7Si3, Li13Si4, and Li22Si5.119 Peaks in the polarization
curve during lithiation of silicon are frequently assigned to these
phases, and some evidence exists to indicate these phases may be
formed during electrochemical cycling.66,120 In many cases,
a single long voltage plateau is observed near 100 mV (vs. Li/Li+)
during cathodic polarization, suggesting continual lithiation of
an amorphous alloy rather than sequential formation of distinct
lithium silicide phases.121123 When silicon electrodes are charged
to below 50 mV (vs. Li/Li+), a peak in the differential capacity
curve due to the formation of a crystalline Li15Si4 phase has been
reported.124
This journal is The Royal Society of Chemistry 2011

In many cases, the initial charge capacity of both pure silicon
and silicon composite anodes is near the theoretical capacity. An
irreversible capacity loss due to SEI formation is seen in the first
cycle, followed by more stable cycling with little capacity fade if
mechanical fracture of the electrode can be avoided. Irreversible
capacity loss is clearly tied to the degree of expansion during
lithiation. Electrode pulverization during cycling can cause
lithium trapping in the active material, loss of electrical contact,
and progressive consumption of active material resulting from
continual electrolyte exposure during expansion and contraction
during cycling, all of which contribute to low Coulombic effi-
ciency.
The crystallinity of pristine silicon anodes changes markedly
after a single charge/discharge cycle. During the first lithiation
cycle, crystalline silicon undergoes a phase transition to produce
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an amorphous alloy.125 Because amorphous materials experience
isotropic material stress during volumetric changes, formation of
an amorphous phase is beneficial for reducing the risk of stress
fracture during electrochemical alloying. Therefore, by limiting
the upper and lower voltage cut-offs, the amorphous-to-crys-
talline transitions can be avoided, increasing the reversibility and
capacity of alloy electrodes.122124 The depth of charge/discharge
can additionally be controlled to limit the degree of lithiation and
volumetric growth and thus mitigate electrode pulverization and
delamination. These tactics have been successful in extending the
cycle life of intermetallic alloy anodes, but comes at the cost of
limiting the capacity. The use of inactive matrixes to buffer
volume expansion and adding conductive additives can enhance
cycling stability, but the presence of inactive material also
decreases the energy density. Nevertheless, lowering the capacity
to improve reversibility and cycle lifetime may be an acceptable
trade-off, since it is the total battery capacity rather than the
capacity of the anode alone that determines the energy density of
the battery. The cell specific capacity (neglecting the weight
contribution of the inactive components of the battery) can be
calculated1 based on the specific capacity of the anode and
cathode materials. The effect of anode capacity on energy density
is illustrated in Fig. 2, which shows the theoretical capacity of
Fig. 2 Theoretical cell specific capacity as a function of the anode
specific capacity, considering only the active silicon (anode) and LiCoO2
(cathode) masses.
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a hypothetical cell comprised of a Si anode and LiCoO2 cathode
(the theoretical capacity of LiCoO2 is 147 mAhg1) based on only
the active anode and cathode materials. The cell specific capacity
increases as the anode specific capacity increases until the latter
reaches about 2000 mAhg1, after which cell capacity gains from
further increasing the anode capacity level off. Thus, in the
absence of significant improvement in cathode capacity, limiting
the anode capacity to improve cycle life and stability will not
appreciably reduce overall cell capacity.
3. Advantages of nanostructured or nanoscale
electrodes
Nanostructured or nanoscale electrodes can be engineered with
morphologies such as nanowire arrays or ordered mesoporous
structures to provide the necessary volume of free space to
accommodate expansion during alloying, thus minimizing
material stress and electrode pulverization to achieve greater
reversibility and cycling stability.4,79 The nature of the stress
experienced by the active material during lithiation/delithiation is
seen to depend on morphology. Thin silicon films, which can
have strong adhesion to the substrate, have been shown to
undergo anisotropic volume changes.30,36 Particles, on the other
hand, are not constrained by substrate adhesion and therefore
expand isotropically.108
Nanoscale dimensions allow quick relaxation of stress, making
nanoparticles more resistant to fracture than bulk particles.
Comparison of the calculated misfit stress energy in partially
delithiated particles (consisting of a lithiated core and delithiated
shell) suggests fracture should not occur during cycling for
particles having diameters of 10 nm or less.126 Other calculations
focusing on the Li-Sn system, which undergoes a similar volume
expansion during electrochemical alloying, suggest that particles
with diameters less than 200 nm will resist fracture.127 Indeed,
a reduction in particle diameter is correlated with an increase in
cycling stability. For example, LixSn alloys with particle
diameters ranging from 200400 nm have been shown to resist
fracture and demonstrate improved Coulombic efficiency
compared to larger micron sized particles.88 Because both silicon
and tin experience similar volumetric changes during lithiation, it
can be expected that comparable improvements are possible for
nanocrystalline Si anodes.
The use of nanoscale morphologies may also enhance the rate
capability and specific capacity. As expected, the capacity of
silicon electrodes decreases at high charge/discharge rates, due to
low lithium ionic conductivity in silicon and sluggish mass
transfer at the electrode interface.5 By reducing electrode
dimensionality to increase the surface-to-volume ratio and
provide shorter lithium diffusion distances, electrode polariza-
tion may be reduced, allowing high capacities to be realized. For
emerging high capacity mobile energy storage applications (such
as in plug-in electrical vehicles), the volumetric capacity is
increasingly more important than the gravimetric capacity, as
space is at premium when the total power demand is high.
However, it is difficult to determine typical volumetric capacities
of reported nanostructured silicon anodes, as so far very few
published reports clearly state the volumetric capacity, instead
favoring gravimetric capacity. To fully evaluate the potential
advantages of nanostructured silicon anodes over conventional
Energy Environ. Sci., 2011, 4, 5672 | 59

graphite in mobile applications, it will be useful to closely
examine this metrics for comparison.
The capacity, reversibility, and cycling life can vary widely
between nanostructured or nanoscale silicon anodes with similar
morphology and particle size. These differences likely result from
differences in reported synthesis; binder, additive and electrolyte
composition; the ratio of active material, conductive additives
and binder; processing parameters such as vacuum drying,
annealing, and hydraulic pressing; and the depth of charge/
discharge, voltage cut-offs, and charge/discharge rates during
cycling. The wide variation in electrochemical performance
reported for a given morphology makes it difficult to categori-
cally state that any particular morphology is superior; hence, the
focus of the survey section will be on general trends that emerge,
along with some representative data.
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3.1 Nanostructure morphologiesthin films
Thin silicon films have demonstrated the highest capacities and
longest cycle lives due to the small amount of active material
limiting total volumetric expansion. The performance of thin
films improves as film thickness decreases, consistent with the
Griffith-Irwin relation, which states that the critical fracture
stress increases as film thickness decreases:126,127
K with 150 nm n-type films showing a lower reversible capacity
sfracture p (1)
pd
where sfracture is the critical fracture stress, K is the fracture
toughness of the material, and d is the film thickness.
The volumetric expansion during lithiation of thin films has
been shown to occur anisotropically, with expansion occurring
perpendicular to the film surface.30 On the other hand, contrac-
tion during delithiation occurs both perpendicular to and in
plane with the substrate, leading to cracking of the film after the
first discharge cycle. Scanning electron and optical microscope
observation of electrochemically cycled thin films reveals that the
cracked films, which form islands resembling mudflats, remain
attached to the substrate after delithiation.30,32 Fig. 3 shows the
morphology of a thin silicon film after lithiation and delithia-
tion.30 The copper substrate is visible through the larger cracks,
and many smaller cracks can be seen in the film. Following the
initial fracture, the active material can be cycled without
Fig. 3 Optical micrograph of a cracked thin silicon film after lithiation
and delithiation. Reproduced from Ref. 30 by permission of the Elec-
trochemical Society.
60 | Energy Environ. Sci., 2011, 4, 5672
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additional film cracking, and in optimized anodes capacity loss
after the first cycle is limited because electrical contact between
the active material and the current collector is maintained.
The main limitation of thin film electrodes derives from the
small mass of active material and the resultant low cell capacity.
Nonetheless, silicon thin film anodes have demonstrated that
high capacities using silicon anodes are possible if we can manage
material stress during cycling.
3.1.1 Silicon thin films. Silicon films with thicknesses of
50 nm or less exhibit the best reversibility and highest capacities.
Amorphous n-type silicon films with a thickness of 50 nm
vacuum deposited onto nickel substrates exhibited an initial
capacity of approximately 3750 mAhg1 (Fig. 4), and a reversible
capacity near 3800 mAhg1 after 200 cycles at 1C.13 (Charge rates
are typically given in terms of the fraction of the theoretical
capacity that can be charged over a period of one hour per gram
of active material at a given charge current. For example, a rate
of 1C corresponds to a charge current of 4.2 A per gram of
silicon, and a rate of C/5 corresponds to a charge current of 0.84
A per gram of silicon). These amorphous films were able to
sustain high capacity even at high discharge rates, maintaining
a reversible capacity as high as 3100 mAhg1 after 100 cycles at
12C. Anode performance decreases as film thickness increases,
near 2300 mAhg1 after 200 cycles. Despite the small film
thicknesses, which require only short lithium diffusion distances,
the capacity is still seen to decrease with increasing cycling rates,
as the diffusion of lithium in silicon is still quite low.120,128
Silicon anode capacities sometimes increase over the first few
cycles before a stable capacity is maintained. Such increasing
capacity during initial cycling has been reported to result from
activation of crystalline silicon as it becomes amorphous during
cycling, because higher lithium mobility in amorphous silicon
allows lithium insertion into larger portions of the electrode as
cycling progresses.54 In the above case, the films were amorphous
prior to cycling, suggesting additional causes exist. An additional
cause of activation may derive from enhanced diffusion known
to occur in nanocrystalline solids as a consequence of the high
density of grain boundaries. If micro-cracking occurs during the
initial cycles to form new internal surfaces that are not exposed to
the electrolyte and therefore do not increase irreversible reac-
tions, enhanced lithium diffusion along the crack surfaces may
occur, reducing polarization. By the Griffith-Irwin relation, the
Fig. 4 Specific capacity of a 50 nm thick amorphous silicon electrode at
1C and 2C rates. Reproduced from Ref. 13 by permission from Elsevier.
This journal is The Royal Society of Chemistry 2011
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active material is predicted to become resistant to further

cracking after a sufficient crack density has been achieved (i.e. the
grains become sufficiently small), thus resulting in a leveling-off
of material activation after a few charge/discharge cycles.
Intrinsic silicon films exhibited lower reversible capacities, as
seen in a 50 nm intrinsic silicon film that had a reversible capacity
near 1850 mAhg1 after 5 cycles,13 suggesting that dopant
concentrations must play an important role in improving
capacity and stability. Enhanced reversibility and capacity in
doped electrodes has been reported in carbon-based electrodes
with substitutional boron or phosphorus doping, due to an
increase in the interlayer spacing with dopant substitution to
permit more facile lithium insertion.129131 In the case of alloy Fig. 5 Specific capacity of a bare silicon thin film and three fullerene-
anodes, it is not expected that doping would increase reversibility coated silicon thin films. Reproduced from Ref. 33 by permission of
via a similar mechanism, because low concentrations of dopants Elsevier.
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will not alter the degree of volumetric expansion appreciably. It is

clear there must be an alternative explanation for enhanced
3.1.2 Alloy or composite thin films. Sputtered films of silicon
performance in doped silicon anodes. The high capacities seen in
transition metal binary and ternary alloys SixM1-x (M Cr + Ni,
the n-type films compared to intrinsic silicon may arise from
Fe, Mn) have been reported to act as composites in which the
reduced ohmic polarization or more uniform alloying of the
electrochemically active silicon and inactive transition metal
anode during cycling. Since unlithiated intrinsic silicon is a rather
matrix are intimately mixed, with the capacity decreasing as the
poor electrical conductor, it may be more favorable to further
inactive transition metal content increases.34 When the electrode
lithiate regions containing the lower lithium alloys before fresh
was pure silicon, the capacity reached 3000 mAhg1. For tran-
silicon is lithiated. If this is the case, large stress gradients
sition metal contents of 30% or less, the capacity varied linearly
resulting from localized expansion gradients could lead to frac-
with the silicon content, and was largely independent of the
ture and lowered capacities. For doped silicon, higher electrical
transition metal identity. X-ray diffraction (XRD) indicated that
conductivity would be expected both before and after lithiation,
amorphous silicon with a mean grain diameter of about 2 nm
which could encourage more uniform lithiation of the electrode
(identified as extremely broad peaks in the diffractograms) were
and minimize stress gradients, providing more reversible cycling
present, with the intensity of the silicon peak decreasing as
at higher capacities.
transition metal content increased. As the transition metal
High initial capacities are possible for moderately thick silicon
content increased further to 4045%, the capacity approached
films, but the reversible capacity and cycling lifetime decreases
zero, consistent with a fully alloyed system in which no pure
with increasing films thickness. A survey of the literature reveals
silicon nanoclusters remained.
that the reversible capacities of silicon films up to 250 nm thick
The cycling lifetime of thin SiMox alloy films with an average
are typically near 3000 mAhg1, and capacities between 1000
thickness of 4 mm increased as the molybdenum content
2500 mAhg1 are reported for thicknesses higher than this. Radio
increased.35 The uneven morphology of these films (Fig. 6a),
frequency magnetron sputtered 250 nm thick amorphous silicon
which reflected the rough copper surface used as the current
films demonstrated reversible capacity as high as 3800 mAhg1
collector, may have contributed to the cycling stability of the
over 29 cycles, before a rapid decline was observed.31,32 In
films by allowing more isotropic expansion near the films
contrast, the reversible capacity of a 1 mm thick film could be
surface. The capacity of the films increased over the first 20
maintained at 3000 mAhg1 for only 13 cycles, followed by quick
cycles, indicating activation of the films, then began to decline.
decline. The marked capacity fade began during lithiation for
Although the initial discharge capacity of the optimal composi-
both electrodes, initiated by delamination of the film from the
tion SiMo0.79 was lower than that of a pure silicon film, the
copper substrate, as verified by SEM examination of cycled
reversible capacity of the alloy was higher than the pure silicon
anodes.
film after 100 cycles, delivering 1180 mAhg1 compared to
Silicon thin films have shown improved performance when the
1000 mAhg1 for silicon (Fig. 6b).
surface exposed to the electrolyte was coated with polymerized
Although good reversibility and high capacities are possible
fullerenes to improve SEI layer formation.33 Reversible capa-
using silicon and silicon composite films, the requirement to use
cities as high as 3000 mAhg1 were reported for 300 nm thick
extremely thin films to achieve reasonable cycling lifetimes
silicon films, higher than typically seen for uncoated films with
hinders the commercial application of batteries using silicon thin
comparable thickness. The degree of polymerization was
film anodes, due to the low quantity of active material and the
controlled by varying the plasma power during plasma evapo-
resulting low capacity and power density in thin films.
ration of the coating. Fig. 5 shows that the stabilizing effect of the
fullerene layer increases as the degree of polymerization is
increased. The capacity of uncoated thin films declines rapidly,
3.2 Nanostructure morphologiesnanowires and nanotubes
before it stabilizes at a value lower than conventional graphite
electrodes. The capacities of the fullerene-coated films declined 3.2.1 Silicon nanowires and nanotubes. Silicon nanowires and
more slowly, and all showed capacities between 2500 nanotubes have shown high discharge capacities and stable
3000 mAhg1 at the 50th cycle. cycling over tens of cycles, with reversible capacities as high as

This journal is The Royal Society of Chemistry 2011 Energy Environ. Sci., 2011, 4, 5672 | 61

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Fig. 6 a) Plan-view SEM image of SiMo0.79 thin film after 50 cycles.
b) Specific capacity of SiMox (0 # x # 0.79) thin film electrodes.
Reproduced from Ref. 35 by permission of Elsevier.
approximately 3400 mAhg1.5457,59,66 Nanowire and nanotube-
based electrodes can accommodate material expansion during
cycling (Fig. 7a), and can form a direct current pathway when
nanowires are grown directly onto the current collector.55 This
facile strain relaxation resulting from the small dimension of
nanowires and nanotubes was demonstrated by partially coating
a Si nanowire with electrochemically-inactive nickel. TEM
images of the nanowire before and after cycling showed that the
nanowire deformed without fracturing (Fig. 7b7c). The ability
for silicon nanowires to deform without fracture may contribute
to the high reversible capacities observed.
Because the surface-to-volume ratio is high for this
morphology, the formation of a stable SEI layer is very impor-
tant. Irreversible capacity losses as high as 38% in the first cycle
have been reported in silicon nanowire-based anodes.59 The
nanowire surfaces become rough during electrochemical cycling
(Fig. 7b7d) and porous structures resulting from slow diffusion
of silicon atoms (the Kirkendall effect) have also been reported
which could lead to significant SEI formation and increase the
amount of active material consumed in irreversible reactions.55,56
The increase of electrode resistivity that accompanies the
crystalline-to-amorphous transition can be minimized by
utilizing crystalline/amorphous core/shell structures via partial
lithiation of silicon nanostructures to create an amorphous shell
on the crystalline nanowires.56 The lithiation of crystalline and
amorphous silicon occur at approximately 120 and 200 mV (vs.
Li/Li+), respectively, hence preferential lithiation of the
62 | Energy Environ. Sci., 2011, 4, 5672
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Fig. 7 a) Schematic illustration of a silicon nanowire-based anode. The
nanowires are deposited directly onto the current collector to provide a 1-
D electron conduction pathway. b c) TEM of a pristine Si nanowire
partially coated with Ni b) before and c) after electrochemical cycling.
d) SEM of Si nanowires after electrochemical cycling. Reproduced from
Ref. 55 by permission of Nature Publishing Group.
amorphous shell can be carried out while preserving the higher
conductivity crystalline core simply by controlling the potential
during charging.56 Doping nanowires to increase their electrical
conductivity has also been shown to improve capacity retention
at high charge/discharge rates.66
Silicon nanotubes have demonstrated reversible capacities
above 2600 and 2100 mAhg1 over 50 cycles at rates of C/20 and
C/5 respectively (Fig. 8).57 Nanotubes undergo highly anisotropic
expansion, exhibiting small ( 35%) axial expansion and mark-
edly larger ( 120%) radial expansion. It has been proposed that
the expansion anisotropy results from comparatively facile
accommodation of expansion in the radial direction by the inner
and outer free surfaces of the tube. Formation of an SEI layer on
the inner surface of the nanotubes is believed to have been
inhibited, although definitive evidence to support this has not
been presented.
3.2.2 Composite nanowires and nanotubes. One-dimensional
nanocomposites containing silicon nanowires with amorphous
carbon coatings,58,59,62,63 silicon coatings on carbon nanotubes
(CNTs)67 or carbon nanofibers (CNFs),60 and silicon coatings on
metal oxide nanotubes61 have been investigated for the possibility
to enhance strain relaxation and minimize the deleterious reac-
tion of silicon with the electrolyte and subsequent SEI formation
and capacity loss in these high surface area nanostructures.
Arrays of thin crystalline silicon nanowires ( 6.5 nm diameter)
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Fig. 8 a) Schematic illustration of the anisotropic volume change in
nanotubes during cycling. b) Specific capacity and Coulombic efficiency
of silicon nanotubes cycled at rates of 0.05C (squares) and 0.2C (circles).
Reproduced from Ref. 57 by permission of the American Chemical
Society.
Fig. 9 a) Schematic illustrating the synthesis of Si/carbon core/shell
nanowires using mesoporous SBA-15 as the template. b) Specific capacity
and Coulombic efficiency of carbon-coated silicon nanowires. Repro-
duced from Ref. 58 by permission of the American Chemical Society.
with an amorphous carbon coating synthesized through
impregnation of mesoporous templates (Fig. 9a) have shown an
initial reversible capacity as high as 3163 mAhg1, with 87%
This journal is The Royal Society of Chemistry 2011
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capacity retention after 80 cycles at C/5 (Fig. 9b).58 The high
capacity retention suggests that the integrity of the carbon
coating was maintained during cycling, preventing further side
reactions between silicon and the electrolyte. Carbon-coated
silicon nanowires with diameters ranging from 20300 nm
showed lower reversible capacity (1326 mAhg1 after 40 cycles),
which likely resulted from the observed crumbling of the nano-
wires after cycling.59 CVD deposition of silicon onto commercial
carbon nanofibers (CNFs) also yielded good cycling perfor-
mance, with reversible capacities a high as 1650 mAhg1 after
50 cycles.60 SnO2 nanotubes with a thin Si coating on the inner
pore surface (Fig. 10a) showed a capacity of 1600 mAhg1 after
90 cycles (Fig. 10b) compared to less than 400 mAhg1 for
uncoated nanotubes.61 The high reversible capacity illustrates
that maintaining pore or void space can enhance the perfor-
mance of nanoscale silicon anodes. Although some degradation
of the nanotube walls was seen, the inner pore volumes provided
sufficient void space to buffer the volume expansion during
lithiation.
Si nanowires and related one-dimensional (1-D) nano-
structures have demonstrated facile strain relaxation, suggesting
this morphology may withstand the stresses during cycling and
avoid pulverization. Deposition directly onto the current
Fig. 10 a) Schematic illustration of the synthesis of Si-coated SnO2
nanotubes using Al2O3 membranes as a template. b) Specific capacity of
SnO2 nanotubes (filled circles) and silicon-coated SnO2 nanotubes (open
squares). Reproduced from Ref. 61 by permission of the Royal Society of
Chemistry.
Energy Environ. Sci., 2011, 4, 5672 | 63
 View Article Online

collector and the 1-D electrical conduction pathway further
makes conductive additives unnecessary. However, significant
challenges including low-throughput syntheses, high reactivity
with the electrolyte, and low active material masses remain.
Hence, it remains to be seen if nanowire-based batteries can be
commercially viable for applications in large batteries using
current technology.
3.3 Nanostructure morphologiesnanoparticles
Particle-based anodes combining electrochemically active
silicon nanoparticles mixed with conductive additives and
binders may have an advantage because the often simple
particle syntheses can be easily scaled up. The capacity of
particulate anodes containing conductive additives and either
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3.3.2 Composite silicon nanoparticles. Composite silicon
nanoparticle-based anodes utilize a matrix that does not undergo
large volume expansion during lithiation. Because the matrix
does not experience significant volumetric change, it may buffer
the significant expansion of silicon, maintain the structural
integrity of the electrode, and enhance stability by reducing
silicon aggregation or electrochemical sintering. Many compos-
ites also have significant void space within or between particles,
which can further accommodate volumetric expansion. The
amount of expansion in composite nanoparticle-based anodes
decreases as the amount of active Si decreases. In situ measure-
ment of the thickness of composite anodes comprised of silicon
particles, graphite, and electrochemically-inactive polymer
microspheres during cycling showed that the amount of volume
expansion of the anode decreases as the percentage of the inac-

Si or Si-based composite nanoparticles is seen to increase as tive component increased (Fig. 11).77 Even after delithiation, the
silicon content increases, however, higher silicon content and electrode volume remained larger than in the original delithiated
the concomitant expansion increase leads to lower reversible state, which reflects both the amorphization of the silicon
capacity. By decreasing the particle size, cycling stability can be component and the formation of a SEI layer during cycling.
enhanced compared to larger particles cycled under the same
conditions, with less pulverization of particles observed in SEM
micrographs of the cycled materials.88,89 Irreversible capacity
losses in the first cycle are correlated with the nanoparticle
diameter, with the irreversible capacity increasing as nano-
particle diameter decreases.114 Nanoparticle size should there-
fore be optimized to achieve a balance between managing
both material stress and SEI layer formation. A uniform
distribution of silicon particles within the inactive matrix to
provide isotropic volume expansion is also critical to mini-
mizing the mechanical stress during lithiation.61

3.3.1 Silicon nanoparticles. Micron-sized silicon powder

anodes have been shown to lose over 90% of their initial capacity
within 5 cycles.78,89,90 Nanoparticulate silicon anodes with small
diameters can cycle reversibly with moderately high capacity if
sufficient conductive additive is added to provide efficient elec-
tron transport between the active particles and current collector.
The most stable reversible capacity attained in silicon particle-
based anodes was achieved using 100 nm diameter silicon
nanoparticles when the state of charge was limited to minimize
volumetric expansion.91 By limiting the charge capacity, the
authors demonstrated that stable capacity as high as 960 mAhg1
could be achieved over 700 cycles. Silicon nanoparticles with
a mean diameter of 78 nm that were mechanically ground in
a 1 : 1 weight ratio with carbon black showed a reversible
capacity above 1700 mAhg1 over ten cycles when the cycling
voltage was limited to between 0.00.8 V to limit lithiation and
volumetric expansion.89 Smaller silicon nanoparticles (with
diameters ranging from 1020 nm) showed reversible capacities
over 2000 mAhg1.114 In each of these reports, conductive addi-
tives were added to achieve good electrical conduction, and they
may have buffered the volume expansion as well.
The limited cycling lifetime of particulate-based anodes may
be attributed to a combination of delamination of the particulate
films with repeated expansion/contraction, irreversible reactions Fig. 11 Change of electrode thickness during a single lithiation/deli-
involving the electrolyte, and poor electrical conductivity thiation cycle for a) Si/graphite composite electrode, b) Si/graphite
resulting from a discontinuous current pathway. To address composite electrode containing 5% polymer microspheres, and c) Si/
these possible causes, research has turned towards the use of graphite composite electrode containing 10% polymer microspheres.
composite nanoparticles. Reproduced from Ref. 77 by permission of Elsevier.

64 | Energy Environ. Sci., 2011, 4, 5672 This journal is The Royal Society of Chemistry 2011

A good matrix material should be an electronic and ionic
conductor to facilitate charge transport between the silicon
particles and current collector and assist lithium transport
between the electrolyte and active material. Because exposure of
silicon to the electrolyte results in progressive SEI formation
during cycling, an elastic matrix that coats silicon conformally
and resists fracture during cycling could improve SEI stability to
reduce irreversible capacity and enhance cyclability.
The use of an silicon/inactive matrix was first demonstrated
using a LixSi/Li2.6Sn composite.15 Preferential lithiation of the
LixSi was achieved by restricting the upper and lower potentials
within a voltage region in which Li2.6Sn is electrochemically
inactive. Nickel/silicon, silver/silicon, and titanium carbide/
silicon composites have since shown that stable cycling with
small capacity decreases per cycle could be achieved, with
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reversible capacities 30240% higher than graphite.79,86,87,93,94
However, the bulk of research into silicon composite anodes has
focused on carbon matrixes because of carbons abundance, well-
understood chemistry, and the advantages that carbon can offer
over other possible matrix materials.
The benefits of a carbon matrix are threefold: first, carbon is
highly conductive, and provides efficient electron transport;
second, carbon is lightweight and ductile, so it is able to
accommodate volume expansion by the active material; and
lastly, carbon is well known to form stable SEI layers in aprotic
organic electrolytes, which may minimize capacity loss due to
irreversible reactions. In addition, carbon coatings on silicon
electrodes have been reported to modify the SEI morphology.
For example, carbon-coated silicon electrodes exhibited smooth
surfaces with limited pore structure, compared to the visibly
cracked and porous morphology seen with pure silicon elec-
trodes.78
Silicon/carbon composites are typically synthesized by
mechanical milling of the active and matrix materials, or via
pyrolysis of carbon and silicon precursors to yield silicon
embedded in a carbonaceous matrix. The carbon matrix in
nanocomposites often has limited insertion capacity relative to
graphite, and does not contribute appreciably to the capacity of
silicon nanocomposites. Nonetheless, this does not appear to be
a detriment to composite electrodes, which have demonstrated
better cycling and higher capacities when compared to silicon/
graphite mixture anodes.64 The uniform carbon deposition
during pyrolysis or prolonged ball milling in many composites
results in intimate contact between carbon and silicon, enhancing
conduction and surface passivation.
3.3.2.1 Nanocomposites synthesized via ball milling. The
reversible capacities of ball milled nanocomposites typically
range from 5001000 mAhg1.6887,132134 The high capacities of
ball milled composites may arise from the small particle sizes
(typically on the order of a few tens of nanometers), and may
additionally benefit from efficient dispersal of highly conductive
additives such as graphite, carbon blacks, and carbon nanotubes
with the active material in ball milled composites. Furthermore,
the abundant interparticle void spaces that can result from ball
milling may help manage volume changes to provide improved
cycling stability.
An anode based on silicon nanopowder ball milled with
different types of carbon black and cellulose fibers demonstrated
This journal is The Royal Society of Chemistry 2011
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Fig. 12 Specific capacities of electrodes using pure Si nanoparticles
(n-Si) (squares), n-Si/cellulose (triangles), n-Si/cellulose/XE2 (circles);
and n-Si/cellulose/Super P (stars), respectively. Open symbols correspond
to discharge (delithiation) and closed symbols correspond to charge
(lithiation). Reproduced from Ref. 85 by permission of Elsevier.
a reversible capacity of 2560 mAhg1 in the second cycle and
a reversible capacity of 1800 mAhg1 after 50 cycles (Fig. 12).85
The capacity and reversibility were enhanced by the addition of
the inactive carbons. The composite using XE2 carbon black
achieved higher capacity than the composite using Super P
carbon black, probably because the smaller XE2 particles could
fill the void spaces more efficiently to provide better electrical
contact with silicon. Nanocomposites synthesized by milling Si
nanopowder with graphite and single-walled carbon nanotubes
showed an initial discharge capacity above 1100 mAhg1, with
reversible capacities over 1000 mAhg1 after 30 cycles.107 Even
longer cycling lifetimes can be achieved by combining ball milling
with pyrolysis of carbon-containing precursors to yield
a protective carbon layer overcoating the nanosized electroactive
silicon. This method has demonstrated reversible capacity as
high as 650 mAhg1 over 200 cycles and a small capacity loss (less
than 0.05% per cycle) after the irreversible loss in the first cycle,
behavior consistent with the formation of a stable SEI layer on
carbon-based electrodes.72 Higher yet reversible capacities were
reported for nanocomposites synthesized by ball milling of Si
powder followed by pyrolysis of benzene.90 Reversible capacities
of 1000 mAhg1 were reported, although fewer cycles (55 cycles)
were examined in this case.
3.3.2.2 Nanocomposites synthesized via pyrolysis. Silicon/
carbon composites synthesized via pyrolysis of organic precur-
sors mixed with nanoparticulate silicon78,80,81,83,84,95,97,102,103 or
direct pyrolysis of single-source organosilicon precursors101,105
often display reversible capacities higher than graphite, but lower
than those of ball milled silicon/carbon composites. The revers-
ible capacities demonstrated typically range from about 300700
mAhg1 over a few dozen cycles,78,80,81,83,84,95,97,103,105,113,114,135
although a few notable exceptions using hierarchical composite
structures will be discussed below. These relatively modest
capacities may be due in part to the higher percentages of the
inactive species that adds to the anode mass but does not
contribute to the capacity. Other contributions to the lower
capacities may include the larger size of silicon particles (100 nm
Energy Environ. Sci., 2011, 4, 5672 | 65

or greater in diameter) which often agglomerate into even larger
particles that are more vulnerable to fracture and pulverization
during cycling, and formation of an oxide layer between
the silicon and carbon coating during pyrolysis with oxygen-
containing organic precursors.97 Nanocomposites synthesized
using citric acid as the carbon source have shown moderately
high reversible capacities, with the best nanocompsite showing
a reversible capacity of 1120 mAhg1 after 100 cycles.95 Similar
reversible capacities over more limited cycling have also been
reported for nanocomposites using various polymers as the
carbon source.76
The pyrolysis or annealing temperature of carbon/silicon
nanocomposites can have a marked influence on the capacity and
cycling retention. Increasing the heat treatment temperature can
reduce first cycle irreversible capacity loss by reducing the
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porosity of the carbon coating and decreasing the surface area
available to react with the electrolyte.73 High temperature
pyrolysis reduces the total carbon content.81 Annealing at higher
temperatures also results in thinner carbon layers, due to an
increase of the degree of carbon layer ordering.95,136 The degree
of layer ordering can be correlated with the capacity, due to the
limited lithium insertion into ordered carbon than in disordered
carbons.96
High reversible capacities have been reported for hierarchical
porous nanocomposites synthesized using pyrolysis. A reversible
capacity at 1C of 1530 mAhg1 after 100 cycles with a per cycle
capacity loss just over 0.5% was achieved using a hierarchical
silicon/carbon composite synthesized by silicon and subsequent
carbon deposition onto an annealed carbon black scaffold to
obtain a carbon black/silicon/amorphous carbon structure
Fig. 13 a) Schematic drawing of a hierarchical composite comprised of silicon particles deposited onto an annealed carbon black framework, and
b) The specific capacity of the hierarchical silicon/carbon composite. Reproduced from Ref. 100 by permission of Nature Publishing Group.
66 | Energy Environ. Sci., 2011, 4, 5672
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(Fig. 13).100 Even after 100 cycles, the capacity was quite stable
and the Coulombic efficiency was near 100%. This rather
impressive performance may be the result of the interesting
hierarchical and porous nature of the silicon/carbon composite.
The annealed carbon black scaffold, which has only limited
electroactivity (100mAhg1),100 is not expected to fracture due to
expansion during lithiation, and the continuous electron current
path provided by the scaffold may also reduce ohmic polariza-
tion. The second carbon coating process likely serves to protect
the electroactive silicon from side reactions by facilitating the
formation of a stable SEI layer.
3.4 Nanostructure morphologiesmesoporous electrodes
Some notable examples of high capacity particulate composite
electrodes are found with porous morphologies that address both
the volumetric expansion and irreversible reactions following
electrolyte exposure.9 Stable cycling with enhanced capacity has
been reported for mesoporous carbon or metal oxides elec-
trodes,137140 suggesting this morphology could successfully
manage volumetric changes in silicon anodes if SEI formation
can be controlled. Macroporous crystalline silicon particles
coated with < 10 nm of amorphous carbon demonstrated
a reversible capacity of 2780 mAhg1 after 100 cycles, with an
irreversible capacity of 11% in the first cycle.110 The macroporous
structure, which was preserved during cycling, enhances cycling
lifetime and reversibility by acting as an expansion buffer to
prevent electrode pulverization and subsequent loss of electrical
conductivity. The irreversible capacity loss is lower in this
composite than the best performing silicon nanowire anodes,
This journal is The Royal Society of Chemistry 2011

suggesting that the porous structure can successfully manage the
stresses associate with expansion. Additionally, coating the
silicon microstructure with sufficiently thick carbon layers may
lead to the formation of a stable SEI layer, reducing electrolyte
decomposition at the surface.
Nanocomposites that use mesoporous carbon frameworks to
support silicon nanoparticles have exhibited high capacity and
reversibility.100,111 Carbon inverse-opals coated with amorphous
silicon (carbon/silicon inverse-opal) synthesized via templating
with ordered colloidal spheres and subsequent silicon deposition
(Fig. 14) showed a capacity above 2100 mAhg1 after 145 cycles,
whereas the capacity of a silicon inverse-opal coated with
amorphous carbon (silicon/carbon inverse-opal) was completely
lost by the 11th cycle.111 The capacity retention and Coulombic
efficiency increased with increasing pore size (Table 1), presum-
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ably due to the greater ability to buffer the volume expansion
with increasing pore volume. The drastic difference in cycling
stability resulted from the highly different mechanical stability of
these nanostructures. Carbon provides a stable framework for
the composite due to its low volume expansion during lithiation.
SEM images revealed that the framework of the carbon/silicon
inverse-opal, which undergoes less volume expansion, remained
intact after electrochemical cycling. On the other hand, the cycled
silicon/carbon inverse-opal collapsed completely, leading to the
loss of capacity.
3.5 Summary of nanoscale and nanostructured silicon anode
performance
As we have discussed, high capacities and reversible cycling can
be achieved using nanoscale and nanostructured silicon anodes.
However, the performance for a given morphology varies from
report to report. Data Tables ESI-1 to ESI-7 in the electronic
supplementary information summarize the morphology,
composition, and method of preparation of those nanoscale and
nanostructured silicon anodes reported in the recent literature,
along with their electrochemical performance when the data have
been clearly and reliably presented or can be estimated. When the
appropriate electrochemical data was given in the report, we use
the data directly. In all other cases, we have estimated the values
from the information provided. For full details of the electro-
chemical performance, the reader is referred to the original
report. In the tables, Qd1 corresponds to the first discharge
(delithiation) capacity. The irreversible capacity in the first cycle
(Qirr1) is calculated as the difference between the first charge
Fig. 14 A carbon inverse-opal coated with amorphous silicon a) before
cycling, and b) after 145 lithiation/delithiation cycles. Reproduced from
Ref. 111 with permission from Wiley-VCH Verlag GmbH & Co.
This journal is The Royal Society of Chemistry 2011
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(lithiation) and discharge capacities. The reversible capacity
(Qr,N) is the discharge capacity in the Nth cycle.
Each of the morphologies we have reviewed has unique
advantages and challenges to be overcome. Using current
synthetic techniques, the low throughput synthesis of thin films,
nanowires and nanotubes, and other nanostructured morphol-
ogies could lead to high initial costs, at least until more scalable
and inexpensive preparation techniques are developed. The hope
is that the increased costs of these nanomaterials may be offset by
their high capacities, though the very low cost of battery-grade
graphite is actually quite hard to compete with. Nanoparticulate
morphologies synthesized via ball milling or pyrolysis have lower
cost, high-throughput syntheses, although more modest capac-
ities have been demonstrated by active materials synthesized
using these methods thus far. An additional challenge facing
many nanoscale morphologies is the lower amount of active
material in nanostructured electrodes when compared to bulk
materials, which could result in lower actual total capacity for
per unit area of the electrodes. When moving from bulk to
nanostructured morphologies, we need to make sure that the
increase in capacity gained by nanostructuring will indeed
improve the total cell capacity. Additionally, more attention
needs to be paid to the volumetric capacity, as opposed to just the
gravimetric capacity, since the former is the limiting factor for
high energy density batteries in practical applications.
4. Other factors influencing stability and
performance
In addition to structure and morphology, several other factors
influence the capacity and cycling lifetime of nanoscale and
nanostructured silicon anodes, including solvent, additive, and
binder compositions, as well as substrate effects, which deter-
mine the nature of the passivation layer and mechanical prop-
erties of the electrode. For nanoscale morphologies with large
surface-to-volume ratios, surface passivation is perhaps the most
challenging to control. Understanding how these factors influ-
ence the composition and morphology of the SEI layer is
therefore essential.
The difficulty in forming a stable passivation layer on nano-
structured silicon electrodes in particular is caused by the
expansion mismatch between silicon and the SEI layer. This
mismatch can lead to cracking of the SEI layer and further
reduction of the electrolyte on freshly exposed silicon surface and
continuous capacity loss. Focus has therefore turned towards
modifying the electrolytes, either by replacing carbonate-based
electrolytes with new solvent compositions, or through the use of
additives to facilitate healing when fracture does occur.
4.1.1 SEI layer formationeffect of electrolyte composition.
Electrolyte composition can greatly influence both the
morphology and composition of the SEI layer. Ethylene
carbonate (EC) is usually part of the solvent mixture, due to its
high dielectric constant and ability for form stable SEI products
on graphite.78,141,142 Although fewer studies have been performed
on silicon electrodes, it appears that similar reduction products
are formed on the silicon electrode, in addition to species such as
siloxanes and fluorinated silicon species that are products of side
reactions between silicon and the electrolyte.42,50,78,116,143
Energy Environ. Sci., 2011, 4, 5672 | 67

Table 1 Capacity performance of an anode using a carbon inverse-opal
coated with amorphous silicon for various templating sphere diameters.
Reproduced from Ref. 111 with permission from Wiley-VCH Verlag
GmbH & Co
250 480 890
Sphere size (nm)
Cycle Film thickness (mm) 5 10 5 10 15 5 10 15
1 Capacity 2406 1890 1905 2557 1736 2165 2195 2374
(mAh/g)
Coulombic 71.2 67.3 75.5 76.5 75.7 78.1 79.5 77.5
efficiency (%)
145 Capacity 88.6 56.2 82.7 86.9 72.4 87.6 84.1 91.0
(mAh/g)
Coulombic 97.6 95.6 98.2 98.8 98.4 98.2 96.8 97.8
efficiency (%)
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Less is known about the composition of the SEI layer that
forms in other electrolytes, such as those based on room
temperature ionic liquids (RTILs) and mixtures of RTILs with
polymers that are being considered as alternatives to organic-
based electrolytes due to their low flammability and larger
solvent stability window. While there are no studies detailing the
SEI composition on silicon electrodes in RTILs, it appears that
a passivating layer does exist. The lower potential limit of RTILs
and RTIL/polymer mixtures typically ranges from 0 to 1.5 V (vs.
Li/Li+) and depends on the both the ionic liquid and any co-
solvents present.5 The electrochemical potential of silicon
therefore lies outside the window of thermodynamic stability for
some RTIL solvent compositions. Studies of graphite electrodes
cycled in RTILs show SEI formation can occur both in neat
RTILs, and in RTILs combined with molecular additives such as
EC or vinylene carbonate (VC).144,145
Stable cycling of amorphous silicon has been reported using 1-
methyl-1-propylpiperidinium bis(trifluoromethylsufonyl)imide
(MPPpTFSI) with the lithium bis(trifluoromethylfulfonyl)imide
salt (LiTFSI).44 A detailed study of the passivation layer was not
included, however, the large irreversible capacity in the first cycle
(approximately 28%) suggests electrode passivation from elec-
trolyte decomposition may have occurred.
4.1.2 SEI layer formationeffect of additives. The incorpo-
ration of additives into electrolytes has been considered for
enhancing the stability of the passivation layer. Since additives
alter the SEI composition, both SEI stability and its effect on
ionic conductivity must be considered.
Lithium bis(oxalato) borate (LiBOB), which undergoes
reductive decomposition at the silicon surface at higher poten-
tials than commonly-used EC and LiPF6, is proposed to improve
cycling stability by encouraging the formation of a less porous
SEI layer, thus minimizing the formation of electrochemically
inactive silicon-containing reaction products on the electrode
surface.43 LiBOB may block surface reactions with in situ
generated HF to prevent the formation of inactive SiF62 or
SiPF5.43,146 However, the addition of LiBOB may increase
concentration polarization due to lower ionic conductivity in
LiBOB-based electrolytes compared to LiPF6.147
The relationship between electrolyte ionic conductivity,
interfacial resistance, and cell impedance is complex. LiBOB has
shown promise for reducing the cell impedance when combined
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with other lithium salts. For example, LiBF4-based electrolytes
have demonstrated lower charge transfer resistance at graphite
electrodes than LiPF6-based electrolytes, but cycling stability is
poor due to the poor ability to form a stable SEI layer.148 The
addition of LiBOB to LiBF4-PC based electrolytes has been
shown to enable stable SEI formation on graphite electrodes and
improve cycling stability.148 It is a point of dispute at this time
whether the impedance of cells containing LiBOB are greater or
less than those containing LiPF6; the conflicting trends reported
may be due to different salt concentrations used in the individual
studies.142,147
The cycling stability possible in cells using LiBOB has been
demonstrated for a 200 nm thick amorphous silicon film that
achieved a reversible capacity as high as 3000 mAhg1 over 100
cycles.43 Such high reversible capacity in silicon films with
thicknesses greater than 100 nm have only been demonstrated
over several dozens of charge/discharge cycles in electrolytes
without LiBOB.31,32,41 X-ray photoelectron spectroscopy (XPS)
and Fourier transform infrared spectroscopy (FTIR) analysis
have shown that the SEI layer on electrodes cycled in electrolytes
containing LiBOB are similar to those formed in LiPF6-based
electrolytes, although lower signal intensity corresponding to
Li2CO3, LiOH, and Li2O was found using LiBOB electrolyte.
Electrodes cycled with LiBOB electrolytes additionally have
lithium oxalate (Li2C2O4) incorporated into the SEI layer, which
may be better at protecting against further electrolyte reaction
after the initial SEI formation.
VC is reduced at higher potential than EC, thus it can greatly
influence SEI composition directly on the electrode surface.142
When studied as an additive for graphite-based electrodes, VC
was found to yield reduction products that exhibit lower lithium
ion conductivity than EC reduction products, increasing the cell
impedance.142 Increased interfacial resistance has been reported
previously to result from electrochemical polymerization during
cycling.116,147 Despite this apparent drawback, the addition of VC
has improved both the Coulombic efficiency and cycling reten-
tion of silicon electrodes in at least one study, with the electrode
maintaining 50% of the initial capacity after 500 cycles.116 In the
absence of VC, the capacity dropped markedly before the 100th
cycle, and the electrode failed before the 200th cycle. SEM
imaging revealed that the electrode cycled with VC had a smooth
surface with small cracks believed to form during delithiation,
compared to a much rougher surface with protruding crystallites
and an inhomogeneous appearance without VC. In addition, the
impedance of the SEI layers were reported to remain constant for
the electrode cycled with VC but increased with each cycle
without VC.
The addition of fluoroethylene carbonate (FEC) to alkyl
carbonate solvents with LiPF6 has also been shown to enhance
capacity retention and increase Coulombic efficiency.42 The
discharge capacity retention of 200 nm thick silicon after 80
cycles was 88.5% and 67.9% for electrodes cycled with and
without FEC respectively. A smoother passivation layer was
observed on the surface of the electrode cycled in FEC, sug-
gesting that the additive may encourage formation of a more
stable or faster healing SEI layer. Investigation of the differential
capacity suggests that FEC is reduced at higher potentials than
EC, altering the SEI composition to include fluorinated silicon
species and forming a more stable passivation layer. It has been
This journal is The Royal Society of Chemistry 2011
 View Article Online

suggested that fluorine can shorten the length of oligomer chains 4.3 Binder influence
present in the SEI layer, leading to compact passivation films.142
The type of binder used in particulate electrodes can greatly
Silane-based additives such as monomethoxy trimethyl silane
influence the cycling lifetime. Poly(vinylidene) difluoride (PVdF)
(CH3OSi(CH3)3), dimethoxy dimethyl silane ((CH3O)2Si(CH3)2),
has been the most frequently used binder in bulk powder elec-
and trimethoxy methyl silane ((CH3O)3SiCH3), have been
trodes, but this thermoplastic binder cannot sustain the elonga-
demonstrated to decrease the extent of SEI formation and
tion that occurs during volumetric expansion, leading to rapid
improve cycle life of thin silicon films by reducing the
capacity fade. Electrode polarization has been found to increase
consumption of active material.48,50,52 The SEI mass was deter-
during cycling when using PVdF, suggesting degrading electrical
mined by using an electrochemical quartz crystal microbalance
contact after repeated electrode expansion/contraction.90 The
to measure the mass change prior to the onset of lithiation. The
ability of PVdF to maintain cycling stability can be enhanced by
alkoxy silane functionalites are believed to protect the anode
heat treatment prior to electrochemical cycling, although severe
surface by reacting with the silicon surface hydroxyls to form
capacity fade is still seen within a few tens of cycles.150
stable ^SiOSi^ bonds, making the surfaces less conducive to
Poly(acrylic) acid (PAA) has been shown to improve cycle life
electrolyte reduction and SEI layer formation.48 FTIR investi-
by enhancing the adhesion of graphite electrodes to copper
gation revealed that silane addition encouraged formation of
Published on 16 November 2010. Downloaded on 15/12/2013 00:17:41.

current collectors.151 PAA also improved cycling stability of

stable alkyl carbonate salts (ROCO2 Mn+, R alkyl and M
Li or Si), carboxylic acid metal salt functionalities (RCO2 Mn+,
M Li or Si), and PF-containing species, in contrast to the
primarily PF-containing species layer formed in the absence of
silane.50 The enhanced cycling lifetime suggests that alkyl
carbonates and carboxylic acid metal salt functionalities effec-
tively passivate the silicon surface. Smooth films were seen on
electrode surfaces after cycling when silane additive was present,
whereas the surface morphology after cycling without silane was
visibly rougher.
4.2 Substrate influence
Delamination of the active layer from the current collector
contributes to anode capacity degradation. Modification of the
metal surface and the addition of buffer layers to provide greater
adhesion could therefore improve capacity retention and cycling
lifetimes of thin film silicon anodes. Electrochemical roughening
of nickel or copper substrate surfaces has been used to improve
adhesion of silicon films to the substrate.38,41,46,49,51 Surface
modification could create anchor points for the deposited active
material to adhere to, thus allowing electrical contact with the
substrate to be maintained even if the active film itself shows
cracking. This technique has been successful for attaining
reversible capacities near 1000 mAhg1 over 20 cycles for a thick
6 mm silicon film.49 Despite this improvement, the capacity is still
lower than nanoparticle composite electrodes, which have shown
twice this capacity for 100 or more cycles.110,111 Improved film
adhesion has also been reported for silicon thin films sputtered
onto copper foils that had been pretreated using lanthanum
Plasma Immersion Ion Implantation (PIII).149 Deposition of thin
Ni layers on roughened copper substrates was reported to
improve initial capacity and reduce the irreversible capacity loss
in silicon thin film electrodes, although rapid deterioration of the
capacity after the first cycle still occurred due to delamination of
the buffer layer from the copper substrate.46 Heat treatments
could improve binder adhesion to both the substrate and active
material and have additionally been shown to increase cycling
lifetimes.41,150 Annealing silicon films sputtered onto roughened
copper substrates has been reported to increase capacity reten-
tion from 61.3% to 78.5% for 500 cycles by promoting interdif-
fusion of silicon and copper at the interface to improve the film
adhesion strength.51
a silicon/carbon composite, both when used alone and when
mixed with sodium carboxymethylcellulose (SCMC).152 This
enhancement may result from the formation of chemical linkages
between the composite and these acidic binders. Both carbon and
silicon surfaces contain hydroxyl functionalities that can react
with carboxylic acid functionalized binders in an esterification
reaction to tether the active material to the binder.153
Sodium carboxymethylcellulose (SCMC) is a water soluble
elastomeric binder that can be blended with styrene butadiene
rubber (SBR) to achieve high elongation without tearing. The
elastomeric nature combined with the ability of SCMC to tether
to the active material are proposed to extend cycling lifetimes in
silicon powder electrodes.91,154 Electrodes using nanoscale ( 100
nm) silicon powder processed in buffered solution (pH 3.0)
with SBR-SCMC demonstrated a reversible capacity of
960 mAhg1 over 700 cycles, a cycling lifetime unprecedented in
powder-based silicon anodes without SBR-SCMC.91 Ester link-
ages confirmed using FTIR measurements suggest that tethering
was responsible for the marked improvement in the cyclability of
the alloy electrodes. Silicon and carbon-coated silicon electrodes
using SBR/SCMC in a 1 : 1 weight ratio demonstrated enhanced
cycling stability compared to electrodes using PVdF, with stable
capacities of approximately 600 and 1000 mAhg1 respectively
over 55 cycles.90 A control electrode using PVdF failed after 5
cycles, with the capacity quickly dropping to zero.
4.4 Conductive additives
The choice of the conductive additive can have a significant
impact on electrochemical performance. To reduce polarization,
a continuous electron-conducting pathway must be formed. The
addition of carbon nanotubes, which have smaller diameters
compared to the active material, was shown to enhance both
capacity and cycling stability by forming a more efficient
percolation pathway compared to when larger carbon black
particles were used (Fig. 15).63 However, CNT-containing
composites can suffer high irreversible capacity loss to SEI
formation, due to the high surface area available to react with the
electrolyte.107 The reversible capacity has also been shown to
increase as the carbon black particle size decreases, suggesting
better interparticle contact can be achieved using smaller carbon
black particles.85

This journal is The Royal Society of Chemistry 2011 Energy Environ. Sci., 2011, 4, 5672 | 69

Published on 16 November 2010. Downloaded on 15/12/2013 00:17:41.
Fig. 15 Specific capacity of uncoated and carbon-coated Si nanowires
using either carbon black (red and blue circles) or multi-walled carbon
nanotubes (gold circles) as the conductive additive. Reproduced from
Ref. 63 by permission of the Americal Chemical Society.
5. Summary and perspective
The discussion in this review has illustrated that silicon anodes
have advantages over conventional graphite anodes in lithium
batteries, but significant challenges need to be overcome before
silicon anodes can be utilized in practical lithium batteries.
Morphology can have a major impact on the performance and
cyclability of the silicon anode. Bulk electrodes fail within a few
charge/discharge cycles due to the extremely large volumetric
change that occurs during lithiation and delithiation. Nanoscale
morphologies have the potential to achieve long cycling lifetimes
and good reversibility if challenges such as stress management
and formation of a stable passivation layer during cycling can be
overcome. Over the last decade, tremendous progress has been
made in addressing these challenges by using nanoscale or
nanostructured silicon anodes, such as thin films, 1-D nanowires
or nanotubes, nanoparticles, mesoporous nanostructures, and
their respective nanocomposites. Despite the variations of
reported performance, a consistent trend has been emerging that
storage capacities as high as 20002500 mAhg1 for thin film
silicon anodes and 10002000 mAhg1 in other silicon nano-
structure morphologies with rather impressive cycling lifetimes
up to a couple hundred cycles at practical charge/discharge rate
can be reproducibly achieved. Long cycling lifetimes have most
frequently been observed when four critical factors were properly
addressed: i) use of nanoscale-dimension silicon to allow the
relaxation of the strain and stress during the volume expansion/
contraction associated with lithiation/delithiation; ii) incorpo-
ration of void/free space or softer inactive material matrices or
additives to accommodate the volume expansion; iii) efficient
electronic and ionic conduction from silicon to the current
collectors that can be maintained during cycling; and iv)
furthermore, the formation of a stable and non-porous passiv-
ating SEI layer that can tolerate the silicon expansion and avoid
cracking, or can be healed readily so that continual capacity loss
can be minimized.
These lessons suggest that future research should explore more
structurally and compositionally complex hierarchical composite
nanostructures with internal void/pore space, in addition to the
70 | Energy Environ. Sci., 2011, 4, 5672
View Article Online
simple one-component silicon nanostructures already extensively
investigated. Considering the potential large-scale energy appli-
cations of rechargeable lithium batteries, such as in hybrid and
plug-in electric vehicles or electrical power storage, the scal-
ability, manufacturability, and cost of the nanomaterials will also
be important to the eventual success in their practical applica-
tions. Although the volumetric capacity has not often been
reported for nanostructured silicon anodes so far, more attention
should be paid to this important parameter in future research.
Particulate hierarchical composite nanostructures that can both
manage strain/stress and the surface passivation may be the most
promising direction for large-scale applications. For example,
composite mesoporous particulate anodes could be attractive:
the strain/stress can be addressed by the nanoscale dimension
and the volume expansion accommodated by the void space,
although the ability to form a stable SEI layer without high
irreversible capacity in the first cycle has not been well studied
with mesoporous electrodes and may be difficult to achieve due
to the extremely high surface-to-volume ratio. Composites in
which silicon is conformally coated with an amorphous carbon
layer could facilitate the formation of a stable SEI layer. The
expansion mismatch between silicon and the SEI layer during
cycling and resultant cracking of the SEI layer causes capacity
degradation, therefore methods to limit SEI layer cracking, such
as designing the proper nanostructure geometry and controlling
the degree of lithiation to minimize the expansion, and using
additives to encourage quick healing of the layer during cycling
need to be further investigated. It is quite promising that
continual development of these and other strategies and diverse
varieties of silicon anode nanomaterials will lead to the practical
applications of silicon anodes in practical lithium batteries at
a large scale.
Acknowledgements
We thank the University of Wisconsin-Madison graduate school,
the Sloan Research Fellowship, the Research Corporation
through a Cottrell Scholar Award, the ACS ExxonMobil Solid
State Chemistry Fellowship, and the DuPont Young Professor
Grant for support. We thank Prof. Y.-M. Chiang for helpful
discussions. S. J. also thanks the support of his research by NIH,
DOE, and NSF.
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