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Asymmetric Supercapacitor Electrodes and Devices


Nitin Choudhary, Chao Li, Julian Moore, Narasimha Nagaiah, Lei Zhai,
Yeonwoong Jung,* and Jayan Thomas*

It has also been estimated that the world-


The world is recently witnessing an explosive development of novel electronic wide net electric-power generation will
and optoelectronic devices that demand more-reliable power sources that nearly double over the next 25 years, i.e.,
combine higher energy density and longer-term durability. Supercapacitors from 21.6 trillion kilowatt-hours (kW h)
in 2012 to 25.8 trillion kW h in 2020 and
have become one of the most promising energy-storage systems, as they pre-
to 36.5 trillion kW h in 2040.[5] In spite of
sent multifold advantages of high power density, fast charging–discharging, a plethora of research carried out in the
and long cyclic stability. However, the intrinsically low energy density inherent field of batteries (lithium-ion batteries, in
to traditional supercapacitors severely limits their widespread applications, particular), spanning from small gadgets
triggering researchers to explore new types of supercapacitors with improved to heavy electric vehicles, we are on the
performance. Asymmetric supercapacitors (ASCs) assembled using two verge of a power revolution with renewed
interest in supercapacitors.[6–9] Unlike bat-
dissimilar electrode materials offer a distinct advantage of wide operational teries, supercapacitors not only charge
voltage window, and thereby significantly enhance the energy density. Recent faster but are more reliable owing to their
progress made in the field of ASCs is critically reviewed, with the main focus indefinite lifespan, nonvulnerability to
on an extensive survey of the materials developed for ASC electrodes, as well temperature change, and nontoxicity in
as covering the progress made in the fabrication of ASC devices over the last nature.[10–13]
A supercapacitor generally consists
few decades. Current challenges and a future outlook of the field of ASCs are
of two electrodes (anode and cathode)
also discussed. separated by an electrolyte (aqueous or
organic) and a separator that permits the
transfer of ions while keeping the elec-
1. Introduction trodes electrically insulated from each other. They are further
classified into electric double-layer capacitors (EDLCs) and
Due to the rapid increase in the global energy consumption pseudocapacitors, depending on the type of charge-storage
of fossil fuels and the world’s population explosion, there has mechanism. In EDLCs, the charges are stored due to the sur-
been an urgent demand for the development of alternative face adsorption of the ions from the electrolyte as a result of the
energy sources that are clean, low cost, compact, and efficient. electrostatic attraction, thus forming two charged layers (double
The intermittent nature of conventional energy sources such layer). Electrode materials play a significant role in providing
as wind, solar, hydroelectric, and biomass prevents them from high perfromance for supercapacitors. For EDLC electrodes,
being selected for the provider of sustainable energy technolo- the main requirements are their high surface area, fast charge/
gies in any near future. Certainly, sustainable electric-power discharge rates, and high conductivity. In most cases, EDLCs
sources such as batteries and supercapacitors are expected to are constructed using carbon-based electrode materials (porous
continuously remain as the dominant energy models for world- carbon, carbon nanotubes (CNTs), and graphene) as they repre-
wide energy usage, as they have been so for several decades.[1–4] sent high surface area, nontoxicity, controllable porosity, good

Dr. N. Choudhary, Dr. C. Li, J. Moore, Prof. L. Zhai, Prof. Y. Jung, Prof. L. Zhai
Prof. J. Thomas Department of Chemistry
NanoScience Technology Center University of Central Florida
University of Central Florida Orlando, FL 32826, USA
Orlando, FL 32826, USA Prof. Y. Jung
E-mail: yeonwoong.jung@ucf.edu; Jayan.Thomas@ucf.edu Department of Electrical and Computer Engineering
Dr. N. Nagaiah University of Central Florida
Center for Advanced Turbines and Energy Research (CATER) Orlando, FL 32826, USA
Mechanical and Aerospace Engineering University of Central Florida Prof. J. Thomas
Orlando, FL 32826, USA CREOL
Prof. L. Zhai, Prof. Y. Jung, Prof. J. Thomas College of Optics and Photonics
Department of Materials Science and Engineering University of Central Florida
University of Central Florida Orlando, FL 32826, USA
Orlando, FL 32826, USA
DOI: 10.1002/adma.201605336

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electronic conductivity, and availability in various forms like
tubes, powders, composites, sheets, and aerogels.[14] Unlike Yeonwoong Jung is an
EDLCs, pseudocapacitors store charges through fast and revers- assistant professor at
ible oxidation/reduction (Faradiac) reactions occuring at the NanoScience Technology
electrode/electrolyte interfaces, as well as in the bulk near the Center (NSTC), Materials
surface of the electrode. Pseudocapacitors show higher capaci- Science and Engineering,
tance as compared to EDLC-type devices due to the additional and Electrical and Computer
charges transferred within the defined potential, but they typi- Engineering at the University
cally have inferior cycle life due to active material degradation of Central Florida (UCF). He
as a result of Faradaic reactions. Metal oxides and conductive received his Ph.D. in mate-
polymers are widely used as pseudocapacitive electrode mate- rials science and engineering
rials due to their fast reversible redox reactions, cost-effective- from the University of
ness, easy processability, and relatively longer cyclic stabillity.[15] Pennsylvania, Philadelphia,
Despite the advantages of high power density and much higher USA. He joined UCF in 2015 after completing his postdoc-
cycle life in EDLCs and pseudocapacitors, their intrinsically low toral training at Yale University. His research group at UCF
energy density (amount of energy stored per unit weight) have currently focuses on developing 2D layered materials and
held them back from outperforming batteries for widespread their hybrid systems for electronics, energy, and environ-
commercial applications.[16–18] Currently, supercapacitors are mental applications.
mainly used in heavy machinery and other types of equipment
Jayan Thomas is an associate
that require high power. As a signature of its reliability, NASA
professor at NanoScience
uses supercapacitor packets in the drill that astronauts use for
Technology Center (NSTC),
their space walk to perform repair work on the International
College of Optics and
Space Station.[19] In additon, Airbus 380 uses supercapacitors on
Photonics (CREOL) and
its emergency doors as a testimony to their reliability.[12] How-
College of Engineering and
ever, supercapacitors are used only as backup power sources to
Computer Science at the
aid batteries in electric cars, since their energy density is not as
University of Central Florida
high as batteries.[15,20] For example, Toyota uses ultracapacitors
(UCF). After receiving his
to add about 480 horsepower to their hybrid race car, TS040.[21]
Ph.D. from Cochin University
Maxwell technologies, a well-known supercapacitor manufac-
of Science and Technology in
turer partially rely on supercapacitors for the operation of their
India, he joined the College
hybrid buses with stop–start engines.[22] Besides electric vehi-
of Optical Sciences, University of Arizona in 2001 as a
cles, supercapacitors are in demand for remotely located wind
research faculty. He moved to UCF in 2011 and is currently
turbines that need bursts of power to adjust the turbine blades
working on the development of energy-storage devices,
during wind changes.[23] Batteries fail to serve these needs due
wearables, solar cells, and photorefractive polymers.
to unwanted chemical reactions and physical changes to the
active chemicals used during high-power requirements. Fur-
thermore, the advent of next-generation portable, flexible, and for the anode and the cathode. The reason for the higher energy
wearable electronics and optoelectronics devices requires min- density (E) achieved in ASCs is due to the higher operating
iaturized energy-storage systems with unique advantages of voltage (V). The energy density (E)[28–32] is given by:
flexibility and light weight.[9,24–27] Hence, there is a huge surge
for further improving the energy density of supercapacitor tech- 1
E = CV 2 (1)
nologies (which is currently 5–35% of the Li-ion batteries) to 2
meet industrial demands.
Consider a win–win situation where the fundamental prin- Nevertheless, the specific capacitance (C) of a superccapac-
ciples behind batteries and supercapacitors work together to itor can be enhanced by optimizing the intrinsic properties, like
reach the common goal of higher energy density and power porosity, electrical conductivity, and chemical stability of the
density. One such design is “asymmetric supercapacitors electrode materials, as well as rationally engineering them into
(ASCs)”, which, unlike traditional supercapacitors, consist of low-dimensional nanostructures (quantum dots, nano-onions,
two dissimilar electrodes, i.e., a battery-type Faradaic electrode nanorods, sheets, foams, etc.) and making novel electrode
(cathode) as an energy source and a capacitor-type electrode designs like composites, core/shells, and heterostructures.[33–37]
(anode) as a power source. Typically, in a symmetric superca- Figure 1a illustrates the principle of ASCs, where two dissimilar
pacitor, the working voltage is limited to less than 1.0 V because materials are assembled together as anode and cathode. The
of the thermodynamic breakdown potential of water molecules Ragone plot given in Figure 1b compares the energy and power
when aqueous electrolytes are used. Nevertheless, the working densities of various energy-storage devices. It is apparent that
voltage can be improved beyond 2.5 V by using organic electro- ASCs deliver significantly higher power density as comapred
lytes. However, these organic electrolytes are sometimes toxic to batteries, fuel cells, and symmetric supercapacitors. In addi-
and not enviornmentally benign for certain applications. There- tion, the energy density of asymmetric devices comparable to
fore, a feasible approach to achieve higher working voltage for LIBs suggests their widespread use for next-generation elec-
aqueous electrolytes is to use two different electrode materials tronics and energy-storage devices. Figure 1c shows a year-wise

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Figure 1.  a) Schematic showing typical construction of an asymmetric supercapacitor. b) Ragone plot comparing the energy and power densities
of various state-of-art supercapacitors and batteries with ASCs. c) Increasing trend in the number of publications on ASCs during the last decade
(2006–2015). d) Some possible application areas of ASC devices. c) Searched by SciFinder Scholar: https://scifinder.cas.org and American Chemical
Society database: https://www.acs.org/content/acs/en.html), September 20th, 2016. d) Reproduced with permission.[38] Copyright 2015, Wiley-VCH.

publication list demonstrating the increasing trend of studying (MXenes) are are also introduced. Finally, the fabrication of
ASCs. Some of the application areas that demand the increase next-generation ASC electrodes and devices are extensively dis-
in the use of ASCs include flexible electronics, e-textiles, trans- cussed in the context of emerging technologies such as flexible
portation, etc., and are shown in Figure 1d. and wearable technologies.
Here, we discuss the recent developments in the field of Electrochemical symmetric supercapacitors made using
ASCs with the main focus on the synthesis, properties, and per- carbon electrodes exhibit low energy density in aqueous electro-
formances of the state-of-the-art materials for anode and cath- lytes as a result of the small operating-voltage window. There-
odes. Carbon-based materials such as activated carbon (AC), fore, all the commercially available supercapacitors use organic
porous carbon, carbon nanotubes (CNTs), graphene, and gra- electrolytes, attaining a cell voltage of 2.5–2.85 V, with their
phene oxide (GO) are generally employed for negative (capaci- energy density reaching as high as 5–10 W h kg−1. However,
tive) electrodes owing to their high surface area and electro- ASCs using aqueous electrolytes can reach a cell voltage of more
static charge-storage mechanisms at electrode/electrolyte inter- than 2.0 V[39] and are likely to replace symmetric supercapaci-
faces. Being pseudocapacitive in nature, some metal oxides tors employing organic electrolytes. In addition, large operation
and nitrides have also been utilized as anode materials. The voltages with extremely high energy densities can be achieved in
positive electrode counterparts are generally pseudocapacitive ASCs by using non-aqueous or ionic-liquid electrolytes owing to
in nature, which include metal oxides and carbonaceous mate- their higher dissociation voltage. However, studies on ASCs in
rials. In addition to the material-property considerations, the organic electrolytres are still sparse. Khomenko et al.[40] studied
design aspects of electrode structures are extensively reviewed, the perfromance of a hybrid ASC made with all-carbon-based
covering tailored nanostructures such as nanorods, nanowires, hybrid electrodes i.e., graphite and AC for the negative and posi-
nanospheres, nanosheets, and nanoribbons. Recently discov- tive electrodes, respectively, in two organic electrolytes: 1 mol L−1
ered novel two-dimensional (2D) materials such as transition- tetraethylammonium tetrafluoroborate (Et4NBF4) in acetoni-
metal dichalcogenides (TMDs) and transition-metal carbides trile (AN) and 1 mol L−1 lithium hexafluorophosphate (LiPF6)

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in a mixture of ethylene carbonate (EC) and dimethyl carbonate and that the term “hybrid supercapacitor” should be used for
(DMC). It was found that the hybrid ASC could be operated at a those devices with a battery electrode. We completely agree with
maximum voltage of 4.5 V and exhibited a very high energy den- these suggestions; however, to avoid confusion for the reader,
sity of 103.8 W h kg−1. Considering the fact that high pseudoca- we follow the terminology used in the respective cited paper.
pacitance in metal oxides might result in significant increase The reader should bear in mind that many reports interchange-
in the energy density, Wang et al.[41] reported a non-aqueous ably use these two terms.
activated-mesocarbon microbead (AMCMB)//MnO2 nanowire-
sphere (negative//positive electrodes) hybrid supercapacitor
using 1 m Et4NBF4 in AN as an electrolyte. This hybrid super- 3. Selection of Electrode Materials
capacitor operates over a wide voltage range of 0–3 V and dis-
plays a high specific capacitance of 228 F g−1 and a high specific As discussed above and according to Equation (1), the working
energy of 128 W h kg−1. The high ionic resistance of organic voltage of an ASC should be maximized to achieve a high
electrolytes is one of the potential problems while assembling energy density. The selection of the electrode materials plays a
a supercapacitor device, as it tends to increase the equivalent critical role in determining the voltage window of the device. A
series resistance (ESR) and thereby lowers the capacitance. In fundamental understanding of the different ways to widen the
this regard, Foo et al.[42] demonstrated an ASC assembled using voltage window in supercapacitors is not completely known.
free-standing V2O5–rGO as the anode and free-standing rGO However, the work function of the metal oxides used as elec-
as the cathode with LiClO4 as the organic electrolyte. The flex- trode materials is directly related to the oxidation–reduction
ible ASC device, without using separate current collectors and reaction.[47] The electrode materials with the largest difference
binders, facilitated a large ionic conduction and a wide poten- in work function can provide the highest voltage window in
tial window of (1.5–4.0 V) with a high areal capacitance of asymmetric supercapacitors. An estimate of the working poten-
511.7 mF cm−2. Recently, Wang et al.[43] reported a high energy tial can be obtained from Equation (2):[48,49]
density of 58.2 W h kg−1, superior cyclic stability (88% retention
after 10 000 cylces) in organic ASCs with CNT-paper-supported
PPy (CNT@PPy) and poly(1,5-diaminoanthraquinone) (CNT@
( )
E = E 0 + ∆E 1 + ∆E 2 = 1/F ω β − ω α N A + ∆E 1 + ∆E 2 (2)

PDAA) as the cathode and anode, respectively. Besides organic


electrolytes, ionic-liquid electrolytes have been used for higher where ΔE1 and ΔE2 represent the positive and negative sur-
voltage operation of supercapacitors (≥3.0 V).[44,45] Ionic elec- face electrode potentials repectively; ωα and ωβ are their
trolytes are nonflammable and nontoxic in nature, as well as respective work functions, and NA is the Avogadro’s number.
highly desirable for their high working-temperature range. Chang et al.[50] showed that ASC electrodes (anode and
cathode) with the largest difference in work function provide
the highest working voltage. For example, among various
2. Distinction between Terminologies Used: metal oxides, they selected MnO2 and CoO3 as positive and
negative electrodes having work functions of −4.4 eV and
Pseudocapacitors, Asymmetric Supercapacitors
−6.2 eV (both from vacuum level), respectively. The assem-
and Hybrid Supercapacitors bled ASCs exhibited a large operation voltage window of 2 V.
A slight increase in the operating voltage from the work-
Recently, Brousse et al.[46] reported a clear distinction between function difference is due to the adsorption of ions on the
pseudocapacitors and hybrid supercapacitors. In a three-elec- surface of the electrode, which modifies the work-function
trode geometry, pseudocapcitance is provided by electrode values of the electrodes.
materials that can show activated-carbon-like capacitance. Even However, from the materials’s perspective, the factors that
though the capacitance is due to Faradaic reactions, within a decide the appropriateness of an electrode materials are: i) sur-
given voltage window, these materials show a linear depend- face area: since most of the charge via EDLC or pseudocapaci-
ence of charges stored with changing potential. Unlike acti- tance is stored at or near the surface of the electrode material,
vated carbon in EDLCs, the charge-storage mechanism in nanoarchitecturing can highly enhance the surface area of the
pseudocapacitors involves the exchange of electrons (Faradaic electrode materials. ii) Electronic/ionic conductivity: limited
reaction). Materials like RuO2 and MnO2, which clearly show conduction of electrons/ions through the electrode materials
activated-carbon-like (EDLC-like) curves in cyclic voltammetry leads to low rate capability and higher electrochemical series
(CV) and galvanic charge–discharge (GCD) measurements can resistance (ESR), thereby resulting in low specific capacitance.
be easily categorized as pseudocapacitive materials. It has been Binder-free integration of electrodes, open pore structures,
proposed that battery-type electrodes like LiMn2O4, PbO2, etc. and composites with highly conductive materials are critical
should not be considered as pseudocapacitive electrode mate- approaches to enhance the electronic conductivity. iii) Mechan-
rials. In addition, the terms “ASCs” and “hybrid supercapaci- ical/chemical stability: the cyclic stability of a supercapacitor
tors” are used without a clear distinction in many reports. In depends on the mechanical/chemical robustness of the elec-
several instances, hybrid supercapacitors are also referred to as trode materials. Direct fabrication of electrode materials on
ASCs, as they use two separate electrodes, even though the CV current collectors, surface passivation, and composites with
curves show battery-type behavior. Brousse et al.[46] suggested chemically/mechanically more stable electroactive materials are
that the term “asymmetric supercapacitor” should be used only viable approaches for better cycle life. In addition, depending
for those devices where a pseudocapacitive electrode is used on the application, the toxicity and cost effectivenss of the active

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materials used in an electrode design should also be considered 4.1.1. Activated Carbon
during materials selection.
Among the various carbonaceous materials, activated carbons
(ACs) have been the first choice from research and commer-
4. Negative Electrode Materials (Anode) cial perspectives over the last 40 years due to their merits of
low cost, large theoretical surface area (≈3000 m2 g−1) and a
4.1. Carbon-Based Materials
broad pore-size tunability, ranging from macropores (>50 nm)
to nanopores (<2 nm).[14,51–54] Since the capacitive mechanism
The 21st century has predominantly become the carbon age, as for ACs is mainly physical adsorption/desorption, a large por-
carbon is the building block of almost all new energy devices, tion of the micropores remains inaccessible to the electrolyte
including Li-ion batteries, supercapacitors, ultracapacitors, and because of the incompatible pore size with electrolyte ions,
hydrogen-storage devices. Carbon-based materials are the most which significantly drops the usable surface area and the spe-
prospective candidates for anode materials in ASCs owing to their cific capacitance (Csp).[57] The capacitance of ACs with different
low cost, abundance, nontoxicity, and environmentally friendly pore sizes greatly depends on the type of the electrolyte used,
nature, as well as high electronic conductivity and outstanding and it has been suggested that ACs with pore sizes in the range
mechanical stability. These materials generally work as elec- 0.4–0.7 nm are readily available for electroadsorption with
trochemical double-layer capacitors (EDLCs); a tunable porous aqueous electrolytes, whereas a pore size of about 0.8 nm is best
structure and carbon surface chemistry, as well as large surface suited for most organic electrolytes.[51,52,55] Largeot et al.[55] sug-
area and high electrical conductivity, are desired attributes in tai- gested that a maximum EDLC could be observed in ACs with
loring electrode properties to achieve optimum performance. pores of size similar to that of electrolyte ions (Figure 2a,b),
The general electrode reaction at the carbon negative elec- while pores whose size is largely deviated from ion size can
trode in an ASC can be represented as: result in significant loss of the capacitance. Hence, it is impera-
tive to control the pore-size distribution in ACs to maximize the

Carbon + K + + e − ← 
charging
→ Carbon/K (3)
 energy/power density. Templates made of metal–organic frame-
discharging
works (MOFs) such as silica, zeolite, and MgO, have been suc-
+ cessfully employed to tailor the pore size in ACs.[58,59] Besides
where, K is a cation.

Figure 2.  a) AC capacitance as a function of pore size. The images on the right show the size of the electrolyte ions that are within the range of the
AC pore size. The maximum capacitance was obtained when the pore size was similar to the size of the ions used. b) C–V curve showing typical EDLC
behavior in AC. c) SEM image showing the 3D hierarchical porous carbon electrode structure. d) Csp as a function of current density ranging from 0.5
to 50 A g−1. a,b) Reproduced with permission.[55] Copyright 2008, ACS Publishing. c,d) Reproduced with permission.[56] Copyright 2013, RSC Publishing.

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the large surface area and controlled porosity, the surface func- the 1990s. In spite of their moderately small theoretical sur-
tionalization of ACs plays an important role in improving their face areas (≈50–1315 m2 g−1), they exhibited higher capaci-
capacitive performance. Surface-functionalization methods tances over other ACs. This is attributed to their unique
introduce heteroatoms (oxygen, nitrogen, boron, and sulfur) tubular structures and the high density of mesopores, which
into the carbon scaffold and facilitate better adsorption of ions allow fast charge transport and large accessibility of electrolyte
by making them hydrophilic in nature.[60–62] It is expected that ions.[80,81] The initial work on supercapacitors based on CNTs
the presence of functional groups on ACs endows Faradaic were mainly carried out with randomly oriented and entangled
charge-transfer reactions, resulting in ≈5–10% increase in multiwalled CNTs (MWCNTs), exhibiting a Csp in the range
Csp.[63] For example, Kim et al.[64] observed that a mild thermal of 102–135 F g−1.[82,83] Compared to MWCNTs, single-walled
oxidation of ACs enhances the Csp to ≈37%. Unlike oxygen- nanotubes (SWNTs) show better electrochemical performances
functionalized ACs, nitrogen-doped ACs are more stable, and due to their large specific surface area (≈1 600 m2 g−1), high
a significant pseudocapacitance reaction with both aqueous and aspect ratio, and better accessibility to the electrolyte ions.[84–86]
organic electrolytes can be realized.[62,65] Huang et al.[66] intro- An et al.[87] found a maximum specific capacitance of 180 F g−1
duced sulfur-modified ACs for supercapacitors and verified in arc-discharge-produced SWNT electrodes. Aligned CNTs are
almost 40% increment in the Csp. highly preferred over entangled CNTs as they present unbun-
ACs form efficient negative electrode materials in ASCs dled structures, providing more mesopores and accessible sur-
when combined with metal oxides as positive electrode mate- faces. Moreover, they provide lower contact resistance during
rials. Some of the AC-based ASCs designs developed so far the course of the charging–discharging process, leading to
include AC//Ni(OH)2,[67] AC//MnO2,[68] AC//LiMn2O4,[69] and large energy and power densities.[88,89] Chen et al.[90] reported
AC//V2O5.[70] Among the various metal oxides, MnO2 is con- a high capacitance of 365 F g−1 in highly ordered MWNT-array
sidered the most promising positive-electrode material due to electrodes fabricated using the anodic aluminum oxide (AAO)
its high abundance, nontoxic nature, and high theoretical Csp template. Later, Lu et al.[91] reported a template-free chemical
(1370 F g−1).[71,72] Kim et al.[64] fabricated an ASC with function- vapor deposition (CVD) growth of aligned MWCNTs elec-
alized ACs as the negative electrode and MnO2/SiC nanoneedle trodes, exhibiting a higher capacitance of 440 F g−1. Kim and
composites as the positive electrode. The optimized ASC could co-workers directly grew vertically aligned CNTs on conductive
be operated in a voltage window of 0–1.9 V and exhibited a Csp carbon papers using water-assisted CVD,[92] which exhibited a
of 59.9 F g−1 with excellent maximum energy and power den- Csp of about 200 F g−1 at 20 A g−1.
sity of 30.06 W h kg−1 and 113.92 W kg−1, respectively. Three- In addition to the inherent EDLC mechanism offered
dimensional (3D) porous ACs are desired for better perfor- by CNTs, their capacitive performances have been further
mances as they not only facilitate continuous electron pathways enhanced by combining them with other materials such as
for good electrical contacts, but also provide shorter diffusion metal oxides, ACs, and CPs.[93–95] These additives introduce the
paths for electrolyte ions.[73] Quie et al.[56] presented function- advantages of high specific capacitance (pseudocapacitance),
alized 3D hierarchical porous carbon structures (Figure 2c) excellent conductivity, and/or large surface areas to the CNT
with large surface area (2870 m2 g−1) and excellent electrical matrices. Negative ASC electrodes based on nitrogen-doped
conductivity (5.6 S cm−1). The 3D hybrid electrodes showed a AC-coated MWCNT composites show a high specific capaci-
high capacitance (≈318 F g−1) (Figure 2d), excellent rate perfor- tance of 311.7 F g−1.[96] The improved electrical conductivity
mance, and capacitance retention above 90% in both aqueous in asymmetric devices resulted in a high operational voltage
and organic electrolytes. Recently, carbon cloth (CC) is drawing window of 1.9 V and an energy density of 26.4 mW h g−1.
significant attention as a promising negative electrode material Zhang et al.[97] investigated synergetic effects of Co–Al lay-
because of its high conductivity, low-cost, and high mechanical ered double hydroxide (LDH) mixed with MWCNTs, achieving
flexibility, suitable for flexible solid-state supercapacitors.[74,75] a specific capacitance of 342 F g−1. Binders have been used
Wang et al.[76] demonstrated a high areal capacitance of to incorporate CNTs with other pseudocapacitive materials,
756 mF cm−2 in functionalized CC electrodes. The CC//TiN@ which inevitably increases the dead volume in the composite
MnO2 ASC delivered a remarkable cyclic stability without any electrodes.[98] Zhang et al.[99,100] grew a 3D CNT-array network
capacitance decay after 70 000 cycles. directly on a tantalum (Ta) foil current collector, followed by the
deposition of PANI and MnO2 nanoflowers to construct hybrid
composites (Figure 3a). The transmission electron microscopy
4.1.2. Carbon Nanotubes (TEM) image in Figure 3b shows that MnO2 nanoflowers tend
to nucleate at the junctions of CNTs rather than at their curved
Despite the great use of AC materials as ASC electrodes, the surfaces. These binder-free composites presented good syner-
inaccessibility of the electrolyte ions into their micropores gistic effects; a very high Csp of 1030 F g−1 was achieved for
and/or interior atoms at higher scan rates still remains the PANI–CNTs, and a long cycle life with only 3% capacity loss
central issue that limits their effective capacitances.[77] In after 20 000 cycles for a MnO2–CNTs electrode (Figure 3c).
addition, their poor electrical conductivity leads to a higher The intrinsic mechanical flexibility of CNTs makes them suit-
internal resistance that prevents them from being used in able for flexible energy-storage systems toward flexible superca-
high-power-density supercapacitors.[78] Alternatively, carbon pacitors.[101,102] In an early report, Chen et al.[103] demonstrated a
nanotubes (CNTs) have been suggested as a supercapacitor facile method to grow 3D MWNT flexible, lightweight electrodes
electrode material, initially proposed by Niu et al.[79] back in directly on various substrates (carbon, metal foils, etc.), which

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Figure 3.  a) Schematic showing the procedure for the preparation of a MnO2 nanoflowers/CNTA composite electrode. b) TEM image showing MnO2
nanoflowers grown at the CNT junctions. c) Capacitance retention curves up to 20 000 cycles. A–c) Reproduced with permission.[100] Copyright 2008,
ACS Publishing.

essentially shaped the idea of integrating CNTs for flexible cific capacitance of up to 550 F g−1, outperforming almost every
supercapacitors. Recently, Qiu et al.[104] fabricated a 3D electrode EDLC electrode material, including ACs, CNTs, mesoporous
structure with vertically aligned CNTs directly grown on carbon carbon, and xerogels.[31,111,112] The schematic of Figure 4 illus-
nanofibers (VACNTs/CNFs). The combination of high charge- trates the merits and demerits of ACs, CNTs, and graphene
storage capacity in the branched VACNTs with the highly con- for EDLC supercapacitors.[113] The nonuniform distribution
ducting CNFs enabled a high specific energy of 70.7 W h kg−1 of pore size in AC limits the access of electrolyte ions: a large
and excellent cycle performance to be delivered, with 97.0% fraction of the ACs remains unused, resulting in small capaci-
retention even after 20 000 charging/discharging cycles. In tance (Figure 4a). Although CNTs present higher electrical
recent years, the applications of CNT fibers to supercapacitors conductivity than ACs and graphene, they tend to easily stack
have evolved toward the development of highly flexible woven into bundles, and only the outer portion of the stack is available
or knitted fabrics/textiles with excellent wearability.[105] ASCs for ion adsorption (Figure 4b). This in turn leads to poor elec-
made with CNT yarn as the negative electrode and CNT@MnO2 trochemical performance. Graphene and its derivatives have
composite yarn as the positive electrode delivered about five- shown a great combination of desired properties (conductivity,
times-higher energy density (42.0 W h kg−1) and power density surface area, mechanical strength), which leads to better elec-
(483.7 W kg−1) as compared to a symmetric supercapacitor made trochemical performance as compared to ACs and CNTs.[111,114]
of CNT//CNT.[106] Despite enormous research efforts on CNTs, However, the tendency of graphene sheets to form irreversible
the bottleneck of transferring this technology to the marketplace agglomerates of graphite via van der Waals interactions leads to
is the lack of efficient and scalable manufacturing methods. significant surface area loss (Figure 4c), which, in turn, limits
Entanglement in CNTs is a major problem that results in poor ion diffusion and Csp.[34,115,116] Several methods, including gas–
efficiency as it limits ionic transport. Furthermore, purification solid reduction processes, treatment with weak reducing agents,
of CNTs and its associated high cost are another limiting factor. and adding a spacer between graphene nanosheets, have been
addressed to counter the graphene restacking problem.[45,117,118]
Liu et al.[119] proposed a unique curved morphology that
4.1.3. Graphene prevents the re-stacking of graphene nanosheets, as well as
enables the formation of mesopores accessible to ionic elec-
Graphene, an atomically thick 2D carbon layer, is an emerging trolytes, pushing the energy-density level to 90 W h kg−1. Qin
negative-electrode material owing to its exceptionally large et al.[113] proposed the idea of using CNT spacers in between
theoretical surface area (2630 m2 g−1), excellent EDLC mecha- graphene sheets to reduce their agglomeration and internal
nism, ballistic electrical and thermal conductivities, and great resistances, as well as improving the accessibility for electro-
mechanical strength.[107–110] The high intrinsic double-layer lyte ions (Figure 4d). In addition, CNTs function as a binder
capacitance (≈21 µF cm−2) in graphene can provide a large spe- for graphene, rendering mechanical stability and longer cycle

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for ultralightweight electrode materials,
owing to their large surface area, intercon-
nected micro-/macroporous structures,
excellent electrical conductivity, and sta-
bility.[135–138] Their unique 3D architecture
can effectively prevent the agglomeration
of graphene nanosheets, as well as facilitate
fast ionic transportation. In addition, their
self-supporting nature circumvents the use
of electrochemically inactive binders.[139–141]
Gao et al.[34] prepared graphene hydrogels
via the reduction of well-dispersed graphite
oxide solution, achieving Csp of ≈150 F g−1 at
20 mV s−1. Tang et al.[142] fabricated a novel
ASC based on a highly porous graphene
foam (GF) negative electrode prepared by
mild reduction. The fabricated ASC device
was found to work in a voltage window
of 1.6 V with an excellent energy density
Figure 4.  Schematic illustration of the intrinsic limitations of different carbon materials. a) AC: of 34.5 W h kg−1 at the power density of
having large surface area, but many pores are inaccessible by electrolyte ions. b) CNTs: form 547 W kg−1. Recently, our research group
bundles and only the outer surface is available for electrolyte–CNT interaction. c) Graphene developed a functionalized graphene aerogel
sheets: tend to agglomerate due to van der Waal interactions and thereby electrolyte ions
(GA) by conformally doping palladium
refrain from reaching small pores. d) Graphene/CNT composite: CNTs act as spacer and
binder from graphene sheets, as well as provide large conduction pathways to electrons and (Pd) nanoparticles on graphene nanosheets
ions. A–d) Reproduced with permission.[113] Copyright 2011, RSC Publishing. (P-GA) followed by a lyophilization and
two-step reduction method, as shown in
life. SWNT–graphene composite electrodes prepared by this Figure 5a.[132] Figure 5b–d show the scanning electron micro­
method reached a Csp of 290 F g−1 in aqueous electrolyte.[113] scopy (SEM) images of GA and P-GA samples. It is evident
Metal oxides and/or CPs have been widely used to make from the figures that Pd nanoparticles were embedded into the
composites with graphene for high-performance supercapaci- GA with a uniform dispersion. The introduction of Pd nanopar-
tors.[120–123] MnO2 has been incorporated into graphene, as ticles enabled a significant reduction of the electrical resistivity
compared to other metal oxides, due to its environmentally by 50 times (i.e., from 950 to 16 Ω cm). Additionally, a negative
friendly nature and ability to work as spacer sheets.[123–125] Yu electrode based on P-GA showed a Csp of 175.8 F g−1 at a scan
et al.[126] developed graphene/MnO2 nanocomposites wrapped rate of 5 mV s−1, which is more than 3 times enhancement as
with CNTs and demonstrated improved electrochemical per- compared to that without Pd doping (51.9 F g−1). The MnO2//P-
formances by ≈45%, offering a specific capacitance value as GA ASC delivered an average energy density of ≈13.9 W h kg−1
high as 380 F g−1. Wang et al.[127] synthesized a hybrid elec- at a power density of ≈13.3 kW kg−1 (Figure 5e,f).
trode material by loading Ni(OH)2 pseudocapacitive nanoplates
on graphene sheets. This electrode exhibits a very high Csp
of ≈1335 F g−1 at the charge and discharge current density of 4.2. Metal Oxides
2.8 A g−1. Usually, chemically reduced or functionalized gra-
phene suffers from poor electrical conductivity (100–200 S m−1) Although carbon-based materials hold great potential as nega-
and thereby lower electrochemical performances have been tive electrodes, their intrinsically low Csp and low energy den-
observed in several instances.[128] Composites of graphene and sity are major drawbacks. Hence, it is imperative to explore new
conducting polymers (CPs) have been employed to mitigate materials that simultaneously exhibit high capacitance, as well
this problem, as CPs offer low cost, high conductivity, and high as high conductivity. In this regard, metal oxides are promising,
theoretical capacitance.[129,130] Zhang et al.[131] prepared gra- as they rely on a pseudocapacitive charge-storage mechanism,
phene/PANI nanofiber composites by in situ polymerization of in which fast reversible redox reactions occur near the elec-
aniline with graphene oxide. These composites showed a high trode surfaces, offering high capacitance and energy densities.
Csp of 480 F g−1 at a current density of 0.1 A g−1. Among various metal oxides, ferric oxide (Fe2O3) presents a
Recently, Wang et al.[133] achieved a large Csp of 356 F g−1, high theoretical Csp, an ideal voltage window, cost-effectiveness,
even at a high current desnity of 20.0 Ag−1 after 1000 cycles abundance, and environmental friendliness.[143–146] However,
in PANI/graphene oxide composites. Even though graphene- its conductivity (≈10−14 S cm−1) severely limits its resultant
based composite electrodes using metal oxides and/or CPs have capacitance and power capability. Constructing Fe2O3 in nano-
shown great improvements in the Csp, these materials usually structures, such as nanorods/nanotubes,[147] quantum dots,[30]
suffer from inferior power performance and cyclicity due to nanosheets,[144,148] and nanoparticles[101,149,150] has been pursued
their pseudocapacitive nature.[120,134] Recently, 3D graphene- to alleviate this issue, as it can provide short diffusion paths to
based frameworks (3DGFs) such as sponges, foams, hydro- electrons, thereby improving the electronic conductivity. Yang
gels, and aerogels have been emerging as potential materials et al.[151] designed a flexible ASC based on Fe2O3 nanotubes

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Figure 5.  a) Schematic illustration showing the fabrication process of P-GA. b,c) SEM images of the GA (b) and P-GA (c). d) HRTEM images of P-GA.
e) Schematic showing ASC device construction using MnO2 and P-GA electrodes. f) Ragone plot reflecting the superiority of P-GA nanostructures
over other electrode materials. The inset shows a red LED powered by using two devices connected in series. a–f) Reproduced with permission.[132]
Copyright 2015, Elsevier Publishing.

grown on a flexible carbon cloth as an the anode, and MnO2 nanowire array structure in which the α-Fe2O3 nanowire array
nanorods as the cathode. The flexible device worked in a large was electrodeposited on carbon fiber followed by thin-film dep-
voltage window of 1.6 V and exhibited excellent energy density osition of PANI polymer. A significant enhancement in the Csp
of 0.55 mW h cm−3. Another strategy employed to circumvent from 33.93 mF cm−2 to 103 mF cm−2 in the α-Fe2O3@PANI
the electrical-conductivity issue is to make Fe2O3 nanocompos- electrode was noticed, as well as a cyclic stability of 95.77%
ites with conductive agents like carbonaceous materials and after 10 000 cycles. Recently, Zeng et al.[153] reported a flexible
conducting polymers. Xia et al.[30] fabricated large-scale Fe2O3 Ti-doped Fe2O3/PEDOT core–shell nanoarray on carbon cloth,
quantum dots (QDs) (≈2 nm) decorated with functionalized exhibiting a significantly high areal capacitance of 1.15 F cm−2
graphene sheets (FGS). The well-dispersed Fe2O3 QD elec- with 96% capacitance retention after 30 000 cycles.
trodes without graphene agglomeration exhibited a very high Molybdenum trioxide (MoO3) and tungsten trioxide (WO3)
Csp of 347 F g−1 in liquid electrolytes. Recently, Liu et al.[152] are also promising candidates for anode materials in ASCs
developed Fe2O3 nanodot negative electrodes supported on due to their high theoretical specific capacity and thin sheet-
N-doped graphene sheets that resulted in a long cyclic stability like structure that facilitate the fast insertion/removal of even
of about 75.3% capacitance retention after 100 000 cycles. The smaller electrolyte ions.[154,155] Similar to Fe2O3, they also suffer
bottleneck of using carbon-based materials for Fe2O3 compos- from poor electrical conductivity, and, thereby, loading addi-
ites is their affinity in forming organic compounds that are not tional active materials with high surface area and high conduc-
environmentally friendly. CP coatings have been alternatively tivity is required to overcome this problem. Sun et al.[156] assem-
pursued to enhance the Csp and the stability of Fe2O3. Li and bled an ASC device based on free-standing CNT–tungsten oxide
co-workers[147] fabricated a novel 3D α-Fe2O3@PANI core–shell (WO3) hybrid films prepared by vacuum filtration and physical

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vapor deposition (PVD) methods (Figure 6a). The resulting 4.3. Metal Nitrides
device showed a high capacitance (2.6 F cm−3), an extended
operating voltage (1.4 V), and high power/energy densities. In Metal nitrides are emerging anode materials that are supe-
addition, the ASC exhibits 75.8% capacitance retention after rior to metal oxides in terms of electrical conductivity
50 000 cycles. (Figure 6b). These devices were able to charge (4000–55 500 S cm−1) and pseudocapacitive behavior, providing
a mobile phone, as shown in Figure 6c. Despite the enhanced high power and energy densities for ASCs.[163,164] Among the
capacitive performance, the poor corrosion resistance of various nitrides, titanium nitride (TiN) has been the most
carbon materials in the electrochemical window of some metal widely studied anode due to its high electrical conductivity
oxides is a potential drawback. Therefore, several research and mechanical stability. Despite the development of TiN in
groups have developed carbon MoO3 or WO3 anodes for high various morphologies, such as nanotubes,[165] nanosheets,[166]
performance ASCs. Li et al.[157] demonstrated a ZnO@MoO3 and mesoporous microspheres,[167] the fast irreversible oxidi-
core–shell nanocable supercapacitor electrode where the ZnO zation of these materials in aqueous solution impedes their
nanorod core provided a high electrical conductivity whereas electrochemical stability.[168] Choi et al.[169] reported that a TiN
the thin MoO3 layer shell enabled a fast, reversible Faradaic electrode could retain only 28% of its initial capacitance in
reaction and provided a short ion diffusion path, leading to a alkaline electrolyte solution after just 400 cycles. Lu et al.[170]
Csp of 236 F g−1, which is much higher than that of pristine demonstrated a novel core–shell structure in which TiN nanow-
MoO3 nanoparticles. Recently, Wang et al.[158] reported WO3@ ires were covered with ultrathin amorphous carbon protective
Ppy core@shell nanowire arrays for novel negative electrodes layers.[171] The TiN–carbon core–shell electrode demonstrated
in ASCs. The core–shell nanowire electrode exhibited a high a remarkable 91.3% retention in aqueous electrolyte after
areal capacitance of 253 mF cm−2 and the ASC device showed 15 000 cycles without any oxidation. Similarly, TiN was com-
a high volumetric capacitance up to 2.865 F cm−3 and good sta- bined with more stable materials like graphene,[172,173] TiO2,[174]
bility. Besides these, other metal oxides, such as manganese VN,[175] MnO2,[176] and CPs to form core–shell structures to
oxides (e.g., MnO2),[159] indium oxides (e.g., In2O3),[160] bis- improve its cycle stability and rate performance. For example,
muth oxides (e.g., Bi2O3),[162] etc. have been recently explored Zhu et al.[177] fabricated an all-nitride-based ASC device using
as emerging negative-electrode materials for advanced ASC atomic layer deposition (ALD)-grown TiN and Fe2N on verti-
applications. cally aligned graphene-nanosheet electrodes. The ASCs based

Figure 6.  a) Schematic diagram showing the preparation of a WO3–CNT electrode. b) Cycle performance and Coulombic efficiency of the ASC device for
50 000 cycles at a current density of 1 mA cm−2. The inset shows the CV curves of the 1st cycle and the 50 000th cycle. c) Three ASC devices connected
in series can charge a cell phone. d) SEM images of the as-prepared WON nanowires. e) TEM image showing the rough surface of the WON nanowire.
The inset shows its polycrystalline nature. c) Cyclic stability of WON electrode over 100 000 cycles, measured at 100 mV s−1. The insets are CV curves
of the WON electrode after 100, 50 000, and 100 000 cycles. A–c) Reproduced with permission.[156] Copyright 2015, RSC Publishing. d–f) Reproduced
with permission.[161] Copyright 2015, Wiley-VCH.

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on them yielded a capacitance of 58 F g−1 in the solid elec- It is because the bulk of the material is exposed to the redox
trolyte, which was stable up to 20 000 cycles. The substantial reactions, unlike EDLC where the adsorption of ions takes
improvement was attributed to the ultrahigh surface area of the place only at the surface layers. In this section, we will discuss
vertically aligned graphene and the enhanced coverage of the important redox-active materials like conductive polymers (e.g.,
active nitride materials over graphene enabled by the ALD. polyaniline (PANI), poly(3,4-ethylenedioxythiophene) (PEDOT),
Vanadium nitride (VN) is considered another prom- polypyrrole (PPy)) and transition-metal oxides/hydroxides
ising electrode material due to its high theoretical Csp (up to (MnO2, RuO2, V2O5, and Ni(OH)2).
1340 F g−1), reversible and fast redox Faradaic response, and The general cathode reaction can be given as:
excellent electrical conductivity (≈104 S cm−1).[178,179] The pio-
neer work by Choi et al.[180] demonstrated a pseudocapacitive 
MnO2 /M ← 
charging
→ MnO2 + M+ + e − (4)
behavior of nanostructured VN electrodes offering a high Csp of discharging

≈400 F g−1 at a scan rate of 50 mV s−1. However, VN electrodes


become unstable in aqueous electrolytes due to the irreversible where M+ is the cation.
formation of vanadium oxide, which leads to significant perfor-
mance decay upon cycling.[178,180,181] Li et al.[178] utilized LiCl/
poly(vinyl alcohol)(PVA) polymer electrolyte to stabilize the 5.1. Conductive Polymers
porous VN nanowires. The ASC device employing stabilized
VN nanowires as the anode and vanadium oxide (VOx) NWs Conducting polymers (CPs) are promising ASC electrode
as the cathode achieved a high capacitance retention of 95.3% materials because of their high electrical conductivity, large
after 10 000 cycles. Furthermore, VN composites with CNTs charge/discharge cycles and high pseudocapacitance.[189–191]
were developed to enhance the electrical conductivity and rate PANI, PEDOT, polythiophene (PTh), and PPy are the com-
capabilities.[182] Ghimbeu et al.[183] prepared highly porous VN/ monly used CPs electrodes. One main drawback is that CPs
CNTs composites by sol–gel and temperature-programmed expand/shrink during the intercalation/deintercalation process,
ammonia-reduction methods, demonstrating high capacitance which leads to the mechanical failure of the electrodes when
retention (58%) as compared to pure VN (7%) at a higher cur- subjected to longer cycling, resulting in fading of the electro-
rent densiy of 30 A g−1. chemical performance and stability. Sharma et al.[192] observed
Dong et al.[184] synthesized TiN/VN composite electrodes and a 50% decrement in initial capacitance just after 1000 cycles in
reported a Csp of 170 F g−1 at a scan rate of 2 mV s−1. The excel- a PPy-based supercapacitor electrode. Similarly, the loss of Csp
lent performance was attributed to the fast transportation of of PANI nanorods was ≈29.5% after 1000 cycles.[193] Hence, low
electrons owing to the structural integrity of the VN interfaced cycling stability is the major concern associated with CP-based
with TiN. Similarly, Zhou et al.[185] reported the fabrication electrodes.
of mesoporous coaxial TiN–VN core–shell structures. These Proper design of the polymer microstructure and mor-
hybrid electrodes exhibited a high Csp of 247.5 F g−1 at 2 mV s−1 phology has been explored to enhance the electrochemical
with an excellent rate capability owing to their high surface area energy-storage ability and cycling stability of CPs-based elec-
and electrical conductivity. trodes. It has been observed that constructing CPs in the forms
Besides TiN and VN, molybdenum- and tungsten-based of nanofibers, nanorods, nanowires, and nanotubes can signifi-
nitrides have also been pursued to improve electrochemical cantly overcome their poor cyclic stability by providing short
stabilities.[186,187] Li et al.[188] studied the electrochemical per- diffusion lengths to maximize the electrolyte exposure. For
formance of molybdenum nitride (MO2N) nanoparticles as example, Wang et al.[194] observed 95% capacitance retention
ASC electrodes, and achieved a Csp of 172 F g−1 in 1 m H2SO4 after 3000 cycles in ordered nanoscale PANI whiskers in 1 m
electrolyte. Very recently, Yu et al.[161] synthesized tungsten H2SO4 solution. The vertical nanowire construction of CPs is
oxynitride (WON) nanowires on carbon cloths by the nitrida- even more intriguing for energy storage, as compared to dis-
tion of WO3 precursor nanowires (Figure 6d,e). The WON ASC ordered networks, because: i) each nanowire contributes to the
anode showed a high volumetric capacitance of 4.95 F cm−3 at capacitance, as it is directly connected to conducting substrates;
12.5 mA cm−3. Most importantly, an unprecedented cycling sta- ii) the 1D structure allows fast charge transport with short
bility with only 7% capacitance loss even after 100 000 cycles diffusion paths; and iii) the interface between the nanowires
was reported, which is amongst the best cycling performance can accommodate large volume expansions without cracking.
ever reported for metal nitrides or oxynitrides (Figure 6f). Huang et al.[195] fabricated PPy nanowire arrays using one-
step electropolymerization and compared their performances
with disordered nanowires and compact films made of same
5. Positive Electrode Materials (Cathode) materials. Figure 7a–c show the SEM images of the different
morphologies of the PPy in the forms of film, nanowire net-
Positive electrodes for ASCs generally utilize the materials that work, and nanowire arrays. Figure 7d shows that ion transport
exhibit a large amount of pseudocapacitance originating from is much easier in the nanowire arrays as compared to the film
the Faradaic charge transfer via fast and reversible redox reac- or entangled nanowire network, achieving a high capacitance of
tions, electrosorption/desorption, or via intercalation/deinterca- about 566 F g−1, while the networks and the film showed capac-
lation of the electrolyte with the electrode. The pseudocapacitive itances of 414 and 378 F g−1, respectively (Figure 7e). Ordered
behavior is generally accompanied by a high Csp and relatively PANI nanowire arrays were also explored, and Wang et al.[196]
high energy density, as compared to the EDLC mechanism. reported a dramatically high capacitance of 950 F g−1 in PANI

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Figure 7.  a–c) SEM images of conducting PPy film (a), PPy nanowire network (b), and PPy nanowire arrays (c). d) Ion-transport pathways through
different PPy geometries. e,f) Csp (e) and capacitance retention (f) of PPy with different morphologies. a–f) Reproduced with permission.[195] Copyright
2010, RSC Publishing.

nanowire arrays, attributed to their unique structure and mul- composite up to 3000 cycles. Very recently, Kurra et al.[201] built
tiple oxidation states. a flexible solid-state ASC based on all-nanostructured CPs,
Another strategy explored to enhance the mechanical i.e., PEDOT was used as the anode and PANI was used as the
strength, conductivity, and cyclic stability of CPs is to make cathode. The asymmetric device showed a maximum power
composites with carbon-based materials.[197] CNTs are con- density of 2.8 kW L−1 at an energy density of 9 W h L-1.
sidered as an effective additive because of their exceptional
mechanical properties, large surface areas, and superior elec-
trical conductivities, all of which can help to mitigate the 5.2. Metal Oxides
cycle degradation problems in pristine CPs.[198] Zhang et al.[99]
used a hierarchical porous PANI/CNT composite for the elec- 5.2.1. Ruthenium Oxide (RuO2)
trodes, and demonstrated a high Csp (1030 F g−1) and supe-
rior rate capability and stability (95% capacity retention after RuO2 is a promising electrode material for ASCs due to its high
5000 cycles). Similarly, graphene has also been pursued, owing specific capacitance, reversible redox reactions with large poten-
to its excellent conductivity, large surface area, and superior tial window, and longer cycle life. Among its two phases, i.e.,
chemical stability. Wang et al.[194] reported the first graphene/ crystalline phase (rutile RuO2) and amorphous hydrous phase
PANI-composite-based supercapacitor electrodes with a capaci- (RuO2·xH2O), the latter is generally more promising owing to
tance of 233 F g−1, which was about two times greater com- its ultrahigh pseudocapacitance and large active reaction sites,
pared to pure graphene electrodes. Yan et al.[199] synthesized as well as the high electron and proton conductivities.[202,203]
graphene/PANI composites and demonstrated a very high Especially, nanostructured RuO2 in various morphologies like
capacitance of 1046 F g−1 at 1 mV s−1. In addition, the energy nanoparticles, nanoneedles, nanorods, and nanofibers have
density of the graphene/PANI composite reached 39 W h g−1 at shown remarkable electrochemical performance.[204,205] Hu
a power density of 70 kW kg−1. et al.[206] reported a nanotubular (NT) arrayed porous elec-
CPs have demonstrated a great potential for low-cost, light- trode made of RuO2·xH2O. This 3D mesoporous architec-
weight, and highly flexible supercapacitor electrodes as stand- tured material with hydrous nature and metallic conductivity
alone materials or composites. Wei et al.[200] demonstrated exhibited a Csp of 740 F g−1, which was increased to 1300 F g−1
a flexible supercapacitor device made of PANI nanowires after annealing in air at 200 °C for 2 h. Despite the exceptional
deposited on a cloth-supported SWCNT flexible substrate. pseudocapacitive properties, RuO2 is not suitable for large-
The PANI/SWNT/cloth composite electrode showed a capaci- area commercialization due to its low abundance and high
tance of 410 F g−1, which is much higher than that of SWNT/ cost. As an alternative, RuO2-based composites, with cheaper
cloth (60 F g−1) and PANI/cloth (290 F g−1) electrodes. In addi- materials possessing high capacitive properties, were pur-
tion, a high capacitance retention of 90% was observed in the sued, and carbonaceous materials (AC, CNTs, carbon aerosols,

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graphene) have been widely utilized.[207–209] Lee et al.[210] fab- RuO2 composites anchored to graphene not only suppress
ricated MWNT/RuO2 composite electrodes by impregnating the agglomeration and restacking of the graphene but also
RuO2 into MWNTs in an acidic solution. The capacitance was increase the available surface area and provide electron-con-
measured for the films of different RuO2 loading, revealing ductive networks. Wu et al.[120] showed that hydrous RuO2 nan-
Csp per mass as high as 628 F g−1. Das et al.[211] showed even oparticles (size ≈5–20 nm) were homogeneously anchored on
more promising results by electrodepositing RuO2 on highly the graphene sheets and demonstrated a high Csp of 570 F g−1,
porous SWNT films, achieving a Csp of 1715 F g−1 with regard enhanced rate capability, excellent electrochemical stability
to the weight of RuO2. Another potential problem with RuO2- (97.9% retention after 1000 cycles), and high energy density
based electrodes is the possible cracking of the material due (20.1 W h kg−1). In a recent report, Kaner et.al.[215] demon-
to the strain developed during the charging–discharging strated miniaturized and interdigitated supercapacitors made
cycles, leading to a poor long-term stability.[212,213] To solve of 3D porous RuO2 nanoparticles anchored to graphene sheets
this problem, Wang et al.[214] developed a novel core–shell- (Figure 8a). The high-resolution TEM (HRTEM) image in
templated approach to fabricate CNT-supported hollow-struc- Figure 8b reveals that multiple layers of the graphene sheets
tured (hRuO2) nanoparticles. The hRuO2/CNT nanocomposite wrapped around each RuO2 nanoparticle. These electrodes
electrode showed a high specific capacitance of 655.0 F g−1 at exhibited an ultrahigh Csp of 1139 F g−1 with excellent rate
a current density of 5 A g−1 without any crack formation. Sev- capability (Figure 8c). Furthermore, ASCs employing the gra-
eral variations of RuO2 nanostructures anchored, wrapped, or phene sheet/RuO2 as the positive electrode and an AC negative
encapsulated with graphene have shown good synergy and electrode demonstrated an extremely high energy density of
significant improvement in their electrochemical properties. 55 W h kg−1 at a power density of 12 kW kg−1.

Figure 8.  a) Microfabrication process of LSG/RuO2 interdigitated micro-supercapacitors via direct laser writing on a DVD disc using a LightScribe
DVD burner. b) A high-magnification TEM image illustrating complete wrapping of the RuO2 nanoparticles (NP) by the LSG sheets. c) The gravimetric
capacitance retention of LSG and LSG/RuO2 electrodes as a function of the applied current density. d) Facile redox method for controlled nanostruc-
tured MnO2 growth on CNT surface. e) TEM images showing MnO2 coverage over the surface of a CNT. f) The cyclic curve of a MnO2–CNT nanowire
composite at 2 A g−1. a–c) Reproduced with permission.[215] Copyright 2015, Elsevier Publishing. d–f) Reproduced with permission.[216] Copyright 2015,
Elsevier Publishing.

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CPs were incorporated into RuO2,[217–220] which helps in pre- demonstrated the direct growth of MnO2 in a CNT matrix by
venting the aggregation of hydrous RuO2 by steric and electro- a facile thermal decomposition of manganese nitrates. The
static effects, as well as improving the adhesion of RuO2 to the MnO2/CNT composite exhibited a Csp of 568 F g−1 and an
current collectors. A tubular RuO2/PEDOT composite electrode excellent cyclic stability of 88% after 2500 charge–discharge
exhibited a dramatically high Csp of 1217 F g−1, which was attrib- cycles. Besides the thermal-decomposition method, other effec-
uted to their high surface area, providing short diffusion paths tive methods, such as electro-deposition,[245] the microwave-
and low ionic resistance for the diffusion of counter-ions.[221] In assisted method,[246] and hydrothermal[247] and redox deposition
order to make more-cost-effective composites, RuO2 has been methods[248] have been extensively employed to attach MnO2
combined with cheap metal oxides such as MnO2, VOx, TiO2, onto the side walls of CNTs. For example, MnOx nanoparticles
MoO3, and SnO2 to form composite oxide electrodes.[222–225] electro-deposited onto CNT nanosheets resulted in improved
performance, exhibiting a high Csp of 1250 F g−1 with a high
rate capability.[249] In a recent study, Huang et al.[216] demon-
5.2.2. Manganese Oxide (MnO2) strated a facile redox approach for the controlled growth of
MnO2 nanostructures on CNTs, revealing the influence of
MnO2 is a promising electrode material for pseudocapacitor replacing CNTs on electrochemical properties (Figure 8d,e).
applications owing to its higher electrochemical performance, The resulting MnO2–CNT electrode exhibited a maximum Csp
low cost, and environment benign nature.[226–229] The low sur- of 247.9 F g−1, and an extraordinary cycle life, retaining 92.8%
face area and poor electronic/ionic conductivity of MnO2 are two retention of initial capacitance after 5000 cycles (Figure 8f).
major problems that hinder their practical uses. Engineering the Furthermore, aligned CNTs have been preferred over non-
morphology of MnO2 into nanostructures is considered to be a aligned CNTs because of their low contact resistance, large
viable approach to enhance its electrochemical performance. 1D specific surface area, and fast electron-transfer kinetics. Zhang
MnO2 nanostructures generally provide short diffusion paths for et al.[100] realized well-dispersed MnO2 nanoflower structures
ions and electrons, as well as offer large surface areas, resulting on vertically aligned CNTs, achieving excellent rate capability
in high charge/discharge capacities. Qu et al.[68] tested the per- (50.8%), high capacitance, and long cycle life (3% capacitance
formance of MnO2 nanorods in different electrolytes (Li2SO4, loss after 20 000 cycles). Amade et al.[250] further optimized the
Na2SO4, and K2SO4) prepared by precipitation reaction methods. parameters to fabricate dense, long, and vertically aligned CNT
The nanorods show the largest capacitance (201 F g−1) in Li2SO4, composites with a thin layer of MnO2, reporting a significant
while an excellent cycling behavior with only 6% loss of initial enhancement in Csp (642 F g−1). MnO2–CNT composites have
capacitance after 23 000 cycles. MnO2 nanowires were preferred also been used to make flexible supercapacitor devices.[251]
over nanorods as they provide a larger specific surface area and Gu et al.[252] reported an all-solid-state asymmetric stretchable
shorter diffusion paths for protons.[230] Wu et al.[231] reported supercapacitor using a wrinkled MnO2/CNT hybrid film as the
that MnO2 nanowires (≈8–16 nm in diameter) exhibited a positive electrode and a wrinkled Fe2O3/CNT composite film
higher capacitance of 350 F g−1 as compared to MnO2 nanorods as the negative electrode. The ASC devices showed a supreme
(≈15–35 nm in diameter) with a capacitance of 243 F g−1. energy density of 45.8 W h kg−1 along with very high cyclic sta-
Similarly, several studies showed that single-crystal α-MnO2 bility, retaining 98.9% Csp even after 10 000 cycles.
nanowires with a pore size between 3 and 30 nm exhibited a Graphene nanosheets and its derivatives have also been
Csp value as high as 466 F g−1 along with good cyclic stabili- explored to make MnO2 nanocomposite electrodes.[253,254]
ties.[232–234] However, the use of extensive processes, expensive Wu et al.[31] studied the performance of ASCs using a MnO2
reagents, and time-consuming operations are the major con- nanowire/graphene composite as the positive electrode and gra-
cerns that restrict them for industrial-scale production. phene as the negative electrode in aqueous Na2SO4 solutions. It
Incorporating MnO2 with other materials of high surface was discovered that nanostructured MnO2 prevented the aggre-
area and electrical conductivity have been extensively inves- gation of graphene sheets caused by van der Waals interactions,
tigated to extend the working voltage and to improve the sta- generating a large electrochemical active surface area and porous
bility of the resulting electrodes. Most of the reports pertaining structures suitable for energy storage. Moreover, the ASC device
to MnO2 composites are with carbonaceous materials such as based on graphene/MnO2 operated in a high voltage window of
ACs, CNTs, and graphene.[235–237] Gao et al.[238] fabricated a 0–2.0 V and exhibited a high energy density of 30.4 W h kg−1.
hybrid supercapacitor based on MnO2/AC composite as the pos- Cheng et al.[255] fabricated binder-free graphene/MnO2 superca-
itive electrode and AC as the negative electrode. They showed pacitor electrodes in which MnO2 was deposited directly on gra-
that the AC not only worked as a conducting agent but also phene using in situ anodic electrodeposition. The Csp reported in
served as an active element in enhancing the capacitance, as this study was 328 F g−1 and the power density was 25.8 kW kg−1,
well as the power and energy densities. Supercapacitors based which is suitable for high-power applications. The advent of
on mesoporous-MnO2/AC composites are receiving signifi- 2D planar capacitive materials enables the fabrication of much
cant attention because the Csp and the rate capability of MnO2 thinner, compact, and flexible ASC devices,[256,257] while the
greatly depend on the pore size of the active materials.[239,240] non-2D structures of MnO2 restrict it from being integrated into
CNTs are other promising materials to be incorporated, owing planar devices. Peng et al.[258] prepared ultrathin 2D MnO2/gra-
to their outstanding structural and electrical properties, high phene hybrid planar supercapacitors based on ultrathin δ-MnO2
external surfaces, and good chemical stability. Initial studies nanosheets integrated with graphene sheets. This unique design
on MnO2/CNT nanocomposites[241–243] exhibited a capacitance enabled a high Csp of 267 F g−1 at a current density of 0.2 A g−1
comparable to AC-based MnO2 composites. Chen et al.[244] with capacitance retention of 92% after 7000 charge/discharge

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cycles. In addition, the planar supercapacitors showed supe- more than 90% capacitance retention after 4000 cycles and the
rior flexibility and robust cyclability with a capacitance decay of energy density was reported upto 107 W h kg−1 at a power den-
only 10% after 1000 times of folding/unfolding. Later, Zhang sity of 9.4 kW kg−1. Very recently, Liang et al.[270] developed a
et al.[259] reported highly flexible, all-solid-state ASCs based on facile approach to fabricate ultrafine porous V2O5 nanowires on
MnO2/graphene as the positive electrode and CNT/graphene as a 3D Ni foam current collector. The porous Ni base not only
the negative electrode. Their ASC devices could be cycled revers- served as a 3D conductive framework for the large loading of
ibly in a high-voltage region of 0–1.8 V with a maximum energy active V2O5 materials but also helped V2O5 to expose a greater
density of 31.8 W h kg−1. Recently, Zhang et al.[260] demonstrated number of active sites for electrochemical reactions. A high
fiber ASCs using hierarchical MnO2/graphene/carbon fiber (CF) capacitance of 832 F g−1 with high energy density and power
as the positive electrode and graphene hydrogel (GH)/copper densities of 115.7 W h kg−1 and 25 kW kg−1, respectively, was
wire (CW) as the negative electrode. The as-prepared superca- observed in 1 m Na2SO4 solution. Carbonaceous materials such
pacitor was highly flexible and could be operated reversibly in a as CNTs, graphene, carbon nanofibers, and CPs have been
voltage window of 0–1.6 V, delivering a high areal energy density employed to boost the electrical conductivity, as well as loading
of 18.1 µW h cm−2. amount of active materials.[271–274] Chen et al.[275] developed
supercapacitor composites based on V2O5 nanowires interpen-
etrating into conductive porous CNT scaffolds via an in situ
5.2.3. Vanadium Pentoxide (V2O5) hydrothermal process. The nanocomposite electrode achieved
a capacitance upto 440 F g−1 at a current density of 0.25 A g−1.
V2O5 is an intercalation compound that has attracted significant ASCs based on V2O5/CNT hybrid composites exhibited an
attention as a potential candidate for pseudocapacitors due to excellent energy density of 16 W h kg−1 at a power density
its high energy density and low cost, as well as variable oxida- of 75 W kg−1. A very high capacitance (1308 F g−1) has been
tion states (+2 to +5) and ease of fabrication.[261,262] Engineering reported for self-standing carbon-nanofiber papers with 3 nm-
V2O5 into nanostructures has been pursued to overcome the thick deposited V2O5 layers through cyclic voltammetry meas-
limitation of poor electrical conductivity (10−2 to 10−3 S cm−1) urements.[276] Xu et al.[277] utilized a hydrothermal approach to
in V2O5 by improving the electrochemical kinetics, shortening fabricate graphene/V2O5-xerogel nanocomposites. The pres-
the diffusion length of the electrolyte ions.[263,264] Lee et al.[265] ence of the graphene improves the specific surface area of the
synthesized V2O5 electrodes by quenching V2O5 fine powders at V2O5 xerogels almost 2 times as compared to V2O5-only xero-
950 °C into deionized water. They reported a Csp of 346 F g−1 in gels, along with enhanced electrical conductivity, which in
aqueous KCl solution. V2O5 nanofibers prepared by Srinivasan turn delivered a good capacitance of 195.4 F g−1 at a current
et al.[266] showed a Csp of 190 F g−1 in aqueous KCl. To further density of 1 A g−1. Guo et al.[278] fabricated a novel electrode
improve the capacitive properties, 3D porous V2O5 nanostruc- structure in which PEDOT was sandwiched between layered
tures have been developed by several research groups.[267,268] MnO2 (LMO) with layered V2O5 (LVO) into an LVO/PEDOT/
For example, Zhu et al.[269] reported a freeze-drying process for LMO geometry (Figure 9a). ASCs built from an LVO/PEDOT/
the large-scale production of 3D V2O5 electrodes that achieved LMO cathode and AC anode showed an extraordinary energy
a high Csp of 451 F g−1. Interestingly, the 3D V2O5 renders density of 39.2 W h kg−1 (based on the active materials) in a

Figure 9.  a) Schematic images showing the fabrication of process of LVO\PEDOT\LMO. b) Energy and power densities of ASC. c) Camera images
showing a green LED powered using two LVO\PEDOT\LMO||AC supercapacitors connected in series. d) Schematic representation for the coaxial
coating of Ni(OH)2 onto the o-CNT surface. e) SEM images of the o-CNT/Ni(OH)2 composite. f) Comparison of the Csp between pure Ni(OH)2 and
0-CNT/Ni(OH)2 composite. a–c) Reproduced with permission.[278] Copyright 2015, Elsevier Publishing. d–f) Reproduced with permission.[280] Copyright
2015, Elsevier Publishing.

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Na2SO4 aqueous electrolyte (Figure 9b), and good cycle sta- 1000 cycles. ASCs based on amorphous Ni(OH)2@3D Ni//
bility (93.5% capacitance retention after 3000 cycles). Figure 9c AC in aqueous electrolytes could be cycled reversibly in a
shows a green LED powered by connecting two ASCs in series. high voltage window of 0–1.3 V, achieving Csp of 92.8 F g−1
Zhou et al., recently reported an all-solid-state flexible ASC at 1 A g−1. Yang et al.[294] fabricated 3D nanoporous Ni(OH)2
with bamboo-like composites of V2O5/polyindole@activated thin films that delivered a high capacitance of ≈1765 F g−1.
carbon cloth (ACC) as the positive electrode while rGO@ACC ASC devices using porous-AC negative electrodes delivered a
was used as the negative electrode material.[279] The ACC cur- capacitance of 192 F g−1 with energy and power densities of
rent collector provided an excellent flexibility and high conduc- 68 W h kg−1 and 44 kW kg−1, respectively.
tivity, as well as a greater number of open channels for rapid Ni(OH)2 can also form composites with ACs, CNTs, and
ion transport. Moreover, highly conducting polyindole (PIn) graphene nanosheets to enhance electrochemical perfor-
was incorporated, and the V2O5/PIn@ACC electrode exhibited mance. Tang et al.[295] reported a binder-free, nanocomposite
a high Csp of 535.5 F g−1 at 1 A g−1, much higher than that of electrode of Ni(OH)2 with CNTs grown on nickel foams.
V2O5@ACC (304.7 F g−1). The assembled ASC device exhibited Without CNTs, these nanocomposites showed excellent capac-
an excellent cycling performance with a high retention rate of itive behaviors, but the low Ni(OH)2 loading of the nickel
91.1% after 5000 cycles. form considerably reduced the areal capacitance down to
1.6 F cm−2. The nanoarchitectured Ni(OH)2/CNT/NF electrode
exhibited a high Csp of 3300 F g−1 owing to the high Ni(OH)2
5.2.4. Nickel Hydroxide (Ni(OH)2) loading of 4.85 mg cm−2 with a substantial improvement in
areal capacitance to 16 F cm−2. In a recent study, Salunkhe et
Nickel hydroxide Ni(OH)2 has been widely used as a posi- al.[280] reported a CNT/Ni(OH)2 composite where Ni(OH)2 is
tive electrode material in nickel-based batteries but it is also deposited coaxially on oxidized CNTs to achieve 3D structures
suitable for electrochemical supercapacitors due to its high for an easy access of electrolyte ions (Figure 9d). Figure 9e
theoretical Csp (2082 F g−1), cost effectiveness, and avail- shows an SEM image of the 3D coaxial composite. A very
ability in various morphologies.[127,281,282] The early studies high capacitance (≈1368 F g−1) was observed in comparison to
reported that hydrous Ni(OH)2 makes highly capacitive posi- bare Ni(OH)2, which exhibited a Csp of 265 F g−1 (Figure 9f).
tive-electrode materials with Csp as high as 1000 F g−1.[283,284] ASCs with CNT–Ni(OH)2 and rGO electrodes operated at a
However, similar to other metal oxides, Ni(OH)2 also suffers high voltage window of 1.8 V, with a high energy density of
from poor stability, low conductivity, and poor cycle perfor- 35 W h kg−1 at a power density of 1.8 kW kg−1. Graphene and
mance due to the large volume change during the charging– graphene oxide (GO) nanosheets have been employed as excel-
discharging processes. Heteroatom doping of cobalt (Co) and lent 2D supports to load Ni(OH)2 for better electrochemical
Zinc (Zn) has been employed to enhance the electrochemical performance. Yan et al.[296] prepared a flowerlike Ni(OH)2 and
performance of Ni(OH)2.[285,286] Co helps in improving the decorated it with rGO to make positive electrodes for ASCs,
electrical conductivity, whereas Zn introduces disordering and porous graphene as negative electrodes. The Ni(OH)2/
into the Ni(OH)2 lattice, maximizing the active-material uti- graphene hybrid electrode showed a high Csp of 1735 F g−1
lization and ion-conduction paths. For better performances, and the Ni(OH)2/graphene//porous graphene ASC device
porous Ni(OH)2 structures are of immense importance as retained 94.3% Csp after 3000 cycles. In another effort by Wu
they provide short diffusion paths for ion-diffusion, high et al.[297] a facile electrostatic-induced method was employed
active area, and good strain accommodation during the to grow highly crystalline and stacked Ni(OH)2 nanosheets on
charge–discharge process. Kong et al.[287] reported loosely graphene. The as-prepared hybrid Ni(OH)2/graphene com-
packed Ni(OH)2-based nanoflakes, which allowed facile elec- posite demonstrated a high Csp (1503 F g−1 at 2 mV s−1) and
trolyte penetration for significant redox reactions, delivering an excellent cycle stability up to 6000 cycles at higher scan
a high Csp of 2055 F g−1 at 0.625 Ag−1. A 3D conducting rates. The superior performance was attributed to the intimate
Ni foam has been widely used to directly grow 3D porous binding between Ni(OH)2 and graphene nanosheets with
Ni(OH)2 thin films without the use of any binders.[288–290] good wettability.
Yang et al.[291] reported a maximum capacitance of 3108 F g−1 Amorphous Ni(OH)2 nanosphere electrodes have been
in electrodeposited Ni(OH)2 coatings on Ni foams in porous explored for ASCs, which resulted in high capacitance
and 3D nanostructures. However, the large weight of the Ni (153 F g−1) and high energy density (35.7 W h kg−1) at a power
foam limits the gravimetric capacitances, and lighter conduc- density of 490 W kg−1.[77] Ni(OH)2 composites with other
tive backbone elements are required to mitigate this issue. oxides have also shown intriguing electrochemical properties.
Ruoff et al.[292] reported a binder-free composite of Ni(OH)2 Co(OH)2–Ni(OH)2 composites have been fabricated to achieve
with ultrathin graphite (UGF), in which the free-standing 3D higher Csp compared to Ni(OH)2 or NiO.[298,299] Zhong et al.[300]
UGF network offers high electrical conductivity and porosity. showed that Co3O4/Ni(OH)2 composite mesoporous nanosheet
ASCs employing Ni(OH)2/UGF as the positive electrode and networks achieved a high Csp of 1144 F g−1 at 5 mV s−1 and
graphite oxide as the negative electrode exhibited a very high long-term cyclability. Ni(OH)2 composites with CPs were devel-
power density of 44 kW kg−1, which was much higher than oped to improve electrical conductivity. Yang et al.[301] fabricated
those of many of the commercially available traditional super- NiO/Ni(OH)2 nanoflowers encapsulated in 3D PEDOT on
capacitors. Su et al.[293] fabricated amorphous Ni(OH)2@3D contra wires through a mild electrochemical route. This hybrid
Ni core–shell electrodes which exhibited a very high Csp of electrode delivered a high Csp of 404.1 mF cm−2 (or 80.8 F cm−3)
2848 F g−1 at 1 mV s−1 and an electrochemical stability over at a current density of 4 mAcm−2.

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6. Emerging 2D Supercapacitor Electrodes 107 times more conductive than their semiconducting counter-
parts. Figure 10a shows an SEM image of the electrode based
Beyond the paradigm set by the capacitive performance of gra- on the 1T-MoS2 nanosheets. These binder-free electrodes exhib-
phene, there has been a surge of interest in other exotic 2D ited outstanding electrochemical performances, delivering a
materials for ASCs. In this context, inorganic 2D materials high volumetric capacitance of ≈400–700 F cm−3 (Figure 10b,c)
like transition-metal dichalcogenides (TMDs) are gaining sig- with an excellent capacitance retention of 97% over 5000 cycles
nificant interest owing their large surface area, unique crystal in a variety of aqueous and organic electrolytes. This superi-
structures, and extraordinary electrochemical properties.[302–304] ority in performance was attributed to facile ion intercalation
Molybdenum disulfide (MoS2), in particular has become one into the 1T-MoS2 layers due to their hydrophilicity coupled
of the promising materials, owing to its large electrical double- with their metallic characters. Choudhary et al.[314] reported
layer capacitance (EDLC) and pseudocapacitance with varying supercapacitor performances of porous 3R-MoS2 in a 3D
Mo oxidation states (+2 to +6).[305–307] The presence of dif- structure directly deposited on flexible substrates (i.e., copper,
ferent MoS2 polytypes, i.e., hexagonal 2H (semiconducting), polyimide). These uniquely structured 3D porous materials
1T (metallic), and rhombohedral 3R (stable at standard con- facilitated a large intercalation of electrolyte ions and exhib-
ditions) makes it even more intriguing for ASCs. 2H and 3R ited a high areal capacitance of 33 mF cm−2 (≈330 F cm−3) in
phases are not preferred due to their limited electrical conduc- 0.5 m H2SO4 electrolyte and a ≈97% capacitance retention over
tivities, which generally requires electrically conducting addi- 5000 cycles. Vertically aligned MoS2 nanosheets are gaining sig-
tives (CNTs, graphene, etc) or surface functionalizations.[308,309] nificant interest as promising supercapacitor electrodes due to
Chhowalla et al.[310] developed supercapacitor electrodes based their high aspect ratio and extensively exposed sides with 2D
on mechanically exfoliated 1T MoS2 nanosheets that were about edges having high chemical reactivity. Tour et al.[315] fabricated

Figure 10.  a) SEM image of the mechanically stacked 1T-MoS2 nanosheets. b) CV curves of 1T MoS2 electrode in 0.5 M sulphate-based electrolytes
at scan rates of 20 mV s−1. c) Volumetric capacitance of 1T MoS2 as a function of scan rate in different electrolyte solutions. d) The structure of the
different phases of the MAX family during MXene growth. e) SEM images of Ti3AlC2 before (untreated MAX phase) particle and after (MXene) the HF
treatment. f) CV measurements for a 5 mm-thick MXene electrode at different scan rates in 1 M H2SO4. a–c) Reproduced with permission.[310] Copyright
2015, Nature Publishing. d) Reproduced with permission.[311] Copyright 2014, Wiley-VCH. e) Reproduced with permission.[312] Copyright 2012, ACS
Publishing. f) Reproduced with permission.[313] Copyright 2014, Nature Publishing.

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edge-oriented/vertically aligned MoS2 nanosheets and utilized separated by liquid/gel electrolytes and an ion-porous separator
them for flexible supercapacitor electrodes, demonstrating a material. The main benefits of this configuration are the ability
high areal capacitance up to 12.5 mF cm−2. to directly deposit, grow, and precisely implement different
A new family of 2D materials recently developed are the ter- types of materials and architectures. In this section, three sub-
nary layered carbides and nitrides called MXenes with the gen- categories of sandwich-type device configurations are described,
eral formula of Mn+1AXn (MAX), where M stands for early tran- namely devices built on carbon-cloth materials, metal scaffolds,
sition metal, A is an element from the groups IIIA or IVA (Al, and other conductive substrates.
Si, Sn, In), X for carbon or nitrogen, and n = 1, 2, or 3. MXenes
are derived by etching away the element A from the MAX group.
Figure 10d represents the structural evolution of the different 7.1.1. Carbon-Cloth-Material Configuration
phases of a MAX family during the MXnene growth.[311] Naguib
et al.[312] presented the first experimental evidence of MXene 2D Being significantly low in cost, highly conductive, and
layers exfoliated by the immersion of various MAX phases into mechanically flexible, carbon cloth has been widely used for
hydrofluoric acid (HF). Figure 10e shows typical SEM images ASCs.[151,318–321] Carbon cloth is compatible with various depo-
of a Ti2AlC2 particle before and after successful exfoliation of sition techniques, as well as electrode materials. Zhai et al.[322]
its MAX phase, demonstrating a nicely stacked layered struc- have recently reported a carbon cloth with incorporated oxygen-
ture. MXenes show high metallic conductivity and hydrophi- deficient V6O13−x nanowires as a novel anode material for ASCs.
licity analogous to graphene, and have tremendous potential for V3O7 nanowires were hydrothermally grown on carbon-cloth
ASCs. These studies suggest the exploration of ≈60 other mate- substrates followed by annealing in a nitrogen atmosphere
rials belonging to the family of Mxenes. Mxenes combine the in the presence of a sulfur vapor source to produce sulfur-
properties of ceramics and metals and exhibit high hardness doped V6O13−x. Likewise, the cathode also employed a carbon-
and melting points, high stability, and good corrosion resistance cloth current collector, which served as a scaffold for rGO and
at high temperatures. The excellent electrical conductivity and electrodeposited MnO2 nanoparticles. ASC devices based on
unique layered morphology of Mxenes make them particularly these anode and cathodes delivered an excellent volumetric
suitable for ASCs. Ghidiu et al.[313] synthesized Ti3C2Tx clays energy density of 45 W h kg−1 with an average power density
that could be rolled and shaped into the conductive solids of of 478.5 W kg−1. Another recent study reports flexible ASCs
desired forms. The rolled films used as supercapacitor elec- based on Co9S8 nanorods as the cathode and Co3O4@RuO2
trodes exhibited an extraordinary volumetric capacitance of 900 nanosheets as the anode integrated on woven carbon-cloth sub-
F cm−3 in 1 m H2SO4 (Figure 10f). Yohan et al.[316] demonstrated strates (Figure 11a).[323] KOH solutions and poly(vinyl alcohol)
the influence of intercalation surface treatments on the capaci- (PVA)/KOH were used as a liquid electrolyte and a solid elec-
tive performance of Ti3C2. The modified surface chemistry gen- trolyte, respectively. The resulting ASCs showed an energy den-
erated oxygen-containing functional groups leading to a high sity of 1.21 mW h cm−3 and power density of 13.29 W cm−3 in
capacitance of 415 F cm−3 at 5 A g−1. Delaminated MXenes have aqueous electrolytes.
a high aspect ratio and are used as nanofillers in polymer nano- Electrochemical deposition is another highly appreciated
composites for flexible supercapacitors. Ling et al.[317] reported approach to fabricate sandwich-type ASCs on carbon mate-
a highly flexible and conductive Ti3C2Tx/PVA-KOH composite rials. A novel one-step electrodeposition of nickel cobalt sulfide
electrode that achieved a volumetric capacitance of 530 F cm−3 (Ni–Co–S) onto carbon cloth exhibited an excellent Csp of
at 2 mV s−1 with an electrical conductivity of 2.2 × 104 S m−1, a 1418 F g−1 at 5 A g−1 and 1285 F g−1 at 100 A g−1 as the cathode
tensile strength of 30 Mpa, and a Young’s modulus of 3 GPa. material.[324] The schematic in Figure 11b shows this cathode
Despite the interesting properties of MXenes, their easy oxida- along with a porous graphene film on a carbon cloth as the
tion under anodic potential in aqueous electrolytes is a potential anode, demonstrating a typical sandwich-type configuration. ASC
problem that limits their further applications. devices based on them demonstrated outstanding electrochem-
ical performance, such as a high energy density of 60 W h kg−1
at a power density of 1.8 kW kg−1 with robust long-term cycling
7. Devices
stability up to 50 000 cycles. These deposition techniques have
Generally, ASCs are made of positive pseudocapacitive elec- been applied to fabricate more-complex nanostructured elec-
trodes and negative EDLC-based electrodes with electrolyte in trodes, such as one-dimensional core–shell nanowire electrodes.
between. In order to design ASC devices that are lightweight, Li et al.[318] reported high-performance and flexible ASC devices
robust, and reliable with exceptional functional characteristics; by hydrothermally growing hydrogen-treated titanium dioxide
the configuration of the two dissimilar electrodes with tailored (H-TiO2) nanowires as the core (conducting scaffold) on carbon
properties and geometries is of prime importance and must be cloths. An electrochemical deposition of MnO2 onto the H-TiO2
considered seriously. In the following sections, various device nanowires realized positive electrodes in a configuration of
configurations will be discussed. core–shell-structured H-TiO2@MnO2 and negative electrodes
of H-TiO2@C were fabricated by another hydrothermal method.
These core–shell nanowire ASC devices achieved a maximum
7.1. Sandwich-Type energy density of 0.30 mW h cm−3. Physical vapor deposition
(PVD) presents another route for forming high-surface-area
Sandwich-type ASCs are the most typical device configura- nanostructures. Wang et al.[74] reported a WO3−x nanowire struc-
tion, which consists of two flat electrodes sandwiched together, ture grown radially on carbon fabrics by a catalyst-free PVD

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Figure 11.  Carbon-cloth configurations. a) Schematic illustration of the as-assembled ASC on carbon cloth. The zoomed-in SEM image is for Co9S8
and Co3O4@RuO2. b) Schematic representation of a Ni–Co–S nanosheet-array cathode grown on carbon cloth sandwiched between a porous gra-
phene anode on carbon cloth. c) The concept of metal-scaffold ASCs based on graphene/MnO2 nanosphere composite as the positive electrode and
graphene/MoO3 nanosheet as the negative electrode. d,e) HRTEM images of graphene–MnO2 cathode (d) and graphene–MoO3 anode (e) materials.
a) Reproduced with permission.[323] Copyright 2013, ACS Publishing. b) Reproduced with permission.[324] Copyright 2014, ACS Publishing. c–e) Repro-
duced with permission.[50] Copyright 2013, Wiley-VCH.

method in an oxygen environment. Furthermore, a pseudoca- frequently used due to its high conductivity, structural robust-
pacitive core–shell structure was obtained by electrochemically ness, and low cost. A common method of loading active mate-
depositing MoO3−x onto these WO3−x nanowires. rials onto metal scaffolds is to prepare a slurry of the materials
Other forms of carbon, such as carbon papers also serve as and coat them onto the current collectors.[50] Figure 11c shows
potential current collectors in ASC devices.[47,142,325,326] A flex- a schematic of an ASC device where a graphene/MnO2 nano-
ible rGO/MnO2 cathode was developed by adding MnO2 pre- sphere cathode and a graphene/MoO3 nanosheet anode were
cursors into graphene oxide solutions followed by the vacuum prepared by mixing 80 wt% electroactive material with 15 wt%
filtration of the GO/MnO2 suspension, resulting in rGO/MnO2 carbon black and 5 wt% poly(vinylidene fluoride) in the form
in the form of a paper. The anode was prepared by the same of a slurry. The slurry of the active material was coated onto
method but without including MnO2 into the rGO paper mate- a Ni foil substrate and excess slurry was removed by heating
rial. The resulting free-standing ASC devices with large flex- at 120 °C for 12 h. Figure 11d,e show the HRTEM images of
ibility and high conductivity offered a large areal capacitance the active anode and the cathode materials where MnO2 nano-
as high as 897 mF cm−2, which is considerably higher than spheres and MoO3 nanosheets were uniformly wrapped with
that of other flexible carbon-based ASCs.[327] Similarly, SWNT graphene. The ASC device delivered a high energy density of
membrane-based electrodes were prepared by filtering an 42.6 W h kg−1 at a power density of 276 W kg−1 and a maximum
SWNT solution through a porous alumina filter.[160] MnO2 and Csp of 307 F g−1. In many cases, it is necessary to physically
In2O3 nanowires were subsequently grown on the SWNT mem- press the active materials onto the metal scaffolds to ensure
brane to form MnO2 nanowire/SWNT as the positive electrode good mechanical contact with the current collectors.[330–332]
and In2O3 nanowire/ SWNT as the negative electrode. These For example, Wei et al.[333] reported an excellent cycle life with
hybrid nanostructured ASC devices exhibited a Csp of 184 F g−1, 97.3% capacitance retention after 1000 cycles in ASCs based on
an energy density of 25.5 W h kg−1 and a power density of graphene/MnO2 and activated carbon nanofibers with firmly
50.3 kW kg−1. pressed slurries of electrode materials. The device yielded a
maximum energy density of 51.1 W h kg−1 and power density
of 198 kW kg−1 with a high voltage range upto 1.8 V and a Csp
7.1.2. Metal Scaffolds of 113.5 F g−1.
Instead of the mechanical pressing, the direct growth of
Metal scaffolds refer to any type of metal foam or foil that is active materials on the metal scaffolds can make full use of
used as a current collector for the active material in an ASC their inherently high surface area.[334–341] Liu et al.[342] devel-
system.[34,282,328,329] Among the many available ones, nickel is oped a 3D CoO@polypyrrole nanowire array cathode grown on

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Ni foams by using a hydrothermal synthesis. This asymmetric shaped electrodes held together in different configurations can
device with AC as the anode material showed high energy den- form a new class of fiber-type supercapacitors, which form suit-
sity of 43.5 W h kg−1 and an energy density of 11.8 W h kg−1 able building blocks for wearable energy textiles. These fiber-
at a power density of 5.5 kW kg−1. A more recent device based type supercapacitors include side-by-side (parallel design),
on Ni(OH)2 directly grown on a Ni foil by using anodic elec- twist-type, coaxial-type, and wrap-type configurations. These
trodeposition and hydrothermal synthesis showed a maximum unique designs make the resulting textiles lightweight, allowing
energy density of 68 W h kg−1 and a maximum power density for their easy integration into wearable devices to achieve mul-
of 44 kW kg−1, while maintaining 90% of its capacitance over tifunctionality, including sensing,[353–355] communication,[356,357]
10 000 cycles.[294] Other chemical methods have also been used and storage.[358] Here, we discuss the recent development of
to directly grow electrode materials on metal-scaffold current fiber-type ASCs in various configurations.
collectors. A thermal CVD to grow CNTs on a Ni foam current
collector followed by a chemical bath deposition (CBD) to coat
the CNTs with Ni(OH)2 was utilized to fabricate cathode elec- 7.2.1. Side-by-Side (Parallel Configuration)
trodes. When paired with an AC on a Ni foam anode, the ASC
device achieved a maximum energy density of 50.6 W h kg−1.[295] Side-by-side fiber supercapacitors are fabricated by keeping two
fiber-shaped electrodes parallel to each other, separated by a
gel/polymer electrolyte and supported by a planar substrate.[359]
7.1.3. Other Substrates Yu et al.[360] developed micro-sized cable-type ASCs using a
nitrogen-doped rGO/SWCNT fiber as a capacitive-type fiber
Several other materials have been investigated as substrates (anode) and MnO2-deposited rGO/SWCNT fiber as a Faradaic-
to fabricate sandwich-type ASC devices including indium type fiber (cathode). A schematic of the fabrication process
tin oxide (ITO),[343] conducting polymers,[201,344–347] organic and concept of the parallel configuration is demonstrated in
materials, etc.[348,349] ITO is a notable current collector due Figure 12a. This device was capable of operating in a voltage
to its high conductivity and availability. Recently, ultrathin window of 1.8 V and showed excellent cycling stability of 87%
films of poly(3,4-ethylenedioxythiophene) (PEDOT) has capacitance retention after 10 000 cycles with the volumetric
been prepared by electropolymerization on steel and ITO energy and power density of 5 mW h cm−3 and 929 mW cm−3,
substrates, achieving a superior Coulomb efficiency of 97% respectively. These side-by-side ASC devices can be scaled
and Csp of 270 F g−1.[350] Moreover, MnO2 (cathode) and up by incorporating more fiber electrodes on the planar sub-
polypyrrole (anode) were electrodeposited on rGO-coated strate. Zhang et al.[361] reported another fiber-type asymmetric
ITO substrates to fabricate solid-state ASC devices. The ITO device assembled by two different functionalized carbonaceous
substrates were initially dipped in positively charged 1 wt% fibers: carbon fiber (CF)@RGO@MnO2 and CF@thick rGO
poly(ethyleneimine) (PEI) solution for 1 h to promote the (TRGO). The device exhibited excellent stability and flexibility
adhesion of negatively charged rGO nanosheets. The rGO in a 1.6 V high voltage window, yielding a high volume energy
was then deposited onto the ITO using cyclic voltammetry density of 1.23 mW h cm−3 along with an areal energy density
followed by electrodeposition of MnO2 and polypyrrole. This of 18.5 µW h cm−2.
ASC device based on these electrodes exhibited a power den- Jin et al.[363] also developed a fiber-based micro-ASC device
sity of 7.4 kW kg−1 and energy density of 16 W h kg−1.[351] using carbon nanoparticle (CNP)-coated-carbon fibers (CFs)
Carbon nanofibers derived from bacterial-cellulose (BC) have and achieved high porosity, flexibility, light weight, and simple
also been employed as low-cost, abundant, and environ- processing. MnO2-nanosheet-grown CF@CNPs (MCNP) and
mentally friendly electrodes for ASCs. Yu et al.[352] reported functionalized CF@CNPs (FCNP) were employed as posi-
the annealing of BC pellicles (p-BC) at 1000 °C for 2 h in tive and negative electrodes. The assembled ASC device could
nitrogen followed by immersion in a reaction solution and to operate at 1.8 V, exhibiting a high volumetric energy density
obtain p-BC@MnO2. By replacing the immersion step with a and power density of 2.1 mW h cm−3 and 8 W cm−3, respec-
hydrothermal reduction, nitrogen-doped p-BC (p-BC/N) was tively. A commercial LED could be powered for 2 min by three
also obtained. An ASC device based on this material yielded ASCs connected in series with 2-second charging.
an energy density of 32.91 W h kg−1 and an outstanding
power density of 284.64 kW kg−1 maintaining 95.4% of its
initial capacitance after 2000 cycles. 7.2.2. Twist-Type Configuration

Due to the emerging demand for fabric electronics for var-


7.2. Fiber-Type ious applications, like sensors,[364–367] solar cells,[368–370] and
batteries,[371–374] stand-alone fiber supercapacitors without
With the increasing demand for wearable technologies, highly any supports are desirable, as they can be easily woven into
flexible, bendable, and twistable energy-storage devices have the fabric. A twist-type configuration is one such design that
been explored. The planar-type supercapacitors discussed above is based on two fiber electrodes loaded with different active
do not offer sufficient flexibility and/or bendability required materials and which are twisted together to construct a fiber-
to weave them into e-textiles or wearables. In addition, planar shaped ASC device. Su et al.[106] developed the first twist-type
devices will occupy more space on the human body and cause ASC by assembling as-spun CNT yarn as a negative electrode
unease by blocking air flow. In this context, 1D cylindrically and CNT@MnO2 composite yarn as a positive electrode. This

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Figure 12.  a) Schematic representation of micro-supercapacitor fabrication in a side-by-side configuration. b) Schematic illustration of twisted CNT@
PANI positive electrode and functionalized CNT negative electrode. c) Image of an ASC woven into a glove at 0° and 180° bending angles. d) Capaci-
tance ratio of the ASC under different applied strains (0–100%) at a scan rate of 100 mV s−1. The inset shows the CV curves of the FASC measured
at different applied tensile strains. a) Reproduced with permission.[360] Copyright 2014, Wiley-VCH. b–d) Reproduced with permission.[362] Copyright
2015, Elsevier Publishing.

asymmetric twist architecture was operable upto 2.0 V and 7.2.3. Coaxial-Helix Type Configuration
was mechanically stable even after 2000 cycles of folding and
unfolding. Moreover, this ASC device resulted in high energy ASCs based on electrodes in coaxial-helix configurations have
and power density of 42 W h kg−1 and 483.7 W kg−1, respec- been recently explored, where a typical wire- or fiber-type elec-
tively. Another example of a twisted ASC device was developed trode is wrapped with another electrode resembling a core–
by Jin et al.[362] They prepared carbon-fiber-thread@polyani- shell configuration.[260,376,377] Dong et al.[378] recently developed
line as a positive electrode and functionalized carbon-fiber a coaxial-helix ASC device by a Ni(OH)2-nanowire fiber elec-
thread as a negative electrode (Figure 12b). An ASC device trode with an ordered-mesoporous-carbon fiber electrode. Due
based on these electrodes achieved a volumetric energy den- to the high aspect ratio of the Ni(OH)2-nanowire and high cell
sity up to 2 mW h cm−3 with a 1.6 V high voltage window. voltage (1.5 V), this device displayed a high Csp of 6.67 mF cm−1
For the purpose of demonstration for practical applications, (35.67 mF cm−2) and a high specific energy density of
this device was woven into a glove and its mechanical flex- 0.01 mW h cm−2 (2.16 mW h cm−3). Wang et al.[379] integrated
ibility was tested (Figure 12c). The capacitance of the stretch- a coaxial-helix ASC device onto a photodetector by employing
able twisted ASC device remained almost unchanged even at a graphene as both negative electrode and light-sensitive mate-
strain of 100% (Figure 12d). Cheng et al.[375] designed a ternary rial. The positive electrode was fabricated by growing Co3O4
hybrid positive electrode by growing MnO2 nanosheets onto nanowires on nickel fibers. More recently, Thomas et al.[380]
a PEDOT:Polystyrene Sulfonate (PSS)-coated CNT fiber. The developed a novel 2-in-1 coil-type ASC electrical cable based on
ASC device developed from the twisted MnO2/PEDOT:PSS/ the coaxially assembled electrodes, which was capable of both
CNT electrode with an ordered-microporous-carbon/CNT storing energy and transmitting electricity independently. The
hybrid negative electrode achieved a high working voltage of cathode was fabricated by growing CuO nanowhiskers (NWs)
1.8 V along with a high energy density of 11.3 mW h cm−3. on the surface of a copper wire via air oxidation followed by
The presence of the good adhesive agent (i.e., PEDOT:PSS) MnO2 electrodeposition to form the core–shell structure. A thin
in between the MnO2 and CNT renders an excellent cyclic layer of a AuPd current collector was sputter-coated on CuO
stability of 85% capacitance retention after 10 000 charge–dis- NWs prior to MnO2 deposition. The anode was prepared by
charge cycles and unchanged performance after bending and hydrothermally growing FeOOH nanorods onto carbon fibers
releasing 5000 times. followed by conversion of the FeOOH to Fe2O3. The fabrication

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process of the devices is shown in the schematic in Figure 13a. With this design, a good protection has been provided for
The 2-in-1 ASC device possessed a maximum potential window ASC devices by avoiding any direct damage to the outer
of 1.8 V and a volumetric Csp of 1.6 F cm−3 at 0.13 A cm−3, and electrode. Selvan et al.[381] recently demonstrated a wire-type
it could be easily bent at various angles (Figure 13b) without ASC utilizing a stainless-steel and a copper wire as current
sacrificing much of its performance. The SEM and TEM collectors. The cathode materials were prepared by coating
images in Figure 13c and 13d, respectively, reveal that MnO2 the copper wire in β-Ni(OH)2 while the anode (stainless
was conformally deposited onto each CuO NW (precoated with steel) was coated with AC. The as-prepared electrodes were
metal alloy). Being able to combine the functionality of an ASC coated with a PVA–KOH gel electrolyte and subsequently
and a typical electrical cable, the unique design demonstrates a inserted into a rubber tube, which creates a cable-shaped
new wave of integrated electrical components. ASC as shown in Figure 13e. The electrochemical reliability
of the device was tested under bending conditions. Figure 13f
shows that the CV curves of the wrap-type ASC remained
7.2.4. Wrap-Type Configurations unchanged irrespective of mechanical bending. This device
exhibited a maximum potential window of 1.4 V and a gravi-
Wrap-type ASCs are designed by wrapping up two electrodes metric capacitance of 37.5 F g−1 at 2 mA, delivering a max-
together in parallel with nonconducting polymer electrolytes. imum energy density of 9.8 W h kg−1 at a power density of

Figure 13.  a) Reconstructed 3D image of coaxial-helix ASC. b) Camera images showing different bending states. c,d) SEM (c) and TEM (d) images
showing conformal growth of MnO2 on CuO NWs. e) Schematic showing the steps involved in making the wrap-type device. f) CV curves of the device
under normal and bending states. a–d) Reproduced with permission.[380] Copyright 2015, Wiley-VCH. e,f) Reproduced with permission.[381] Copyright
2014, RSC Publishing.

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154 W kg−1. Liu et al.[382] designed another wrap-type ASC been reviewed and novel fiber-type ASC devices are particu-
employing MnO2 and V2O5 as two electrode materials. The larly highlighted. With the advent of miniaturized/flexible
device was packed with a piece of transparent silicon tube electronics, these devices are anticipated to be very promising
that wrapped the two electrodes together. Recently, Cai as they can be easily knitted into fabrics/textiles, presenting
et al.[383] demonstrated an ASC device by packing two elec- excellent wearability.
trodes into poly(tetrafluoroethylene) (PTFE) tubes, where In the present age of electric and hybrid vehicles, smart
graphene fiber (GF)/NiCo2S4 and GF worked as the positive electricity grid systems, and advanced consumer electronics,
and negative electrodes, respectively. At a voltage of 1.5 V, a supercapacitors can play a crucial role in providing the
maximum energy density of 12.3 mW h cm−3 and power den- required high energy and power density for these systems.
sity of 1.6 W cm−3 were reached. Yu et al.[384] demonstrated an Currently, supercapacitors play a supporting role in many
ASC device wrapping two carbon-fiber electrodes with a PVA/ of these applications, basically because of their inferior
LiCl solid electrolyte. They used MnO2 nanosheets arrays energy density. Li-ion batteries can provide an energy-storage
on carbon fiber prepared by a hydrothermal method as the capacity of more than 200 W h kg−1, whereas that for normal
positive electrode and graphene/carbon fibers prepared by symmetric supercapacitors ranges only 5–10 W h kg−1.
the dip-coating method as the negative electrode. This ASC However considerable research progress in ASCs has wit-
device exhibited a maximum operational voltage window of nessed the accomplishment of an energy density of about
1.5 V, a high Csp of 87.1 F g−1, and a promising energy density 40 W h kg−1, making them prospective energy-storage sys-
of 27.2 W h kg−1. Table 1 summarizes the various parameters tems next to Li-ion batteries. It is our outlook that the next-
of the ASC devices based on the different configurations of generation supercapacitors could be able to provide an energy
the electrode materials discussed here. density close to that of thin-film batteries (about 100 W h kg−1)
soon. However, significant efforts are needed to compete or
outperform existing or newly developed Li–air batteries, as
8. Conclusions and Outlook their research is simultaneously growing. In addition to the
large operational voltage window in ASCs, the development
We have extensively reviewed various materials developed of new electrode materials with rational designs/superior
for positive and negative electrodes in ASCs and compared architectures is required to achieve highly enhanced surface
their advantages and disadvantages. These materials include area, good electronic conductivity, and better ion-transport
metal oxides, conductive polymers, traditional carbonaceous pathways to further accomplish better energy density. The
materials, and recently developed carbon-based nanomate- combination of different capacitive materials in the form of
rials, such as CNT and graphene. Metal oxides such as MnO2, composites should be a viable approach to achieve enhanced
RuO2, Fe3O4, and V2O5 have made significant progress as specific surface area, high porosity, large potential window,
both the anode and cathode materials with reasonably high and superior electron/ion conductivity through synergistic
specific capacitance, environmental friendliness, and abun- effects. However, a deep understanding of these synergisitic
dance. However, their poor electrical conductivity undermines effects/material interactions and optimization of parameters
their cyclic stability and power density. Conductive polymers like composition of constituent materials and mass loading
present added advantages of enhanced conductivity, flex- of active materials is required to ensure real capacitive per-
ibility, and ease of processing, while their volume expansion/ fromances. In this context, composites or hybrid electrode
shrinking during the charge–discharge process limits their designs made by employing 1D, 2D, and 3D nanostruc-
cyclic stability. Recently developed carbon-based nanomaterials tured materials like nanospheres, nanowires/nanorods, and
such as CNT and graphene present unprecedented opportuni- nanoaerogels would be more intriguing as nanomaterials pos-
ties owing to their unique structures. CNTs have been widely sess high surface area, provide short diffusion paths for ions/
explored owing to their extremely high electrical conduc- electrons, and offer more electrochemically active sites for
tivity and fast ion-transport properties, but their integration large pseudocapacitance. However, integration of electrodes
with commercial processing and high cost associated with on metal current collectors requires mechanically/chemi-
their purification remain challenging. Graphene-based mate- cally stable interfaces (ideally, binder-free), which will ensure
rials are expected to offer distinct advantages owing to their long cycle life, as well as high electronic/ionic conductivities.
unique combination of excellent mechanical, electrical, and The advancement of novel 2D nanomaterials like TMDs[388]
thermal properties. 2D materials such as TMDs and MXenes and MXenes is greatly expected to reshape the entire energy
have demonstrated remarkable potential exhibiting large- research, provided their stability issues and high produc-
surface areas for EDLC, and the presence of multiple oxida- tion costs are resolved. Another promising direction in ASC
tion states for pseudocapacitance. The main drawback is their research would be their integration with electrical-energy
inferior electrical conductivity and their tendency to re-stack transmission[389] or energy-harvesting devices like solar
via van der Waals forces, which impedes the ion transport. cells.[390] These self-powered multifunctional systems should
With significant progress in improving the quality of electrode find niche applications in wearable technologies. Moreover,
materials, there has been a parallel research interest in devel- the fabrication of high-performance ASCs from laboratory
oping ASC devices with enhanced properties and novel multi- research to industrial-scale fabrication is highly desirable. We
functionalities, such as lightweight, ultrathin, highly flexible, sincerely hope that the existing and future endeavors in ASCs
portable/wearable energy-storage devices. Several approaches can accomplish the ambitious goal of achieving energy den-
to design ASC devices in more-efficient configurations have sity close to thin-film batteries.

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Table 1.  Performance of ASCs in various device configurations.

Device Category Electrode Operating Device Ref.


Configuration Voltage [V] performance
Anode Cathode Energy density Power density
Sandwitch type Carbon-based VOS-NWs on carbon cloth MnO2@graphene 1.8 0.87 mW h cm−3 9 mW cm−3 [322]
Co3O4@RuO2 nanosheet Co9S8 nanorod 1.6 1.44 mW h cm−3 0.89 W cm−3 [323]
on carbon cloth
Oxygen-deficient Fe2O3 nanorods MnO2 on carbon cloth 1.6 0.41 mW h cm−3 0.1 W cm−3 [145]
Porous graphene on carbon cloth Ni–Co–S on carbon cloth 1.8 60 W h kg−1 1.8 kW kg−1 [324]
H-TiO2@carbon cloth Core–shell structures 1.8 59 W h kg−1 45 kW kg−1 [318]
H-TiO2@ MnO2
rGO paper rGO@ MnO2 1.5 11.5 µW h cm−2 3.8 mW cm−2 [327]
In2O3 NWs@SWNTs MnO2 NWs@SWNTs 2.0 25.5 W h kg−1 50.3 kW kg −1 [160]
Ni(OH)2 on carbon fiber CNT on carbon fiber 1.4 41.1 W h kg−1 1.4 kW kg−1 [321]
Ppy carbon fiber paper rG @cMWCNT 1.6 28.6 W h kg−1 15.1 kW kg−1 [325]
AC nanofibers Graphene/MnO2 Slurry 1.8 51.1 W h kg−1 198 kW kg−1 [333]
pressed on nickel foam
Porous graphene Ni(OH)2/graphene slurry on 1.6 77.8 W h kg−1 174.7 kW kg−1 [296]
nickel foam
Activated polyaniline-derived Ni–Co oxide nanosheets 1.6 41.6 W h kg−1 16 kW kg−1 [331]
carbon slurry on nickel gauze
AC Ni@CoO@Ppy on nickel 1.8 11.8 W h kg−1 5.5 kW kg−1 [342]
foam
Porous activated carbon Ni(OH)2 grow on nickel foam 1.6 68 W h kg−1 44 kW kg−1 [294]
AC Ni(OH)2@CNT grow on 1.8 50.6 W h kg−1 95 kW kg−1 [295]
nickel foam
Other substrates Ppy@rGO MnO2@rGO 1.8 16 W h kg−1 7.4 kW kg−1 [351]
on PEI/ITO substrate
PEDOT@Au@PEN PANI@Au@PEN 1.6 9 mW h cm−3 2.8 mW cm−3 [201]
Ni@AC@filter paper Ni@MnO2@filter paper 2.5 0.78 mW h cm−3 2.5 mW cm−3 [385]
Ppy@rGO MnO2@carbon nanofiber on 2.0 32.91 W h kg−1 284.64 kW kg−1 [352]
bacterial-cellulose substrate
Fiber-type Side-by-side N-doped rGO@SWCNT fiber MnO2@rGO@SWCNT fiber 1.8 5 mW h cm−3 929 mW cm−3 [360]
Graphene–CNT hybrid fiber MnO2@core–sheath gra- 1.6 11.9 µW h cm−3 _____ [359]
phene fiber
CF@thick rGO CF@rGO@MnO2 1.6 1.23 mW h cm−3 0.27 W cm−3 [361]
CF@CNPs MnO2@CF@CNPs 1.8 2.1 mW h cm−3 8 W cm−3 [363]
Twist-type CNT yarn MnO2@CNT composite yarn 2.0 42 W h kg−1 483.7 W kg−1 [106]
Carbon-fiber thread (CFT) CFT@polyaniline 1.6 2 mW h cm−3 11 W cm−3 [362]
Porous carbon@CF Copper hexacyanoferrate@CF 2.0 10.6 W h kg−1 50.6 W kg−1 [386]
Microporous carbon@CNT MnO2@PEDOT:PSS@CNT 1.8 11.3 mW h cm−3 0.03 W cm−3 [375]
Co-axial helix type Mesoporous carbon fiber Ni(OH)2 nanowire fiber 1.5 2.16 mW h cm−3 1.6 W cm−3 [378]
Graphene Co3O4 NW on nickel fiber 1.5 0.62 mW h cm−3 1.47 W cm−3 [379]
rGO CNT@Ni(OH)2 1.8 45 W h kg−1 1.8 kW kg−1 [280]
Fe2O3@carbon fiber CuO NW on copper wire 1.8 0.85 mW h cm−3 0.1 W cm−3 [380]
Wrap type Activated carbon@stainless steel β-Ni(OH)2@Cu wire 1.4 9.8 W h kg−1 154 W kg−1 [381]
V2O5&PANI@CF MnO2@CF 2.0 0.34 mW h cm−2 1.5 mW cm−2 [382]
GF-802 Graphene fiber@NiCo2S4 1.5 12.3 mW h cm−3 1.6 mW cm−3 [383]
GH/CW MnO2@graphene/CF 1.6 0.63 mW h cm−3 0.2 W cm−3 [260]
graphene@CF MnO2@CF 1.5 27.2 W h kg−1 979.7 W kg−1 [387]

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Acknowledgements [30] H. Xia, C. Hong, B. Li, B. Zhao, Z. Lin, M. Zheng, S. V. Savilov,


S. M. Aldoshin, Adv. Funct. Mater. 2015, 25, 627.
J.T. acknowledges the National Science Foundation (CAREER: ECCS- [31] Z.-S. Wu, W. Ren, D.-W. Wang, F. Li, B. Liu, H.-M. Cheng, ACS
1351757) for partial financial support. Y.J. acknowledges the financial Nano 2010, 4, 5835.
support from a start-up fund from the University of Central Florida. [32] Y. Zhu, S. Murali, W. Cai, X. Li, J. W. Suk, J. R. Potts, R. S. Ruoff,
Adv. Mater. 2010, 22, 3906.
Received: October 3, 2016
[33] G. Wang, L. Zhang, J. Zhang, Chem. Soc. Rev. 2012, 41, 797.
Revised: November 27, 2016
[34] H. Gao, F. Xiao, C. B. Ching, H. Duan, ACS Appl. Mater. Interfaces
Published online: February 28, 2017
2012, 4, 2801.
[35] M. A. Bavio, G. G. Acosta, T. Kessler, Int. J. Energy Res. 2015, 39,
2053.
[36] Y. Huang, J. Liang, Y. Chen, Small 2012, 8, 1805.
[1] M. Gidwani, A. Bhagwani, N. Rohra, Int. J. Eng. Inventions 2014, 4, [37] F. Wang, S. Xiao, Y. Hou, C. Hu, L. Liu, Y. Wu, RSC Adv. 2013, 3,
22. 13059.
[2] B. Scrosati, J. Hassoun, Y.-K. Sun, Energy Environ. Sci. 2011, 4, [38] K. Jost, D. P. Durkin, L. M. Haverhals, E. K. Brown,
3287. M. Langenstein, H. C. De Long, P. C. Trulove, Y. Gogotsi, G. Dion,
[3] C. Liu, F. Li, L.-P. Ma, H.-M. Cheng, Adv. Mater. 2010, 22, E28. Adv. Energy Mater. 2015, 5, 1401286.
[4] M. Winter, R. J. Brodd, Chem. Rev. 2004, 104, 4245. [39] H. Jiang, C. Li, T. Sun, J. Ma, Nanoscale 2012, 4, 807.
[5] U. S. Energy-Information-Administration, International Energy [40] V. Khomenko, E. Raymundo-Piñero, F. Béguin, J. Power Sources
Outlook, Washington, DC, USA 2016. 2008, 177, 643.
[6] B. E. Conway, J. Electrochem. Soc. 1991, 138, 1539. [41] H.-Q. Wang, Z.-S. Li, Y.-G. Huang, Q.-Y. Li, X.-Y. Wang, J. Mater.
[7] J. R. Miller, P. Simon, Science 2008, 321, 651. Chem. 2010, 20, 3883.
[8] Y. Wang, Y. Xia, Adv. Mater. 2013, 25, 5336. [42] C. Y. Foo, A. Sumboja, D. J. H. Tan, J. Wang, P. S. Lee, Adv. Energy
[9] K. Xie, B. Wei, Adv. Mater. 2014, 26, 3592. Mater. 2014, 4, 1400236.
[10] B. E. Conway, Electrochemical Supercapacitors: Scientific Fundamen- [43] X. Wang, C. Yang, G. Wang, J. Mater. Chem. A 2016, 4, 14839.
tals, Technological Applications, Kluwer Academic/Plenum Press, [44] Y. Chen, X. Zhang, D. Zhang, P. Yu, Y. Ma, Carbon 2011, 49, 573.
New York, 1999. [45] X. Zhang, D. Zhao, Y. Zhao, P. Tang, Y. Shen, C. Xu, H. Li, Y. Xiao,
[11] Z. L. Wang, Nano Today 2010, 5, 540. J. Mater. Chem. A 2013, 1, 3706.
[12] P. Simon, Y. Gogotsi, Nat. Mater. 2008, 7, 845. [46] T. Brousse, D. Belanger, J. W. Long, J. Electrochem. Soc. 2015, 162,
[13] J. Kondoh, I. Ishii, H. Yamaguchi, A. Murata, K. Otani, K. Sakuta, A5185.
N. Higuchi, S. Sekine, M. Kamimoto, Energy Convers. Manage. [47] A. Singh, A. Chandra, Sci. Rep. 2015, 5, 15551.
2000, 41, 1863. [48] J. Cheng, M. Sprik, Phys. Chem. Chem. Phys. 2012, 14, 11245.
[14] L. L. Zhang, X. S. Zhao, Chem. Soc. Rev. 2009, 38, 2520. [49] S. Trasatti, Pure Appl. Chem. 1986, 58, 955.
[15] M. Lu, F. Benguin, E. Frackowiak, Supercapacitors: Materials, Sys- [50] J. Chang, M. Jin, F. Yao, T. H. Kim, V. T. Le, H. Yue, F. Gunes, B. Li,
tems, and Applications, Wiley-VCH, Weinheim, Germany 2013, A. Ghosh, S. Xie, Y. H. Lee, Adv. Funct. Mater. 2013, 23, 5074.
p. 207. [51] G. Salitra, A. Soffer, L. Eliad, Y. Cohen, D. Aurbach, J. Electrochem.
[16] A. Burke, J. Power Sources 2000, 91, 37. Soc. 2000, 147, 2486.
[17] P. J. Hall, E. J. Bain, Energy Policy 2008, 36, 4352. [52] E. Raymundo-Piñero, K. Kierzek, J. Machnikowski, F. Béguin,
[18] I. Hadjipaschalis, A. Poullikkas, V. Efthimiou, Renewable Sustain- Carbon 2006, 44, 2498.
able Energy Rev. 2009, 13, 1513. [53] Y. Zhai, Y. Dou, D. Zhao, P. F. Fulvio, R. T. Mayes, S. Dai, Adv.
[19] In NASA-Tech Briefs: Engineering Solutions for Design & Manufac- Mater. 2011, 23, 4828.
turing, John H. Glenn Research Center, Cleveland, OH, USA 2007. [54] Z. Yu, L. Tetard, L. Zhai, J. Thomas, Energy Environ. Sci. 2015, 8,
[20] T. A. S mith, J. P. Mars, G. A. Turner, in 2002 IEEE 33rd Annual 702.
Power Electronics Specialists Conf., PESC 02., Vol. 1, IEEE, Piscat- [55] C. Largeot, C. Portet, J. Chmiola, P.-L. Taberna, Y. Gogotsi,
away, NJ, USA 2002, pp. 124, DOI: 10.1109/PSEC.2002.1023857 P. Simon, J. Am. Chem. Soc. 2008, 130, 2730.
[21] J. German, Hybrid Vehicles: Technology Development and Cost [56] L. Qie, W. Chen, H. Xu, X. Xiong, Y. Jiang, F. Zou, X. Hu, Y. Xin,
Reduction, ICCT technical Brief No. 1, July 2015. Z. Zhang, Y. Huang, Energy Environ. Sci. 2013, 6, 2497.
[22] Maxwell Technologies, Inc., http://www.maxwell.com/solutions/ [57] K. Kierzek, E. Frackowiak, G. Lota, G. Gryglewicz, J. Machnikowski,
transportation/auto/start-stop-micro-hybrid (accessed: Feb 07, Electrochim. Acta 2004, 49, 515.
2017). [58] Z. B. Wen, S. Tian, L. L. Liu, Y. P. Wu, Controlled Nanofabrication,
[23] E. Naswali, C. Alexander, H. Y. Han, D. Naviaux, A. Bistrika, Pan Stanford Publishing, Singapore 2012, pp. 473.
A. V. Jouanne, A. Yokochi, T. K. A. Brekken, in 2011 IEEE Energy [59] C. J. Meyers, S. D. Shah, S. C. Patel, R. M. Sneeringer, C. A. Bessel,
Conversion Congress, Exposition, IEEE, Piscataway, NJ, USA 2011, N. R. Dollahon, R. A. Leising, E. S. Takeuchi, J. Phys. Chem. B
p. 298, DOI: 10.1109/ECCE.2011.6063783. 2001, 105, 2143.
[24] X. Wang, X. Lu, B. Liu, D. Chen, Y. Tong, G. Shen, Adv. Mater. [60] R. R. A. Rios, D. E. Alves, I. Dalmázio, S. F. V. Bento, C. L. Donnici,
2014, 26, 4763. R. M. Lago, Mater. Res. 2003, 6, 129.
[25] L. Li, Z. Wu, S. Yuan, X.-B. Zhang, Energy Environ. Sci. 2014, 7, [61] B. Duong, Z. Yu, P. Gangopadhyay, S. Seraphin,
2101. N. Peyghambarian, J. Thomas, Adv. Mater. Interfaces 2014, 1,
[26] S. M. Mirvakili, M. N. Mirvakili, P. Englezos, J. D. W. Madden, 1300014.
I. W. Hunter, ACS Appl. Mater. Interfaces 2015, 7, 13882. [62] W. Li, D. Chen, Z. Li, Y. Shi, Y. Wan, J. Huang, J. Yang, D. Zhao,
[27] X. Lu, M. Yu, G. Wang, Y. Tong, Y. Li, Energy Environ. Sci. 2014, 7, Z. Jiang, Electrochem. Commun. 2007, 9, 569.
2160. [63] H. Pan, C. K. Poh, Y. P. Feng, J. Lin, Chem. Mater. 2007, 19,
[28] X. Lu, G. Li, Y. Tong, Sci. China, Ser. E: Technol. Sci. 2015, 58, 1799. 6120.
[29] M. Vangari, T. Pryor, L. Jiang, J. Energy Eng. 2013, 139, 72. [64] M. Kim, J. Kim, Phys. Chem. Chem. Phys. 2014, 16, 11323.

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PROGRESS REPORT
[65] D. Hulicova-Jurcakova, M. Kodama, S. Shiraishi, H. Hatori, [101] X. Zhao, C. Johnston, P. S. Grant, J. Mater. Chem. 2009, 19, 8755.
Z. H. Zhu, G. Q. Lu, Adv. Funct. Mater. 2009, 19, 1800. [102] S.-L. Chou, J.-Z. Wang, S.-Y. Chew, H.-K. Liu, S.-X. Dou, Electro-
[66] Y. Huang, S. L. Candelaria, Y. Li, Z. Li, J. Tian, L. Zhang, G. Cao, J. chem. Commun. 2008, 10, 1724.
Power Sources 2014, 252, 90. [103] J. Chen, A. I. Minett, Y. Liu, C. Lynam, P. Sherrell, C. Wang,
[67] J.-W. Lang, L.-B. Kong, M. Liu, Y.-C. Luo, L. Kang, J. Solid State Elec- G. G. Wallace, Adv. Mater. 2008, 20, 566.
trochem. 2010, 14, 1533. [104] Y. Qiu, G. Li, Y. Hou, Z. Pan, H. Li, W. Li, M. Liu, F. Ye, X. Yang,
[68] Q. Qu, P. Zhang, B. Wang, Y. Chen, S. Tian, Y. Wu, R. Holze, J. Y. Zhang, Chem. Mater. 2015, 27, 1194.
Phys. Chem. C 2009, 113, 14020. [105] J. Tao, N. Liu, W. Ma, L. Ding, L. Li, J. Su, Y. Gao, Sci. Rep. 2013,
[69] D. Cericola, P. W. Ruch, R. Kötz, P. Novák, A. Wokaun, Electro- 3, 2286.
chem. Commun. 2010, 12, 812. [106] S. Fenghua, M. Menghe, Nanotechnology 2014, 25, 135401.
[70] Q. T. Qu, Y. Shi, L. L. Li, W. L. Guo, Y. P. Wu, H. P. Zhang, [107] M. F. El-Kady, V. Strong, S. Dubin, R. B. Kaner, Science 2012, 335,
S. Y. Guan, R. Holze, Electrochem. Commun. 2009, 11, 1325. 1326.
[71] S.-B. Ma, K.-W. Nam, W.-S. Yoon, X.-Q. Yang, K.-Y. Ahn, K.-H. Oh, [108] K. S. Novoselov, V. I. Falko, L. Colombo, P. R. Gellert,
K.-B. Kim, J. Power Sources 2008, 178, 483. M. G. Schwab, K. Kim, Nature 2012, 490, 192.
[72] S. Chen, J. Zhu, Q. Han, Z. Zheng, Y. Yang, X. Wang, Cryst. Growth [109] S. Stankovich, D. A. Dikin, G. H. B. Dommett, K. M. Kohlhaas,
Des. 2009, 9, 4356. E. J. Zimney, E. A. Stach, R. D. Piner, S. T. Nguyen, R. S. Ruoff,
[73] H. Jiang, P. S. Lee, C. Li, Energy Environ. Sci. 2013, 6, 41. Nature 2006, 442, 282.
[74] X. Xiao, T. Ding, L. Yuan, Y. Shen, Q. Zhong, X. Zhang, Y. Cao, [110] Y. Zhu, S. Murali, M. D. Stoller, K. J. Ganesh, W. Cai, P. J. Ferreira,
B. Hu, T. Zhai, L. Gong, J. Chen, Y. Tong, J. Zhou, Z. L. Wang, Adv. A. Pirkle, R. M. Wallace, K. A. Cychosz, M. Thommes, D. Su,
Energy Mater. 2012, 2, 1328. E. A. Stach, R. S. Ruoff, Science 2011, 332, 1537.
[75] G. Wang, X. Lu, Y. Ling, T. Zhai, H. Wang, Y. Tong, Y. Li, ACS Nano [111] H. A. Becerril, J. Mao, Z. Liu, R. M. Stoltenberg, Z. Bao, Y. Chen,
2012, 6, 10296. ACS Nano 2008, 2, 463.
[76] W. Wang, W. Liu, Y. Zeng, Y. Han, M. Yu, X. Lu, Y. Tong, Adv. Mater. [112] A. G. Pandolfo, A. F. Hollenkamp, J. Power Sources 2006,
2015, 27, 3572. 157, 11.
[77] H. B. Li, M. H. Yu, F. X. Wang, P. Liu, Y. Liang, J. Xiao, C. X. Wang, [113] Q. Cheng, J. Tang, J. Ma, H. Zhang, N. Shinya, L.-C. Qin, Phys.
Y. X. Tong, G. W. Yang, Nat. Commun. 2013, 4, 1894. Chem. Chem. Phys. 2011, 13, 17615.
[78] L. Qie, W.-M. Chen, Z.-H. Wang, Q.-G. Shao, X. Li, L.-X. Yuan, [114] V. C. Tung, M. J. Allen, Y. Yang, R. B. Kaner, Nat. Nanotechnol.
X.-L. Hu, W.-X. Zhang, Y.-H. Huang, Adv. Mater. 2012, 24, 2047. 2009, 4, 25.
[79] C. Niu, E. K. Sichel, R. Hoch, D. Moy, H. Tennent, Appl. Phys. Lett. [115] X. Cao, Z. Yin, H. Zhang, Energy Environ. Sci. 2014, 7, 1850.
1997, 70, 1480. [116] Y. Gong, S. Yang, L. Zhan, L. Ma, R. Vajtai, P. M. Ajayan, Adv.
[80] H. Pan, J. Li, Y. Feng, Nanoscale Res. Lett. 2010, 5, 654. Funct. Mater. 2014, 24, 125.
[81] R. A. Fisher, M. R. Watt, W. Jud Ready, ECS J. Solid State Sci. [117] Y. Wang, Z. Shi, Y. Huang, Y. Ma, C. Wang, M. Chen, Y. Chen, J.
Technol. 2013, 2, M3170. Phys. Chem. C 2009, 113, 13103.
[82] E. Frackowiak, K. Jurewicz, S. Delpeux, F. Béguin, J. Power Sources [118] Y. Wang, Y. Wu, Y. Huang, F. Zhang, X. Yang, Y. Ma, Y. Chen, J.
2001, 97–98, 822. Phys. Chem. C 2011, 115, 23192.
[83] E. Frackowiak, K. Metenier, V. Bertagna, F. Beguin, Appl. Phys. Lett. [119] C. Liu, Z. Yu, D. Neff, A. Zhamu, B. Z. Jang, Nano Lett. 2010, 10,
2000, 77, 2421. 4863.
[84] L. Dai, D. W. Chang, J.-B. Baek, W. Lu, Small 2012, 8, 1130. [120] Z.-S. Wu, D.-W. Wang, W. Ren, J. Zhao, G. Zhou, F. Li,
[85] R. H. Baughman, A. A. Zakhidov, W. A. de Heer, Science 2002, 297, H.-M. Cheng, Adv. Funct. Mater. 2010, 20, 3595.
787. [121] J.-K. Chang, M.-T. Lee, W.-T. Tsai, M.-J. Deng, H.-F. Cheng,
[86] H. Zhang, G. Cao, Y. Yang, Z. Gu, J. Electrochem. Soc. 2008, 155, I. W. Sun, Langmuir 2009, 25, 11955.
K19. [122] S. Chen, J. Zhu, X. Wang, ACS Nano 2010, 4, 6212.
[87] K. H. An, W. S. Kim, Y. S. Park, J. M. Moon, D. J. Bae, S. C. Lim, [123] J. Yan, Z. Fan, T. Wei, W. Qian, M. Zhang, F. Wei, Carbon 2010, 48,
Y. S. Lee, Y. H. Lee, Adv. Funct. Mater. 2001, 11, 387. 3825.
[88] M. Saghafi, F. Mahboubi, S. Mohajerzadeh, R. Holze, Synth. Met. [124] Y. Li, N. Zhao, C. Shi, E. Liu, C. He, J. Phys. Chem. C 2012, 116,
2014, 195, 252. 25226.
[89] K. Byungwoo, C. Haegeun, K. Woong, Nanotechnology 2012, 23, [125] F. Tu, T. Wu, S. Liu, G. Jin, C. Pan, Electrochim. Acta 2013, 106,
155401. 406.
[90] Q.-L. Chen, K.-H. Xue, W. Shen, F.-F. Tao, S.-Y. Yin, W. Xu, Electro- [126] G. Yu, L. Hu, N. Liu, H. Wang, M. Vosgueritchian, Y. Yang, Y. Cui,
chim. Acta 2004, 49, 4157. Z. Bao, Nano Lett. 2011, 11, 4438.
[91] W. Lu, L. Qu, K. Henry, L. Dai, J. Power Sources 2009, 189, 1270. [127] H. Wang, H. S. Casalongue, Y. Liang, H. Dai, J. Am. Chem. Soc.
[92] B. Kim, H. Chung, W. Kim, J. Phys. Chem. C 2010, 114, 15223. 2010, 132, 7472.
[93] W. Lu, R. Hartman, L. Qu, L. Dai, J. Phys. Chem. Lett. 2011, 2, 655. [128] S. Park, R. S. Ruoff, Nat. Nanotechnol. 2009, 4, 217.
[94] Z. Spitalsky, D. Tasis, K. Papagelis, C. Galiotis, Prog. Polym. Sci. [129] V. Gupta, N. Miura, J. Power Sources 2006, 157, 616.
2010, 35, 357. [130] J. L. Vickery, A. J. Patil, S. Mann, Adv. Mater. 2009, 21, 2180.
[95] M. Wu, G. A. Snook, G. Z. Chen, D. J. Fray, Electrochem. Commun. [131] K. Zhang, L. L. Zhang, X. S. Zhao, J. Wu, Chem. Mater. 2010, 22,
2004, 6, 499. 1392.
[96] K. Shi, I. Zhitomirsky, ChemElectroChem 2015, 2, 396. [132] Z. Yu, M. McInnis, J. Calderon, S. Seal, L. Zhai, J. Thomas, Nano
[97] L. Su, X. Zhang, C. Yuan, B. Gao, J. Electrochem. Soc. 2008, 155, Energy 2015, 11, 611.
A110. [133] J. Wang, H. Xian, T. Peng, H. Sun, F. Zheng, RSC Adv. 2015, 5,
[98] M. D. Stoller, R. S. Ruoff, Energy Environ. Sci. 2010, 3, 1294. 13607.
[99] H. Zhang, G. Cao, Z. Wang, Y. Yang, Z. Shi, Z. Gu, Electrochem. [134] L. L. Zhang, S. Zhao, X. N. Tian, X. S. Zhao, Langmuir 2010, 26,
Commun. 2008, 10, 1056. 17624.
[100] H. Zhang, G. Cao, Z. Wang, Y. Yang, Z. Shi, Z. Gu, Nano Lett. [135] Z.-S. Wu, A. Winter, L. Chen, Y. Sun, A. Turchanin, X. Feng,
2008, 8, 2664. K. Müllen, Adv. Mater. 2012, 24, 5130.

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[136] B. G. Choi, M. Yang, W. H. Hong, J. W. Choi, Y. S. Huh, ACS Nano [170] X. Lu, G. Wang, T. Zhai, M. Yu, S. Xie, Y. Ling, C. Liang, Y. Tong,
2012, 6, 4020. Y. Li, Nano Lett. 2012, 12, 5376.
[137] H.-P. Cong, X.-C. Ren, P. Wang, S.-H. Yu, ACS Nano 2012, 6, 2693. [171] X. Lu, T. Liu, T. Zhai, G. Wang, M. Yu, S. Xie, Y. Ling, C. Liang,
[138] X.-L. Wu, T. Wen, H.-L. Guo, S. Yang, X. Wang, A.-W. Xu, ACS Nano Y. Tong, Y. Li, Adv. Energy Mater. 2014, 4, 1300994.
2013, 7, 3589. [172] Y. Yue, P. Han, X. He, K. Zhang, Z. Liu, C. Zhang, S. Dong, L. Gu,
[139] G. Zhou, L.-C. Yin, D.-W. Wang, L. Li, S. Pei, I. R. Gentle, F. Li, G. Cui, J. Mater. Chem. 2012, 22, 4938.
H.-M. Cheng, ACS Nano 2013, 7, 5367. [173] Y. Qiu, K. Yan, S. Yang, L. Jin, H. Deng, W. Li, ACS Nano 2010, 4,
[140] X. Fan, C. Yu, Z. Ling, J. Yang, J. Qiu, ACS Appl. Mater. Interfaces 6515.
2013, 5, 2104. [174] M.-S. Balogun, C. Li, Y. Zeng, M. Yu, Q. Wu, M. Wu, X. Lu, Y. Tong,
[141] Q. Lu, Y. Chen, W. Li, J. G. Chen, J. Q. Xiao, F. Jiao, J. Mater. Chem. J. Power Sources 2014, 272, 946.
A 2013, 1, 2331. [175] H. Pang, S. J. Ee, Y. Dong, X. Dong, P. Chen, ChemElectroChem
[142] Q. Tang, M. Chen, L. Wang, G. Wang, J. Power Sources 2015, 273, 2014, 1, 1027.
654. [176] Z. Wang, Z. Li, J. Feng, S. Yan, W. Luo, J. Liu, T. Yu, Z. Zou, Phys.
[143] K. K. Lee, S. Deng, H. M. Fan, S. Mhaisalkar, H. R. Tan, E. S. Tok, Chem. Chem. Phys. 2014, 16, 8521.
K. P. Loh, W. S. Chin, C. H. Sow, Nanoscale 2012, 4, 2958. [177] C. Zhu, P. Yang, D. Chao, X. Wang, X. Zhang, S. Chen, B. K. Tay,
[144] Q. Qu, S. Yang, X. Feng, Adv. Mater. 2011, 23, 5574. H. Huang, H. Zhang, W. Mai, H. J. Fan, Adv. Mater. 2015, 27, 4566.
[145] X. Lu, Y. Zeng, M. Yu, T. Zhai, C. Liang, S. Xie, M.-S. Balogun, [178] X. Lu, M. Yu, T. Zhai, G. Wang, S. Xie, T. Liu, C. Liang, Y. Tong,
Y. Tong, Adv. Mater. 2014, 26, 3148. Y. Li, Nano Lett. 2013, 13, 2628.
[146] D. Wang, Y. Li, Q. Wang, T. Wang, J. Solid State Electrochem. 2012, [179] R. Wang, X. Yan, J. Lang, Z. Zheng, P. Zhang, J. Mater. Chem. A
16, 2095. 2014, 2, 12724.
[147] X.-F. Lu, X.-Y. Chen, W. Zhou, Y.-X. Tong, G.-R. Li, ACS Appl. Mater. [180] D. Choi, G. E. Blomgren, P. N. Kumta, Adv. Mater. 2006, 18, 1178.
Interfaces 2015, 7, 14843. [181] D. Choi, P. N. Kumta, Electrochem. Solid-State Lett. 2005, 8, A418.
[148] Y.-C. Chen, Y.-G. Lin, Y.-K. Hsu, S.-C. Yen, K.-H. Chen, L.-C. Chen, [182] Z.-H. Gao, H. Zhang, G.-P. Cao, M.-F. Han, Y.-S. Yang, Electro-
Small 2014, 10, 3803. chim. Acta 2013, 87, 375.
[149] H. Wang, Z. Xu, H. Yi, H. Wei, Z. Guo, X. Wang, Nano Energy [183] C. M. Ghimbeu, E. Raymundo-Pinero, P. Fioux, F. Beguin,
2014, 7, 86. C. Vix-Guterl, J. Mater. Chem. 2011, 21, 13268.
[150] C. Guan, J. Liu, Y. Wang, L. Mao, Z. Fan, Z. Shen, H. Zhang, [184] S. Dong, X. Chen, L. Gu, X. Zhou, H. Wang, Z. Liu, P. Han, J. Yao,
J. Wang, ACS Nano 2015, 9, 5198. L. Wang, G. Cui, L. Chen, Mater. Res. Bull. 2011, 46, 835.
[151] P. Yang, Y. Ding, Z. Lin, Z. Chen, Y. Li, P. Qiang, M. Ebrahimi, [185] X. Zhou, C. Shang, L. Gu, S. Dong, X. Chen, P. Han, L. Li, J. Yao,
W. Mai, C. P. Wong, Z. L. Wang, Nano Lett. 2014, 14, 731. Z. Liu, H. Xu, Y. Zhu, G. Cui, ACS Appl. Mater. Interfaces 2011, 3,
[152] L. Liu, J. Lang, P. Zhang, B. Hu, X. Yan, ACS Appl. Mater. Interfaces 3058.
2016, 8, 9335. [186] T. C. Liu, W. G. Pell, B. E. Conway, S. L. Roberson, J. Electrochem.
[153] Y. Zeng, Y. Han, Y. Zhao, Y. Zeng, M. Yu, Y. Liu, H. Tang, Y. Tong, Soc. 1998, 145, 1882.
X. Lu, Adv. Energy Mater. 2015, 5, 1402176. [187] Y.-J. Ting, K. Lian, N. Kherani, ECS Trans. 2011, 35, 133.
[154] W. Tang, L. Liu, S. Tian, L. Li, Y. Yue, Y. Wu, K. Zhu, Chem. [188] X.-l. Li, Y. Xing, H. Wang, H.-l. Wang, W.-d. Wang, X.-y. Chen, Trans.
Commun. 2011, 47, 10058. Nonferrous Metals Soc. China 2009, 19, 620.
[155] K.-H. Chang, C.-C. Hu, C.-M. Huang, Y.-L. Liu, C.-I. Chang, J. Power [189] B. A. Bolto, R. McNeill, D. E. Weiss, Aust. J. Chem. 1963, 16, 1090.
Sources 2011, 196, 2387. [190] H. Shirakawa, E. J. Louis, A. G. MacDiarmid, C. K. Chiang,
[156] P. Sun, Z. Deng, P. Yang, X. Yu, Y. Chen, Z. Liang, H. Meng, A. J. Heeger, J. Chem. Soc., Chem. Commun. 1977, 578.
W. Xie, S. Tan, W. Mai, J. Mater. Chem. A 2015, 3, 12076. [191] R. Ramya, R. Sivasubramanian, M. V. Sangaranarayanan, Electro-
[157] G.-R. Li, Z.-L. Wang, F.-L. Zheng, Y.-N. Ou, Y.-X. Tong, J. Mater. chim. Acta 2013, 101, 109.
Chem. 2011, 21, 4217. [192] R. K. Sharma, A. C. Rastogi, S. B. Desu, Electrochim. Acta 2008, 53,
[158] F. Wang, X. Zhan, Z. Cheng, Z. Wang, Q. Wang, K. Xu, M. Safdar, 7690.
J. He, Small 2015, 11, 749. [193] Z.-z. Zhu, G.-c. Wang, M.-q. Sun, X.-w. Li, C.-z. Li, Electrochim.
[159] W. Ma, H. Nan, Z. Gu, B. Geng, X. Zhang, J. Mater. Chem. A 2015, Acta 2011, 56, 1366.
3, 5442. [194] Y. G. Wang, H. Q. Li, Y. Y. Xia, Adv. Mater. 2006, 18, 2619.
[160] P.-C. Chen, G. Shen, Y. Shi, H. Chen, C. Zhou, ACS Nano 2010, 4, [195] J. Huang, K. Wang, Z. Wei, J. Mater. Chem. 2010, 20, 1117.
4403. [196] K. Wang, J. Huang, Z. Wei, J. Phys. Chem. C 2010, 114, 8062.
[161] M. Yu, Y. Han, X. Cheng, L. Hu, Y. Zeng, M. Chen, F. Cheng, X. Lu, [197] V. Khomenko, E. Frackowiak, F. Béguin, Electrochim. Acta 2005, 50,
Y. Tong, Adv. Mater. 2015, 27, 3085. 2499.
[162] H. Xu, X. Hu, H. Yang, Y. Sun, C. Hu, Y. Huang, Adv. Energy Mater. [198] J. Benson, I. Kovalenko, S. Boukhalfa, D. Lashmore,
2015, 5, 1401882. M. Sanghadasa, G. Yushin, Adv. Mater. 2013, 25, 6625.
[163] M.-S. Balogun, W. Qiu, W. Wang, P. Fang, X. Lu, Y. Tong, J. Mater. [199] J. Yan, T. Wei, B. Shao, Z. Fan, W. Qian, M. Zhang, F. Wei, Carbon
Chem. A 2015, 3, 1364. 2010, 48, 487.
[164] Y. Yue, P. Han, S. Dong, K. Zhang, C. Zhang, C. Shang, G. Cui, [200] K. Wang, P. Zhao, X. Zhou, H. Wu, Z. Wei, J. Mater. Chem. 2011,
Chin. Sci. Bull. 2012, 57, 4111. 21, 16373.
[165] S. A. Al-Thabaiti, R. Hahn, N. Liu, R. Kirchgeorg, S. So, P. Schmuki, [201] N. Kurra, R. Wang, H. N. Alshareef, J. Mater. Chem. A 2015, 3,
S. N. Basahel, S. M. Bawaked, Chem. Commun. 2014, 50, 7368.
7960. [202] J. P. Zheng, P. J. Cygan, T. R. Jow, J. Electrochem. Soc. 1995, 142,
[166] T.-T. Chen, H.-P. Liu, Y.-J. Wei, I. C. Chang, M.-H. Yang, 2699.
Y.-S. Lin, K.-L. Chan, H.-T. Chiu, C.-Y. Lee, Nanoscale 2014, 6, [203] U. M. Patil, S. B. Kulkarni, V. S. Jamadade, C. D. Lokhande, J. Alloys
5106. Compd. 2011, 509, 1677.
[167] J. H. Bang, K. S. Suslick, Adv. Mater. 2009, 21, 3186. [204] M. Subhramannia, B. K. Balan, B. R. Sathe, I. S. Mulla, V. K. Pillai,
[168] B. Avasarala, P. Haldar, Electrochim. Acta 2010, 55, 9024. J. Phys. Chem. C 2007, 111, 16593.
[169] D. Choi, P. N. Kumta, J. Electrochem. Soc. 2006, 153, A2298. [205] V. D. Patake, C. D. Lokhande, Appl. Surf. Sci. 2008, 254, 2820.

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PROGRESS REPORT
[206] C.-C. Hu, K.-H. Chang, M.-C. Lin, Y.-T. Wu, Nano Lett. 2006, 6, [245] W. Chen, R. B. Rakhi, L. Hu, X. Xie, Y. Cui, H. N. Alshareef, Nano
2690. Lett. 2011, 11, 5165.
[207] S. Yan, H. Wang, P. Qu, Y. Zhang, Z. Xiao, Synth. Met. 2009, 159, [246] J. Yan, Z. Fan, T. Wei, J. Cheng, B. Shao, K. Wang, L. Song,
158. M. Zhang, J. Power Sources 2009, 194, 1202.
[208] C. Zhang, Y. Xie, M. Zhao, A. E. Pentecost, Z. Ling, J. Wang, [247] H. Xia, M. Lai, L. Lu, J. Mater. Chem. 2010, 20, 6896.
D. Long, L. Ling, W. Qiao, ACS Appl. Mater. Interfaces 2014, 6, [248] S.-B. Ma, K.-Y. Ahn, E.-S. Lee, K.-H. Oh, K.-B. Kim, Carbon 2007,
9751. 45, 375.
[209] Y. Lee, B. Kim, H. J. Jung, J. H. Shim, Y. Lee, C. Lee, J. M. Baik, [249] J.-H. Kim, K. H. Lee, L. J. Overzet, G. S. Lee, Nano Lett. 2011, 11,
W. Kim, M. H. Kim, Mater. Lett. 2012, 89, 115. 2611.
[210] J.-K. Lee, H. M. Pathan, K.-D. Jung, O.-S. Joo, J. Power Sources [250] R. Amade, E. Jover, B. Caglar, T. Mutlu, E. Bertran, J. Power Sources
2006, 159, 1527. 2011, 196, 5779.
[211] R. K. Das, B. Liu, J. R. Reynolds, A. G. Rinzler, Nano Lett. 2009, 9, [251] L. Hu, W. Chen, X. Xie, N. Liu, Y. Yang, H. Wu, Y. Yao, M. Pasta,
677. H. N. Alshareef, Y. Cui, ACS Nano 2011, 5, 8904.
[212] A. Ghosh, Y. H. Lee, ChemSusChem 2012, 5, 480. [252] T. Gu, B. Wei, J. Mater. Chem. A 2016, 4, 12289.
[213] M. Zhi, C. Xiang, J. Li, M. Li, N. Wu, Nanoscale 2013, 5, 72. [253] W. Lv, D.-M. Tang, Y.-B. He, C.-H. You, Z.-Q. Shi, X.-C. Chen,
[214] P. Wang, Y. Xu, H. Liu, Y. Chen, J. Yang, Q. Tan, Nano Energy 2015, C.-M. Chen, P.-X. Hou, C. Liu, Q.-H. Yang, ACS Nano 2009, 3,
15, 116. 3730.
[215] J. Y. Hwang, M. F. El-Kady, Y. Wang, L. Wang, Y. Shao, K. Marsh, [254] L. Tang, Y. Wang, Y. Li, H. Feng, J. Lu, J. Li, Adv. Funct. Mater. 2009,
J. M. Ko, R. B. Kaner, Nano Energy 2015, 18, 57. 19, 2782.
[216] H. Huang, W. Zhang, Y. Fu, X. Wang, Electrochim. Acta 2015, 152, [255] Q. Cheng, J. Tang, J. Ma, H. Zhang, N. Shinya, L.-C. Qin, Carbon
480. 2011, 49, 2917.
[217] J.-i. Hong, I.-H. Yeo, W.-k. Paik, J. Electrochem. Soc. 2001, 148, [256] D. Pech, M. Brunet, H. Durou, P. Huang, V. Mochalin, Y. Gogotsi,
A156. P.-L. Taberna, P. Simon, Nat. Nanotechnol. 2010, 5, 651.
[218] S. F. Shaikh, J. Y. Lim, O.-S. Joo, Curr. Appl. Phys. 2013, 13, 758. [257] J. Lin, C. Zhang, Z. Yan, Y. Zhu, Z. Peng, R. H. Hauge, D. Natelson,
[219] X. Li, W. Gan, F. Zheng, L. Li, N. Zhu, X. Huang, Synth. Met. 2012, J. M. Tour, Nano Lett. 2013, 13, 72.
162, 953. [258] L. Peng, X. Peng, B. Liu, C. Wu, Y. Xie, G. Yu, Nano Lett. 2013, 13,
[220] S. Cho, M. Kim, J. Jang, ACS Appl. Mater. Interfaces 2015, 7, 10213. 2151.
[221] R. Liu, J. Duay, T. Lane, S. Bok Lee, Phys. Chem. Chem. Phys. 2010, [259] Z. Zhang, F. Xiao, L. Qian, J. Xiao, S. Wang, Y. Liu, Adv. Energy
12, 4309. Mater. 2014, 4, 1400064.
[222] J. Lei, X. Chen, J. Semicond. 2015, 36, 083006. [260] Z. Zhang, F. Xiao, S. Wang, J. Mater. Chem. A 2015, 3, 11215.
[223] Y. R. Ahn, C. R. Park, S. M. Jo, D. Y. Kim, Appl. Phys. Lett. 2007, 90, [261] J.-M. Li, K.-H. Chang, C.-C. Hu, Electrochem. Commun. 2010, 12,
122106. 1800.
[224] W. Yong-gang, Z. Xiao-gang, Electrochim. Acta 2004, 49, 1957. [262] Q. T. Qu, L. L. Liu, Y. P. Wu, R. Holze, Electrochim. Acta 2013, 96,
[225] H.-K. Kim, S.-H. Choi, Y. S. Yoon, S.-Y. Chang, Y.-W. Ok, T.-Y. Seong, 8.
Thin Solid Films 2005, 475, 54. [263] T. Zhai, H. Liu, H. Li, X. Fang, M. Liao, L. Li, H. Zhou, Y. Koide,
[226] H. Y. Lee, J. B. Goodenough, J. Solid State Chem. 1999, 144, 220. Y. Bando, D. Golberg, Adv. Mater. 2010, 22, 2547.
[227] C.-C. Hu, C.-C. Wang, J. Electrochem. Soc. 2003, 150, A1079. [264] B. Saravanakumar, K. K. Purushothaman, G. Muralidharan, J. Elec-
[228] Y. X. Zhang, M. Huang, F. Li, X. L. Wang, Z. Q. Wen, J. Power troanal. Chem. 2015, 758, 111.
Sources 2014, 246, 449. [265] H. Y. Lee, J. B. Goodenough, J. Solid State Chem. 1999, 148, 81.
[229] Y. Dai, S. Tang, X. Wang, X. Huang, C. Zhu, Z. Hang, X. Meng, [266] G. Wee, H. Z. Soh, Y. L. Cheah, S. G. Mhaisalkar, M. Srinivasan, J.
Chem. Lett. 2014, 43, 122. Mater. Chem. 2010, 20, 6720.
[230] B. Yin, S. Zhang, Y. Jiao, Y. Liu, F. Qu, X. Wu, CrystEngComm 2014, [267] M. Li, G. Sun, P. Yin, C. Ruan, K. Ai, ACS Appl. Mater. Interfaces
16, 9999. 2013, 5, 11462.
[231] M.-S. Wu, Appl. Phys. Lett. 2005, 87, 153102. [268] J. Yang, T. Lan, J. Liu, Y. Song, M. Wei, Electrochim. Acta 2013, 105,
[232] M. Xu, L. Kong, W. Zhou, H. Li, J. Phys. Chem. C 2007, 111, 489.
19141. [269] J. Zhu, L. Cao, Y. Wu, Y. Gong, Z. Liu, H. E. Hoster, Y. Zhang,
[233] W. Xiao, H. Xia, J. Y. H. Fuh, L. Lu, J. Power Sources 2009, 193, 935. S. Zhang, S. Yang, Q. Yan, P. M. Ajayan, R. Vajtai, Nano Lett. 2013,
[234] M. G. Deng, Y. F. Chen, Adv. Mater. Res. 2010, 152–153, 1551. 13, 5408.
[235] A. Yuan, Q. Zhang, Electrochem. Commun. 2006, 8, 1173. [270] K. Liang, X. Tang, W. Hu, Y. Yang, ChemElectroChem 2016, 3, 704.
[236] S. W. Lee, J. Kim, S. Chen, P. T. Hammond, Y. Shao-Horn, ACS [271] Z. Chen, V. Augustyn, J. Wen, Y. Zhang, M. Shen, B. Dunn, Y. Lu,
Nano 2010, 4, 3889. Adv. Mater. 2011, 23, 791.
[237] Y. Shao, H. Wang, Q. Zhang, Y. Li, J. Mater. Chem. C 2013, 1, 1245. [272] J. S. Bonso, A. Rahy, S. D. Perera, N. Nour, O. Seitz, Y. J. Chabal,
[238] P.-C. Gao, A.-H. Lu, W.-C. Li, J. Power Sources 2011, 196, 4095. K. J. Balkus Jr., J. P. Ferraris, D. J. Yang, J. Power Sources 2012, 203,
[239] S. Kondrat, C. R. Perez, V. Presser, Y. Gogotsi, A. A. Kornyshev, 227.
Energy Environ. Sci. 2012, 5, 6474. [273] M. Lee, S. K. Balasingam, H. Y. Jeong, W. G. Hong, H.-B.-R. Lee,
[240] Y.-T. Wang, A.-H. Lu, W.-C. Li, Microporous Mesoporous Mater. 2012, B. H. Kim, Y. Jun, Sci. Rep. 2015, 5, 8151.
153, 247. [274] C. X. Guo, K. Sun, J. Ouyang, X. Lu, Chem. Mater. 2015, 27, 5813.
[241] C. Y. Lee, H. M. Tsai, H. J. Chuang, S. Y. Li, P. Lin, T. Y. Tseng, J. [275] Z. Chen, Y. Qin, D. Weng, Q. Xiao, Y. Peng, X. Wang, H. Li, F. Wei,
Electrochem. Soc. 2005, 152, A716. Y. Lu, Adv. Funct. Mater. 2009, 19, 3420.
[242] E. Raymundo-Piñero, V. Khomenko, E. Frackowiak, F. Béguin, J. [276] A. Ghosh, E. J. Ra, M. Jin, H.-K. Jeong, T. H. Kim, C. Biswas,
Electrochem. Soc. 2005, 152, A229. Y. H. Lee, Adv. Funct. Mater. 2011, 21, 2541.
[243] G.-X. Wang, B.-L. Zhang, Z.-L. Yu, M.-Z. Qu, Solid State Ionics [277] J. Xu, H. Sun, Z. Li, S. Lu, X. Zhang, S. Jiang, Q. Zhu,
2005, 176, 1169. G. S. Zakharova, Solid State Ionics 2014, 262, 234.
[244] Z. Fan, J. Chen, M. Wang, K. Cui, H. Zhou, Y. Kuang, Diamond [278] C. X. Guo, G. Yilmaz, S. Chen, S. Chen, X. Lu, Nano Energy 2015,
Relat. Mater. 2006, 15, 1478. 12, 76.

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[279] X. Zhou, Q. Chen, A. Wang, J. Xu, S. Wu, J. Shen, ACS Appl. Mater. [312] M. Naguib, O. Mashtalir, J. Carle, V. Presser, J. Lu, L. Hultman,
Interfaces 2016, 8, 3776. Y. Gogotsi, M. W. Barsoum, ACS Nano 2012, 6, 1322.
[280] R. R. Salunkhe, J. Lin, V. Malgras, S. X. Dou, J. H. Kim, Y. Yamauchi, [313] M. Ghidiu, M. R. Lukatskaya, M.-Q. Zhao, Y. Gogotsi,
Nano Energy 2015, 11, 211. M. W. Barsoum, Nature 2014, 516, 78.
[281] Y.-w. Li, Z.-l. Yin, J.-h. Yao, W.-m. Zhao, C.-j. Liu, S.-k. Zhong, Trans. [314] N. Choudhary, M. Patel, Y.-H. Ho, N. B. Dahotre, W. Lee,
Nonferrous Metals Soc. China 2010, 20, s249. J. Y. Hwang, W. Choi, J. Mater. Chem. A 2015, 3, 24049.
[282] L. Xu, Y.-S. Ding, C.-H. Chen, L. Zhao, C. Rimkus, R. Joesten, [315] Y. Yang, H. Fei, G. Ruan, C. Xiang, J. M. Tour, Adv. Mater. 2014, 26,
S. L. Suib, Chem. Mater. 2008, 20, 308. 8163.
[283] Y. Hu, Y. V. Tolmachev, D. A. Scherson, J. Electroanal. Chem. 1999, [316] Y. Dall’Agnese, M. R. Lukatskaya, K. M. Cook, P.-L. Taberna,
468, 64. Y. Gogotsi, P. Simon, Electrochem. Commun. 2014, 48, 118.
[284] A. L. Beliakov, A. M. Brintsev, presented at the 7th Int. Seminar [317] Z. Ling, C. E. Ren, M.-Q. Zhao, J. Yang, J. M. Giammarco, J. Qiu,
on Double-Layer Capacitors and Similar Energy Storage Devices, M. W. Barsoum, Y. Gogotsi, Proc. Natl. Acad. Sci. USA 2014, 111,
Deerfield Beach, FL, USA, December 1997. 16676.
[285] M. Oshitani, H. Yufu, K. Takashima, S. Tsuji, Y. Matsumaru, J. Elec- [318] X. Lu, M. Yu, G. Wang, T. Zhai, S. Xie, Y. Ling, Y. Tong, Y. Li, Adv.
trochem. Soc. 1989, 136, 1590. Mater. 2013, 25, 267.
[286] J. H. Park, O. O. Park, K. H. Shin, C. S. Jin, J. H. Kim, Electrochem. [319] Z. Algharaibeh, P. G. Pickup, Electrochem. Commun. 2011, 13,
Solid-State Lett. 2002, 5, H7. 147.
[287] J.-W. Lang, L.-B. Kong, W.-J. Wu, M. Liu, Y.-C. Luo, L. Kang, J. Solid [320] P. Chen, H. Chen, J. Qiu, C. Zhou, Nano Res. 2010, 3, 594.
State Electrochem. 2008, 13, 333. [321] D. Ghosh, M. Mandal, C. K. Das, Langmuir 2015, 31, 7835.
[288] T. Xiao, X. Hu, B. Heng, X. Chen, W. Huang, W. Tao, H. Wang, [322] T. Zhai, X. Lu, Y. Ling, M. Yu, G. Wang, T. Liu, C. Liang, Y. Tong,
Y. Tang, X. Tan, X. Huang, J. Alloys Compd. 2013, 549, 147. Y. Li, Adv. Mater. 2014, 26, 5869.
[289] X. Cao, Y. Shi, W. Shi, G. Lu, X. Huang, Q. Yan, Q. Zhang, [323] J. Xu, Q. Wang, X. Wang, Q. Xiang, B. Liang, D. Chen, G. Shen,
H. Zhang, Small 2011, 7, 3163. ACS Nano 2013, 7, 5453.
[290] J. Huang, P. Xu, D. Cao, X. Zhou, S. Yang, Y. Li, G. Wang, J. Power [324] W. Chen, C. Xia, H. N. Alshareef, ACS Nano 2014, 8, 9531.
Sources 2014, 246, 371. [325] C. Yang, J. Shen, C. Wang, H. Fei, H. Bao, G. Wang, J. Mater.
[291] G.-W. Yang, C.-L. Xu, H.-L. Li, Chem. Commun. 2008, 6537. Chem. A 2014, 2, 1458.
[292] J. Ji, L. L. Zhang, H. Ji, Y. Li, X. Zhao, X. Bai, X. Fan, F. Zhang, [326] F. Estaline Amitha, A. Leela Mohana Reddy, S. Ramaprabhu, J.
R. S. Ruoff, ACS Nano 2013, 7, 6237. Nanopart. Res. 2009, 11, 725.
[293] Y.-Z. Su, K. Xiao, N. Li, Z.-Q. Liu, S.-Z. Qiao, J. Mater. Chem. A [327] A. Sumboja, C. Y. Foo, X. Wang, P. S. Lee, Adv. Mater. 2013, 25,
2014, 2, 13845. 2809.
[294] Y. Yang, L. Li, G. Ruan, H. Fei, C. Xiang, X. Fan, J. M. Tour, ACS [328] Y. Zhao, W. Ran, J. He, Y. Huang, Z. Liu, W. Liu, Y. Tang, L. Zhang,
Nano 2014, 8, 9622. D. Gao, F. Gao, Small 2015, 11, 1310.
[295] Z. Tang, C.-h. Tang, H. Gong, Adv. Funct. Mater. 2012, 22, 1272. [329] Y. Ren, L. Gao, J. Am. Ceram. Soc. 2010, 93, 3560.
[296] J. Yan, Z. Fan, W. Sun, G. Ning, T. Wei, Q. Zhang, R. Zhang, L. Zhi, [330] G. Xiao-yan, D. Jian-cheng, Mater. Lett. 2007, 61, 621.
F. Wei, Adv. Funct. Mater. 2012, 22, 2632. [331] R. Wang, X. Yan, Sci. Rep. 2014, 4, 3712.
[297] Z. Wu, X.-L. Huang, Z.-L. Wang, J.-J. Xu, H.-G. Wang, X.-B. Zhang, [332] T.-W. Lin, C.-S. Dai, K.-C. Hung, Sci. Rep. 2014, 4, 7274.
Sci. Rep. 2014, 4, 3669. [333] Z. Fan, J. Yan, T. Wei, L. Zhi, G. Ning, T. Li, F. Wei, Adv. Funct.
[298] L. Su, L. Gong, J. Gao, J. Power Sources 2012, 209, 141. Mater. 2011, 21, 2366.
[299] M. Li, S. Xu, Y. Zhu, P. Yang, L. Wang, P. K. Chu, J. Alloys Compd. [334] C. Xia, Q. Jiang, C. Zhao, P. M. Beaujuge, H. N. Alshareef, Nano
2014, 589, 364. Energy 2016, 24, 78.
[300] J.-H. Zhong, A.-L. Wang, G.-R. Li, J.-W. Wang, Y.-N. Ou, Y.-X. Tong, [335] J. Wang, S. Liu, X. Zhang, X. Liu, X. Liu, N. Li, J. Zhao, Y. Li, Elec-
J. Mater. Chem. 2012, 22, 5656. trochim. Acta 2016, 213, 663.
[301] H. Yang, H. Xu, M. Li, L. Zhang, Y. Huang, X. Hu, ACS Appl. Mater. [336] H. Cheng, H. M. Duong, D. Jewell, RSC Adv. 2016, 6, 36954.
Interfaces 2016, 8, 1774. [337] C.-h. Tang, X. Yin, H. Gong, ACS Appl. Mater. Interfaces 2013, 5,
[302] H. Wang, H. Feng, J. Li, Small 2014, 10, 2165. 10574.
[303] B. Mendoza-Sánchez, Y. Gogotsi, Adv. Mater. 2016, 28, 6104. [338] J. L. Yin, J. Y. Park, J. Solid State Electrochem. 2015, 19, 2391.
[304] N. Choudhary, J. Park, J. Y. Hwang, H.-S. Chung, K. H. Dumas, [339] X. Liu, L. Yu, Mater. Lett. 2004, 58, 1327.
S. I. Khondaker, W. Choi, Y. Jung, Sci. Rep. 2016, 6, 25456. [340] X. Kong, X. Liu, Y. He, D. Zhang, X. Wang, Y. Li, Mater. Chem.
[305] N. Choudhary, M. D. Patel, J. Park, B. Sirota, W. Choi, J. Mater. Res. Phys. 2007, 106, 375.
2016, 31, 824. [341] F. Luan, G. Wang, Y. Ling, X. Lu, H. Wang, Y. Tong, X. X. Liu, Y. Li,
[306] Y. Jung, Y. Zhou, J. J. Cha, Inorg. Chem. Front. 2016, 3, 452. Nanoscale 2013, 5, 7984.
[307] G. R. Bhimanapati, Z. Lin, V. Meunier, Y. Jung, J. Cha, S. Das, [342] C. Zhou, Y. Zhang, Y. Li, J. Liu, Nano Lett. 2013, 13, 2078.
D. Xiao, Y. Son, M. S. Strano, V. R. Cooper, L. Liang, S. G. Louie, [343] I. Ryu, M. Yang, H. Kwon, H. K. Park, Y. R. Do, S. B. Lee, S. Yim,
E. Ringe, W. Zhou, S. S. Kim, R. R. Naik, B. G. Sumpter, Langmuir 2014, 30, 1704.
H. Terrones, F. Xia, Y. Wang, J. Zhu, D. Akinwande, N. Alem, [344] Y. Zhou, H. Xu, N. Lachman, M. Ghaffari, S. Wu, Y. Liu, A. Ugur,
J. A. Schuller, R. E. Schaak, M. Terrones, J. A. Robinson, ACS Nano K. K. Gleason, B. L. Wardle, Q. M. Zhang, Nano Energy 2014, 9,
2015, 9, 11509. 176.
[308] K.-J. Huang, L. Wang, Y.-J. Liu, Y.-M. Liu, H.-B. Wang, T. Gan, [345] P. Tang, L. Han, L. Zhang, ACS Appl. Mater. Interfaces 2014, 6,
L.-L. Wang, Int. J. Hydrogen Energy 2013, 38, 14027. 10506.
[309] M. A. Bissett, I. A. Kinloch, R. A. W. Dryfe, ACS Appl. Mater. Inter- [346] H. R. Ghenaatian, M. F. Mousavi, M. S. Rahmanifar, Electrochim.
faces 2015, 7, 17388. Acta 2012, 78, 212.
[310] M. Acerce, D. Voiry, M. Chhowalla, Nat. Nanotechnol. 2015, 10, [347] V. Khomenko, E. Raymundo-Piñero, E. Frackowiak, F. Béguin,
313. Appl. Phys. A 2006, 82, 567.
[311] M. Naguib, V. N. Mochalin, M. W. Barsoum, Y. Gogotsi, Adv. [348] P. Tammela, Z. Wang, S. Frykstrand, P. Zhang, I.-M. Sintorn,
Mater. 2014, 26, 992. L. Nyholm, M. Stromme, RSC Adv. 2015, 5, 16405.

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PROGRESS REPORT
[349] D. F. Zeigler, S. L. Candelaria, K. A. Mazzio, T. R. Martin, [371] G. Zhou, F. Li, H.-M. Cheng, Energy Environ. Sci. 2014, 7,
E. Uchaker, S.-L. Suraru, L. J. Kang, G. Cao, C. K. Luscombe, 1307.
Macromolecules 2015, 48, 5196. [372] Y. Liu, S. Gorgutsa, C. Santato, M. Skorobogatiy, J. Electrochem.
[350] D. Aradilla, F. Estrany, E. Armelin, C. Alemán, Thin Solid Films Soc. 2012, 159, A349.
2012, 520, 4402. [373] J. Ren, Y. Zhang, W. Bai, X. Chen, Z. Zhang, X. Fang, W. Weng,
[351] W.-H. Khoh, J.-D. Hong, Colloids Surf., A 2014, 456, 26. Y. Wang, H. Peng, Angew. Chem. 2014, 126, 7998.
[352] L. F. Chen, Z. H. Huang, H. W. Liang, Q. F. Guan, S. H. Yu, Adv. [374] Y. Luo, J. Luo, J. Jiang, W. Zhou, H. Yang, X. Qi, H. Zhang,
Mater. 2013, 25, 4746. H. J. Fan, D. Y. W. Yu, C. M. Li, T. Yu, Energy Environ. Sci. 2012, 5,
[353] B. S. Shim, W. Chen, C. Doty, C. Xu, N. A. Kotov, Nano Lett. 2008, 6559.
8, 4151. [375] X. Cheng, J. Zhang, J. Ren, N. Liu, P. Chen, Y. Zhang, J. Deng,
[354] K. Cherenack, C. Zysset, T. Kinkeldei, N. Münzenrieder, G. Tröster, Y. Wang, H. Peng, J. Phys. Chem. C 2016, 120, 9685.
Adv. Mater. 2010, 22, 5178. [376] H. Xu, X. Hu, Y. Sun, H. Yang, X. Liu, Y. Huang, Nano Res. 2014,
[355] K. Laxminarayana, N. Jalili, Textile Res. J. 2005, 75, 670. 8, 1148.
[356] L. Buechley, in 2006 10th IEEE Int. Symp. Wearable Computers, [377] P. Xu, B. Wei, Z. Cao, J. Zheng, K. Gong, F. Li, J. Yu, Q. Li, W. Lu,
IEEE, Piscataway, NJ, USA 2006, pp. 83. J.-H. Byun, B.-S. Kim, Y. Yan, T.-W. Chou, ACS Nano 2015, 9,
[357] D. Marculescu, R. Marculescu, N. H. Zamora, P. Stanley-Marbell, 6088.
P. K. Khosla, S. Park, S. Jayaraman, S. Jung, C. Lauterbach, [378] X. Dong, Z. Guo, Y. Song, M. Hou, J. Wang, Y. Wang, Y. Xia, Adv.
W. Weber, Proc. IEEE 2003, 91, 1995. Funct. Mater. 2014, 24, 3405.
[358] L. Hu, F. La Mantia, H. Wu, X. Xie, J. McDonough, M. Pasta, [379] X. Wang, B. Liu, R. Liu, Q. Wang, X. Hou, D. Chen, R. Wang,
Y. Cui, Adv. Energy Mater. 2011, 1, 1012. G. Shen, Angew. Chem. Int., Ed. Engl. 2014, 53, 1849.
[359] B. Zheng, T. Huang, L. Kou, X. Zhao, K. Gopalsamy, C. Gao, J. [380] Z. Yu, J. Moore, J. Calderon, L. Zhai, J. Thomas, Small 2015, 11,
Mater. Chem. A 2014, 2, 9736. 5289.
[360] D. Yu, K. Goh, Q. Zhang, L. Wei, H. Wang, W. Jiang, Y. Chen, Adv. [381] S. T. Senthilkumar, R. Kalai Selvan, Phys. Chem. Chem. Phys. 2014,
Mater. 2014, 26, 6790. 16, 15692.
[361] Z. Zhang, F. Xiao, J. Xiao, S. Wang, J. Mater. Chem. A 2015, 3, [382] W. Liu, N. Liu, Y. Shi, Y. Chen, C. Yang, J. Tao, S. Wang, Y. Wang,
11817. J. Su, L. Li, Y. Gao, J. Mater. Chem. A 2015, 3, 13461.
[362] H. Jin, L. Zhou, C. L. Mak, H. Huang, W. M. Tang, H. L. W. Chan, [383] W. Cai, T. Lai, J. Lai, H. Xie, L. Ouyang, J. Ye, C. Yu, Sci. Rep. 2016,
Nano Energy 2015, 11, 662. 6, 26890.
[363] H. Jin, L. Zhou, C. L. Mak, H. Huang, W. M. Tang, H. L. Wa Chan, [384] N. Yu, H. Yin, W. Zhang, Y. Liu, Z. Tang, M.-Q. Zhu, Adv. Energy
J. Mater. Chem. A 2015, 3, 15633. Mater. 2016, 6, 1501458.
[364] D. P. J. Cotton, I. M. Graz, S. P. Lacour, IEEE Sens. J. 2009, 9, 2008. [385] L. Zhang, P. Zhu, F. Zhou, W. Zeng, H. Su, G. Li, J. Gao, R. Sun,
[365] T. Yamada, Y. Hayamizu, Y. Yamamoto, Y. Yomogida, A. Izadi- C.-p. Wong, ACS Nano 2016, 10, 1273.
Najafabadi, D. N. Futaba, K. Hata, Nat. Nanotechnol. 2011, 6, 296. [386] S. T. Senthilkumar, J. Kim, Y. Wang, H. Huang, Y. Kim, J. Mater.
[366] M. Stoppa, A. Chiolerio, Sensors 2014, 14, 11957. Chem. A 2016, 4, 4934.
[367] M. Amjadi, A. Pichitpajongkit, S. Lee, S. Ryu, I. Park, ACS Nano [387] N. Yu, H. Yin, W. Zhang, Y. Liu, Z. Tang, M.-Q. Zhu, Adv. Energy
2014, 8, 5154. Mater. 2016, 6, 1501458.
[368] D. J. Lipomi, B. C. K. Tee, M. Vosgueritchian, Z. Bao, Adv. Mater. [388] N. Choudhary, C. Li, H.-S. Chung, J. Moore, J. Thomas, Y. Jung,
2011, 23, 1771. ACS Nano 2016, 10, 10726.
[369] M. Kaltenbrunner, M. S. White, E. D. Głowacki, T. Sekitani, [389] Z. Yu, J. Thomas, Adv. Mater. 2014, 26, 4279.
T. Someya, N. S. Sariciftci, S. Bauer, Nat. Commun. 2012, 3, 770. [390] C. Li, M. M. Islam, J. Moore, J. Sleppy, C. Morrison,
[370] D. J. Lipomi, H. Chong, M. Vosgueritchian, J. Mei, Z. Bao, Sol. K. Konstantinov, S. X. Dou, C. Renduchintala, J. Thomas, Nat.
Energy Mater. Sol. Cells 2012, 107, 355. Commun. 2016, 7, 13319.

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