Supercapacitor

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Recent Advances in Design and Fabrication of

Electrochemical Supercapacitors with High Energy
Densities
Jun Yan, Qian Wang, Tong Wei, and Zhuangjun Fan*
emerging ecological concerns.[2,5] Among
various energy conversion and storage
In recent years, tremendous research effort has been aimed at increasing the
devices, lithium-ion batteries (LIBs)[6] and
energy density of supercapacitors without sacrificing high power capability
[7,8] are at the forefront as
supercapacitors
so that they reach the levels achieved in batteries and at lowering fabrication
illustrated in the Ragone plot (Figure 1).
costs. For this purpose, two important problems have to be solved: first, it is
Although their high energy densities can
critical to develop ways to design high performance electrode materials for
be achieved as high as 180 Wh kg1, LIBs
supercapacitors; second, it is necessary to achieve controllably assembled
usually suffer from a somewhat slow power
delivery or uptake.[5] Upon that, the widesupercapacitor types (such as symmetric capacitors including double-layer
spread application of LIBs is thus greatly
and pseudo-capacitors, asymmetric capacitors, and Li-ion capacitors). The
inhibited, especially in energy-storage sysexplosive growth of research in this field makes this review timely. Recent
tems where fast and higher-power storage
progress in the research and development of high performance electrode
devices are highly required.[5,9] As a consematerials and high-energy supercapacitors is summarized. Several key issues
quence, this heavy burden has been given
to the supercapacitors.[10]
for improving the energy densities of supercapacitors and some mutual
Supercapacitors, also known as elecrelationships among various effecting parameters are reviewed, and chaltrochemical
capacitors or ultracapacitors,
lenges and perspectives in this exciting field are also discussed. This provides
have attracted a great deal of attention
fundamental insight into supercapacitors and offers an important guideline
from both industry and academia due to
for future design of advanced next-generation supercapacitors for industrial
their high power density, superior rate
and consumer applications.
capability, rapid charging/discharging
rate, long cycle life (>100 000 cycles),
simple principles, fast dynamics of charge
propagation
and
low
maintenance cost.[17,18] Since General
1. Introduction
Electric for the first time demonstrated and patented in 1957,[19]
Due to the rapid development of the global economy, the
supercapacitors have continued to attract considerable attention
growing human population worldwide, a fast-growing market
from both scientists and engineers as indicated by the number
for portable electronic devices, and the development of hybrid
of published articles in this area (Figure 2). In addition, they
electric vehicles, global energy consumption has been accelerating at an alarming rate.[13] The exhaustion of global energy
will soon become unavoidable in the near future at current consumption rate. It is reported that our global energy needs will
roughly double by mid-century and triple by 2100.[4] Thus, there
has been an ever-increasing and urgent demand for vigorous
development of not only clean, renewable, and sustainable
alternative energies (solar, wind, and tide), but also advanced,
low-cost, and environmentally friendly energy conversion and
storage devices to satisfy the needs of modern society and
Dr. J. Yan, Q. Wang, Prof. T. Wei, Prof. Z. J. Fan
Key Laboratory of Superlight Materials
and Surface Technology
Ministry of Education, College of Material Science
and Chemical Engineering
Harbin Engineering University
Harbin, 150001, P. R. China
E-mail: fanzhj666@163.com
DOI: 10.1002/aenm.201300816
Adv. Energy Mater. 2014, 4, 1300816
Figure 1. Specific power against specific energy, also called a Ragone

plot, for various electrical energy storage devices. Data obtained from
Ref. [11] ( ), [12] ( ), [13] ( ), [14] ( ), [15] ( ) and [16] ( ).
2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
wileyonlinelibrary.com
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Figure 2. Trends in the number of publications on supercapacitors (data

obtained from Web of Science on Aug 27, 2013).
have triggered an explosion of interest for a wide and growing

range of applications where require high power density such as
energy back-up systems, consumer portable devices, electrical/
hybrid electric vehicles and other devices.[5,10,20] Supercapacitors currently bridge the power gap between batteries and traditional solid state and electrolytic capacitors, delivering higher
power bursts than batteries and storing more energy than
capacitors. Although the energy density of most of the commercially available supercapacitors (less than 10 Wh kg1) is much
higher than conventional dielectric capacitors, it is still significantly lower than batteries and fuel cells.[18] With the rapid
development of the global economy, there is an urgent need
for supercapacitors with high stored energy. Thus, tremendous
research effort has been performed aiming at increasing the
energy density of supercapacitors without sacrificing their high
power capability to be close to or even beyond that of batteries
as well as lowing fabrication costs all over the world in recent
years.[11,14,2124]
The field of research and development of high energy density
supercapacitors is currently undergoing an exciting development with increasing achievements. In spite of many reviews
exploring numerous materials applied in supercapacitors, such
as carbon based materials, metal oxides or conducting polymers, metal oxide-carbon hybrid materials and the design of
nanostructured materials,[17,2432] there are just several reviews
focusing specifically on supercapacitors with high energy densities as a whole.[33,34] As we all know, an increasing number
of significant breakthroughs have been made on advanced electrode materials with high specific capacitance (SC) in recent
years. Therefore, it is feasible to achieve high energy density
for supercapacitors originated from high capacitance of the
electrodes.
Apart from advanced electrode materials, there are other
major parameters that are important in determining high
energy density of supercapacitors, such as electrolytes,
assemble types of supercapacitor and reasonable matching of
negative/positive electrodes. With the new emergence of graphene, redox-active electrolytes, and carbon/carbon supercapacitors with high working voltage in recent years, the research
in supercapacitors with high energy density is springing up
1300816 (2 of 43)
Jun Yan received his PhD

degree in material science
from Harbin Engineering
University in 2010 and carried
out his post-doctoral research
at Harbin Engineering
University (2010-2012). Now,
he is a Lecturer in the College
of Material Science and
Chemical Engineering, Harbin
Engineering University. His
research interests mainly
focus on design, synthesis, and functionalization of carbon
nanomaterials as well as their applications in electrochemical energy conversion and storage devices.
Zhuangjun Fan received

his PhD in 2003 from the
Institute of Coal Chemistry,
Chinese Academy of Sciences.
He became a full professor
in the College of Material
Science and Chemical
Engineering in 2006, and he
is now the director of the
Institue of Advanced Carbon
Based Materials at Harbin
Engineering University. His
research interests focus on the design and controlled synthesis of carbon nanomaterials, such as carbon nanotubes
and graphene, and their application in energy-related areas
such as supercapacitors, Li-ion batteries, and full cells.
around the world. Therefore, it is imperative and important

to provide timely updates on progress in this promising field,
and systematically present these key issues for improving the
energy densities of supercapacitors as well as deeply reveal the
mutual relationships among various effecting parameters along
with some discussions on challenges and perspectives. This
review fills this potential gap focusing solely on the research
progress in high energy density supercapacitors with comprehensive tables provided. We first provide a brief introduction
to the basic principles and performances of supercapacitors. A
variety of promising strategies to improve the energy densities
of supercapacitors are also briefly discussed, followed by an indepth summary of significant research progress in the development of high energy density supercapacitor technologies
demonstrated in recent years. Particular emphasis is focused
on recent research breakthroughs achieved by rational design
and development of various recently emerging positive/negative electrode materials with high SC to maximize the electrochemical performance of the devices. Considerable aqueous
and non-aqueous electrolytes springing up in supercapacitors
over the past several years as well as recently designed and
fabricated asymmetric supercapacitors (ASCs) appeared in
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literature are highlighted. However, we do not claim that this

review covers all of the published work about supercapacitors
owing to the explosion of publications in this exciting field. We
apologize to those authors whose work we have left out. Finally,
the prospects and future developments in this exciting field of
high-power and high-energy supercapacitors are also suggested.
2. Important Parameters for High Energy Density

Supercapacitors
The performances of supercapacitors are mainly evaluated
based on the following aspects:[17] 1) a high SC; 2) a substantially high power density; 3) a relatively high energy density;
4) an excellent cyclability; 5) fast charge/discharge rates within
seconds; 6) low self-discharging; 7) safe operation, and 8) low
cost. It is well-known that several factors significantly affect the
performances of a supercapacitor as summarized by Pandolfo
and Hollenkamp in their review,[19] such as pore structure of
electroactive materials (specific surface area (SSA) and pore size
distribution (PSD)), intrinsic properties of the electrolyte, microstructure/morphology and electrical conductivity of electroactive
materials, and the interface between electrode and electrolyte. In
addition to the above factors, there are some other influencing
parameters, such as operating voltage, reasonable matching
of negative/positive electrode, and asymmetric design, that
strongly affect the energy density for supercapacitors.
A two-electrode supercapacitor cell can be considered as two
capacitors in series, and the total capacitance (CT) of the cell
can be calculated as follows:
1/CT = 1/Cp + 1/Cn
(1)
in which Cp and Cn are the capacitance of the positive and negative electrodes based on a three-electrode setup, respectively.
If the two electrodes are identical (Cp = Cn), the corresponding
supercapacitor is called a symmetric supercapacitor and the
total capacitance CT will be one half of either ones capacitance.
In other case, i.e., the positive and negative electrodes use different materials corresponding to ASCs, and CT will depend on
the relative smaller value between Cp and Cn.
Energy and power densities are two crucial parameters for
evaluating the electrochemical performance of supercapacitors.
The maximum energy (E in Wh kg1) and power densities (P in
W kg1) of a supercapacitor can be obtained using Equations (2)
and (3), respectively:[3,17]
E = C V 2 /2
(2)
P = V 2 /4R
(3)
where CT is the total capacitance of the cell (in F); V (in V) is the
cells operating voltage, which is determined by the thermodynamic stability (stability window) of an electrolyte and dependent
upon electroactive electrode materials; and R is the equivalent
series resistance (ESR, in ), composed of the intrinsic resistance of the electroactive materials, contact resistance between
the electroactive materials and the current collector, diffusion
resistance of ions in the electrode materials and through the
separator, and ionic resistance of electrolytes. Therefore, in
order to achieve excellent performance for a supercapacitor, it
Figure 3. Schematic illustration of different approaches to improve

energy density of a supercapacitor.
is of critical significance for it to simultaneously possess high

SC, wide operating cell voltage, and minimum ESR. Nowadays,
from a practical point of view, the most important challenge
facing material scientists and engineers worldwide is to increase
the energy density higher than 10 Wh kg1 with low fabrication
cost while using environmentally friendly materials.
Based on Equation (2), the important parameters for high
energy density supercapacitors are shown in Figure 3. This
is an effective approach to improve energy density through
increasing the capacitance, which can be realized by improving
the SC of both positive and negative electrodes. Therefore,
there has been an explosion of interest in designing and developing advanced nanostructured electrode materials with high
SC in supercapacitor research and development in recent
years. To be specific, with regard to the carbon materials, the
increase of SC can be realized through increasing the SSA and
optimizing the pore sizes and PSD by developing hierarchically
porous structure without sacrificing the good electrical conductivity. As for the pseudocapacitive materials, it can be achieved
by synthesizing nanosized electroactive materials with large
SSA to provide sufficient electroactive sites for faradaic reactions and creating hierarchical porosity of electroactive materials with excellent conductivity to ensure sufficient electrolyte
ions and electrons participating in the faradaic reactions at high
rates simultaneously. Moreover, the enhancement of SC can be
achieved by introducing redox species to contribute additional
faradic pseudocapacitance to the overall capacitance, such as
doping function groups/heteroatoms (including N, O, S, B, and
P) to carbon materials and adoption of redox-active electrolytes.
On the other hand, the energy density of a supercapacitor is
also proportional to the square of the operating voltage. Thus,
increasing the operation voltage is regarded as a promising
strategy to improve the energy density of a supercapacitor and
can be achieved by selecting a proper electrolyte with a large operating voltage, for instance, organic electrolytes (up to 2.53.0 V)
and ionic liquids (ILs, up to 4 V). Moreover, an attractive alternative approach to maximize the operating voltage window is
to develop ASCs because organic electrolytes are usually more
expensive and flammable as well as less conductive than aqueous
electrolytes;[11,15] this has created considerable interest from scientific community over the past years. For an ASC, a battery-like
Faradaic electrode (as energy source) and a capacitive electrode
(as power source) are combined in a cell system in which both
electrical double-layer capacitance and faradaic pseudo-capacitance mechanisms occur simultaneously. Therefore, ASC possesses the advantages of both supercapacitors (rate, cycle life)
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and advanced batteries (energy density). In the following sections, an in-depth summary of the significant research progress
in the development of high energy density supercapacitor technologies demonstrated in recent years will be discussed.
3. Electrode Materials with High SC

Nanostructured materials have significantly accelerated the
development of supercapacitors because of their several advantages over bulk counterparts as described below: 1) Nanostructured materials can be designed to have a high SSA, which
provides more ion adsorption or active sites for the formation of
electrical double-layer and charge-transfer reactions, resulting
in the enhanced SC. 2) Nanoscale active materials have short
diffusion and transport pathways of electrolyte ions within
the particles, facilitating the transport of electrolyte ions and
accordingly improving the effective electrochemical utilization
of active materials and high rate charge/discharge capability.
In classical electrochemistry theory, the ion diffusion time constant () can be expressed by the Equation (4):
J = L 2 / 2D
(4)
where L is ion diffusion length and D is ion transport coefficient.[31] It is obvious that the ion diffusion time decreases with
decreasing particle sizes. 3) The small size of particles could
effectively buffer the stress from the expansion and shrinkage
of the electrodes during the charge/discharge process, preventing the pulverization of electrode and improving the cycle
stability. 4) The large surface area of nanostructured materials
increases the contact area between electrode and electrolyte,
resulting in higher ion flux compared to the bulk one.
In general, the electrode materials can be categorized into
three principal types, namely porous carbon materials,[17,3539]
transition metal oxides and hydroxides,[4042] and electrically
conducting polymers,[4042] as shown in Figure 4.
Figure 5. a) Schematic illustration of an EDLC in its charged state.

b) Schematic of a commercial spirally wound double layer capacitor.
c) Assembled device weighing 500 g and rated for 2600 F. d) A small
button cell, which is just 1.6 mm in height and stores 5 F. Panels (bd)
reproduced with permission.[5] Copyright 2008, Macmillan Publishers Ltd.
store charge electrostatically through reversible adsorption of

electrolyte ions onto the electroactive materials (Figure 5). The
surface electrode charge generation involves surface dissociation and ion adsorption from both the electrolyte and crystal
lattice defects,[5] thus there is no charge transfer across the electrode/electrolyte interface and energy storage is a true capacitance effect.[44]
The capacitance (C) of an electrical double-layer at each electrode/electrolyte interface is generally assumed to follow that of
a parallel-plated capacitor (Equation (5):[5,17]
g rg 0
A
d
3.1. Porous Carbon Materials
C =
Porous carbon materials are commonly used as electrode materials for electrical double-layer supercapacitors (EDLCs) that
where r (a dimensionless constant) is the relative dielectric

constant of electrolyte; 0 (in F m1) is the dielectric constant of
the vacuum; d (in m) is the effective thickness of the electrical
double-layer; and A (in m2 g1) is the SSA of the electrode accessible to the electrolyte ions. It has been demonstrated the thickness of the electrical double-layer, which is dependent upon the
electrolyte concentration and the size of electrolyte ions, is on
the order of 0.51 nm for concentrated electrolytes. The electrical double-layer capacitance is estimated to be 1020 F cm2
for a smooth electrode depending on the used electrolyte, as
demonstrated by Ktz and Carlen.[45] SC obtained in aqueous
alkaline or acid electrolytes is generally higher than in organic
electrolytes and ionic liquids, but organic electrolytes are more
widely used in practical applications because they can provide a
higher operation voltage.
Commonly, porous carbon materials in different forms
such as activated carbons (ACs),[4655] carbon xerogels,[8,5661]
carbon nanotubes (CNTs),[23,6269] mesoporous carbons,[48]
templated carbons,[7073] carbide-derived carbons (CDCs),[7477]
graphene,[35,7886] porous carbon spheres,[8794] and carbon
Figure 4. Capacitive performance of various electrode materials reported

in the literature. Reproduced with permission.[43] Copyright 2008, The
Electrochemical Society.
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3.1.1. Activated Carbon

ACs have been the most commonly used electrode materials
for EDLCs over the past years due to their high SSA, moderate
REVIEW
onions,[20,95101] have been investigated extensively as the electrode materials of supercapacitors. It has been demonstrated
both theoretically and experimentally that several factors significantly affect the electrochemical performances of carbon
materials including SSA, electrical conductivity, pore size and
distribution, and pore volume.[5,102105]
It is usually anticipated that the larger SSA, the higher SC.
Initial research on carbon materials was directed towards significantly increasing the pore volume by developing materials
with large SSA. However, the increase in capacitance is relatively
limited because not all micropores in the carbon materials are
electrochemically accessible to from the electrical double-layer
when they are immersed in electrolytes. It has been demonstrated that there is no linear relationship between the SSA and
the capacitance, i.e., the SC of various carbon materials does not
increase linearly with SSA. Despite ACs possessing SSA as high
as 25003000 m2 g1, only a relatively small SC <10 F cm2
was obtained compared to the theoretical capacitance of EDLCs
(1525 F cm2).[107] Conversely, activated carbon fiber with a
SSA of only 1000 m2 g1 exhibits extremely high capacitance
corresponding to those for conventional AC with a SSA of
3000 m2 g1.[51] A large number of attempts have been made to
determine the relationship between porosity and SC of carbon
materials.[105,106,108,109] An adequate pore size is more important than a high surface area to obtain high values of capacitance,[108] and the optimal pore sizes are found to be 0.7 and
0.8 nm in aqueous media and organic electrolytes, respectively
(Figure 6a).[108] Moreover, CDC with the pore size of 0.81.0 nm
exhibited a high specific surface capacitance due to the desolvation of ions upon entering the micropores (Figure 6b).[106,109] All
of the above observations indicate that micropores are electrochemically accessible by the electrolyte ions to form an electrical
double-layer and are of great importance to maximize the SC.
Nevertheless, the desolvation process usually leads to the ESR in
microporous carbons but not in mesoporous and macroporous
carbons. Raising the temperature may facilitate the desolvation
process due to a negative entropy change.[110] Recently, Largeot et
al. have experimentally determined the relationship between the
ion size and the pore size of CDCs without the presence of solvent in the system and concluded that the pore sizes very close to
those of the ion sizes could result in the maximum double-layer
capacitance (Figure 6b).[105] Both larger and smaller pores lead
to a significant drop in capacitance. This phenomenon was also
verified in aqueous electrolyte in a recent study conducted by the
same group.[111] These interesting findings challenged the longheld axiom that only those pores larger than the size of solvated
electrolyte ions are capable of forming a double-layer and contributing to the charge storage due to the ion sieving effect.
These above observations can only be found for particular
carbon materials. Thus, the relationship between pore size and
SC should be thoroughly investigated both theoretically and
experimentally, which is advantageous for designing advanced
carbon materials with maximized electrochemical performance
and optimal pore structure.
Figure 6. a) Specific surface capacitance vs. average pore size shows a

decreasing trend with increasing pore size above 1 nm. Reproduced with
permission.[106] Copyright 2006, American Association for the Advancement of Science. b) Normalized capacitance change as a function of
the pore size of CDC samples. Samples were prepared at different temperatures in ethyl-methylimidazolium/trifluoro-methane-sulphonylimide
(EMI-TFSI) IL at 60 C. Inset shows the structure and size of the EMI
and TFSI ions. The maximum capacitance is obtained when the pore size
is in the same range as the maximum ion dimension. Reproduced with
permission.[105] Copyright 2008, American Chemical Society.
cost, excellent chemical and thermal stability as well as relatively good electrical conductivity. ACs are derived from various
types of carbon-rich organic precursors (coconut shells, wood,
pitch, coal, polymers, etc.) by carbonization in inert atmosphere with subsequent physical and/or chemical activation to
increase the SSA and pore volume. After the activation process,
the SSA and porosity of the resulting materials are significantly
enhanced compared with the carbonized samples. Depending
on the activation process and the used carbon precursors, a
variety of ACs with different physicochemical properties and
well developed SSA as large as 3000 m2 g1 have been prepared
and used as electrodes for supercapacitors over the past years
(Table 1).
Due to the electrical double-layer storage mechanism of
carbon materials, high surface areas, more electrolyte ions
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Table 1. AC materials for EDLC electrodes reported recently in the literature.
Carbon source
Activation
method
SBET
[m2 g1]
Ca)
[F g1]
Potential
[V]
Scan rate
Emax
[Wh kg1]
Cycles
CRb)
[%]
Coal tar pitch
KOH
1003
224 (2)
1.0
0.1 A g1
7.84
1000
98.5
KOH (6)
[48]
Mesophase pitch
KOH
2258
145 (2)
2.5
20 A g1
31
Et4NBF4 (1)
[112]
Coke
KOH
1397
350.9 (2)
1.0
2 mA cm2
6000
40
H2SO4 (1)
[113]
Lignite
KOH
2580
377 (2)
1.0
0.05 A g1
500
92.8
KOH (3)
[114]
Petroleum coke
KOH
1590
330 (2)
1.0
0.02 A g1
21.2
200
93.5
KOH (6)
[115]
Deoiled asphalt
NaOH
1778
235 (2)
1.0
0.05 A g1
KOH (7)
[116]
g1
[117]
Electrolyte
[mol L1]
Ref.
Green needle coke
KOH
3347
348 (2)
1.0
0.05 A
1000
91.4
KOH (6)
Camellia oleifera shell
ZnCl2
1935
374 (3)
1.0
0.2 A g1
5000
91.3
H2SO4 (1)
[118]
Rice hull
NaOH
3969
368 (3)
1.0
2 mV s1
KOH (6)
[119]
Coconut shell
Steam
1532
192 (2)
0.8
1.0 A g1
38.5
3000
61.3
KOH (6)
[47]
Walnut-shell
KOH
2390
202.8 (2)
0.9
1 mA cm2
1000
79.4
H2SO4 (3)
[120]
Argan seed shells
KOH
2100
355 (3)
0.75
0.125 A g1
H2SO4 (1)
[121]
Beer lees
KOH
3557
188 (2)
0.9
1 mA cm
H2SO4 (0.1)
[122]
Sugar cane bagasse
ZnCl2
1788
300 (2)
1.0
0.25 A g1
10.0
5000
83
H2SO4 (1)
[123]
Coffee grounds
ZnCl2
1019
368 (2)
1.2
0.05 A g1
20.0
10000
95
H2SO4 (1)
[124]
Corn grains
KOH
3199
257 (2)
0.9
1 mA cm2
KOH (6)
[125]
[126]
Coffee endocarp
CO2
709
176 (3)
0.9
10 mA
H2SO4 (1)
Sunflower seed shell
KOH
2509
311 (2)
0.9
0.25 A g1
9.0
30%KOH
[127]
Pig bones
KOH
2157
185 (2)
1.0
0.05 A g1
KOH (7)
[128]
Cellulose
KOH
2457
187 (2)
2.3
0.1 A g1
TEABF4 (1)
[129]
Potato starch
KOH
2342
335 (2)
1.0
0.05 A g1
900
90
KOH (6)
[130]
Bamboo
KOH
1293
55 (2)
1 mA cm2
30%H2SO4
[131]
KOH
2967
232 (2)
2.3
0.1 A g
TEABF4 (1)
[132]
Apricot shell
NaOH
2074
339 (2)
1.0
0.05 A g1
KOH (6)
[132]
Pistachio shells
Steam
1096
120 (3)
1.0
10 mV s1
H2SO4 (0.5)
[133]
Eucalyptus wood
Fish scale
KOH
2273
168 (2)
1.0
0.05 A g
KOH (7)
[134]
Wheat straw
KOH
2316
251.1 (2)
2.0
2 mV s1
MeEt3NBF4
(1.2)
[135]
Rubber wood saw
CO2
683.6
33.7 (3)
1.0
1 mV s1
H2SO4 (1)
[136]
Firwoods
KOH
1064
180 (3)
1.0
10 mV s1
H2SO4 (0.5)
[133]
Tea leaves
KOH
2841
330 (3)
1.0
1.0 A g1
2000
92
KOH (2)
[137]
D-glucosamine
KOH
571
300 (3)
0.8
0.1 A g1
50.0
2000
93
H2SO4 (1)
[138]
Sucrose
CO2
2102
163 (2)
0.6
1 mV s1
10000
100
H2SO4 (1)
[139]
Phenolic resin
CO2
1025
56.0 (2)
3.5
2 mA cm2
70.0
EMImBF4
[140]
g1
H3PO4
633
220 (2)
1.0
5.0 A
16.3
H2SO4 (1)
[141]
Polyfurfuryl alcohol
KOH
2600
150 (2)
2.5
0.15 A g1
32.0
5000
90
Et4NBF4 (1)
[142]
PANI
KOH
1976
455 (3)
1.0
1 mV s1
2000
88.7
KOH (6)
[143]
2.3
10000
92
EMImBF4
[52]
BDD copolymer
PPy
a)The
KOH
3432
290 (2)
0.1 A g
numbers 2 and 3 refer to two- and three-electrode tests, respectively.; b)CR = capacitance retention.
can be accumulated at the electrode/electrolyte interface.

Therefore, many approaches have been used to increase the
SSA of carbon materials, including heat treatment, alkaline
treatment, physical or chemical activation, and plasma surface treatment.[51,108,144149] In addition to SSA, PSD is a significant factor affecting the electrochemical performances
of ACs. Generally, narrowing PSD leads to an increase in
1300816 (6 of 43)
capacitance and stored energy density due to the increase in

surface area of regular pore distributions vs. broad distributions of pores,[9] which means that monodispersed pores and
elaborately optimized PSD would be an ideal candidate for the
energy storage of supercapacitors.[150] More recently, Kondrat
et al. demonstrated that the optimal pore size providing the
maximal energy density increases with increasing operating
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Figure 7. a) Scanning electron microscopy (SEM) image, b) pore size

distribution, c) CV curves, and d) SC of hydrothermal synthesized carbon
samples at three different temperatures. Reproduced with permission.[129]
Copyright 2011, Wiley VCH.
REVIEW
voltage and saturates at high voltages both theoretically and

experimentally.[150]
The initial carbon precursors have an important influence
on the formation mechanism and SSA as well as electrochemical performances. Various petroleum coke, pitch, and
coal are the most commonly used precursors for commercial AC productions.[48,114,117,151153] Depending on different
activation conditions, a variety of ACs with different SSA of
9003500 m2 g1, and SC of 200350 F g1 in aqueous electrolytes and 130220 F g1 in non-aqueous electrolytes have been
obtained. Given the decreased availability of fossil fuels, plenty of
biomass-derived ACs have attracted tremendous attention in the
past few years. They were synthesized from natural precursors,
such as nutshells,[47,120,132,133] seaweeds,[154,155] woods,[133,156,157]
starch,[129,130] corn grains,[125] banana fibers,[158] saccharides,[129,139,159] coffee grounds,[124,160] and others.[128,129,131,134,137]
Hydrothermal carbonization is an increasingly popular route for
the synthesis of porous carbon materials from natural biomass
because of its low cost, low temperature, environmental benignity without the need to use toxic chemicals, and a high content
of functional groups in resulting materials. Recently, hydrothermal carbonization of cellulose, potato starch, and eucalyptus wood sawdust followed by KOH activation[129] exhibited
a promising process for obtaining high SSA (21252967 m2 g1)
and large micropore volume (0.741.20 cm3 g1) of activated
carbon (Figure 7). Unfortunately, ACs derived from natural precursors usually suffer from significant variation of their properties, which is seriously detrimental for EDLC use in automotive
applications. Thus, various synthetic polymers such as phenol
formaldehyde resins,[149,161,162] polystyrene-based resins,[163] polyfurfuryl alcohols,[142,164] polyaniline (PANI),[143] and polypyrrole
(PPy)[52] have been actively investigated as promising alternative
precursors and received considerable interests in recent years
due to their low cost, commercial availability, uniform structure, and high chemical purity. Yan et al. synthesized AC by
carbonization of rod-shaped PANI and subsequent KOH activation, which showed high SC (455 F g1) and a remarkable rate
Figure 8. a) Transmission electron microscopy (TEM) image and b) SC

of PANI-derived AC. Reproduced with permission.[143] Copyright 2010,
Elsevier. c) Non-local density functional theory (NL-DFT) PSD and d) SC
of the of PPy-derived ACs activated at three different temperatures. Reproduced with permission.[52] Copyright 2012, Wiley VCH.
capability due to its high SSA (1976 m2 g1), narrow PSD (<3
nm), and short diffusion length (Figure 8a,b).[143] Recently, Wei
and co-workers demonstrated the preparation of ACs from PPy
using a one-step KOH activation process.[52] The as-produced
carbon material possessed 0.54 nm pores with a pore volume
of 2.39 cm3 g1 and ultrahigh SSA up to 3432 m2 g1, resulting
in high SC of up to 300 F g1 in IL at 60 C; this is a more than
two-fold improvement compared to state-of-the-art commercial
carbons and other recently reported novel carbon materials
(Figure 8c,d).
Moreover, activation methods and conditions also play significant roles in the porosity and electrochemical performance of
ACs.[123,139,141,165,166] Due to lesser extent of carbon etching than
chemical activation, ACs through physical activation processes
usually have relative low SSA (6802420 cm2 g1, Table 1) and
pore volume, high bulk density, high yields, and low SC (33.7
206 and 56172 F g1 in aqueous and non-aqueous electrolytes,
respectively).[47,126,133,136] Generally, CO2 physical activation can
produce a larger content of microporosity (50%78%) than
steam activation (19%48%). A moderate increase in activation
time can lead to enhanced SSA and pore volume of ACs.[159]
During the chemical activation, activating conditions such
as activating temperature, time, and mass ratio of activating
agent/precursor are several key factors affecting the yields,
SSA, and pore structure of the prepared ACs; these accordingly
affect their capacitive performances.[52,117,138,149] Typically, high
activating temperature, long activating time, and large mass
ratio of activating agent/precursor will lead to the enhanced
SSA, pore volume, and average pore size.[43,52] However, excessive activation will give rise to large pore volume, low bulk
density, and low electrical conductivity, resulting in the loss of
power deliver and low volumetric energy density.
Furthermore, surface functionalities have an important
impact on the wettability of the electrode. The surface functionalities may also induce faradaic redox reactions, contributing
some additional capacitance to the total capacitance.[50,138,155,167]
High oxygen content carbon obtained by the pyrolysis of
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seaweeds for symmetric supercapacitors exhibited a SC of

125 F g1 and a high energy density of 10.7 Wh kg1 with a cell
voltage of 1.6 V.[154] However, it has been demonstrated that the
presence of surface functionalities or moisture usually leads
to the poor stability of electrodes during cycling, an increased
series resistance, an increase of leakage current, decomposition
of the organic electrolyte, and deterioration of capacitance.[19]
Thus, surface chemistry of ACs should be elaborately optimized to enhance the long-term cycling stability.
Nowadays, a variety of ACs produced through physical or
chemical activation from various precursors are the most extensively used electrode materials for commercial supercapacitors. Nevertheless, their practical applications are still limited
to some extent as the energy density is still relative low and
the control of PSD and pore structure is still a great challenge.
Therefore, it is of great significance to design and produce ACs
with elaborately tailored PSD, minimized pore tortuosity, interconnected pore structure, short pore length, and controlled
surface chemistry, facilitating the ion transport and enhancing
energy storage without sacrificing power capability and cycle
life.
3.1.2. Templated Carbons
Most porous carbon materials have a very wide PSD with pores
randomly connected, much more disordered and complicated
structures, resulting in poor conductivity, ionic transport,
and very limited rate capability for supercapacitor applications. Additionally, it is extremely difficult to precisely control
the structure of conventional carbons at the nanometer level.
Therefore, templating method is considered to be an effective,
unique, and versatile way to provide well-designed and precisely
controlled carbon materials.[168] The resulting carbons exhibit a
medium SSA, high porosity, well controlled narrow PSD, and
an interconnected pore network, making them intriguing candidates for energy storage applications. Until now, there have
been significant advances in the synthesis of nanostructured
carbons through templating methods.[17] Generally, the synthetic procedure for templated carbons involves impregnation
of carbon precursors (e.g., sucrose, propylene, pitch, furfuryl
alcohol, phenolic resin, or polymer solution) into the porous
structure of the template, carbonization treatment, followed
by the removal of the template to liberate the resulting porous
carbon. According to the used templates, templating technology
can be classified into hard-template and soft-template methods.
The former refers to replication synthesis with pre-synthesized
hard templates through infiltration, carbonization, and removal
of templates. Various inorganic materials, such as silica
nanoparticles,[169] zeolites,[73] anodic aluminum oxide (AAO)
films,[170] mesoporous silica,[171] CaCO3,[172] and MgO,[48] have
been used as hard templates. Contrarily, the latter is defined
as self-assembly with soft templates through the cocondensation and carbonization process without the need for removal
of template. Various commercial available triblock copolymers
PEO-PPO-PEO (PO: propylene oxide; EO: ethylene oxide),
such as F127 (EO106PO70EO106),[173] P123 (EO20PO70EO20),[174]
F108 (EO132PO50EO132),[175] have been widely used as the soft
templates in recent years. Depending upon the used templates and carbon precursors, microporous, mesoporous, and
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Figure 9. Schematic representation of templating synthesis of various

porous carbons with different templates.
macroporous carbons with different structures can be prepared

using templating methods (Figure 9).
Various porous carbons with controllable micropores,
mesopores, and/or macropores prepared with different templates and precursors have been investigated intensively for
supercapacitors.[70,73,76,171,176181] Due to their walls with uniform thickness of <1 nm, zeolites (e.g., zeolite Y and X13) have
been recognized as ideal templates for microporous carbon production. Microporous carbons are prepared as inverse replicas
of zeolites through carbonization of the precursors infiltrated in
nanochannels of zeolites, followed by removal of the siliceous
framework. A microporous carbon with 3D arrayed and mutually connected 1.2-nm nanopores was obtained with FAU zeolite as template and the resulting material displayed very large
volumetric SSA of 1590 m2 cm3.[73] Additionally, such carbon
exhibited both very high gravimetric (140190 F g1) and volumetric (7583 F cm3) SC at a very high current up to 20 A g1
in an organic electrolyte.
Although microporous carbons possess ultrahigh SSA, large
SC and energy density, micropores are adverse to the rapid
transport of electrolyte ions, resulting in poor rate capability
and power density. Therefore, much effort has been devoted
to synthesizing mesoporous carbons. Following the first report
on the synthesis of mesoporous carbons using a MCM-48 silica
template,[182] a series of mesoporous carbons with different
pore structures have been reported using various mesoporous
silica templates, such as SBA-15,[171] hexagonal MSU-H, and
3D cubic KIT-6.[178] With regard to the obtained mesoporous
carbons, their pore size and pore volume can be systematically
varied through tuning the pore size of template.[171,177]
Moreover, mesoporous carbons can also be synthesized using
CaCO3, MgO particles, or precursors of MgO, such as Mg(OH)2,
magnesium acetate, magnesium citrate, and magnesium gluconate, as the templates.[48,76,172,183,184] The pore size of porous
carbon is governed by the size and shape of inorganic template
that can be removed more easily with dilute hydrochloric acid or
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REVIEW
citric acid. Carbon nanocage with high SSA (2053 m2 g1) and
high purity prepared by an in situ MgO template method with
benzene precursor was adopted as supercapacitor electrodes
and showed remarkable performance with SC of 260 F g1 and
quite good electrochemical stability (10% deterioration after
10 000 cycles).[76] In addition, mesoporous carbon can also be
produced using CNT-based composites as templates, such as
MWNT@mesoporous silica[185] and MWNT/MnO2.[87] Recently,
Zhao and co-workers demonstrated the synthesis of MWNT@
mesoporous carbon composite with core-shell configuration
using MWNT@mesoporous silica and furfural alcohol as template and carbon resource, respectively.[185] Such composite
exhibited greatly enhanced SC from 9.0 to 48.4 F g1 and 6.8
to 60.2 F g1 in 1.0 M (C2H5)4NBF4 and 6.0 M KOH, good rate
performance with 60% retention of the initial capacitance at
20 A g1 and high cyclability (94% after 1000 cycles).
As a novel class of porous material, metal-organic frameworks (MOFs) have permanent nanoscaled cavities and open
channels providing congential conditions for small molecules
to access, thus have recently been demonstrated as potential templates to synthesize porous carbons.[72,186188] In this
synthetic method, furfuryl alcohol is impregnated and subsequently polymerized inside the micropores of MOFs. During
the carbonization process, the formation of porous carbon
networks and the decomposition of MOFs happen simultaneously. MOFs act as both the sacrificial template and a supplementary carbon source. As a result, the SSA of the resulting
porous carbons can achieve 5003400 m2 g1 with pore volume
ranging from 0.13 to 3.14 cm3, contributing to a SC as high as
110310 F g1 in aqueous electrolytes.[72,186188]
In the hard template synthesis, the use of silica makes the
preparation complicated, high-cost and time-consuming, and
therefore unsuitable for large-scale production and industrial applications. Additionally, the removal of silica requires
extremely corrosive and toxic hydrofluoric acid. Thus, a great
deal of effort has been made to develop a simple route for
synthesizing porous carbons with homogeneous pore sizes.
Recently, a soft-template method using various commercially
available triblock copolymers has attracted particular attention to produce carbons with micropores and unique size due
to the decomposition of soft templates above 400 C.[189,190] In
this synthetic method, the templating species are mixed with
organic precursors in solution and occluded in the growing
carbon frame, generating pores in carbons after their removal.
Such templating can be regarded as endotemplating, contrary
to exotemplating in which the templates are materials with
structural pores where the carbon frame is formed. Commonly,
the structures of the obtained carbons are flexible and their
generation intimately depends on temperature, type of solvent,
and ionic strength. Recently, ordered graphitic mesoporous
carbon nanocomposites with tunable mesopore sizes was prepared by a brick-and-mortar soft-templating approach with
phenolic resins as carbon sources and triblock copolymers
(F127) as templates.[190] In the carbon nanocomposite, phenolic resin-based mesoporous carbons act as the mortar to
highly conductive carbon blacks and carbon onions (bricks).
After carbonization, carbons with larger mesopore volumes,
widths, and excellent electrical conductivity were obtained,
resulting in a SC of 50 F g1 in organic electrolyte. Xia and
Figure 10. Schematic representation of the highly ordered MCNAs.

Reproduced with permission.[189] Copyright 2010, The Royal Society of
Chemistry.
co-workers demonstrated the facile synthesis of highly ordered

mesoporous carbon nanofiber arrays (MCNAs) with triblock
copolymer Pluronic P123 and natural crab shell as the soft- and
hard-templates, respectively (Figure 10).[189] The obtained materials were composed of a mesoporous carbon nanofiber (70 nm
in mean diameter and 11 nm in mesopore), an interspacing
void (70 nm) between nanofibers and 1 micrometer of pores
between nanofiber arrays. The MCNAs exhibited a SSA of
1266 m2 g1 with a large pore volume of 4.3 cm3. A maximum
SC of 152 F g1 can be obtained in organic electrolyte, which is
much higher than that of CMK-3 (90 F g1). Additionally, 95%
of the initial SC could be maintained after 1000 cycles. The
remarkable electrochemical performance could be attributed to
the unique structure providing a more favorable path for penetration and transportation of electrolyte ions and good electronic conductivity. The soft-template method is an economical,
fast, and environmentally friendly route to synthesize porous
carbon materials with large mesopores and high SSA.
Rate capability is an important factor for the practical applications of supercapacitors, especially in the case of high current densities. A good electrochemical energy storage device
is expected to provide high energy density (or SC) at a high
charge-discharge rate.[9] Commonly, porous carbons suffer
from serious electrolyte kinetic problems owing to the innerpore ion-transport resistance and long ion diffusion distance.
Hierarchically porous carbon, combining different pore size
systems in nanocarbons, can provide highly efficient mass
transport through macro/mesopores and a large SSA from the
micro/mesopores to achieve excellent performances and thus
have exhibited great potential for high performance supercapacitor applications in recent years.[176,179,180,191193] The hierarchical carbons are usually produced through impregnation
of pre-synthesized macroporous templates with precursor
sols, carbonization of precursors, and liberation of macropore
voids. Based on this strategy, 3D ordered/aperiodic hierarchical
porous graphitic carbon (HPGC) was successfully prepared
using Ni(OH)2 nanoparticles as template and phenolic resin
as the carbon precursor and exhibited super-high energy and
power densities as a electrode materials for high-rate supercapacitor in both aqueous and organic electrolytes.[180] Such
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REVIEW
Figure 11. a) Schematic representation of the 3D hierarchical porous

texture. b) Ragone plot comparing the performance of HPGC material.
Reproduced with permission.[180] Copyright 2008, Wiley VCH.
impressive performances are believed to be attributed to its

hierarchical structure, namely, macroporous cores as ion-buffering reservoirs, mesoporous walls with smaller ion-transport
resistance, micropores for charge accommodation, and a localized graphitic structure for enhanced electric conductivity
(Figure 11). 3D hierarchical ordered porous carbon (HOPC)
with partially graphitic nanostructures was prepared using
triblock copolymer F127 and monodisperse polystyrene latex
spheres as templates and phenol-formaldehyde resin as carbon
precursor, possessing good graphitization domains, interconnected ordered macropores, mesopores, and micropores
(Figure 12). Despite its low SSA (296 m2 g1) and low gravimetric SC (73.4 F g1), the resulting carbon showed good rate
performance, high area SC (24.8 F cm2), and excellent cycling
performance (10 000).[179]
Templated carbons possess uniform pore sizes, ordered
structure, large pore volumes, and high SSA, making them
promising candidates for supercapacitor with high energy and
power densities. However, templated carbons have some disadvantages such as relatively high production costs, low producibility, and safety considerations. During the synthesis process,
the amount of the used template materials is usually several
times that of the produced carbons and they are not available
by kilogram or ton order, which is not suitable for large-scale
production. On the other hand, some template materials are
expensive and their eventual removal usually requires the use
of highly corrosive and toxic reagents such as HF. Thus, the
potential commercial applications of template carbons have
been seriously suppressed and it is urgent to develop a simple,
economical, and environmentally benign template route to satisfy their broad applications.
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Figure 12. a) Illustration of the synthetic routes to 3D HOPC through

one-pot and evaporation-induced self-assembly. b) SEM and c) TEM
images of the as-prepared 3D HOPC. Reproduced with permission.[179]
Copyright 2012, Wiley VCH.
3.1.3. CDCs
CDCs are generally produced through selective extraction of
non-carbon atoms from carbides (TiC, B4C, ZrC, Ti3SiC2, Ti2AlC,
WC, and SiC) at high-temperature (8001200 C).[75,77,194197]
High-temperature chlorination and vacuum decomposition are
the most widely used approaches for CDC synthesis:
MC + xCl2 MCl2x + C
vacuum
MC(s) M(g) + C(s)
(6)
(7)
The as-synthesized CDCs possess a narrow and tunable

PSD with a sub- precision, an average pore size of 0.62 nm,
and SSA up to 3100 m2 g1,[198] allowing them to exhibit outstanding electrochemical performances in aqueous,[77,194,195]
organic,[75,196,198,199] and IL electrolytes.[105,200,201] The mean pore
size, PSD, pore volume, and SSA of the CDCs can be controlled
and tailored through selecting the precursors and the chlorination conditions.
Since the spatial distribution of carbon atoms in different
carbides may differ substantially even when densities of corresponding CDCs are similar, the microstructure of the precursors may have a crucial impact on the microstructure
(pore size, shape, and volume) of the produced CDCs. Theoretical calculations suggested that a wide range of precursors
could achieve a wide range of theoretical pore volumes from
55% to 85% without further post-treatment.[202] The PSD and
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decrease the particle sizes of CDCs to sub-micrometer dimensions, however, the overall improvement of the power characteristic was demonstrated to be rather moderate.[205] Templated,
ordered, mesoporous silicon CDC was applied in high-rate
supercapacitors for the first time and exhibited a SSA up to
2430 m2 g1, high SC of 170 F g1, outstanding capacitance
retention of 85% at current densities up to 20 A g1 and spectacular energy density (140 Wh kg1) in 1 mol L1 tetraethylammonium tetrafluoroborate in acetonitrile solution.[197]
Another promising strategy to overcome the limitation of
slow ion transport in small pores is to develop/design hierarchical porous CDCs with straight ordered mesopores.[75,200] The
ordered mesoporous channels are favorable for retention and
immersion of the electrolyte and can serve as ion-highways and
allow for very fast ionic transport into the bulk CDCs. Meanwhile, the micropores on the mesopore walls can increase
the SSA to provide more sites for charge storage. Recently,
the same research group produced hierarchical micro- and
mesoporous silicon CDCs with the surface area in the range of
2364 to 2729 m2 g1,[200] which is among the highest values ever
reported for CDCs. Due to the presence of straight mesoporous
channels combined with a high micropore content, the produced carbon not only demonstrated very high SC of 202 F g1
in the aqueous electrolytes, but also showed exceptionally high
power performance with up to 90% of the capacitance retained
when the current density was increased from 0.1 to over
20 A g1. The combination of superb energy and power characteristics of the samples could not be matched by the state-ofthe-art activated carbons or microporous CDCs.[200]
CDCs still have very limited commercial potential due to
their high cost, serious safety and environmental concerns
associated with production, and requirement of high temperature. However, from a research point of view, CDCs are of
importance to study since they can provide valuable information about the effect of pore size, channel structures and other
parameters on the ion diffusion and charge storage in carbon
nanmaterials.
3.1.4. Carbon Nanotubes
Figure 13. ac) TEM images of nano-TiC-CDC synthesized and H2annealed at indicated temperatures. d) Average pore size, pore volume
and SSA for nano-CDC synthesized at 2001200 C and annealed at
600 C. Reproduced with permission.[194] Copyright 2013, Wiley VCH.
CNTs have attracted increasing interest for supercapacitor

applications due to their excellent electrical conductivity, unique
pore structure, exceptional mechanical, chemical and thermal
stability.[17,206,207] However, the SC of CNTs is still low due to
the limitation of their surface area (less than 600 m2 g1).[208,209]
Notably, although the surface area of CNTs is relatively moderate, their area SC can reach up to 50.4 F cm2, which is
higher than those of ACs (2050 F cm2) due to the perfect
electrolyte accessibility by the tube entanglement.[209]
Over the past few years, there has been increasing research
interest in flexible and lightweight energy-storage systems to
meet the demands for portable electronic devices, including
roll-up displays, stretchable integrated circuits, and wearable
systems for personal multimedia or medical devices.[210,211]
Recently, CNTs have been printed on plastics, papers, or
coated on textiles to fabricate thin and flexible supercapacitors.[212215] In these electrodes, CNTs not only act as highly
conductive and flexible active materials, but also increase the
effective surface area in the films maximizing the efficiency of
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SSA are influenced significantly by the chlorination temperature. Generally, low-temperature chlorination (<600 C) results
in very uniform pore size.[203] The PSD of CDCs is narrower
than those of SWNTs and ACs, and comparable to zeolites.
Increasing the chlorination temperature results in enlargement of pores and broader PSD. The obvious changes in PSD
are inherently connected to the changes in the microstructure of CDCs. Uniform, relatively small pores at low chlorination temperature are related with their amorphous structure,
while less uniform and generally broader PSD formed at high
temperature is associated with the graphitic ribbon network
structure.[204] SSA of CDCs varied with chlorination temperature generally follows a bell-shape curve. Initially, the SSA
increases monotonically with the increase of the temperature, which can be attributed to the increase of pore sizes of
CDCs, thus allowing chloride molecules to be removed from
pores more efficiently and increasing the effective SSA. However, above a certain temperature, formation of a substantial
amount of well-organized multiwalled graphite ribbons may
lower the SSA due to the small interwall spacing inaccessible
to N2 and Ar. Gogotsi and co-workers reported the synthesis of
TiC-CDCs with average particle sizes of 2040 nm in the temperature range between 200 and 1200 C (Figure 13).[194] The
low-temperature CDC synthesis yielded subnanometer pores
with broad PSD accompanying a large pore volume associated
with mesopores. When treated at 1000 C, the SSA exhibited
a maximum value (1920 m2 g1), and then decreased at
1200 C thanks to carbon graphitization associated with an
abrupt increase in the average pore size.[194]
Currently, the research into CDCs for supercapacitors has
been focus on the design and development of microporous
materials to improve the capacitive performance. However, the
adverse effect of the micorporous in CDC is relatively slow ion
transport in small pores and thus a moderate rate of charge and
discharge, seriously limiting the power storage characteristics.
One potential approach to boost the power performance is to
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REVIEW
Figure 14. a) Rolled design of the separator with SWNT films and b)
the resulting compact-designed supercapacitor. Reproduced with permission.[212] Copyright 2011, The Royal Society of Chemistry. c) Conductive
textiles are fabricated by dipping textile into an aqueous SWNT ink followed by drying in oven at 120 C for 10 min. d) A thin, 10 cm 10 cm
textile conductor based on a fabric sheet with 100% cotton. Reproduced
with permission.[214] Copyright 2010, American Chemical Society.
thin film CNT supercapacitors. Thin-film supercapacitors fabricated with SWNT-coated plastic serving as both electrodes
and current collectors exhibited very high energy (6 Wh kg1)
and power (70 kW kg1) densities in organic electrolyte.[213] A
compact-designed supercapacitor was fabricated using largescale, free-standing, and flexible SWNT films as both the anode
and cathode; this exhibited high energy density (43.7 Wh kg1)
and power density (193.7 kW kg1) due to the small internal
resistance (Figure 14a).[212] Recently, a stretchable and wearable supercapacitor using SWNTs coated textiles as electrodes
(Figure 14b)[214] has exhibited a high SC of 140 F g1 and
spectacular energy density of 20 Wh kg1 at a specific power
of 10 kW kg1 in 1 mol L1 LiPF6 electrolyte. In addition, it
showed extremely good cycling stability with only 2% variation
and change in capacitance over 130 000 cycles.[214]
Moreover, aligned CNTs (ACNTs) have aroused particular
interest for supercapacitor applications due to their intriguing
advantages over randomly entangled CNTs.[23,69,216] ACNTs possess relatively regular pore structures and conductive channels,
leading to higher effective SSA, facilitating fast ion and electron
transportation and providing improved charge storage/deliver
properties, which is highly desirable for high-rate applications.
Recently, vertically ACNT forests with high SSA synthesized
by water-assisted chemical vapor deposition (CVD) as durable
electrodes for symmetric supercapacitors, could be operated at
a higher voltage (4 V) while maintaining durable full charge/
discharge cyclability with an energy density (94 Wh kg1,
47 Wh L1) and power density (210 kW kg1, 105 kW L1), far
exceeding those of AC both gravimetrically and volumetrically.[23] The ordered pore structure of SWNT electrodes results
in a lower tortuosity, enabling fast ion transport and thus
higher power capability.
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Large contact resistance between active materials and current collectors would greatly limit the power performance.
Therefore, various methods have been employed to reduce
the internal resistance of the CNT electrodes to achieve high
power capabilities.[217224] An effective approach to overcome
this issue is to assemble binder-free CNT films, which can be
realized through layer-by-layer (LBL) assembly[217,218] and electrophoretic deposition (EPD).[219,220] LBL assembly usually consists of repeated and sequential immersion of a substrate into
stable dispersions of negatively and positively charged CNTs.
This allows the precise control of film thickness and morphology through adjusting the immersion times and pH condition of the solution.[217] LBL CNT electrodes were demonstrated
ultrahigh capacitance of 160 F g1 in 1 mol L1 H2SO4, which
is considerably higher than those of ACNTs and conventional
CNTs.[218] Compared to LBL assembly, EPD is relatively quick
to fabricate films, which generally adopts an oppositely charged
metal current collector to attract CNTs in CNT suspension due
to the electrostatic attraction.[219,220] This approach has several
advantages involving short formation time, simple equipments,
suitability for mass production. The fabricated supercapacitors
possess a small resistance, high power density, and superior
frequency response. Despite the low SC of 21 F g1, MWNT
thin films fabricated by this approach exhibited high power
density over 20 kW kg1 and superior frequency response with
a knee at 7560 Hz in a two-electrode system.[219]
Another promising alternative to reduce the internal resistance of CNT electrodes is to grow CNTs directly on conductive
substrates, such as graphite-foil,[221] aluminum,[225,226], Au,[227]
and Inconel alloy.[228,229] This approach minimizes the contact
resistance between the active material and the current-collector
and greatly simplifies electrode fabrication. Talapatra et al.
reported the growth of ACNTs on an Inconel 600 substance
through vapor-phase catalyst delivery, which showed a power
density of 7 kW kg1 at 1 V s1 in 6 mol L1 KOH solution.[228]
Arrays of multi-segmented hybrid nanostructures of CNT and
gold nanowires (AuNW) have been synthesized using a combination of CVD and electrodeposition methods (Figure 15).[227]
Such hybrid structures exhibited excellent electrochemcial
performance with a maximum power density of 48 kW kg1,
much higher than the reported values for CNT-based supercapacitors due to well adhered interface between CNT and AuNW
segments.
Several attempts have been made to improve the SC and
energy density of CNTs by increasing their SSA through
chemical or plasma activation.[216,230232] The activation treatment can not only substantially increase the SSA of CNTs
through opening their end tips and introducing defects while
keeping the nanotubular morphology, but also induce oxygenated functional groups contributing some pseudocapacitance
to the overall SC. Dai and co-workers demonstrated that ACNT
arrays synthesized by vacuum CVD were subjected to oxygen
plasma activation, leading to the opening of CNT end-tips and
increasing of SSA to 400 m2 g1.[216] With the combined contribution from double-layer capacitance and redox pseudocapacitance, the activated ACNTs showed a remarkable capacitance
(440 F g1), high energy density (148 Wh kg1) and high power
density (315 kW kg1) with a high cell voltage (4 V) in IL electrolyte, potentially exceeding those of the current supercapacitor
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technology. In addition, the plasma-activated ACNTs significantly overcome the disadvantage of high viscosity of the ILs by
providing a highly accessible pathway to electrolyte ions. However, oxygenated functional groups induced by activation decorated on CNTs may potentially deteriorate the cycling stability
and cause high leakage current, which is quite undesirable in
practical commercial applications.
In spite of these tremendous achievements, a number
of issues still need to be addressed to further promote the
industrial application of CNTs; these issues include limited
SSA, highly variable purity, high production cost, and limited
availability.
3.1.5. Graphene
Graphene is a 2D single-atom-thick carbon allotrope tightly
arranged in honeycomb lattices and has stimulated enormous
research since its discovery by isolation from bulk graphite
using adhesive tape.[233235] Because of its unique structure, graphene possesses ultrahigh theoretical SSA (2630 m2 g1) and
extraordinary electronic, mechanical, thermal, and optical properties. Thus, the emergence of graphene holds great promise
for potential applications in high-performance supercapacitors.
However, there are still several obstacles significantly inhibiting
its commercial application in supercapacitors.
1) Large-scale synthesis of high-quality graphene. The most
important challenge facing current researchers in this area is
the large-scale synthesis of high-quality graphene. Until now,
tremendous efforts have been made to develop synthesis
methods to achieve large-scale production of graphene with
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REVIEW
Figure 15. a) Schematic showing the fabrication of CNT/AuNW hybrid

structures inside the AAO template. b) SEM image showing the CNT/
AuNW segments and the Cu back layer. c) TEM image clearly showing the
CNT/AuNW interface. Reproduced with permission.[227] Copyright 2008,
The Royal Society of Chemistry.
high quality. Mechanical cleavage from bulk graphite can produce high quality graphene, but the process is rather tedious,
hard to control and the yield is extremely low.[234] Abundant
alternative synthesis routes have been developed to produce
graphene, including epitaxial growth on SiC, CVD growth on
metal substrates and substrate-free gas phase synthesis; however, the uniform growth of single-layer graphene is still a challenge and these methods generally need high temperature, special equipment, and precise control over cooling rates, which
limit their practical application in large-scale production.[236]
Although different methods continue to be explored, chemical
exfoliation of graphite to graphene oxide (GO) followed by controllable reduction might be one of the most promising routes
among all the strategies pursued.[237,238] This method is facile
and scalable, providing the possibility of large-scale production
for a broad range of applications. However, the disadvantage of
this approach is the presence of large amount of defects and
oxygen-containing functional groups during the oxidization
process, resulting in low mobility and electrical conductivity.
Over the past years, graphene synthesized through various
approaches has been investigated intensively as electrode materials for supercapacitors (Table 2).
In 2008, Ruoff and co-workers pioneered supercapacitor
based on hydrazine reduced GO that exhibited a SC of 135
and 99 F g1 in aqueous and organic electrolytes, respectively
(Figure 16).[86] These encouraging results illustrate the exciting
potential of graphene-based materials for high performance,
electrical energy storage devices. Compared to conventional
porous materials, the effective surface area of graphene highly
depends on the number of graphene layers rather than the
distribution of pores at solid state.[86,239] Thus, graphene materials with single or few layers with less agglomeration are
expected to exhibit high effective SSA and excellent electrochemical performance. The gas-solid hydrazine reduced graphene materials displayed a lower degree of agglomeration
with a SSA of 320 m2 g1, which achieved the maximum SC of
205 F g1 at 1.0 V in aqueous electrolyte with an energy density
of 28.5 Wh kg1 at a power density of 10 kW kg1 and excellent
cycle life with 90% capacitance retention after 1200 cycles.[239]
The impressive performance could be attributed to the high
accessibility by electrolyte ions and effective use of SSA and
high electrical conductivity.
Due to the highly toxic and potentially explosive chemical
(hydrazine), many environmentally friendly candidates have
been developed, such as hydrohalic acids,[242] NaBH4,[240,254]
alcohols,[243] vitamin C,[245] urea,[241] glutathione,[246] and
metals.[244,255,256] Yu and co-workers reported the preparation
of ultrathin, transparent films fabricated with NaBH4 reduced
GO for use in supercapacitor applications.[240] These films demonstrated excellent optical transparency, homogeneous morphology, and an ideal electrical double layer behavior with SC of
135 F g1 and a high energy density of 15.4 Wh kg1 in 2 M KCl
electrolyte.[240] The partially reduced GO using HBr showed the
SC of 348 and 158 F g1 in aqueous and IL, respectively, due
to some oxygen functional groups that facilitated the penetration of aqueous electrolyte and introduced pseudocapacitive
effects.[242]
Apart from chemical reduction, graphene can be prepared through thermal exfoliation of GO.[247,249,257] Graphene
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REVIEW
Table 2. Summary of performances of graphene materials prepared through different methods for EDLCs.
Preparation methods
SSA
[m2 g1]
SCa)
[F g1]
Hydrazine reduction
705
135 (2)
10 mA
KOH (5.5)
[86]
99 (2)
10 mA
TEABF4 (1)
[86]
205 (2)
0.1 A g1
28.5
1200 (90%)
KOH (30%)
[239]
g1
[240]
Gas-based hydrazine reduction
320
Scan rate
E
[Wh kg1]
Cycle lifeb)
Electrolyte
[mol L1]
Ref.
NaBH4 reduction
135 (2)
0.75A
15.4
KCl (2)
Urea reduction
590
255 (3)
0.5 A g1
1200 (93%)
KOH (6)
[241]
HBr reduction
348 (3)
0.2 A g1
3000 (100%)
H2SO4 (1)
[242]
158 (3)
0.2 A g1
BMIPF6
[242]
Benzyl alcohol reduction
9.6
35 (2)
25mV s1
KOH (6)
[243]
Zn reduction
220
116 (3)
0.05A g1
5000 (100%)
KOH (6)
[244]
Vitamin C reduction
512
128 (2)
0.05A g1
KOH (6)
[245]
Glutathione reduction
317
238 (3)
0.1 A g
1000 (97%)
H2SO4 (1)
[246]
Low-temperature exfoliation
400
264 (2)
0.1 A g1
100 (97.0%)
KOH (5.5)
[247]
Microwave assisted exfoliation
463
191 (2)
0.15 A g1
KOH (5.0)
[248]
Thermal exfoliation
524
150 (3)
0.1 A g
500 (100%)
KOH (30%)
[249]
Hydrothermal reduction
175 (2)
10 mV s1
KOH (5.0)
[250]
Solvothermal reduction
346
218 (3)
0.4 A g1
700 (100%)
H2SO4 (0.5)
[251]
Electrochemical reduction
165 (3)
20 mV s
8000 (100%)
Na2SO4 (0.1)
[252]
Photocatalytical reduction
220 (2)
1 mV s1
20000 (92%)
H2SO4 (2)
[253]
a)The
numbers 2 and 3 refer to two- and three-electrode tests, respectively; b)The percentage in brackets represents the capacitance retention in the given conditions.
prepared by exfoliation of GO at 1050 C exhibited a SSA of

925 m2 g1 and a SC of 117 F g1 in aqueous H2SO4 electrolyte.[257] In addition, low-temperature exfoliation of GO (200 C)
in a vacuum environment was developed to avoid high energy
Figure 16. a) SEM image of chemically reduced graphene oxide (CRG)

particle surface and b) TEM image showing individual graphene sheets
extending from CRG particle surface. c) Schematic of test cell assembly.
Reproduced with permission.[86] Copyright 2008, American Chemical
Society.
1300816 (14 of 43)
consumption.[247] The as-obtained graphene materials showed

SC of 264 and 122 F g1 in aqueous and organic electrolytes,
respectively. Unfortunately, it is found that the C/O ratio was as
low as 10, indicating the presence of abundant residual oxygencontaining groups.[247] Recently, another simple and versatile
method to simultaneously achieve the exfoliation and reduction
of GO has been realized using convenient and rapid microwave
irradiation.[248] Ruoff et al. treated GO precursor in a commercial microwave oven for less than 1 min to obtain crumpled
graphene with a SSA of 463 m2 g1, which exhibited a SC of
191 F g1 in KOH electrolyte. This simple preparation process
could provide a promising route for the scalable and cost-effective production of graphene materials.
A mild solvothermal method was also adopted to reduce GO
for supercapacitors.[251,258,259] In this process, a relatively low
temperature was used without the addition of reducing agent
and the density of functionalities can be controlled through
changing the reduction time.[258] The obtained materials
showed SC up to 276 F g1 in H2SO4 electrolyte with good rate
performance and cycling stability, which is due to the surface
oxygen-containing groups contributing to large pseudocapacitacne, less aggregation, and good wetting properties.
Electrochemical reduction of GO has been recently put forward as another environmentally friendly strategy toward graphene.[252] In addition, photocatalytically reduced GO with
UV,[260] focused solar,[261] or mercury-lamp[253] is a rapid, chemical-free, cost -ffective route for high throughput production of
graphene without the use of high temperature. Interestingly,
the reduction degree and therefore the electrical conductivity of
reduced GO (RGO) can be controlled by varying the irradiation
time. The mercury-lamp irradiation reduced GO delivered an
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REVIEW
Figure 18. a) Schematic drawings illustrating the leavening process to
prepare RGO foams. b) Schematic diagram and c) optical image of the
flexible RGO foam supercapacitor. Reproduced with permission.[83] Copyright 2012, Wiley VCH.
Figure 17. a,c,e) Digital photographs of graphene hydrogel (a), aerogel

(c), and foam (e). b,d,f) SEM image of the interior microstructures of
graphene hydrogel (b,d) and foam (f). Reproduced with permission from
ref. [250] (a,b); ref. [245] (c); ref. [262] (d); and ref. [83] (e,f). Copyright
2010, American Chemical Society (a,b); copyright 2011, The Royal Society
of Chemistry (c); copyright 2011, The Royal Society of Chemistry (d); and
copyright 2012, Wiley VCH (e,f).
energy density of 5 Wh kg1 at a high power of 1 kW kg1 and

showed superior stability with 92% capacitance retention after
20000 cycles in an H2SO4 aqueous solution.[253]
2) Serious aggregation and restacking of graphene. Another
big challenge for graphene application in supercapacitors lies
in its compact and dense structure that is adverse for the rapid
transport of electrolyte ions during rapid charge/discharge process. Thus, a great deal of efforts have been made to develop
3D self-assemble, macrostructured and binder-free graphene
foams,[83] hydrogels,[250,262] aerogels,[245] and organogels[263] for
high-rate supercapacitors (Figure 17). For instance, lightweight
and electrically conductive RGO foams with open porous and
continuously crosslinked structures can be obtained by an autoclaved leavening and steaming strategy (Figure 18).[83] Thermal
steaming of GO layered films with hydrazine is believed to be
the key to the formation of RGO foams. Compared to regular
RGO layered films (17 F g1), the resulting foams showed significantly improved performance with SC of 110 F g1 for flexible
supercapacitors. Recently, the intrinsic capacitance of graphene
has been experimentally determined to be 21 F cm2,[264] thus
the theoretical SC of graphene would be up to 552 F g1 if the
theoretical SSA (2630 m2 g1) is fully used. That is to say, the
previously reported SC is significantly compromised by the

irreversible agglomeration of graphene sheets. Therefore, the
inhibition of aggregation is of particular importance for graphene sheets as electrode materials in energy storage fields. In
order to minimize the aggregation, a number of efforts have
been devoted, including incorporating spacers (e.g., metal
nanoparticles,[265,266] oxide/hydroxide nanoparticles,[4042,267270]
water molecule,[271] conducting polymers,[272274] carbon nanomaterials[94,275281], preparation of porous or crumpled graphene
sheets,[35,282287] and activation of graphene[79,81]). As a consequence, these attempts can not only facilitate the transport of
electrolyte ions but also greatly enhance the electrochemical
utilization of graphene.[79]
More interestingly, anchoring carbon nanostructures or
metal nanoparticles on 2D graphene sheets may effectively
inhibit the aggregation of sheets and result in a mechanically jammed, exfoliated graphene agglomerate with very high
surface area (Figure 19).[91,94,265,275280,288] Functionalized 2D
graphene sheets and acid-treated 1D CNTs hybrid films via
electrostatic interactions exhibited a nearly rectangular CV
curve and an average SC of 120 F g1 even at a high scan rate
of 1 V s1.[279] A novel strategy was reported to prepare 3D
sandwich-like graphene/CNT composite with CNT pillars in
situ grown in between graphene layers through CVD process
(Figure 19b),[275] which exhibited a maximum SC of 385 F g1
at a 10 mV s1 in 6 M KOH, and a capacitance increase of ca.
20% of the initial capacitance was observed after 2000 cycles,
indicating an excellent electrochemical stability. In another
case, CoMgAl layered double hydroxides were used as both catalysts and the template for the in situ synchronous growth of
graphene and SWNTs from methane by CVD.[281] The obtained
graphene/SWNT composite exhibited a high SSA of 807 m2 g1
and a SC of 98.5 F g1 in an aqueous electrolyte. Such a fabrication method is believed to be easy to scale up for their further
(15 of 43) 1300816
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REVIEW
Figure 19. SEM images of graphene separated by other carbon nanostructures as spacers. a,b) CNTs, c) carbon black, and d) carbon spheres.
Reproduced with permission from ref. [275] (a); ref. [288] (b); ref. [276]
(c); and ref. [91] (d). Copyright 2011, American Chemical Society (a);
copyright 2010, Wiley VCH (b); copyright 2010, Elsevier (c); and copyright
2011, The Royal Society of Chemistry (d).
applications in the fields of composites, energy storage, catalysis, and devices.

Moreover, carbon black nanoparticles can also be used as
spacers to separate graphene sheets through ultrasonication
approach (Figure 19c).[276] Carbon black particles mainly deposited on the edge planes of graphene and could enhance the
electrochemical utilization of graphene layers and facilitate the
electrolyte ions diffusion and migration. As a consequence,
the resulting composite showed SC of 175 F g1 and excellent cycling stability with capacitance retention of 91% after
6000 cycles, superior to those of pure graphene. In addition to
carbon black, carbon spheres were also employed as spacers to
intercalate between graphene sheets to prepare 3D hierarchical
structures (Figure 19d).[91,94] Zhao et al. reported 3D architectures composed of mesoporous carbon spheres intercalated
between graphene sheets by template assisted CVD process.[94]
During the CVD process, the formation of mesoporous carbon
spheres and the reduction of GO occurred simultaneously.
Carbon spheres uniformly intercalated into the slightly crumpled graphene sheets and formed randomly distributed open
channels with hundred nanometer dimensions, providing easy
access of electrolyte to the surface of graphene sheets to form
electric double layers. The 3D carbon electrode exhibited a maximum energy density of 5.5 Wh kg1 and an excellent electrochemical cyclability with 94% capacitance retention after 1000
cycles. The method demonstrated in this work opens up a new
route for the preparation of 3D graphene-based architectures
for supercapacitor applications.
Inspired by the fact that all biological tissues are more or
less hydrated and the hydration can provide strong repulsive
forces to prevent cells and tissues from collapse, Yang and coworkers recently reported an interesting and novel strategy to
prevent the restacking of CRG using water molecules as an
effective spacer to allow the multilayered graphene structure
to behave as monolayered graphene.[271] The solvated graphene
1300816 (16 of 43)
exhibited unprecedented electrochemical performance. High

SC of 215 F g1 at 0.1 A g1 and 156.5 F g1 at 1080 A g1 as well
as a maximum power density of 414.0 kW kg1 were obtained
in an aqueous electrolyte. Notably, the IL-exchanged solvated
graphene film based supercapacitor could offer SC of up to
273.1 F g1 and an energy density and maximum power density
of up to 150.9 Wh kg1 and 776.8 kW kg1, respectively. This
simple, bioinspired strategy will open up numerous opportunities for applications of graphene in a bulk form.
Incorporating pseudocapacacitive materials such as various
metal oxides/hydroxides, conducting polymers into graphene as
spacers to form composites is demonstrated to be an effective
strategy to prevent graphene agglomeration.[4042,267270,272274]
On the one hand, these spacers can effectively suppress the
irreversible restacking to maintain the intrinsic high SSA and
provide more active sites to form EDLs. On the other hand,
these added guest materials may contribute pseduocapacitance
to the overall SC. Unfortunately, this will usually seriously
compromise the cyclability of the electrode due to the inherent
instability of these guest materials under electrochemical conditions.[94] This will be discussed in a later section.
In order to increase the effective utilization of graphene
nanosheets, facilitate electrolyte ion transport, and improve the
rate-performance of graphene electrodes, porous or crumpled
graphene sheets have also been extensively studied for supercapacitors recently.[35,282287,289] For instance, Ning et al. developed
a template CVD approach to synthesize graphene nanomesh on
the gram scale.[283] The porous structure of the graphene nanomesh helped prevent agglomeration of the graphene sheets.
Due to the unique porous structure and high SSA (1654 m2 g1),
the electrode showed high SC of up to 255 F g1, excellent cyclability, and rate performance. Fan and co-workers reported a
facile synthesis of porous graphene through the etching of graphene using KMnO4.[282] Due to its open layered and mesopore
structures that facilitate the efficient access of electrolytes to
the electrode material and shorten the ion diffusion pathway
through the porous sheets, the porous graphene provided SC of
154 F g1 and excellent cycle stability with 88% SC retained after
5000 cycles. In the later work from the same group, highly corrugated graphene sheets (HCGS) were prepared by a rapid, low
cost and scalable approach through rapid cooling the thermal
reduced GO with liquid nitrogen.[286] The wrinkling of the graphene sheets can significantly prevented them from agglomerating and restacking with one another face to face and thus
increased the electrolyte-accessible surface area. The maximum
SC of 349 F g1 at 2mV s1 was obtained for the HCGS electrode in aqueous solution. Additionally, the electrode showed
no capacitance deterioration after 5000 cycles. More recently,
Fengs group developed an efficient and facile strategy to fabricate highly crumpled N-doped graphene sheets (C-NGNSs) by
thermal treatment with cyanamide as the nitrogen source.[35]
The C-NGNSs exhibited significant improvement SC as high as
248.4 F g1, good rate capability, and excellent electrochemical
stability (96.1% retention after 5000 cycles) in organic electrolyte due to the abundant wrinkled structures, high pore volume
(3.42 cm3 g1), high nitrogen doping (10%) and improved
electrical conductivity. Noteworthy, the doped-nitrogen concentration in final C-NGNSs could be tailored by adjusting the
amount of C3N4 or the annealing temperatures.
www.advenergymat.de
Importantly, Ruoff and co-workers presented a novel method

to prepared porous graphene through chemical activation of
RGO powders or papers.[79,81] The activated microwave exfoliated GO (a-MEGO) achieved a high SSA up to 3100 m2 g1,
which could be readily controlled by the ratio of KOH vs. MEGO
(Figure 20). The symmetric supercapacitor based on a-MEGO
(SSA: 2400 m2 g1) offered the SC of 166 F g1 with a measured power density of 250 kW kg1 at an energy density
of 70 Wh kg1. Thus a practical energy density of above
20 Wh kg1 for a packaged device is obtained, which is four times
higher than that reported for hybrid electrochemical devices and
nearly equal to those of lead acid batteries.[81] However, the areanormalized capacitance is relatively low (6 mF cm2), which can
be addressed through doping heteroatoms.
In another interesting work, Yoo et al. employed an inplane fabrication approach for ultrathin supercapacitors based
on electrodes comprised of pristine graphene and multilayer
RGO.[290] The in-plane design is straightforward to implement
and exploits efficiently the surface of each graphene layer for
energy storage. Additionally, the 2D design allows for exploring
the unique electrochemical properties of graphene edges along
with the basal planes of graphene. As a consequence, this novel
supercapacitor device exhibited maximum SC of 247 F g1 and
normalized area SC of 394 F cm2, i.e., 3 times higher than
that of the stacked device (140 F cm2). From a practical point
of view, this device geometry could be easily extended to other
thin-film-based supercapacitors and adapted to various structural and hybrid designs for energy storage devices.[290]
Due to its extremely high theoretical SSA, excellent electrical
conductivity, and outstanding mechanical performance, graphene
has attracted particularly extensive interest from scientific community in applications of supercapacitors in recent years. Despite
tremendous achievements, the researches in this field are just in
the infancy and a number of serious challenges still remain in
practical applications. First, how to prepare high-quality graphene
3.1.6. Heteroatom-Doped Carbon Materials

Although most of porous carbon materials possess high SC,
their electrical conductivity usually suffers from deterioration with increasing porosity and SSA due to the destruction
of conductive pathways, which consequently greatly limits the
power capability. To further enhance the energy density and
power output, the strategy of introducing pseudocapacitance
through doping function groups/heteroatoms (such as N, O, S,
B, and P) to carbon materials has attracted increasing attention
recently.[291296] The heteroatoms providing a pair of electrons
can significantly change the electron donor-acceptor characteristics of carbon materials, which accordingly in turn give pseudocapacitive reaction.[138,147]
The oxygen-containing surface groups formed in most of the
carbon materials are usually acidic in nature, thus introducing
electron-acceptor properties into the carbon surface.[138] The
oxygen-containing functional groups are commonly formed by
carbonization and activation,[297] electrochemical oxidation,[298]
oxidation in O2[299] or HNO3,[298] and oxygen-plasma treatment.[300] In aqueous solution, they can greatly enhance the SC
of carbon materials by improving the surface wettability and
inducing redox reaction that contribute pseudocapacitance to
the overall capacitance as follows:[173]
(8)
>C = O + H+ + e >C OH
COO + H+ + e COOH
>C = O + e >C O
(9)
(10)
However, they would be detrimental in organic electrolytes

due to irreversible reactions between oxygen and the electrolyte
ions, which can cause decomposition of electrolyte, high selfdischarge rates, increase of internal resistance of the electrode
and leakage current, and thereby inferior cycle life.[19,299] In
organic electrolytes, it is favorable to employ hydrophobic functional groups to improve the wettability of the electrode.[301] Surface modification by a sodium oleate surfactant has been proven
to greatly improve the wettability of carbon materials in organic
electrolytes, leading to a high usable SSA, small internal resistance, and consequently increased SC and energy density.[301]
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Figure 20. a) Schematic showing the preparation of a-MEGO. b) Lowmagnification and c) high-resolution SEM images of a 3D MEGO sheet.
d) ADF-STEM image of the same area as (c). e) High resolution phasecontrast electron microscopy image of the thin edge of a MEGO sheet.
f) Exit wave reconstructed TEM image from the edge of a-MEGO. Reproduced with permission.[81] Copyright 2011, American Association for the
Advancement of Science.
with controllable layer thickness on a large scale in a cost-effective

and environmentally friendly way is the major technical obstacle
preventing the further application of graphene as an alternative
to supercapacitor electrodes. Therefore, various low-cost, scalable, effective, and environmentally benign approaches to control
the number of layers, the content of defects and surface functionalities are highly urgent to be developed. Second, graphene materials tend to agglomerate and restack with each other during the
synthesis or electrode preparation process, which is usually unavoidable and result in a low SSA and compromised electrochemical performance. Hence, it is of great significance to take effective measures to inhibit the irreversible restacking to ensure the
utilization of high SSA. Last but not least, a better understanding
of the correlation between the electrochemical performance and
graphene structures, physical properties, and interactions within
hybrids is essential. It is believed that a revolution of clean and
renewable energy materials will be realized after fully exploiting
the potential of graphene.
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REVIEW
Figure 21. Schematic types of N-doping: a) porrolic N, b) pyridinic N,

c) quaternary N, and d) N-oxide.
Among various heteroatoms, N-doping has been investigated most extensively in supercapacitor applications due to
its effect on capacitance in both aqueous and organic electrolytes.[88,138,147,294,302304] Commonly, N-containing functionalities such as pyridinic N, porrolic N, quaternary N, and N-oxide
(Figure 21)[138] have electron-donor properties that can enhance
the wettability of electrodes and improve the electrical conductivity and capacitance performance.[80,138,167,303,305]
The doping of nitrogen can be achieved in a number of different ways, such as treating carbon materials with N-containing
reagents (NH3 and amines)[305] or carbonization/activation
of N-rich carbon precursors, such as melamine,[88,303] cyanamide,[35] polyacrylonitrile,[306] PANI,[50] PPy,[294] and chicken
eggshell membranes.[307] To date, NH3 has been the most frequently employed reagent to treat carbon materials to introduce
nitrogen. When treated with ammonia at high temperatures,
ammonia will decompose into numerous free radicals that can
attack carbon and etch carbon fragments to generate N-enriched
functional groups and increase the porosity.[308] More recently,
Ruoff and co-workers prepared N-doped activated graphene
through introducing ammonia gas during the activation process.[305] The content of nitrogen doping was easily controlled
by varying the flow rate of ammonia gas. It is observed that the
area-normalized capacitance of lightly N-doped activated graphene (2.3 at%) with similar porous structure increased from
6 to 22 F cm2 compared to pristine graphene. The quantum
capacitance is closely related to the N-doping concentration, and
N-doping can provide an effective way to increase the density
of the states of monolayer graphene. The amount of nitrogen
doped into carbons depends upon both the ammoxidation temperature and the flow rate as well as the pressure of ammonia
gas. Chen et al. reported the hierarchically aminated graphene
honeycombs obtained through vacuum assisted thermal expansion of GO followed by amination.[309] With the increase of amination temperature from 200 to 600 C, the introduced nitrogen
increased gradually from 2.79 at% to 3.91 at%, and N-doped
graphene electrode possessed a maximum SC of 207 F g1 and
an energy density of 7.2 Wh kg1.
Commonly, ammoxidation of carbons can result in the
decrease of SSA and pore volume although a further heat treatment could recover the pore parameters. N-enriched functional
groups generated in this manner are usually unstable and the
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content of nitrogen is usually rather low. To overcome this

drawback, various N-enriched precursors can be employed to
synthesize N-doped porous carbons, including PANI,[50,302]
cyanamide,[35] PPy,[294] melamine,[88,291] polyacrylonitrile,[310]
and quinoline.[311] For example, crumpled N-doped graphene
nanosheets using cyanamide as the nitrogen source exhibited a
SC of 248.4 F g1 at 5 mV s1, which is much higher than that
of RGO (106.3 F g1).[35] A supercapacitor based on N-doped
porous carbon nanofibers synthesized by carbonization of
macroscopic-scale carbonaceous nanofibers coated with PPy
showed a reversible SC of 202 F g1 at 1 A g1 and a maximum
power density of 89.57 kW kg1 in aqueous electrolyte.[294] In
addition, a maximum volumetric energy density of 19.6 Wh L1
was obtained for N-doped silk-derived carbon in organic electrolyte.[304] Nevertheless, too much nitrogen content will give
rise to a negative effect on the electrochemical performance
because of the decomposition of the organic electrolytes.[312]
Recently, other approaches such as plasma treatment, CVD
with N-rich carbon precursors as the N source, and hydrothermal carbonization were also used to dope nitrogen into
carbons.[80,138,313] It was reported that N-doped graphene produced by a simple plasma process exhibited a high SC of up to
280 F g1 (four times larger than that of pristine graphene),
excellent cycle life (>200 000), and high power capability. The
outstanding performances presumably resulted from the
N-doped sites at basal planes.[80] However, this process is very
complicated to operate and needs special equipment. N-doped
CNTs were also obtained through thermal CVD with C2H2 and
NH3 gases as carbon and nitrogen sources, respectively.[313] It
was indicated that the SC did not increase with the increase in
nitrogen content entirely. As an alternative, hydrothermal carbonization has attracted tremendous attention in recent years
as it can maintain high content of nitrogen into final carbons,
does not require high temperature (180200 C) and employ
only water as a medium. The maximum SC of 300 F g1 with
an energy density of 50 Wh kg1 was reported for the hydrothermal carbonization N-doped porous carbon.[138] However,
the increase of nitrogen content does not always lead to the
increase of SC, and the relationship between nitrogen content,
SSA, and SC has not been fully understood.
Additionally, other elements such as B, P, and S incorporated into carbons could enhance the electric double-layer
capacitances and further introduce pseudocapacitances to the
electrodes.[141,292,295] Boron is electrodeficient with three valence
electrons and can substitute carbon at the trigonal sites, resulting in
the promotion of oxidation resistance, a shift in Fermi level to conducting band, and corresponding modification of the electronic
structure of carbon.[314] Similar to N-doping, B-doping could
increase the electrical conductivity and electrochemical activity
and produce additional functional groups on the carbon surface,
thereby greatly enhancing the electrochemical performances of
carbon materials. In addition, it was demonstrated to improve
the thermal stability and increase the disorder degree of carbons.
B-doping could also increase the hydrophobicity and wettability
of carbons in organic electrolyte.[315] Recently, innovative B-doped
RGO prepared by a one pot reduction of GO with borane-tetrahydrofuran displayed excellent supercapacitor performance with a
SC of 200 F g1 in aqueous electrolyte.[292] B-doped mesoporous
carbon prepared by co-impregnation and carbonization of sucrose
www.advenergymat.de
capability, and enhanced energy density (8.65 Wh kg1).[293] B-/Pco-doped mesoporous carbon with a SSA of 600 m2 g1 and a
uniform PSD of 6.3 nm was prepared via a facile hydrothermal
approach.[296] The concentration of B and P in carbon materials
can be adjusted by changing the hydrothermal temperature.
Compared with B- or P-doped carbon, co-doped carbon presented superior performance due to the positive function of the
B and P species. However, the enhancement mechanism is still
unclear and, thus, which species played the dominant role is
also ambiguous. Therefore, considerable effort should be made
on the research into doping mechanism to satisfy the increasing
need of chemical doping in various applications such as supercapacitors, LIBs, and fuel cells.
3.2. Faradaic Materials
The primary difference between pseudo-capacitance and electrical double-layer capacitance lies in the fact that pseudocapacitance is intrinsically faradaic. Generally, the faradaic
processes taking place on the electrode materials mainly
involve the following types: reversible adsorption, redox reactions of transition metal oxides, and reversible electrochemical doping/dedoping in electrically conducting polymers.[18]
Therefore, the most commonly used electroactive materials by
material scientists, chemists, and engineers include a variety
of noble or cheap transition metal oxides/hydroxides (such as
RuO2,[321] MnO2,[322,323] Co3O4,[324] NiO,[325] Co(OH)2,[326,327]
and Ni(OH)2),[40] conducting polymers (PANI,[328] PPy,[329] and
polythiophene (PTh)),[330] and oxygen- or nitrogen-containing
surface functional groups.[138]
Due to fast and reversible redox reactions, pseudo-capacitors
can provide much higher SC compared to EDLCs. Unfortunately, pseudo-capacitors usually suffer from low power density
and relatively poor cycling stability, seriously restricting their
further practical applications. The former originates from poor
electrical conductivity of the electroactive materials confining
fast electron transport, while the latter can be attributed to the
readily damaged structure of electrode materials caused by
swelling and shrinkage during the charge/discharge process.
3.2.1. Noble Metal Oxides
Figure 22. a) Fabrication illustration of the supercapacitor based on

B-/N- co-doped graphene aerogels. b) SEM images of the as-prepared
graphene aerogels. c) Ragone plot of the assembled supercapacitors.
Among various oxides, RuO2 has been recognized as the

most promising materials due to its ultrahigh theoretical SC
(2000 F g1), excellent electrical conductivity, wide potential window, long cycle life, and high chemical stability.[331333]
Various RuO2 in the form of porous films,[334] nanorods,[335]
nanosheets,[336] and nanotubes[337] have been extensively studied
for supercapacitor applications (Figure 23). However, the practical
SC of bulk RuO2 in previous reports was usually smaller than
theoretic values due to the high crystalline and power constraints.
It has been demonstrated that the SC of RuO2 strongly
depends on several aspects, such as the SSA and crystallinity,
combined water in RuO2 as well as the electrolyte. Owing to
the pseudocapacitance of RuO2 being mainly derived from the
surface reaction, high SSA can provide more active sites to participate in redox reactions, resulting in high SC. Thus, considerable effort has been made toward enhancing the SSA of RuO2
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and boric acid exhibited substantial improvement of interfacial

capacitance by 1.51.6 times higher than boron-free carbon in
aqueous electrolytes,[314] which could be attributed to the low-level
boron doping showing catalytic effect on oxygen chemisorptions
at edge planes and altering electronic structure of space charge
layer of carbon. P-doping enhances the charge delocalization of
carbon atoms and gives rise to the morphogy of carbons with
many open edge sites.[316] P-enriched microprous carbon with
SSA of 633 m2 g1 prepared by simple H3PO4 activation could
be operated stably at voltages larger than 1.3 V in H2SO4 and
yielded the maximum SC of 220 F g1.[141] Such carbon material also showed a large energy density of 16.3 Wh kg1 and
excellent long cycle life. S-doped mesoporous carbon displayed
excellent supercapacitor performance with 38% increase of SC
compared to S-free mesoporous carbon owing to a larger electrolyte dielectric constant and the charge transfer process facilitated
by further polarization of the surface.[295] Interestingly, the SC
was maintained at a steady level with slight improvement with
the continuous increase of S content, indicating that the presence
of aromatic sulfide crucially modifying the environment of the
carbon surface rather than its concentration.
Nowadays, binary co-doping of heteroatoms into carbons,
such as N-/P-,[317] N-/B-,[293,318,319] and B-/P-[296,320], has attracted
considerable attention due to the strengthened modifying effect
or synergistic effect contributing to excellent performance.
B-doping enhances the sp2-structure of carbon and increases
the content of pyridinic-N sites in the carbon lattice, whereas
P-doping improves the charge delocalization of the carbon atoms
and produces carbon structures with abundant edge sites.[316]
An ASC fabricated with B-/N-codoped carbon (14 at% B and
10 at% N) and MnO2 achieved an energy density of 10 Wh kg1
stable up to 1000 cycles, which is five times more than the symmetric AC system.[319] An all-solid-state supercapacitor based on
3D B-/N-co-doped graphene aerogels (Figure 22) was reported
to exhibite minimized device thickness, high SC, good rate
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REVIEW
Figure 23. Various RuO2 in different morphologies for supercapacitors:

a) porous films, b) nanorods, c) nanosheets, and d) nanotubes. Reproduced with permission from ref. [334] (a); ref. [335] (b); ref. [336] (c); and
ref. [337] (d). Copyright 2009, Wiley VCH (a); copyright 2005, The Royal
Society of Chemistry (b); copyright 2003, Wiley VCH (c); and copyright
2006, American Chemical Society (d).
through preparing RuO2 films on various substrates and synthesizing nanoscaled RuO2 particles.[337340] Amorphous RuO2 thin
films deposited on stainless steel substrates by anodic deposition
showed stable electrochemical performance with a maximum SC
of 1190 F g1 in H2SO4 electrolyte.[340] An amorphous RuO2 commonly exhibits outstanding electrochemical performance since
the redox reaction could take place both on the surface and in the
bulk. RuO2 with high crystallinity is unfavorable for the transport
and diffusion of protons, resulting in large diffusion resistance.[3]
Moreover, the combined water in RuO2 facilitates the diffusion of cations inside the electrode layer occurred by hopping of alkaline and H+ ions between H2O and OH sites.[3]
Hydrous RuO2 (RuO20.5H2O) exhibited a SC as high as
900 F g1, which was more than 1000 times greater than that
of anhydrous RuO2 (0.75 F g1).[341] Hydrous RuO2 nanotubular
arrayed electrodes exhibited unexpectedly high SC of 1300 F g1
with an energy density of 7.5 Wh kg1 and a power density of
4.3 kW kg1 due to 3D mesoporous architecture simultaneously maintaining the facility of electrolyte penetration, the
ease of proton exchange/diffusion and the metallic conductivity
(Figure 23d).[337] Furthermore, the used electrolyte (acid/base
and concentration) also plays a significant role in the electrochemical performance of RuO2.[18,342,343]
Despite the intriguing electrochemical performance of
RuO2, its high cost and scarce source seriously restrict its further commercial application. Therefore, considerable efforts
have been focused on reducing the cost, decreasing the use of
RuO2, and increasing its utilization in recent years. So far, two
potential strategies have been proposed in previous reports:
exploration of cheap metal oxides as alternative candidates
to prepare mixed-oxides (e.g., MnO2, NiO, Co3O4)[342,344,345]
and deposition of RuO2 on low-cost substrates to synthesize
composites (e.g., various forms of carbons and conducting
polymers).[321,331333,346,347]
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Aiming at effectively reducing the use of RuO2 and the fabrication cost of electrodes, it seems quite promising to compose
it with cheap metal oxides to form composite, such as MnO2,
NiO, TiO2, Co3O4, SnO2, and VO2.[344,348350] RuO2xH2O/TiO2
nanocomposite obtained through microwave-assisted hydrothermal route show a maximum SC of 992 F g1 and a power
density of 400 kW kg1 in H2SO4 electrolyte.[350] Sol-gel derived
Ru0.8Sn0.2O2 exhibited the maximum SC of 690 F g1 due to the
high degree of non-stoichiometry and finer particle size of this
binary oxide.[351] The added metal oxides can provide additional
pseudocapacitance to the overall capacitance, facilitate electron
and proton transport, and improve the dispersion degree as
well as decrease the particle size of RuO2 nanoparticles.[352,353]
In addition to RuO2-based mixed oxides, depositing RuO2
nanoparticles on various carbon materials has received
increased attention in past years.[332,333,346] For example, a SC
of 1652 F g1 could be obtained for RuO2nH2O/MWNT electrode in H2SO4 aqueous solution.[346] A RuO2/Ketjen black electrode showed a SC of up to 821 F g1 with energy and power
densities of 12 Wh kg1 and 6 kW kg1, respectively.[354] RGO/
RuO2 composite exhibited high SC (570 F g1 for 38.3% Ru
loading), enhanced rate capability, excellent stability (97.9%
retention after 1000 cycles), high energy density (20.1 Wh kg1),
and power density (10 kW kg1).[333] It has been demonstrated
that highly dispersed nanoscaled RuO2 particles yielded large
SC due to the decreased size resulting in the accessibility of the
inner part of RuO2 to the electrolyte ions. On the other hand,
conductive carbon substrates greatly enhance the electrical
conductivity of RuO2, favor the penetration of ions, and significantly shorten the ion transport distance.[333]
RuO2/polymer composites have also been intensively studied
over the past few years; these include RuO2/PANI,[355358],
RuO2/PPy,[347,359] and RuO2/poly(3,4-ethylenedioxythiophene)
(PEDOT).[360362] For example, a RuO2 embedded PANI electrode prepared by electrodeposition revealed high SC of
474 F g1, ideal cyclical stability, and smaller charge transfer
resistance (2.24 ).[355] RuO2/PPy composite was prepared
through an electrochemical route and yielded a maximum SC
of 681 F g1.[347] RuO2/PEDOT nanotubes synthesized by a stepwise electrochemical deposition method displayed a SC as high
as 1217 F g1 and a high power density of 20 kW kg1 while
maintaining 80% energy density (28 Wh kg1).[360] The uniform
distribution of RuO2 nanoparticles on the conducting polymer
substrates could increase the effective active surface area of
RuO2, providing more active sites to participate in faradic redox
action. In addition, the polymer is expected to play an important role in effectively preventing the agglomeration of RuO2
particles as a stabilizer through both steric and electrostatic
stabilization mechanisms. Meanwhile, the polymers may provide efficient paths to transport electrons due to the superior
electrical conductivity and deliver the proton species as well as
greatly improve the adhesion of RuO2 with current collector to
give rise to the decrease of contact resistance.[360,362]
3.2.2. Transition Metal Oxides/Hydroxides
Despite the high SC and excellent rate capability of amorphous hydrous RuO2, the relatively high cost, low abundance
and environmental harmfulness seriously inhibit its further
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REVIEW
commercialization in supercapacitors. In recent years, considerable efforts have been made on exploiting relative cheap and
environmentally benign materials exhibiting similar electrochemical behavior to that of RuO2 as alternative candidates to
replace RuO2, such as MnO2, NiO, Co3O4, V2O5, etc.[22,41,325,363]
MnO2: As an alternative to RuO2, MnO2 has attracted significant interest as electrode materials for supercapacitors recently
due to its high theoretical SC (1100 F g1), low cost, abundance, and environmentally friendly nature. Until now, two
mechanisms were proposed to explain the MnO2 charge storage
behavior, which involves the faradic reactions occurring on the
surface and in the bulk of the electrode. The first mechanism
based on the surface adsorption of electrolyte cations (C+ = H+,
Li+, Na+ and K+) on MnO2:[364]
(MnO2 )surface + C+ + e (MnOOC)surface
(11)
The second one relies on the intercalation of electrolyte cations in the bulk of MnO2 upon reduction followed by deintercalation upon oxidation:[364]
(12)
MnO2 + C+ + e MnOOC
Notably, both the proposed charge storage mechanisms
involve a redox reaction between the III and IV oxidation states
of Mn.
In the past few years, various MnO2 with different crystalline structures (amorphous, -, -, -, - and -), morphologies
(plate-like, nanorod, hollow sphere, urchin, nanowire, nanotube
and lamellar), and particle sizes have been intensively synthesized and investigated for supercapacitors (Figure 24).[365371]
For instance, hierarchical porous nanostructures assembled
from ultrathin MnO2 nanoflakes showed high SC of 328 F g1
due to the high utilization of MnO2.[367] Ultrafine MnO2 nanowires with sub-10 nm diameters synthesized by a simple process
of hydrothermal treatment with subsequent calcination exhibited an enhanced SC (279 F g1 at 1 A g1), high rate capability (54.5% retention at 20 A g1), and good cycling stability
(1.7% loss after 1000 cycles).[370] Sea urchin shaped -MnO2
consisting of radially grown single crystalline nanorods of
3040 nm in diameter prepared using a simple hydrothermal
method without any template and surfactant achieved the SC
of 120 F g1.[365] So far, many synthesis processes have been
developed to synthesis various nanostructured MnO2 as possible electrode materials for supercapacitors, including low
temperature reduction,[372] chemical co-precipitation,[207] hydrothermal/solvothermal synthesis,[373] sonochemistry,[374] microemulsion route,[375] sol-gel technique,[376] solution combustion technique,[377] solid state reaction,[378] microwave-assisted
synthesis,[379,380] and electrodeposition.[381]
The pseudocapacitive performance of MnO2 also strongly
depends on its crystallinity, microstructure, morphology, content of combined water, etc. The SC is mainly controlled by the
crystal structure and chemically hydrous state, while the cyclability is predominantly governed by the microstructure.[3] Low
crystallinity generally results in low electrical conductivity but
high surface area and porous microstructure, which favors the
transport of electrolyte ions. Therefore, there should be a balance between electrical conductivity and ion transport rate.[367]
Brousse and co-workers systematically investigated the effect
of various crystal structures on the electrochemical performance
Figure 24. Crystalline MnO2 with different morphologies for supercapacitors: a) plate-like, b) nanorod, c) hollow sphere, d) urchin, e) nanowire,
and f) lamellar. Reproduced with permission from ref. [367](a); ref. [366]
(b); ref. [368] (c); ref. [365] (d); ref.[370] (e); and ref. [369] (f). Copyright
2012, The Royal Society of Chemistry (a); copyright 2005, American
Chemical Society (b); copyright 2010, Elsevier (c); copyright 2009, American Chemical Society (d); copyright 2011, The Royal Society of Chemistry
(e); and copyright 2010, Elsevier (f).
of MnO2 and found that the capacitance of the crystallized materials strongly depends upon the crystalline structure, especially
when the size of the tunnels limits the intercalation of cations.[382] The SC increased in the following order: - or -MnO2
with 1D tunnel structure < -MnO2 with 3D tunnel structure <
birnessite -MnO2 with a 2D tunnel structure. Commonly, different synthesis conditions such as synthesis procedures and
acidity of the reaction system can lead to different crystalline
structure of MnO2. In addition, various MnO2 with different
morphologies such as nanwires, nanorods, flower-like microspheres, and nanobundles exhibited SSA of 20300 m2 g1.[365367]
Like 1D nanostructured MnO2 (nanowires, nanotubes), it
has short diffusion path lengths for electrolyte ions and electrons, exhibiting high charge/discharge rates and large SC.[383]
Especially, mesoporous MnO2 nanowire arrays displayed a
capacitance up to 923 F g1 at 5 mV s1.[384] Porous spherical
MnO2 is favorable for the rapid adsorption of electrolyte ions on
MnO2 surface through the interstitial space, thus maintaining
the sufficient faradic reaction between MnO2 and electrolyte
ions. Hierarchical hollow MnO2 nanosphere with large SSA prepared by a template-assisted hydrothermal process exhibited SC
of 299 F g1 and excellent cycling stability.[385] Pillared layered
MnO2 has robust pillaring agents, which can effectively accommodate the structural/mesostructural changes induced by the
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guest ions during the intercalation and de-intercalation process,

demonstrating excellent cycling stability.[386]
Despite its high theoretical SC and low cost, the practical
electrochemical performances of MnO2 are always far below
the expected values due to its poor electrical conductivity and
electrochemical dissolution during cycling, which remains
a serious obstacle to its widespread application in energyrelated applications. In addition, the poor conductivity of MnO2
(105106 S cm1) significantly limits the charge/discharge
rate capability for high-power applications.[387] To overcome
these obstacles, considerable efforts have been made in recent
years, such as incorporating other metal elements into MnO2,
adding metal with excellent conductivity into MnO2 to synthesize composites, and hybridizing MnO2 with excellent electrically conductive components including carbon materials and
conducting polymers.[284,323,387,388]
To improve the electrical conductivity and maximum the
utilization of MnO2, it is extremely vital to possess reliable
electrical connection between MnO2 and current collector for
high-performance MnO2-based electrodes. Currently, considerable research efforts have been made on hybridization of MnO2
with highly conductive metals (such as Au, Ag) or fabricating
coaxial array nanostructures to improve the electrochemical
performance (Figure 25).[387,389,390] The nanoporous metal
allows rapid electron transport through MnO2 and favors fast
ion diffusion of electrolyte ions while also providing electrical
double-layer capacitance, which enhances the pseudocapacitve
behavior of MnO2. Hybrid structures of nanoporous gold and
nanocrystalline MnO2 showed enhanced conductivity, resulting
in SC of the constituent MnO2 (1145 F g1) close to the theoretical value.[387] Recently, Reddy et al. reported multisegmented
Figure 25. Microstructure characterization of MnO2/metal composites.

a) Bright-field TEM image of the nanoporous MnO2/gold hybrid. Reproduced with permission.[387] Copyright 2011, Macmillan Publishers Ltd.
b) SEM image of Au-MnO2/CNT. Reproduced with permission.[391] Copyright 2010, American Chemical Society. c) SEM image of the fabricated
MnO2/Mn/MnO2 nanotube arrays. Reproduced with permission.[390]
Copyright 2012, American Chemical Society. d) TEM image of MnO2/Ag
composite. Reproduced with permission.[392] Copyright 2012, American
Chemical Society.
1300816 (22 of 43)
Figure 26. Schematic diagram showing the fabrication of Au-MnO2/CNT

hybrid coaxial nanotube arrays. Reproduced with permission.[391] Copyright 2010, American Chemical Society.
Au-MnO2/CNT coaxial arrays fabricated inside porous alumina

templates using a combination of electrodeposition, infiltration,
and CVD methods (Figure 26).[391] The well-adhered interface
between Au and MnO2/CNT hybrid segments provided good
electrical contacts between the electrode and current collectors.
As a result, the composite displayed excellent electrochemical
performance with a power density of 33 kW kg1 and an energy
density of 4.5 Wh kg1. Although this strategy may effectively
enhance the rate and cycling performances of MnO2, its energy
and power densities are sacrificed due to small mass loading of
MnO2.
In addition to poor electrical conductivity, low SSA is another
factor that needs to be considered for MnO2. Incorporation of other metal elements (Co, Ni, Al, Mo, V, Fe, etc.) into
MnO2 to form mixed oxides has been considered very promising approach to increase the SSA and electrical conductivity
of MnO2 through introducing more defects and charge carriers.[388,393,394] In addition, doping an appropriate amount of
Co can effectively prevent the dissolution of MnO2 and consequently enhance the electrochemical reversibility and cycling
stability. V doping could inhibit the crystal growth of MnO2,
while Fe doping can improve the structural stability and crystallinity as well as decrease the concentration of unstable Mn3+
ions.[395] Incorporation of metal oxides such as SnO2 and Co3O4
can provide a fast path for electron transport and increase the
electrochemical utilization of amorphous MnO2. For instance,
Co3O4 nanowire@MnO2 core/shell arrays exhibited a high
capacitance (480 F g1) with good cycle performance (2.7%
capacitance loss after 5000 cycles) and remarkable rate capability.[388] SnO2/MnO2 composite showed the maximum SC
as high as 800 F g1 and energy density of 35.4 Wh kg1 at a
power density of 25 kW kg1.[394] The incorporation of Ni led
to a significant change from rod-like to plate-like in the shape,
and yielded a SC of 284 F g1, about two-fold higher than that
of undoped MnO2. However, contradictory results were sometimes obtained for the effect of the incorporation of other elements on the SC of MnO2. In contrast to the beneficial effects,
incorporating Co showed no increase in SC compared to an
undoped sample.[393] Thus, the influence of incorporating other
metal elements on the electrochemical performance needs to
be further understood.
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structure facilitated the fast transport of both

electrolyte ions and electrons within the electrode and improved the electrochemical utilization of MnO2 (Figure 28). Graphene sheets
in the composite acted as both the matrix for
the deposition of MnO2 and the electronic conductive paths. As a result, the resulting composite exhibited the SC of 310 F g1 and high
rate performance (74% at 500 mV s1) as well
as only 4.6% decay in SC after 15 000 cycles.
In addition to CNTs and graphene, other
carbon materials such as exfoliated graphite,
onion-like carbon, carbon foam, carbon
aerogel, carbon fiber, and mesoporous
carbon were also employed as conductive
matrixes to synthesize MnO2/carbon composites.[363,373,399,405,406] Graphite nanoplatelet/
MnO2 composite showed SC of 276.3 F g1 due
to graphite nanoplatelets providing large contact area between MnO2 with electrolyte.[363]
An onion-like carbon/MnO2 composite synthesized by hydrothermal method achieved SC
of 177.5 F g1, much higher than that of pure
Figure 27. Morphology of MnO2 deposited on various carbon substrates. a) CNTs, b) gra[373] 3D structured carbon nanofoam/
phene, c) carbon foam, d) exfoliated graphite, e) graphite nanoplatelet, f) onion-like carbon, MnO2.
g) mesoporous carbon, and h) carbon fiber. Reproduced with permission from ref. [402] (a); MnO2 composite showed an exceptionally high
2
ref. [15] (b); ref. [399] (c); ref. [398] (d); ref. [363] (e); ref. [373] (f); ref. [403] (g); and ref. [404] (h). area-normalized capacitance (1.5 F cm ) and
Copyright 2011, American Chemical Society (a); copyright 2010, American Chemical Society volumetric capacitance (90 F cm3).[399] Carbon
(b); copyright 2007, American Chemical Society (c); copyright 2009, Elsevier (d); copyright aerogel/MnO2 composite prepared by a chem2008, Elsevier (e); copyright 2012, The Royal Society of Chemistry (f); copyright 2006, American ical co-precipitation method has high SC of
Chemical Society (g); and copyright 2012, Elsevier (h).
226.3 F g1 with 60 wt% MnO2 loading.[405]
Mesoporous carbon with 20 wt% MnO2 delivered the improved discharge performance of 223 mAh g1.[406]
To overcome poor electrical conductivity of MnO2, the deposition of MnO2 on various conductive carbon supports is another
The partial dissolution of MnO2 in even mildly acidic and
attractive alternative and has been investigated extensively in the
near-neutral electrolytes during cycling is another vital issue
literature (Figure 27).[396399] The most widely used carbon sublimiting its further applications. Moreover, some mechanical
issues, such as poor structural stability and inferior flexibility
strates are ordered mesoporous carbon, carbon fibers, carbon
of MnO2, also lead to the degradation of SC during long-term
foam, CNTs, graphene, etc.,[42,363,373,396400] which can improve
the electrical conductivity and increase the active surface area
electrochemical cycle tests. To prevent MnO2 from dissoluof MnO2, ensuring its high utilization. MnO2 nanoflower/CNT
tion during cycling and to enhance the mechanical stability
array with hierarchical porous structure, large surface area, and
superior conductivity was prepared by electrodeposition technique.[397] The binder-free electrode exhibited excellent rate
capability, high SC (199 F g1 and 305 F cm3), and long cycle
life. More recently, a sponge supercapacitor was fabricated
using the sponge/CNT/MnO2 composite hybrid electrode with
remarkable performance.[401] The maximum SC of 1230 F g1
was achieved for the composite. In addition, the specific power
and energy were as high as 63 kW kg1 and 31 Wh kg1, respectively. Recently, graphene has also been used as one of the most
appealing substrates to deposit MnO2 nanoparticles.[42,284] A 3D
macroporous graphene/MnO2 composite was obtained through
using polystyrene colloidal particles as a sacrificial template.[284]
3D porous graphene with a large SSA favored rapid transport
of electrolyte ions while maintaining excellent conductivity,
endowing the composite electrode with excellent electrochemical
performances such as SC of 389 F g1 and an energy density
Figure 28. a) Schematic illustration for the synthesis and electrochemical
of 44 Wh kg1. Moreover, graphene/MnO2 was also prepared
performance of graphene/MnO2 composite. b) TEM images of graphenethrough self-limiting deposition of nanoscaled MnO2 particles
78%MnO2 composite. c) SC (based on the composite) at different scan
on graphene sheets under microwave irradiation.[42] The unique
rates. Reproduced with permission.[42] Copyright 2010, Elsevier.
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REVIEW
Figure 29. SEM images of a) PANI/MnO2 coaxial nanofibers, b) graphene/MnO2/PEDOT:PSS nanostructures, c) PTh/MnO2 nanocomposite,
and d) TEM image of MnO2/PPy@CNF composite.[408] Reproduced with
permission from ref. [407] (a); ref. [323] (b); ref. [330] (c); and ref. [408]
(d). Copyright 2012, The Royal Society of Chemistry (a); copyright 2011,
American Chemical Society (b); copyright 2011, Elsevier (c); and copyright 2012, The Royal Society of Chemistry (d).
and flexibility, many effective approaches have been employed

to apply a protective polymer shell on MnO2 and incorporate
various conducting polymers to obtain polymer/MnO2 composite through oxidative polymerization, electrochemical deposition, interfacial polymerization, and self-assembly. The most
commonly used conducting polymers are PANI, PPy, PTh, and
PEDOT (Figure 29).[323,330,407,408] The enhanced mechanical
and electrochemical performances of MnO2/polymer composites are attributed to the synergistic effects between MnO2 and
polymers. Polymers with excellent electrical conductivity, high
stability, and mechanical flexibility act as not only a physical
coating to prevent MnO2 from dissolution but also a conductive path for electron transport. Meanwhile, both MnO2 and
polymer could contribute pseudocapacitance to the overall
capacitance. As for PANI/MnO2 coaxial , it exhibited a high SC
of 383 F g1 and energy density of 53.2 Wh kg1 at a power density of 250 kW kg1.[407] MnO2 embedded PPy composite prepared by electrochemical co-deposition showed remarkably high
SC of 620 F g1 compared to that of pure MnO2 (225 F g1).[409]
MnO2 enriched PEDOT nanowires yielded a very high SC of
410 F g1,[410] and the highly conductive and porous PEDOT substrate favored fast charge/discharge of MnO2 nanoparticles and
prevented them from agglomerating. More recently, appealing
electrochemical properties of ternary composites have also
become a hot topic because of their enhanced electrochemical
performance compared to binary composites.[408,411,412] PANI/
mesoporous carbon/MnO2 ternary composite with 12% MnO2
content possessed an enhanced SC of 695 F g1 and 88% capacitance retention after 1000 cycles.[411] In addition, hierarchical
MnO2/PPy@carbon fiber composite exhibited a superior SC of
705 F g1 due to the improved electrical conductivity and strong
structural integrity.[408] MnO2/CNT/PEDOT composite reached
a SC as high as 427 F g1 and excellent cycling stability (99%
after 1000 cycles),[412] demonstrating that MnO2 was effectively utilized with assistance of CNTs and PEDOT. CNTs not
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only provided high surface for the deposition of MnO2 but also
enhanced the electrical conductivity and mechanical stability of
the electrode. While PEDOT acted as both an effective dispersant and a binder to improve the adhesion to the substrate and
the connection among MnO2/CNT particles.
Interestingly, using mixed-valent manganese oxides is also
an appealing approach to improve the electrochemical performances of MnO2. Mixed-valent compounds commonly contain
donor and acceptor sites separated by a bridge.[413] The coexistence of aliovalent cations may favor the formation of more
ionic defects and electronic defects, which may accelerate the
kinetics of the surface redox reactions. In addition, mismatches
caused by structural differences among different oxide phases
may cause additional defects, favorable for the formation of
porous nanoarchitectures enhancing the transport of charged
species and extending the reaction sites from the surface to the
subsurface of electrode.[413] More recently, Liu and co-workers
reported a nanostructured, mixed-valent manganese oxide
that exhibited anomalously high SC (2530 F g1) while maintaining excellent power density and cycling life.[413] The outstanding performance could be ascribed to the unique mixedvalence state with porous nanostructure, facilitating rapid mass
transport and enhancing surface double-capacitance as well as
promoting facile redox reactions related with charge storage by
both Mn and O sites. Thus, the new charge storage mechanism
may provide crucial insights to rational design of next-generation energy storage devices.
Co3O4/Co(OH)2: Among various metal oxides, Co3O4 has
been regarded as a promising positive with great potential to
replace the state-of-the-art RuO2 due to its low cost, high redox
activity, outstanding theoretical SC (3560 F g1), great reversibility and environmental benignity. Recently, considerable
effort has been dedicated to synthesizing Co3O4 nanostructures
with different morphologies, such as nanosheet, nanowire,
nanotube, aerogel, nanoflower, and microsphere.[324,414,415]
For instance, Co3O4 nanosheet arrays on Ni foam achieved
ultrahigh SC of 2735 F g1 due to its unique 3D hierarchical
structure endowing it with fast ion and electron transport.[324]
Mesoporous Co3O4 nanowires arrays freely standing on Ni
foam delivered SC of 1160 F g1 and maintained 90.4% after
5000 cycles.[416] Co3O4 nanotubes displayed good capacitive
behavior with SC of 574 F g1 owing to the unique structure
and large surface area.[415] In order to enhance the conductivity
of Co3O4 electrode, various carbonaceous materials are introduced to form composite for the application of supercapacitors.[41,417420] Co3O4/CNT composite synthesized by co-precipitation exhibited significantly improved SC (418 F g1) compared
with pure Co3O4 due to the synergistic effects between Co3O4
and CNTs.[417] It has been demonstrated that graphene/Co3O4
composite achieved maximum SC of 243.2 F g1 in aqueous
solution.[41] 3D graphene foam supported Co3O4 nanowires was
capable of delivering SC of 1100 F g1 with excellent cycling
stability.[418] Flexible and free-standing Co3O4/RGO/CNT paper
electrode showed SC of 378 F g1.[419]
Co(OH)2 is also a high capacity positive material for supercapacitors due to its layered structure with large interlayer
spacing, low cost and high theoretical SC of 3460 F g1.
Co(OH)2 nanoflakes potentiodynaically deposited on stainless
steel yielded SC of 890 F g1.[421] Porous Co(OH)2/Ni composite
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REVIEW
was demonstrated to have SC of 1310 F g1 owing to the introduction of Ni improving the electric conductivity.[422] Urchinlike mesoporous Co(OH)2 nanowires displayed SC of 421 F g1
ascribed to their ordered microstructure, hierarchical porosity
and good electronic conductivity.[423] Co(OH)2 is a p-type semiconductor and is kinetically unfavorable to support fast electron transport required by high power density. Therefore, to
further improve its electrochemical performance, constructing
Co(OH)2 with conductive carbon materials such as CNTs and
graphene to form hybrid nanostructure appears to be an effective approach.[424,425] Binder-free Co(OH)2-combined CNT array
electrode produce high capacitance (12.74 F cm3) with superior high-rate performance.[424] Graphene/Co(OH)2 composite
showed significantly higher SC (972.5 F g1) than that of pure
Co(OH)2 (726.1 F g1).[425] So far, Co(OH)2 and its derived composite exhibit high SC in previous reports, however, small mass
loading of active materials and low potential ranges would
greatly limit their practical application in supercapacitors.
NiO/Ni(OH)2: So far, various NiO nanostructures with different morphologies such as nanowires, nanobelts, porous
film, nanoroses, nanorods, nanosheets, and nano/microspheres have been exploited as an alternative candidate material for supercapacitors.[325,426429] NiO nanobelts obtained by a
hydrothermal method manifested SC of 600 F g1 and 95%
SC retention ration after 2000 cycles.[325] NiO nanorod arrays
on Ni foam exhibited an ultrahigh SC of 2018 F g1, high power
density, and good cycling stability due to its high crystallinity,
aligned array structure, and strong bonding of the nanorods to
metallic substrate.[427] Flowerlike NiO hollow nanospheres prepared by microwave-assisted process showed high SC of 585 F
g1 and excellent cycling stability.[429] Despite these promising
progresses, the reported SC of NiO is still lower than its theoretical value and far from its practical application, which can
be ascribed to its poor cycle performance and low conductivity.
To address these challenges, incorporating NiO with CoOx or
conductive carbonaceous materials to form composites seems
to be an effective method.[430] NiO/Ni nanocomposite showed
a remarkably high SC of 900 F g1 and high energy density
(60 Wh kg1) as well as power density (10 kW kg1) due to the
highly activated NiO surface layer and the conductive network
of metal cores.[431] Symmetrical supercapacitors assembled with
sandwiched graphene/NiO hybrid material yielded high SC
of 220 F g1 with almost no deterioration.[268] In such a structure, graphene is tightly fix isolated NiO nanoparticles, which
restricts the restacking of graphene as spacers, leaving ion
transport channels. In another work, NiO decorated on 3D graphene had high SC of 816 F g1 and a good rate capability.[432]
CNT/NiO composite improved the utilization of electroactive
material and delivered capacitance of 384 F g1.[433]
As one of the most promising candidates for RuO2,
Ni(OH)2 has attracted an increasing scientific and technological interest because of its well-defined electrochemical
redox activity, intrinsic high SC (2082 F g1), and relatively low
cost.[38,40,270,434,435] Uniform Ni(OH)2 hierarchical nanostructure assembled from ultrathin nanoflakes exhibited high SC of
1715 F g1 with high rate and good cycling stability.[434] Ni(OH)2
was also reported to be electrodeposited directly on Ni foam at
different temperatures.[436] It was found that the electrodeposition temperature had significant influence on the crystalline
Figure 30. a) SEM image of Ni(OH)2/graphene composite. b) SC of

Ni(OH)2/graphene composite at various discharge current densities.
Reproduced with permission.[270] Copyright 2010, American Chemical
Society.
structure, morphology, SSA, and electrochemical performances.

The maximum SC up to 3357 F g1 was achieved in KOH
aqueous electrolyte. However, the poor electrical conductivity
and the large volume change occurring during the charge/discharge process significantly restrict its practical application in
supercapacitors. Recently, considerable effort has been devoted
to overcoming this serious issue, such as adding conductive
carbon materials, synthesis of nanoscale materials, and combining CoO.[38,40,270,435,437] CoO@Ni(OH)2 displayed high SC of
1340.9 F g1 and 11.5 F cm2, much higher than those of pure
CoO and Ni(OH)2.[38] Recently, Dai and co-workers reported
that single-crystalline Ni(OH)2 hexagonal nanoplates directly
grown on lightly oxidized, graphene sheets yielded high SC of
1335 and 953 F g1 at 2.8 and 45.7 A g1, respectively, with
excellent cycling ability (Figure 30).[270] 3D nanostructures consisting of Ni(OH)2 nanoparticles, CNTs, and CRG displayed SC
up to 1235 F g1.[435] In this structure, CNTs with embedded
Ni(OH)2 nanoparticles acted as pillars for CRG. Therefore, the
composite possessed fast ion and electron transfer, easy access
of pseudoactive species, efficient utilization, and excellent
reversibility. Unfortunately, the composite exhibited a significant SC loss (20%) after only 500 cycles. A composite of low
defect density CNTs doped Ni(OH)2 nanaosheets showed high
SC of 1302.5 F g1, much higher than those of its individual
components.[437] More recently, Huang et al. demonstrated
the fabrication of hierarchical Ni(OH)2 composite with mixedvalent using a facile one-step anodization method.[438] Such a
3D nanoflake structure provided large electrochemically active
surface area and interconnecting nanoscale pore channels for
ion transport. As a result, the composite was demonstrated
to exhibit significantly improved capacitance, 70 times higher
than the reported NiO-TiO2 nanotube array electrode with similar thickness, as well as only a 24% capacitance loss when the
scan rate was increased by 50 times.
Similar to cobalt-based material, although NiO and Ni(OH)2
have high theoretical SC and low cost, their electrochemical
potential windows are relatively low. Thus, it is still a serious
challenge to increase their potential window to satisfy the
requirement in practical commercial applications.
FeOx: Iron oxides (Fe2O3 and Fe3O4) have some advantages
such as low cost, natural abundance, low toxicity, high electrical
conductivity (2 104 S m1 for Fe3O4) and environmental
benignity. However, there are few reports on iron oxides as
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electrode materials for supercapacitor due to their low rate performance arising from kinetic limitations and poor cycling stability originated from large volume expansion occurring during
cycling. Due to low rate performance of iron oxides, their electrochemical performances are generally unsatisfied and need
to be enhanced. To circumvent this issue, constructing nanosacled structure or adding conductive phase such as conducting
polymer and carbon materials seems to be effective approaches.
Highly ordered -Fe2O3 nanotube arrays exhibited high SC of
138 F g1 and remarkable rate capability due to unique nanostructure providing high SSA, fast transport pathways, and
robust structure.[439] However, the electrode had poor cycling
stability with 10% decrease after 500 cycles. Hydrothermal synthesized Fe2O3 was reported to possess SC of 340.5 F g1 and
the electrochemical performance was strongly dependent on its
crystal grain size.[440] A graphene/Fe2O3 nanotube composite
showed SC of 215 F g1, seven times that of pure Fe2O3.[267] Graphene/Fe2O3/PANI ternary composite exhibited maximum SC
of 638 F g1 with an energy density of 107 Wh kg1 at a power
density of 351 W kg1 in KOH solution and displayed only a
negligible decay of 8% after 5000 cycles.[441] The extraordianry
electrochemical performance was believed to arise from the
well-designed structural advantages of the ternary composite
and the good combination as well as the synergistic effects
among the three components. CNT/Fe3O4 composite yielded
SC of 165 F g1 and 85% of the SC remained after 1000
cycles.[442] PPy treated Fe3O4 nanowire electrode composed
of randomly oriented interpenetrating networks exhibited
much higher SC (190 F g1) than that of pristine Fe3O4 electrode (106 F g1).[443] More recently, 2D sandwich-like Fe3O4@
graphene nanocomposites were fabricated based on the direct
growth of FeOOH nanorods on graphene sheets and the subsequent electrochemical transformation of FeOOH to Fe3O4 and
delivered high energy density (85 Wh kg1), excellent rate capability, and good cycle life due to the synergistic effect between
Fe3O4 and graphene.[269] Recently, an external magnetic field
was found to have a great effect on the capacitive performance
of graphene/Fe2O3 composite,[444] which exhibits significant
capacitance enhancement (98.2%154.6%) compared to the
results obtained in the normal conditions owing to the magnetic field playing an important role in restricting interfacial
relaxation process. However, the electrochemical performances
of iron oxides are still not fully up to expectations. Therefore,
iron oxides would be promising electrode materials in supercapacitor applications as long as low electrical conductivity and
poor cycling stability can be effectively solved.
PANI, PPy and PTh in both aqueous and non-aqueous electrolytes, respectively, which is extremely far from the expectation
values and may not meet the practical demands. Additionally, another obstacle inhibit the conducting polymers from
becoming commercially feasible is that they usually suffer
from a poor cyclability due to structural degradation of electrode caused by swelling and shrinking of conducting polymers
during the intercalating/deintercalating process. As a result,
the electrochemical performance is significantly compromised. Therefore, rational structure design is highly desirable
to obtain a stable conducting polymer electrode. Incorporating
conducting polymers with porous rigid backbones seems to be
an effective approach. It has been demonstrated that the electrochemical performance of conducting polymers could be
remarkably enhanced when hybridized with various materials
such as carbon, metal, and metal oxide.[407,445,446]
Carbon/Conducting Polymer Composites: As a 2D monolayer
carbon material with excellent conductivity, high flexibility,
and mechanical stiffness as well as large SSA, graphene has
received considerable attention as a support for various conducting polymers and has been the focus of intense research
for high-performance supercapcitors.[273,447] Yan et al. synthesized graphene/PANI composite using in situ polymerization
(Figure 31a),[273] which exhibited a maximum SC of 1046 F g1
compared to 115 F g1 for pure PANI as well as an energy density of 39 Wh kg1 at a power density of 70 kW kg1. The greatly
enhanced SC is attributed to the synergistic effect between graphene and PANI. PANI nanoparticles on graphene sheets can
not only effectively prevent the agglomeration of sheets, but
also significantly reduce the diffusion and migration length of
electrolyte ions during charge/discharge process. However, the
cycling stability of such composite was rather poor. In order to
overcome this serious problem, the incorporation of 1% CNTs
into the graphene/PANI composite could give rise to remarkably enhanced cycle stability with 94% retention after 1000
3.2.3. Conducting Polymers

As mentioned earlier, conducting polymers are another attractive pseudocapacitive material for application in supercapacitors because of their low cost, environmental friendliness,
high conductivity, and high SC. The pseudocapacitance of
conducting polymers generally stems from the reversible oxidation and reduction of the -conjugated double bonds in polymer networks. The most often studied conducting polymers
in supercapacitor applications are PANI, PPy, PTh, and their
corresponding derivatives. Due to the relative poor conductivity,
SC of 150190, 80100, and 78117 F g1 can be obtained for
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Figure 31. SEM images of a) graphene/PANI, b) GO/PANI, and c) CNT/

PANI composites. d) TEM image of a mesoporous carbon/PANI composite. Reproduced with permission from ref. [273] (a); ref. [450] (b);
ref. [451] (c); and ref. [452] (d). Copyright 2010, Elsevier (a); copyright
2010, American Chemical Society (b); copyright 2012, The Royal Society
of Chemistry (c); and copyright 2006, Wiley VCH (d).
www.advenergymat.de
the external surface of hollow carbon sphere through chemical

oxidation polymerization.[456] The composite displayed the SC
of 525 F g1 in aqueous electrolyte, which was almost twice
that of hollow carbon sphere. A maximum energy density of
17.2 Wh kg1 was achieved for the composite electrode, however, the energy density of the composite electrode with higher
PANI contents declined quickly as the power density increased.
Free standing carbon nanofiber papers were demonstrated to
be an excellent current collector and a high SSA support for
polymers. Recently, flexible carbon nanofiber/PANI composite paper maintaining the pristine flexibility of the carbon
nanofiber paper showed remarkably enhanced SC of 638 F g1
compared with carbon paper (317 F g1), making it attractive
for high-performance flexible capacitors.[457] However, its rate
performance (32.0%) was still relatively poor.
Metal/Metal Oxide/Conducting Polymer Composites: Due
to their excellent conductivity, metals are used as skeletons
to deposit conducting polymers and show enhanced electrochemical performances as electrode materials for supercapcitors.[446,458] For instance, 3D bicontinuous nanoporous Au/
PANI composite films were fabricated through electrochemical polymerization of PANI shell onto nanoporous Au skeletons.[446] The composite showed ultrahigh volumetric capacitance (1500 F cm3) and energy density (0.078 Wh cm3),
which were seven and four orders of magnitude higher than
those of electrolytic capacitors with the same power density up
to 190 W cm3, respectively. The outstanding electrochemical
perforamces could be attributed to the unique bicontinuous
structure facilitating the fast ion diffusion and electron transfer
and accordingly ensuring the sufficient redox reaction of PANI
during the charge/discharge processes.
To improve the faradic reaction activity of transition metal
oxides (MnO2, TiO2 and V2O5), it is feasible to incorporate them
with conducting polymers for enhanced performance.[329,407]
PANI/MnO2 coaxial nanofibers with hierarchical structure
exhibited a high SC of 383 F g1 with estimated energy density of 53.2 Wh kg1 at a power density of 250 W kg1.[407] Such
intriguing electrochemical performance is attributed to the
unique core-shell structure and their synergistic effect between
the PANI core and MnO2 shell. However, the rate performance
(35.1%) and cyclability (75.5% retention after 2000 cycles) are
still far from satisfactory. In another example, PANI nanowire/
TiO2 nanotube array was synthesized through electropolymerizing aniline onto an anodized TiO2 nanotube array,[459] and the
maximum SC of 732 F g1 was obtained with an energy density of 36.6 Wh kg1 and remained 543 F g1 when the current
density increased by 20 times. The outstanding electrochemical
performances are attributed to the unique microstructure of the
electrode with disordered PANI nanowire arrays encapsulated
inside TiO2 nanotubes, providing high SSA, fast diffusion path
for ions, and long-term cycle stability. Unfortunately, the mass
loading of PANI nanowire arrays inside the TiO2 nanotubes
was relative low.
Carbon/Metal Oxide/Conducting Polymer Ternary Composites:
In addition to binary composites, ternary composite that combine the advantages of each component (conducting carbon,
metal oxides, and conducting polymers) have been investigated
intensively to fulfill the supercapacitor application in recent
years. Through taking full advantages of the synergistic effects
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cycles compared to 48% for graphene/PANI composites due

to the existence of highly conductive path as well as enhanced
mechanical strength during the doping/dedoping process.[448]
In another work, graphene/PANI composites synthesized by
electrodeposition showed a high SC of 640 F g1 with a retention ratio of 90% after 1000 charge/discharge cycles.[447] Supercapacitors based on hierarchical graphene/PPy nanosheet
composite prepared through in situ chemical oxidation polymerization delivered high SC of 318.6 F g1 and superior rate
capability as well as cycling stability with 95% retention after
1000 cycles.[449] The large surface areas and short electron
transportation distance were believed to contribute to the high
performance.
Due to the strong van der Waals interaction between neighboring sheets, the agglomeration or restacking of graphene
is usually unavoidable. In order to avoid this drawback, GO
was also employed as supports to grow polymers instead of
graphene.[450,453] Recently, 1D PANI naowires grown on GO
nanosheets possessed a high electrochemical capacitance
(555 F g1) and good cycling stability due to the synergistic
effect of PANI and GO (Figure 31b).[450]
CNT/PANI composite with vertical PANI nanorods grown
on the surface of CNTs prepared by in situ polymerization
exhibited a high SC of 568 F g1 owing to the synergistic effect
between PANI and CNTs (Figure 31c).[451] The capacitance
performance of such a structured electrode material could be
summarized as follows: First, vertical PANI nanorods greatly
increase the SSA of the composite, favoring the ion diffusion from the bulky solution to the surface of the composite.
Second, PANI nanorods with narrow diameters effectively
shorten the charge transport distance, benefiting the penetration of counterions and consequently improving the utilization
of electrode materials. Finally, inner CNTs greatly improve the
conductivity of the electrode, resulting in low power loss and
energy loss. Qu and co-workers reported the super-long CNT
array/PPy composite and investigated the influence of CNT
surface defects on the electrochemical performance of the composite.[454] The physical defects were first introduced into CNT
walls through electrochemical method, allowing the coating of
PPy on both the outer and inner walls of the CNTs. As a result,
the composite presented the highest SC of 587 F g1, which was
ten times higher than that of defect-free counterparts.
In addition to graphene and CNTs, other carbon materials
with high SSA such as carbon nanofibers, carbon monolith,
ACs, mesoporous carbon, and hollow carbon spheres, have
also be utilized as good substrates for conducting polymers
in exploring advanced electrode materials for supercapacitors.[452,455,456] PANI electrochemically deposited on hierarchically porous carbon monolith yielded high SC of 2200 F g1
per weight of PANI at a power density of 0.47 kW kg1 and an
energy density of 300 Wh kg1.[455] However, the SC based on
the composite was just 35 F g1 due to relatively low mass
loading of PANI on carbon monolith. Ordered whiskerlike
PANI grown on mesoporous carbon exhibited SC of 900 F g1
and good rate performance as well as excellent cycling stability
(Figure 31d).[452] Loosely packed nanometer-scale PANI whisker
could create electrochemical accessibility for electrolyte ions
and reduce the transport distance of electrolyte ions, enabling
high utilization of active material. PANI was also deposited on
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REVIEW
from the ternary composite, each component in the composite may play their potential role to a maximum extent. This
strategy may pay an important way for future design of nextgeneration supercapacitors for industrial and consumer applications. Yu et al. developed a conductive wrapping method to
significantly enhance the performance of graphene/MnO2 composite.[323] Through 3D conductive wrapping with PEDOT:PSS,
SC of the electrodes has substantially increased by 45% with
value of 380 F g1. Additionally, the ternary composite also
exhibited excellent cycling performance with >95% capacitance retention after 3000 cycles. Such 3D conductive wrapping
approach can be generalized for designing the next-generation
high-performance energy storage devices. However, the rate
performance of the ternary composite is still unsatisfactory
(70% maintenance from 0.5 to 5 mA cm2) and needs to be
enhanced through optimizing the structure of the composite.
To tackle the poor conductivity of metal oxides applied in
supercapacitors, a ternary nanocomposite film consisting of
MnO2, CNTs, and PEDOT-PSS was designed by Liu and coworkers.[412] Each component in the ternary composite performed a unique and crucial function to yield optimal electrochemical performance. Maximum SC of 427 F g1 was obtained
for the ternary composite with excellent rate. The electrode
showed good cycling stability, retaining over 99% of its initial
SC after 1000 cycles. In such ternary composite, CNTs not only
offered high surface for the deposition of hierarchical MnO2
porous nanospheres but also enhanced the electrical conductivity and the mechanical stability of the composite, resulting
in excellent cyclability. PEDOT-PSS acted as both an effective
dispersant for CNTs/MnO2 and a binder to improve the contact of adjacent CNTs/MnO2 nanoparticles and adhesion of the
composite to the substrate. Highly porous MnO2 nanospheres
provided numerous active sites for contributing large pseudocapacitance. All the above factors in turn contributed the excellent
electrochemical performances for the ternary composite.
To date, although considerable achievements have been made
in synthesize various conducting polymers with nanostructure
and binary nanostructured composites over the past several
years, some issues still need to be addressed, such as complicated
procedures, low loading of active materials, moderate SC and
rate capability as well as poor cycling stability. Therefore, much
effort still need to be devoted to large scale synthesis of novel, low
cost, and environmentally benign multivariate composite and
precisely optimizing the procedure to achieve optimum electrochemical performances for the applications in supercapacitors.
4. Electrolytes
With regard to a supercapacitor, performance is not only
dependent upon the electrode materials, but also heavily
influenced by the electrolytes used. According to Equation (3)
and (4), both energy and power densities are proportional to
the square of operating voltage of the cell, which is determined
by the decomposition voltage of electrolytes. Ideal electrolytes
should fulfil the following requirements: i.e., wide voltage
window, excellent electrochemical stability, high conductivity,
high ionic concentration, small solvated ionic radius, low viscosity, environmental friendliness, low cost, and easy availability
with high purity. Generally, the electrolytes used in supercapacitors can be classified into three types: 1) aqueous electrolytes, 2)
organic electrolytes, and 3) ILs. Each type of electrolyte has its
own merits and demerits.
4.1. Aqueous Electrolytes

Aqueous electrolytes own some advantages such as low cost,
nonflammability, low viscosity, and excellent safety. Compared
with organic electrolytes, aqueous electrolytes have smaller
solvated ions, higher ionic concentration, and higher ionic conductivity. Therefore, supercapacitors commonly provide much
higher SC and power densities in aqueous electrolytes than
those in organic electrolytes. Moreover, aqueous electrolytes can
be easily produced on a large scale and used without the need
of particular conditions while hygroscopic organic ones usually
need strict conditions and complicated processes to avoid the
introduction of moisture.[3] Generally, the selection criteria are
the sizes and radii of hydrated both cations and anions as well
as the ionic conductivity (Table 3). The most commonly used
aqueous electrolytes are KOH, H2SO4, and Na2SO4 for alkaline,
acidic and neutral solutions, respectively. However, the disadvantage of aqueous electrolytes is their voltage window as low
as 1.0 V due to the thermodynamic decomposition of water at
1.229 V and low overpotential for hydrogen evolution. In order
to effectively address this problem, considerable effort has been
made to improve the maximum voltage window of aqueous
solution. Fortunately, fabrication of carbon symmetric supercapacitors in neutral solutions appears to be effective.[87,460,461] As
a result, the maximum voltage window could be successfully
extended to 1.62.2 V.[87,460,461] For instance, an AC symmetric
supercapacitor exhibited SC up to 140 F g1 and could be
Table 3. The radii of hydrated ions and ionic conductivity values.

Ions
Hydrated ion radii

[]
Ionic conductivity
[S cm2 mol1]
Ions
Hydrated ion radii

[]
Ionic conductivity
[S cm2 mol1]
H+
2.82
349.65
OH
3.00
198.00
3.82
38.66
Cl
3.32
76.31
Na+
3.58
50.08
ClO4
3.38
67.30
K+
3.31
73.48
NO3
3.35
71.42
NH4+
3.31
73.50
CO32
3.94
138.60
Mg2+
4.28
106.00
SO42
3.79
160.00
Ca2+
4.12
118.94
Li
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4.2. Organic Electrolytes
Figure 32. a) CV data at 10 mV s1 with gradual 100 mV voltage shift and

b) cyclability (1 A g1) at voltage range of 2.2 V. Reproduced with permission.[461] Copyright 2012, The Royal Society of Chemistry.
charged/discharged over 15 000 cycles without any significant

SC fade with operating voltage of 2.2 V in 1 mol L1 Li2SO4,
making it an interesting alternative for organic electrolytes
(Figure 32).[461]
The maximum cell voltage is essentially limited by the positive electrode. When the maximum potential of the positive
electrode is too high, it will lead to irreversible electro-oxidation
on the active sites of the carbon electrode. It could be pushed
to slightly lower values through controlled chemical oxidation
of carbon with hydrogen peroxide, allowing the maximum
voltage to be slightly increased with an excellent stability.[460] In
addition, the internal resistance can also be decreased in concentrated electrolytes, resulting in large power delivery. However, the highly corrosive electrolytes (strong acid and basic)
will increase the fabrication costs and device weights owing
to using corrosion-resistant current collectors (such as Au, Pt,
Ti, graphite sheets, and conductive carbon paper). Moreover,
Due to the low voltage window of aqueous solutions, the

requirements of high voltage and energy density have forced
us to turn our attention from aqueous electrolytes to organic
ones. Compared with aqueous electrolytes, organic electrolytes
can provide a voltage window as high as 2.53.0 V, giving rise to
energy density 69 times that of the aqueous electrolyte. Generally, the operating voltage is set to 2.5 V to inhibit the electrolyte
from oxidation due to over-charging. More recently, Cheng and
co-workers demonstrated that the electrode potential window
(EPD) of carbon materials was improved to 4.3 V in organic
solution through tuning the electrode potential by controlled
electrochemical charge injection (Figure 33).[462] Benefiting
from the simultaneous achievement of the maximum working
voltage and SC, the energy density of the supercapacitor has
been increased approximately tenfold to a level close to that
of LIBs without loss in power delivery or cyclic stability. This
strategy could be applicable to supercapacitors based on other
aqueous or non-aqueous electrolytes.
Organic electrolytes are typically prepared through dissolving
organic salts such as Et4NBF4, (C2H5)4PBF4 and TEABF4 in
organic solvents to provide mobile ions participating in charge
storage. Today, acetonitrile and PC are the state-of-the-art solvents used in organic supercapacitors.[5] Although the former
is capable of dissolving various organic
salts, the latter is becoming more and more
popular due to the higher flash point, lower
toxicity, wider electrochemical window, and a
wider range of using temperature compared
with the former. However, there are also
some drawbacks for organic electrolytes in
terms of high cost, safety concerns due to the
flammability and toxicity, low conductivity,
and large solvated ion sizes as well as high
viscosity resulting in low SC, high internal
resistance, and low power delivery. Additionally, the organic electrolytes are hygroscopic
and sensitive to moisture, thus the fabrication of supercapacitors must be handled in
an atmosphere free of water and oxygen to
ensure the high voltage and excellent stability
of the electrolytes.
4.3. Ionic Liquids

Figure 33. Charge/discharge profiles (at 0.35 A g1) of a) a conventional symmetric graphene
supercapacitor and b) a graphene supercapacitor with optimized EPW by shifting E0V down to
1.16 V vs. Li/Li+. c) Charge/discharge curves of the graphene supercapacitor with optimized
EPW at different current densities (1 C = 175 mA g1). d) Ragone plot of the carbon supercapacitors with and without optimized EPW (based on the total mass of the active material).
ILs are known as room temperature molten

salts with melting temperatures at or below
room temperature and composed entirely
of highly asymmetric combination of anion
and cation.[463] ILs have attracted considerable interest as promising candidates for
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the concentrate electrolytes will give rise to high self-discharge

rate. Notably, aqueous electrolytes should be deaerated before
the electrochemical measurements to get rid of the dissolved
oxygen.
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REVIEW
supercapacitor electrolytes due to their unique properties

including low vapor pressure, high thermal and chemical stability, low flammability, wide electrochemical voltage window,
and higher conductivity compared to organic electrolyte.
Through elaborate design of both the anion and cation, ILs
with high voltages up to 4 V can be synthesized. A potential
window of 4.2 V has been reported in ILs meaning a sixteenfold increase in energy density compared with aqueous electrolytes.[464] 3D aperiodic HPGC exhibited high energy density of
70 Wh kg1 in ILs, seven times that of the value measured in
aqueous electrolyte.[180] The commonly used ILs for the applications in supercapacitor are imidazolium, pyrrolidinium as
well as asymmetric, aliphatic quaternary ammonium salts with
anions such as tetrafluoroborate, trifluoromethanesulfonate,
bis(trifluoromethanesulfonyl)imide, bis(fluorosulfonyl)imide,
or hexafluorophosphate.[3] However, ILs have some disadvantages such as relatively high cost, high viscosities, and low ionic
conductivity at room temperature.[464] The ionic conductivity
of ILs at room temperature is just several mS cm1, thus they
are commonly employed at higher temperatures, still failing to
meet the requirements for supercapacitors mainly used in the
temperature ranges of 30 to 60 C in practical applications.
Similar to organic electrolytes, ILs are also hygroscopic and
must be handled in an inert atmosphere. Therefore, the design
of ILs with a wide potential range, high conductivity in a wide
temperature range and low cost is still challenging, and will be
of great significance in applying in high performance safe and
green energy storage devices.
4.4. Redox-Active Electrolytes

Recently, redox-active electrolytes have attracted more and more
attention due to the active components, which can contribute
additional pseudocapacitance to the overall capacitance of
supercapacitors.[465467] The commonly used electrochemically
active compounds are hydroquinone, m-phenylenediamine,
KI, lignosulfonates, etc.[465467] A pioneering work reported
carbon electrode in KI electrolyte showing a maximum SC of
1840 F g1 due to the dual roles of iodide ions, i.e., electrolyte
with good ionic conductivity as well as a source of pseudocapacitive effects based on the following reactions:[465]
3I I
3 + 2e
(13)
2I I2 + 2e
(14)
2I
3 3I2 + 2e
(15)
Roldn and co-workers added an electrochemically active

compound (hydroquinone) to four different types of carbonbased supercapacitors.[466] The addition of hydroquinone to the
supporting electrolyte gave rise to a great increase in the capacitance values for all the carbon materials tested (Figure 34a,b).
The maximum SC of 901 F g1 was obtained with an energy
density of 31.3 Wh kg1, which is much higher than those
previously reported carbon-based capacitors. The increase in
capacitance was attributed to the additional pseudocapacitive
contribution from the faradaic reactions of the hydroquinone/
Figure 34. Variation of SC with current density in a) H2SO4 and b) hydroquinone/H2SO4 (1 V). c) Representation of the processes occurring on the
carbon surface: double-layer formation and redox reaction. d) Variation of the SC with the number of cycles for AC-KOH in HQ solution (4.42 mA cm2).
1300816 (30 of 43)
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NiWO4
CuO
Fe2O3
PANI
MoO2
0.5
WO3-x
V2O5
TiO2
Co3O4
MoO3
MnO2
1.0
LiMn2O4
SnO2
RuO2
1.5
Co(OH)2
NiO or Ni(OH)2
Although supercapacitors possess higher power density than

batteries due to the fast charge/discharge processes, they usually suffer from a low energy density (typically 10 Wh kg1)
than betteries.[5] In order to effectively overcome this problem,
ASCs (or hybrid supercapacitors) have aroused more and more
attention and gradually become the hot spot of intense research
over the past years.[11,1315,331] An ASC is fabricated by combining a faradic electrode (as the energy source) and a capacitive
electrode (as the power source) in a cell. The ASC electrodes
operate reversibly in different potential ranges with different
electrochemical mechanisms (Figure 35), thus increasing the
operation voltage and leading to the improvement in energy
density while maintaining a high power density. Therefore, the
key issue for achieving high energy density and power densities in ASCs lies in designing and developing appropriate electrode materials. Currently, two different types of ASCs have
emerged, i.e., pseudocapacitive materials with a capacitive
carbon electrode and lithium-insertion electrodes with a capacitive carbon electrode. One of the most important technological
requirements for assembling ASCs is to optimize the mass
0.0
In aqueous electrolyte
AC
Fe2O3
FeOx
V2O5
ZnO@MoO3
MoO3
-1.5
Fe3O4
-1.0
Bi2O3
In2O3
-0.5
VN
Because supercapacitors are energy storage devices with high

power densities, their internal resistance must be kept low
according to Equation (3). Particular attention must be paid to
the contact resistance between the active material and the current collector since the current collector is the main physical
link between the electrode and the supercapacitor external
junction in the present electrode technology.[5] To realize low
contact resistance, one of the most effective approaches is to
deposit the active material on a metallic current collector owing
to its very low ESR. Generally, decohesion of active materials
from the current collector is one of the predominant reasons
for the increase of ESR during long term cycling tests. In order
to improve mechanical or chemical adhesion of active materials on the current collector, some measures have been proven
effective, such as coating a slurry on the current collector
using aqueous or organic solvents and laminating active materials directly on the current collector without any binder. The
former is the most cost-efficient and widely used process, but
the latter is not efficient enough for thick electrodes to achieve
low ESR.[468] The choice of current collector should satisfy the
following requirements: excellent electrochemical/chemical stability versus electrolyte, low cost, commercial availability, and
high processability.
As for the supercapacitors designed for organic electrolytes, an aluminum foil or grid is the most widely used current collector due to its low price and density, as well as high
electrochemical stability versus standard electrolytes.[468] To
increase the mechanical adhesion between the active material
and current collector, surface treatments have already been
demonstrated to decrease the interface resistance and improve
electrochemical stability at high potentials and interface conductivity, such as electrochemical corrosion, placing conductive
underlayer (several hundreds of nanometersfew micrometers)
between current collector and the active materials layer, and the
use of novel binders (e.,g. acetamide-based binder).
With regard to the supercapacitor working in aqueous electrolytes, the electrolytes are generally based on strong acids
6. ASCs
Potential (V vs. SCE)
5. Current Collectors
(e.g., H2SO4) or strong bases (e.g., KOH),[77,469] in which it is

improper to use an aluminum current collector. In this case,
corrosion-resistant current collectors are usually required
and the frequently used current collectors are Au, Pt, Ti, and
stainless steel.[154,303,387,396] However, such collectors are more
expensive and it is hard to decrease the interface ESR because
they are not easily etched. It is possible to decrease the ESR
by mechanically increasing the roughness of a plain foil with
a specific mill roll. In addition, graphite sheets and conductive carbon paper are widely used in practical application to
reduce ESR due to their excellent conductivity, low density, and
low cost as well as outstanding electrochemical/chemical stability.[173] However, such collectors are mechanically fragile and
can not been freely bent to prepare flexible supercapacitors.
Figure 35. The working potential windows of various electrode materials

in aqueous electrolyte.
(31 of 43) 1300816
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quinone system (Figure 34c). However, further research is necessary to optimize the performance of the system due to the
poor rate capability and cyclability with a decrease of 65% in SC
after 4000 cycles (Figure 34d).
Despite the large pseudocapacitance contributed by the redox
reaction of electrochemically active components, these redoxactive electrolytes can also compromise the rate performance
and cycling stability of supercapacitors due to their intrinsic
poor electrochemical stability. In addition, some electrolyte
systems provide high SC only at the positive electrode, which
cannot be fully exploited because of low SC at the negative one.
On the other hand, some electrolyte systems only contribute
high electrochemical activity in acidic solution, thus significantly preventing the commercially practical application due to
the high cost of corrosion-resistant current collector. Therefore,
numerous research effort still should be focused on scalable
synthesis of fairly stable and highly effective redox mediators
with low cost for negative electrodes or alkaline solutions.
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REVIEW
ratio between the positive and negative electrodes, which can be

calculated through the following equation according to charge
balance between positive and negative electrodes:
m+
C E
=
m
C+ E +
(16)
where m, C, and E are the electrode mass, SC, and the potential range in the charge/discharge process for both electrodes,
respectively.
6.1. Conventional ASCs
In this type of ASC, high SSA carbon materials are generally
employed as the capacitive electrode, whereas the metal oxides
(MnO2, Ni(OH)2, Fe3O4, and RuO2) or conducting polymers
(PANI, PPy) are used as the pseudocapacitive electrode. Nowadays, considerable research effort has been directed at developing novel electrode materials with outstanding performances
and maximizing the operation voltage of the ASCs in aqueous
electrolyte to take full advantage of the different potential windows of the two electrodes. The cell voltage for the ASCs could
be extended to 2.2 V without inducing the decomposition of
water.
Among various transition metal oxides, MnO2 is one of the
most appealing cathode materials. Thus, carbon//MnO2 ASCs
have been widely investigated because of the low cost and low
toxicity. An ASC based on MnO2 and AC could be cycled reversibly between 0 and 1.8 V with an energy density of 28.4 Wh kg1
at 150 W kg1 and maintained 17 Wh kg1 at 2 W kg1.[470] In
addition, that ASC showed excellent cycling stability with less
than 6% loss after 23 000 cycles. Tomko et al. investigated the
effect of electrolytes on the electrochemical performance of an
AC//MnO2 ASC.[471] They found that the nature of the cation
strongly influenced the charge storage capacity of the electrode,
giving rise to the maximum SC of 45 F g1 in MgCl2 solution.
However, an energy density of 22 Wh kg1 and power density
of 11 kW kg1 were achieved in 2 mol L1 CaCl2 solution due to
the large operating voltage. An AC//MnO2 ASC has been cycled
over 10 000 cycles at a constant power density of 1.2 kW kg1
with a voltage of 2.2 V in K2SO4 solution.[472] However, a constant fade in the energy density was observed upon cycling and
only 55% of the initial energy density was retained after 10 000
cycles due to the gas evolution at the electrodes and the corrosion of current collectors during cycling. When the operating
voltage was decreased to 1.5 V, the ASC could be cycled over
more than 23 000 cycles with 76% retention of the initial energy
density. The following up study of the same group reported
long-term electrochemical behavior of the AC//MnO2 ASC
cycled in K2SO4 solution.[473] More than 195 000 cycles were
achieved with maximum cell voltage (2 V), remarkable capacitance retention (87.5% retention), and good resistance stability
as a result of removing dissolved oxygen from the electrolyte,
which limited the corrosion of current collectors. Specific
energy and specific power of 10 Wh kg1 and 16 kW kg1 was
obtained after 195 000 cycles. The electrochemical performance
of AC//MnO2 ASC at low temperature typically below 0 C was
also studied in aqueous solution.[474] Such ASC could be operated below 0 C with less than 5% fade in SC in concentration
1300816 (32 of 43)
LiNO3 solution and showed excellent cycling stability for more

than 15 000 cycles. In order to achieve even higher operating
voltage, an non-aqueous activated mesocarbon microbead//
MnO2 ASC was also fabricated with 1 mol L1 Et4NBF4 in acetonitrile as an electrolyte. Such an ASC displayed high SC of
228 F g1 in a wide voltage range (03.0 V), corresponding to an
energy density of 128 Wh kg1.[475]
More recently, CNTs and graphene were introduced in order
to improve the conductivity of MnO2, which brought about some
innovations in fabricating ASCs.[11,13,284] Flexible energy storage
devices have aroused great interest in many emerging wearable
or rolling-up modern gadgets. Thus flexible supercapacitors
are being extensively investigated to meet aesthetic demands
and the requirements of specific environments. A flexible ASC
was fabricated based on SWNT/In2O3 nanowire and SWNT/
MnO2 nanowire.[11] The optimized ASC exhibited a superior
device performance with SC of 184 F g1, energy density of
25.5 Wh kg1 and power density of 50.3 kW kg1 in a 2 V potential window. ASC with high energy density has been assembled
using graphene/MnO2 and activated carbon nanofibers as positive and negative electrodes, respectively, in aqueous Na2SO4
(Figure 36).[13] An optimized ASC could be cycled reversibly in
voltage window of 1.8 V and achieved maximum energy density of 51.1 Wh kg1. Additionally, such ASC exhibited excellent
long cycle life with 97% SC retained after 1000 cycles. In order
to develop energy storage devices with high power and energy
densities, high-performance supercapacitors were assembled
through building a 3D embossed-chemically modified graphene
(e-CMG).[284] An e-CMG//e-CMG/MnO2 showed remarkable cell
performance with energy density of 44 Wh kg1, power density
of 25 kW kg1, and excellent cycle life. The improved performance could be attributed to the effect of the 3D ion and electron
pathways on capacitive behavior and the wide cell voltage of 2 V.
Ni(OH)2 and NiO have also been intensively used to
assemble ASCs with carbon materials or other metal oxides
Figure 36. a) Schematic illustration, b) Ragone plots, and c) cycling performance of the fabricated activated carbon nanofiber//graphene/MnO2
ASC. Reproduced with permission.[13] Copyright 2011, Wiley VCH.
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it is possible to develop high energy density ASCs.[331,478480] An

aqueous ASC consisting of a PANI nanofiber cathode and a
graphene anode with proper complementary potential windows
was demonstrated to show the energy and power densities of
4.86 Wh kg1 and 8.75 kW kg1, respectively.[480] Ghenaatian
et al. constructed an ASC by employing PPy and self-doped
PANI as the anode and cathode, respectively.[479] The maximum
working potential window of this ASC could be extended to
1.3 V. Such ASC showed the maximum energy and power densities of 22.87 Wh kg1 and 45.2 kW kg1, respectively. Longlife cycling was achieved by removing dissolved oxygen and
using a mild pH electrolyte, greatly limiting the redox activity
of the conducting polymers. MoO3-x@WO3-x core shell nanowires grown on carbon fabric was used as an anode to fabricate
all-solid-state ASCs with PANI as a cathode using H3PO4/
poly(vinyl alcohol) as the electrolyte.[478] The ASC exhibited
high areal capacitance of 216 mF cm2, an energy density of
0.0019 Wh cm3, and high rate capability. The great characteristics, such as low toxicity, flexibility, environmental compatibility,
light weight, and low requirements for packing, endowed the
fabricated all-solid-state ASC promising candidates for applications in energy density, flexible electronics, and other consumer
electronics. An ASC fabricated using RGO modified with RuO2
or PANI as the anode and cathode, respectively, exhibited a significantly improved capacitive performance in comparison with
those of the symmetric supercapacitors fabricated with RGO/
RuO2 or RGO/PANI as the electrodes, which was attributed
to the broadened potential window in an aqueous electrolyte,
resulting in an energy density of 26.3 Wh kg1 and a power
density of 49.8 kW kg1.[331]
Some other metal oxides such as MoO3, PbO2 and Fe2O3
were also employed to assembly ASCs with high energy densities in previous reports.[481483] For instance, an asymmetric
supercapacitor using MoO3 nanoplates as an anode material,
AC as cathode material and Li2SO4 aqueous solution as electrolyte could deliver a high energy density of 45 W h kg1 at
450 W kg1 and maintained 29 W h kg1 even at 2 kW kg1.[482]
The AC//PbO2 ASC delivered the SC of 34 F g1 and the maximum energy density of 29 Wh kg1 in methanesulfonic acid
electrolyte.[481] A very high energy density of 50 Wh kg1 at a
power density of 1000 W kg1 over the potential range 02.8 V
was obtained for the CNT/Fe2O3//CNT ASC.[483] The superior
electrochemical performance was attributed to the incorporation of CNTs into Fe2O3 anode, leading to a decrease of internal
resistance and an improvement in both the ion diffusion behaviour and the integrity of the Fe2O3 containing films.
6.2. Li-Ion Capacitors
From the state-of-the-art point of view, LIBs and supercapacitors are currently recognized to be the most promising energy
storage devices and meet many demands for future practical
applications. Unfortunately, neither typical LIBs nor supercapacitors can fully meet the needs of practical applications,
which require high performance energy storage devices with
high energy and power densities, robust cycle life, and excellent rate capability. LIBs can provide higher energy density
than supercapacitors, however, they generally suffer from a low
(33 of 43) 1300816
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because of the low cost and high theoretical capacitance.[14,21,332]

The VN/NiOx ASC showed a sloping voltage profile from 0.5
to 1.45 V with excellent reversity and delivered SC of 139 F g1
and an energy density of 63 Wh kg1.[476] Tang et al. reported
an additive-free CNT/Ni(OH)2 electrode with high SC of
3300 F g1 and areal SC of 16 F cm2.[21] The ASC assembled
with the CNT/Ni(OH)2 and AC electrodes could achieve a high
cell voltage of 1.8 V and an energy density up to 50.6 Wh kg1,
which is over 10 times higher than that of traditional EDLCs. A
high-voltage ASC was fabricated using graphene/Ni(OH)2 and
porous graphene as the positive and negative electrodes, respectively.[14] After optimization, such ASC displayed intriguing performances with SC of 218.4 F g1 and high energy density of
77.8 Wh kg1. After 3000 cycles, the SC only fades by 5.7% of
the initial SC. The fascinating performances could be attributed
to the high SC and the positive synergistic effects of the two
electrodes. Recently, Dais group developed a graphene/RuO2//
graphene/Ni(OH)2 ASC with high energy and power densities
operating in aqueous solution at a voltage of 1.5 V.[332] RuO2
nanoparticles and Ni(OH)2 nanoplates were grown on high
quality graphene sheets to maximize the SC of these materials.
Such ASC showed a high energy density of 48 Wh kg1 at a
power density of 0.23 kW kg1, and a high power density of
21 kW kg1 at an energy density of 14 Wh kg1. The high performance was attributed to the advanced hybrid electrode materials and their unique pairing. The growth of pseudocapacitive
nanomaterials with high theoretical SC (Ni(OH)2 and RuO2)
on highly conducting graphene sheets afforded optimal SC of
these materials, especially in aqueous electrolytes. Pairing of
these two hybrid electrodes expanded the operating voltage of
the ASC to 1.5 V. All the above gave rise to the much higher
energy densities of the ASC.
Among various transition metal oxides, V2O5 possesses the
unique advantages of high energy density and wide potential
window, making it a promising candidate as an anode material
for ASCs.[22,329,477] An ASC was designed and fabricated using a
thick-film CNT/V2O5 nanowire composite anode and commercial AC cathode with an organic electrolyte.[22] The CNTs and
V2O5 nanowires were intimately intertwined into a hierarchically porous structure, enabling effective electrolyte access to
the electrochemically active materials without limiting charge
transport. The excellent conductivity, high SC, and large voltage
window of the CNT/V2O5 nanocomposite endowed the ASC
devices with an energy density of 40 Wh kg1 at a power density
of 210 W kg1. Even at a high power density of 6300 W kg1,
the device still possessed an energy density of nearly 7.0 Wh
kg1. The ASC assembled with mesoporous carbon supported
MnO2 and CNT/V2O5 nanowire by the same group, exhibited an energy density of 16 Wh kg1 at a power density of
75 W kg1.[477] However, the cycling stability was unsatisfied
with 10% fading of the initial SC after 100 cycles. An assembled PPy@V2O5//AC ASC could be cycled reversibly from 0 to
1.8 V in K2SO4 solution and exhibited excellent cycling behavior
with no more than 5% capacitance loss after 10 000 cycles.[329]
Such ASC yielded the energy density up to 42 Wh kg1, i.e.,
almost twice as high as that of the V2O5//AC supercapacitor
(23 Wh kg1).
Because conducting polymers have some advantages such as
excellent conductivity, ease of synthesis, low cost, and high SC,
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REVIEW
power density and poor cycle life. Additionally, the charging

rate of LIBs are unsatisfied since high-rate charging would give
rise to a high underpotential, resulting in undesirable Li plating
and deterioration of the cell performance.[484] By contrast,
supercapacitors can deliver high power in very short time with
excellent long term stability, but low energy density. To meet
the requirements set by considerable applications, it is urgent
to combine the fast charging rate and high power density of
supercapacitors with high energy density of LIBs, resulting in
the emergence of the Li-ion capacitors.
Various Li-based compounds such as LiMn2O4, Li4Ti5O12,
MnFe2O4, and LiTi2(PO4)3 have been widely used as Li-ion
storage electrodes.[485488] Among these materials, LiMn2O4
has some advantages in terms of low cost, natural abundance,
high safety, ease of preparation, and non-toxicity. LiMn2O4//AC
cell delivered an energy density of 35 Wh kg1 with a voltage
window of 0.81.8 V in Li2SO4 aqueous electrolyte.[489] Using
CNT/MnO2//LiMn2O4 in 1 mol L1 LiClO4 can deliver a energy
density as high as 56 Wh kg1 at a power density of 300 W kg1,
thus demonstrating a high energy density.[490] As a pseudocapacitive material with high-power deliver capability, nanocrystalline MnFe2O4//LiMn2O4 and MnFe2O4/carbon black//
LiMn2O4 in aqueous LiNO3 electrolyte had a maximum operating voltage window of 1.3 V, limited by irreversible reaction
of MnFe2O4 toward reducing potential.[485] The specific power
and specific energy increased with negative-to-positive mass
ratio and achieved the maximum values of 10 Wh kg1. Additionally, the device showed good cycling stability and significantly slow self-discharge.
Alternatively, Li4Ti5O12 as an engineering material for ASCs
have its own merits, such as high columbic efficiency, zerostrain insertion providing little volume change during charge/
discharge, little electrolyte decomposition and low cost. AC/
Li4Ti5O12//AC exhibited a high energy density of 32 Wh kg1
at a high power density of 6 kW kg1 in 1 mol L1 LiPF6 solution in a mixture of EC/DEC.[486] Homogeneous carbon-coated
Li4Ti5O12 microspheres were demonstrated to form an aqueous
ASC as a negative electrode combined with an AC electrode.[487]
Such device retained 95% of its initial capacity after 1000
cycles with a maximum volumetric energy and power density
of 57 Wh L1 and 2600 W L1, respectively. In another work,
the N-enriched carbon/Li4Ti5O12//AC ASC exhibited a high
energy density of 91 and 22 Wh kg1 at power densities of 50
and 4000 W kg1, respectively, which are superior to the values
observed for the AC//AC symmetric electrode system.[488]
LiTi2(PO4)3 seems to be a promising material as negative
electrodes due to the appropriate voltage plateau at 2.5 V vs. Li/
Li+, high theoretical specific capacity of 138 mAh g1, low cost
and environmental benignity.[491] Carbon-coated LiTi2(PO4)3//
AC in Li2SO4 aqueous electrolyte showed a sloping voltage
from 0.3 to 1.5 V and delivered a SC of 30 mAh g1, energy
density of 27 Wh kg1, and excellent cycling stability with 85%
retention of the initial energy density after 1000 cycles.[491]
In summary, ASCs are receiving ever increasing interest
due to their high energy and power densities as well as long
cycle-life. Despite notable progress achieved in developing high
performance ASCs over the past years, some serious challenges
still exist and urgently need to be addressed, such as safety
issues, environment compatibility, fabrication cost, and ease of
1300816 (34 of 43)
manipulation and fabrication. Most of all, the electrochemical

performances of the ASCs cannot satisfy the various demands
of future applications. Although Li-ion capacitors and ASCs
with two different carbon electrodes usually exhibit large operating windows, high energy densities, however, they usually
suffer from poor rate capability and limited long term cycling
stability. In addition, they usually use organic electrolytes,
which are expensive, highly viscous, less conductive, flammable, and toxic. On the contrary, aqueous ASCs offer many
attractive features, such as high safety, use of less toxic, and
lower-cost electrolytes, simplified fabrication procedures. Thus,
there is no doubt that aqueous ASCs will be a highly promising candidate for next-generation energy storage devices. To
boost the development of aqueous ASCs, continuous efforts are
undoubtedly required in developing high-performance energy
storage materials and architectures as well as novel electrolytes. Although aqueous ASC technology is still in its infancy
compared to mature LIB technologies, the intriguing features of aqueous ASCs have endowed them plenty of room to
improve their performances to fulfill the ever increasing energy
demands in future applications.
6.3. Carbon//Carbon Supercapacitors with High Operating
Voltage
Recently, high voltages ranging from 1.5 to 4.5 V have been
developed for supercapacitors with high energy density based
on carbon electrodes in aqueous or nonaqueous electrolytes.
In a pioneering work, graphitic carbon was employed as the
positive electrode materials instead of AC in the AC//graphitic
carbon using an organic electrolyte.[492] The weight ratio of AC
to graphitic carbon were found to have great effects on the electrochemical performance of the cell since anions intercalated
into the interlayer spaces deeply during the charge process at
high AC/graphitic carbon ratios. Bguin and co-workers built
a supercapacitor with commercially available graphite and AC
as negative and positive electrodes, respectively.[493] After optimization, the cell could work in a voltage range from 1.5 to
4.5 V. Gravimetric and volumetric energy densities as high as
103.8 Wh kg1 and 111.8 Wh L1 could be obtained in such a
device while keeping a very good cyclability (over 85%) after
10 000 cycles, much higher than that of symmetric devices. In
a follow-up work of the same group, a supercapacitor based
on only AC for both electrodes was developed in an aqueous
electrolyte (Figure 37).[494] By taking advantage of different
redox reactions of oxygenated functionalities occurring in the
positive and negative ranges of potential, the cell was optimized through utilizing different pseudo-faradaic properties
of carbons in order to increase the capacitance and to shift the
potentials of water decomposition and destructive oxidation of
activated carbon to more negative and positive values, respectively. As a result, the device could be reversibly charged/discharged at 1.6 V with excellent cycle life. The power and energy
densities achieved 40 kW kg1 and 30 Wh kg1, which are comparable with the performance of EDLC in organic electrolyte.
Nowadays, even higher working voltages of 1.92.2 V have
been achieved for carbon//carbon supercapacitors through
elaborately controlling the hydrogen electrosportion on negative
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(35 of 43) 1300816
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increasing the operation voltage window,

such as using proper organic electrolytes or
ionic liquids, and assembling asymmetric
supercapacitors to optimize the potential
range for each electrode so as to widen the
overall cell voltage, is regarded as another
promising strategy to improve the energy
density of a supercapacitor. Notably, it is
highly important to understand the relationship between energy density and affecting
parameters for supercapacitors.
Synthesis of high surface area porous carbons with hierarchical and partially graphitic
structures is required in the future. Although
optimizing the pore structure and PSD is
effective to improve power density, it cannot
profoundly increase the energy density. One
can expect to achieve a high energy density
Figure 37. a) Comparison of the CVs of three-electrode cells with the AC Aox and Box. b) CV by designing electrode materials to combine
curves of an optimized cell, c) Ragone plots, and d) cycling stability. Electrolyte: 1 mol L1 fast and highly reversible pseudocapacitance
H2SO4. Reproduced with permission.[494] Copyright 2010, Elsevier.
with electrical double layer capacitance.
However, one of the great challenges in the
design of hybrid materials is strong interface
bonding between inorganic nanomaterials and porous carbon
electrodes and controlled chemical/electrochemical oxidation
materials to enhance charge transport and increase the rate
of carbon materials.[460,461] An operating voltage up to 1.9 V
capability of electrochemical materials. Thus, future research
with excellent stability over 10 000 charge/discharge cycles has
should be directed towards the development of chemical
been demonstrated for supercapacitors assembled with chemibonding between inorganic nanoparticles and partially funccally oxidized carbon in Li2SO4 aqueous electrolyte.[460] Such a
tionalized carbon materials. In particular, oxygen-containing
voltage value is two times higher than the values generally demfunctional groups can improve the surface wettability of the
onstrated with carbon//carbon supercapacitors in conventional
electrode and have strong coupling with inorganic particles,
aqueous media, while avoiding the disadvantages of the corrotheir side effects such as irreversible reactions with electrolyte
sive properties of acidic and basic electrolytes. Such a good perions, decomposition of electrolyte, high self-discharge rate, and
formance can be attributed to the high over-potential related to
enhanced internal resistance of the electrode, should be carethe hydrogen storage mechanism. The carbon electrode could
fully considered. In this respect, doping heteroatoms such as
be stabilized to some extent when the system operated at high
N, O, S, B, and P may be an effective route for functionalizing
voltage due to the deactivation of the active sites of carbon after
carbon materials while maintaining their super electrochemcontrolled chemical oxidation with hydrogen peroxide.
ical performances.
More recently, a supercapacitor assembled with a pre-lithiRecently, a rapid development of nanocarbons, such as CNTs
ated graphite anode and AC cathode tested in 1 mol L1 LiPF6
and graphene, as electrode materials in high-voltage ionic liquid
solution in a mixture of EC/DEC,[495] delivered a maximum
electrolytes offers an opportunity for expanding the cell voltage
energy density of 55 Wh kg1 for cells operating at 3.14.1 V
and has significantly enhanced the energy density of EDLCs. In
and 100 Wh kg1 when the potential was extended to 2.04.1 V.
addition, the design of a new generation of novel asymmetric
However, the cycling stability of the cell was poor since the
supercapacitors is an interesting ongoing research towards
instability of the prelithiated graphite anode during cycling
achieving high energy density in neutral aqueous electrolytes.
leading to the cell capacity fade. In addition, the positive potenFuture directions of asymmetric supercapacitor design should
tial drift of the pre-lithiated graphite was attributed to the selfinclude simultaneously custom tailored material structures,
discharge of the pre-doped Li probably due to the formation of
optimizing the composition of positive and negative electrode
poor SEI film.
materials, and theoretical or computational modeling/simulation. It must be remembered that with the improvements for
energy densities, the principal advantages of supercapacitors
7. Summary and Outlook
such as high rate capability, high power densities, and long
cycle life, must not be sacrificed. Furthermore, the volumetric
In summary, we have described recent advances in supercaenergy and power densities compared to the whole supercapacpacitors with high energy densities. In view of the high perforitor device should be recommended as a more reliable parammance electrode materials, we have specifically discussed the
eter than the gravimetric ones to evaluate the real performances
material nanostructure ensuring high SC, good rate capability,
of next-generation supercapacitors in future applications such
and excellent cycling stability at a large current (or at a high
as electronics, transportation, and others in which space is
scan rate). Moreover, the energy density of supercapacitor is
quite limited.
strongly dependent on the square of operating voltage. Thus,
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REVIEW
Acknowledgements
The authors acknowledge financial support from the National Science
Foundation of China (51077014, 21003028 and 51202043), Fundamental
Research funds for the Central Universities, Program for New Century
Excellent Talents in University (NCET-10-0050), and Excellent Youth
Foundation of Heilongjiang Province of China (JC201210).
Received: July 12, 2013
Revised: August 29, 2013
Published online: December 23, 2013
[1] S. Chu, A. Majumdar, Nature 2012, 488, 294.

[2] A. S. Arico, P. Bruce, B. Scrosati, J. M. Tarascon, W. Van Schalkwijk,
Nat. Mater. 2005, 4, 366.
[3] G. Wang, L. Zhang, J. Zhang, Chem. Soc. Rev. 2012, 41, 797.
[4] D. G. Nocera, Chem. Soc. Rev. 2009, 38, 13.
[5] P. Simon, Y. Gogotsi, Nat. Mater. 2008, 7, 845.
[6] B. Luo, B. Wang, X. L. Li, Y. Y. Jia, M. H. Liang, L. J. Zhi, Adv. Mater.
2012, 24, 3538.
[7] X. Xiao, X. Liu, H. Zhao, D. Chen, F. Liu, J. Xiang, Z. Hu, Y. Li, Adv.
Mater. 2012, 24, 5762.
[8] H.-C. Chien, W.-Y. Cheng, Y.-H. Wang, S.-Y. Lu, Adv. Funct. Mater.
2012, 22, 5038.
[9] Y. Zhai, Y. Dou, D. Zhao, P. F. Fulvio, R. T. Mayes, S. Dai, Adv.
Mater. 2011, 23, 4828.
[10] J. R. Miller, P. Simon, Science 2008, 321, 651.
[11] P. C. Chen, G. Z. Shen, Y. Shi, H. T. Chen, C. W. Zhou, ACS Nano
2010, 4, 4403.
[12] N. Jha, P. Ramesh, E. Bekyarova, M. E. Itkis, R. C. Haddon, Adv.
Energy Mater. 2012, 2, 438.
[13] Z. Fan, J. Yan, T. Wei, L. Zhi, G. Ning, T. Li, F. Wei, Adv. Funct.
Mater. 2011, 21, 2366.
[14] J. Yan, Z. Fan, W. Sun, G. Ning, T. Wei, Q. Zhang, R. Zhang, L. Zhi,
F. Wei, Adv. Funct. Mater. 2012, 22, 2632.
[15] Z.-S. Wu, W. Ren, D.-W. Wang, F. Li, B. Liu, H.-M. Cheng, ACS
Nano 2010, 4, 5835.
[16] J. Ji, L. L. Zhang, H. Ji, Y. Li, X. Zhao, X. Bai, X. Fan, F. Zhang,
R. S. Ruoff, ACS Nano 2013, 7, 6237.
[17] L. L. Zhang, X. S. Zhao, Chem. Soc. Rev. 2009, 28, 2520.
[18] B. E. Conway, Electrochemical supercapacitors: Scientific fundamentals and technological applications, Kluwer Academic/Plenum,
New York 1999.
[19] A. G. Pandolfo, A. F. Hollenkamp, J. Power Sources 2006, 157, 11.
[20] D. Pech, M. Brunet, H. Durou, P. H. Huang, V. Mochalin,
Y. Gogotsi, P. L. Taberna, P. Simon, Nat. Nanotechnol. 2010, 5,
651.
[21] Z. Tang, C.-h. Tang, H. Gong, Adv. Funct. Mater. 2012, 22, 1272.
[22] Z. Chen, V. Augustyn, J. Wen, Y. W. Zhang, M. Q. Shen, B. Dunn,
Y. F. Lu, Adv. Mater. 2011, 23, 791.
[23] A. Izadi-Najafabadi, S. Yasuda, K. Kobashi, T. Yamada,
D. N. Futaba, H. Hatori, M. Yumura, S. Iijima, K. Hata, Adv. Mater.
2010, 22, E235.
[24] S. J. Guo, S. J. Dong, Chem. Soc. Rev. 2011, 40, 2644.
[25] J. Jiang, Y. Li, J. Liu, X. Huang, C. Yuan, X. W. Lou, Adv. Mater.
2012, 24, 5166.
[26] H. Nishihara, T. Kyotani, Adv. Mater. 2012, 24, 4473.
[27] A. L. M. Reddy, S. R. Gowda, M. M. Shaijumon, P. M. Ajayan, Adv.
Mater. 2012, 24, 5045.
[28] N. G. Sahoo, Y. Pan, L. Li, S. H. Chan, Adv. Mater. 2012, 24, 4203.
[29] J. Zhang, C. M. Li, Chem. Soc. Rev. 2012, 41, 7016.
[30] X. Huang, X. Qi, F. Boey, H. Zhang, Chem. Soc. Rev. 2011, 41, 666.
[31] C. Liu, F. Li, L.-P. Ma, H.-M. Cheng, Adv. Mater. 2010, 22, E28.
[32] M. Pumera, Chem. Soc. Rev. 2010, 39, 4146.
1300816 (36 of 43)
[33] Y. Wang, Y. Xia, Adv. Mater. 2013, 25, 5336.

[34] Y. P. Wu, F. Wang, S. Xiao, Y. Hou, C. L. Hu, L. Liu, RSC Adv. 2013,
3, 13059.
[35] Z. Wen, X. Wang, S. Mao, Z. Bo, H. Kim, S. Cui, G. Lu, X. Feng,
J. Chen, Adv. Mater. 2012, 24, 5610.
[36] A. Ghosh, Y. H. Lee, ChemSusChem 2012, 5, 480.
[37] R. Yuge, T. Manako, K. Nakahara, M. Yasui, S. Iwasa, T. Yoshitake,
Carbon 2012, 50, 5569.
[38] C. Guan, X. Li, Z. Wang, X. Cao, C. Soci, H. Zhang, H. J. Fan, Adv.
Mater. 2012, 24, 4186.
[39] L. Dai, D. W. Chang, J.-B. Baek, W. Lu, Small 2012, 8, 1130.
[40] J. Yan, W. Sun, T. Wei, Q. Zhang, Z. Fan, F. Wei, J. Mater. Chem.
2012, 22, 11494.
[41] J. Yan, T. Wei, W. Qiao, B. Shao, Q. Zhao, L. Zhang, Z. Fan, Electrochim. Acta 2010, 55, 6973.
[42] J. Yan, Z. Fan, T. Wei, W. Qian, M. Zhang, F. Wei, Carbon 2010, 48,
3825.
[43] K. Naoi, P. Simon, Interface 2008, 17, 34.
[44] Y. Zhang, H. Feng, X. Wu, L. Wang, A. Zhang, T. Xia, H. Dong,
X. Li, L. Zhang, Int. J. Hydrogen Energy 2009, 34, 4889.
[45] R. Kotz, M. Carlen, Electrochim. Acta 2000, 45, 2483.
[46] L. Bao, X. Li, Adv. Mater. 2012, 24, 3246.
[47] J. Mi, X.-R. Wang, R.-J. Fan, W.-H. Qu, W.-C. Li, Energy Fuels 2012,
26, 5321.
[48] X. He, R. Li, J. Qiu, K. Xie, P. Ling, M. Yu, X. Zhang, M. Zheng,
Carbon 2012, 50, 4911.
[49] X. Y. Chen, Q. Q. Zhou, Electrochim. Acta 2012, 71, 92.
[50] N. Gavrilov, I. A. Pati, M. Vujkovic, J. Travas-Sejdic,
G. Ciric-Marjanovic, S. V. Mentus, Carbon 2012, 50, 3915.
[51] Y. J. Kim, C.-M. Yang, K. C. Park, K. Kaneko, Y. A. Kim, M. Noguchi,
T. Fujino, S. Oyama, M. Endo, ChemSusChem 2012, 5, 535.
[52] L. Wei, M. Sevilla, A. B. Fuertes, R. Mokaya, G. Yushin, Adv. Funct.
Mater. 2012, 22, 827.
[53] Y. Lv, L. Gan, M. Liu, W. Xiong, Z. Xu, D. Zhu, D. S. Wright, J.
Power Sources 2012, 209, 152.
[54] X.-j. He, T. Wang, J.-s. Qiu, X.-y. Zhang, X.-t. Wang, M.-d. Zheng,
Carbon 2012, 50, 344.
[55] H. Zhu, X. L. Wang, F. Yang, X. R. Yang, Adv. Mater. 2011, 23, 2745.
[56] C. Moreno-Castilla, M. B. Dawidziuk, F. Carrasco-Marin,
Z. Zapata-Benabithe, Carbon 2011, 49, 3808.
[57] C. L. Qin, X. Lu, G. P. Yin, Z. Jin, Q. A. Tan, X. D. Bai, Mater. Chem.
Phys. 2011, 126, 453.
[58] C. Moreno-Castilla, M. B. Dawidziuk, F. Carrasco-Marn,
E. Moralln, Carbon 2012, 50, 3324.
[59] X. Y. Wang, L. Liu, L. H. Yi, C. Y. Hu, X. Y. Zhang, W. Yi, Synth. Met.
2011, 161, 1725.
[60] Y. J. Lee, S. Park, J. G. Seo, J. R. Yoon, J. Yj, I. K. Song, Curr. Appl.
Phys. 2011, 11, 631.
[61] Y. J. Lee, J. C. Jung, S. Park, J. G. Seo, S. H. Baeck, J. R. Yoon, J. Yi,
I. K. Song, Curr. Appl. Phys. 2011, 11, 1.
[62] C. Zheng, W. Qian, C. Cui, Q. Zhang, Y. Jin, M. Zhao, P. Tan,
F. Wei, Carbon 2012, 50, 5167.
[63] A. Al-zubaidi, T. Inoue, T. Matsushita, Y. Ishii, T. Hashimoto,
S. Kawasaki, J. Phys. Chem. C 2012, 116, 7681.
[64] T. I. Lee, J. P. Jeagal, J. H. Choi, W. J. Choi, M. J. Lee, J. Y. Oh,
K. B. Kim, H. K. Baik, Y. Xia, J. M. Myoung, Adv. Mater. 2011, 23,
4711.
[65] P. Hiralal, H. Wang, H. E. Unalan, Y. Liu, M. Rouvala, D. Wei,
P. Andrew, G. A. J. Amaratunga, J. Mater. Chem. 2011, 21, 17810.
[66] Y. Yamada, T. Tanaka, K. Machida, S. Suematsu, K. Tamamitsu,
H. Kataura, H. Hatori, Carbon 2012, 50, 1422.
[67] A. Izadi-Najafabadi, T. Yamada, D. N. Futaba, H. Hatori, S. Iijima,
K. Hata, Electrochem. Commun. 2010, 12, 1678.
[68] A. Izadi-Najafabadi, D. N. Futaba, S. Iijima, K. Hata, J. Am. Chem.
Soc. 2010, 132, 18017.
www.advenergymat.de
[102] M. Seredych, M. Koscinski, M. Sliwinska-Bartkowiak, T. J. Bandosz,

J. Power Sources 2012, 220, 243.
[103] F. Stoeckli, T. A. Centeno, Phys. Chem. Chem. Phys. 2012, 14,
11589.
[104] J. S. Huang, B. G. Sumpter, V. Meunier, Chem. Eur. J. 2008, 14,
6614.
[105] C. Largeot, C. Portet, J. Chmiola, P. L. Taberna, Y. Gogotsi,
P. Simon, J. Am. Chem. Soc. 2008, 130, 2730.
[106] J. Chmiola, G. Yushin, Y. Gogotsi, C. Portet, P. Simon, P. L. Taberna,
Science 2006, 313, 1760.
[107] E. Raymundo-Pinero, F. Leroux, F. Beguin, Adv. Mater. 2006, 18,
1877.
[108] E. Raymundo-Pinero, K. Kierzek, J. Machnikowski, F. Beguin,
Carbon 2006, 44, 2498.
[109] J. Chmiola, G. Yushin, R. Dash, Y. Gogotsi, J. Power Sources 2006,
158, 765.
[110] J. Huang, B. G. Sumpter, V. Meunier, Angew. Chem. Int. Ed. 2008,
47, 520.
[111] J. Segalini, E. Iwama, P. L. Taberna, Y. Gogotsi, P. Simon, Electrochem. Commun. 2012, 15, 63.
[112] D. Y. Zhai, B. H. Li, F. Y. Kang, H. D. Du, C. J. Xu, Microporous
Mesoporous Mater. 2010, 130, 224.
[113] S. Roldan, I. Villar, V. Ruiz, C. Blanco, M. Granda, R. Menendez,
R. Santamaria, Energy Fuels 2010, 24, 3422.
[114] B. L. Xing, C. X. Zhang, L. J. Chen, G. X. Huang, Adv. Mater. Res.
2011, 194-196, 2472.
[115] X. J. He, J. W. Lei, Y. J. Geng, X. Y. Zhang, M. B. Wu, M. D. Zheng,
J. Phys. Chem. Solids 2009, 70, 738.
[116] W. F. Zhang, Z. H. Huang, Z. Guo, C. Li, F. Y. Kang, Mater. Lett.
2010, 64, 1868.
[117] J. Wang, M. M. Chen, C. Y. Wang, J. Z. Wang, J. M. Zheng, J. Power
Sources 2011, 196, 550.
[118] J. T. Zhang, L. Y. Gong, K. Sun, J. C. Jiang, X. G. Zhang, J. Solid
State Electr. 2012, 16, 2179.
[119] H. B. Chen, H. B. Wang, L. F. Yang, Y. Xiao, M. T. Zheng, Y. L. Liu,
H. G. Fu, Int. J. Electrochem. Sci. 2012, 7, 4889.
[120] W.-S. Choi, W.-G. Shim, D.-W. Ryu, M.-J. Hwang, H. Moon,
Microporous Mesoporous Mater. 2012, 155, 274.
[121] A. Elmouwahidi, Z. Zapata-Benabithe, F. Carrasco-Marn,
C. Moreno-Castilla, Biores. Technol. 2012, 111, 185.
[122] S. G. Lee, K. H. Park, W. G. Shim, M. S. Balathanigaimani,
H. Moon, J. Ind. Eng. Chem. 2011, 17, 450.
[123] T. E. Rufford, D. Hulicova-Jurcakova, K. Khosla, Z. Zhu, G. Q. Lu,
[124] T. E. Rufford, D. Hulicova-Jurcakova, Z. H. Zhu, G. Q. Lu, Electrochem. Commun. 2008, 10, 1594.
[125] M. S. Balathanigaimani, W. G. Shim, M. J. Lee, C. Kim, J. W. Lee,
H. Moon, Electrochem. Commun. 2008, 10, 868.
[126] J. M. V. Nabais, J. G. Teixeira, I. Almeida, Biores. Technol. 2011, 102, 2781.
[127] X. A. Li, W. Xing, S. P. Zhuo, J. Zhou, F. Li, S. Z. Qiao, G. Q. Lu,
Biores. Technol. 2011, 102, 1118.
[128] W. T. Huang, H. Zhang, Y. Q. Huang, W. K. Wang, S. C. Wei, Carbon
2011, 49, 838.
[129] L. Wei, M. Sevilla, A. B. Fuertes, R. Mokaya, G. Yushin, Adv. Energy
Mater. 2011, 1, 356.
[130] S. Zhao, C.-Y. Wang, M.-M. Chen, J. Wang, Z.-Q. Shi, J. Phys. Chem.
Solids 2009, 70, 1256.
[131] Y. J. Kim, B. J. Lee, H. Suezaki, T. Chino, Y. Abe, T. Yanagiura,
K. C. Park, M. Endo, Carbon 2006, 44, 1592.
[132] B. Xu, Y. F. Chen, G. Wei, G. P. Cao, H. Zhang, Y. S. Yang, Mater.
Chem. Phys. 2010, 124, 504.
[133] F. C. Wu, R. L. Tseng, C. C. Hu, C. C. Wang, J. Power Sources 2005,
144, 302.
[134] W. X. Chen, H. Zhang, Y. Q. Huang, W. K. Wang, J. Mater. Chem.
2010, 20, 4773.
(37 of 43) 1300816
REVIEW
[69] A. Izadi-Najafabadi, T. Yamada, D. N. Futaba, M. Yudasaka,

H. Takagi, H. Hatori, S. Iijima, K. Hata, ACS Nano 2011, 5, 811.
[70] Y. Korenblit, A. Kajdos, W. C. West, M. C. Smart, E. J. Brandon,
A. Kvit, J. Jagiello, G. Yushin, Adv. Funct. Mater. 2012, 22, 1655.
[71] Z. Chen, D. Weng, H. S. Sohn, M. Cai, Y. F. Lu, RSC Adv. 2012, 2, 1755.
[72] H. L. Jiang, B. Liu, Y. Q. Lan, K. Kuratani, T. Akita, H. Shioyama,
F. Q. Zong, Q. Xu, J. Am. Chem. Soc. 2011, 133, 11854.
[73] H. Itai, H. Nishihara, T. Kogure, T. Kyotani, J. Am. Chem. Soc. 2011,
133, 1165.
[74] L. Borchardt, M. Oschatz, M. Lohe, V. Presser, Y. Gogotsi,
S. Kaskel, Carbon 2012, 50, 3987.
[75] H. J. Liu, J. Wang, C. X. Wang, Y. Y. Xia, Adv. Energy Mater. 2011, 1,
1101.
[76] K. Xie, X. T. Qin, X. Z. Wang, Y. N. Wang, H. S. Tao, Q. Wu,
L. J. Yang, Z. Hu, Adv. Mater. 2012, 24, 347.
[77] V. Presser, L. F. Zhang, J. J. Niu, J. McDonough, C. Perez, H. Fong,
Y. Gogotsi, Adv. Energy Mater. 2011, 1, 423.
[78] C.-M. Chen, Q. Zhang, M.-G. Yang, C.-H. Huang, Y.-G. Yang,
M.-Z. Wang, Carbon 2012, 50, 3572.
[79] L. L. Zhang, X. Zhao, M. D. Stoller, Y. Zhu, H. Ji, S. Murali, Y. Wu,
S. Perales, B. Clevenger, R. S. Ruoff, Nano Lett. 2012, 12, 1806.
[80] H. M. Jeong, J. W. Lee, W. H. Shin, Y. J. Choi, H. J. Shin, J. K. Kang,
J. W. Choi, Nano Lett. 2011, 11, 2472.
[81] Y. Zhu, S. Murali, M. D. Stoller, K. J. Ganesh, W. Cai, P. J. Ferreira,
A. Pirkle, R. M. Wallace, K. A. Cychosz, M. Thommes, D. Su,
E. A. Stach, R. S. Ruoff, Science 2011, 332, 1537.
[82] S. Mao, Z. Wen, H. Kim, G. Lu, P. Hurley, J. Chen, ACS Nano 2012,
6, 7505.
[83] Z. Niu, J. Chen, H. H. Hng, J. Ma, X. Chen, Adv. Mater. 2012, 24,
4144.
[84] F. Liu, S. Y. Song, D. F. Xue, H. J. Zhang, Adv. Mater. 2012, 24,
1089.
[85] M. F. El-Kady, V. Strong, S. Dubin, R. B. Kaner, Science 2012, 335,
1326.
[86] M. D. Stoller, S. J. Park, Y. W. Zhu, J. H. An, R. S. Ruoff, Nano Lett.
2008, 8, 3498.
[87] Q. Wang, J. Yan, Y. Wang, G. Ning, Z. Fan, T. Wei, J. Cheng,
M. Zhang, X. Jing, Carbon 2013, 52, 209.
[88] F. Ma, H. Zhao, L. Sun, Q. Li, L. Huo, T. Xia, S. Gao, G. Pang,
Z. Shi, S. Feng, J. Mater. Chem. 2012, 22, 13464.
[89] J. Shu, R. Ma, M. Shui, D. Wang, N. Long, Y. Ren, R. Zhang, J. Yao,
X. Mao, W. Zheng, S. Gao, RSC Adv. 2012, 2, 5806.
[90] M.-P. Liu, C.-H. Li, H.-B. Du, X.-Z. You, Chem. Commun. 2012, 48,
4950.
[91] C. X. Guo, C. M. Li, Energy Environ. Sci. 2011, 4, 4504.
[92] H. Kim, M. E. Fortunato, H. Xu, J. H. Bang, K. S. Suslick, J. Phys.
Chem. C 2011, 115, 20481.
[93] Z. B. Lei, N. Christov, L. L. Zhang, X. S. Zhao, J. Mater. Chem.
2011, 21, 2274.
[94] Z. Lei, N. Christov, X. S. Zhao, Energy Environ. Sci. 2011, 4, 1866.
[95] J. K. McDonough, A. I. Frolov, V. Presser, J. Niu, C. H. Miller,
T. Ubieto, M. V. Fedorov, Y. Gogotsi, Carbon 2012, 50, 3298.
[96] J. P. Selegue, R. Borgohain, Y.-T. Cheng, J. Li, J. Phys. Chem. C
2012, 116, 15068.
[97] J. Breczko, K. Winkler, M. E. Plonska-Brzezinska, A. Villalta-Cerdas,
L. Echegoyen, J. Mater. Chem. 2010, 20, 7761.
[98] Y. Gao, Y. S. Zhou, M. Qian, X. N. He, J. Redepenning,
P. Goodman, H. M. Li, L. Jiang, Y. F. Lu, Carbon 2013, 51, 52.
[99] E. G. Bushueva, P. S. Galkin, A. V. Okotrub, L. G. Bulusheva,
N. N. Gavrilov, V. L. Kuznetsov, S. I. Moiseekov, Phys. Status. Solidi.
B 2008, 245, 2296.
[100] C. Portet, G. Yushin, Y. Gogotsi, Carbon 2007, 45, 2511.
[101] R. Y. Lin, P. L. Taberna, S. Fantini, V. Presser, C. R. Perez,
F. Malbosc, N. L. Rupesinghe, K. B. K. Teo, Y. Gogotsi, P. Simon,
J. Phys. Chem. Lett. 2011, 2, 2396.
www.advenergymat.de
REVIEW
[135] X. L. Li, C. L. Han, X. Y. Chen, C. W. Shi, Microporous Mesoporous
Mater. 2010, 131, 303.
[136] E. Taer, M. Deraman, I. A. Talib, A. A. Umar, M. Oyama,
R. M. Yunus, Curr. Appl. Phys. 2010, 10, 1071.
[137] C. Peng, X.-b. Yan, R.-t. Wang, J.-w. Lang, Y.-j. Ou, Q.-j. Xue, Electrochim. Acta 2013, 87, 401.
[138] L. Zhao, L.-Z. Fan, M.-Q. Zhou, H. Guan, S. Qiao, M. Antonietti,
M.-M. Titirici, Adv. Mater. 2010, 22, 5202.
[139] L. Wei, G. Yushin, Carbon 2011, 49, 4830.
[140] F. B. Sillars, S. I. Fletcher, M. Mirzaeian, P. J. Hall, Phys. Chem.
Chem. Phys. 2012, 14, 6094.
[141] D. Hulicova-Jurcakova, A. M. Puziy, O. I. Poddubnaya,
F. Suarez-Garcia, J. M. D. Tascon, G. Q. Lu, J. Am. Chem. Soc.
2009, 131, 5026.
[142] V. Ruiz, A. G. Pandolfo, Electrochim. Acta 2010, 55, 7495.
[143] J. Yan, T. Wei, W. M. Qiao, Z. J. Fan, L. J. Zhang, T. Y. Li, Q. K. Zhao,
Electrochem. Commun. 2010, 12, 1279.
[144] M. J. Jung, E. Jeong, S. I. Lee, Y. S. Lee, J. Ind. Eng. Chem. 2012, 18, 642.
[145] T. Ohta, I. T. Kim, M. Egashira, N. Yoshimoto, M. Morita, J. Power
Sources 2012, 198, 408.
[146] D. Tashima, H. Yoshitama, T. Sakoda, A. Okazaki, T. Kawaji,
Electrochim. Acta 2012, 77, 198.
[147] S. L. Candelaria, B. B. Garcia, D. Liu, G. Cao, J. Mater. Chem. 2012,
22, 9884.
[148] J. W. Lim, E. Jeong, M. J. Jung, S. I. Lee, Y. S. Lee, J. Ind. Eng. Chem.
2012, 18, 116.
[149] Y. Lv, F. Zhang, Y. Dou, Y. Zhai, J. Wang, H. Liu, Y. Xia, B. Tu,
D. Zhao, J. Mater. Chem. 2012, 22, 93.
[150] S. Kondrat, C. R. Perez, V. Presser, Y. Gogotsi, A. A. Kornyshev,
Energy Environ. Sci. 2012, 5, 6474.
[151] C.-W. Huang, C.-T. Hsieh, P.-L. Kuo, H. Teng, J. Mater. Chem. 2012,
22, 7314.
[152] D. Lozano-Castello, D. Cazorla-Amoros, A. Linares-Solano,
S. Shiraishi, H. Kurihara, A. Oya, Carbon 2003, 41, 1765.
[153] X. J. He, Y. J. Geng, J. S. Qiu, M. D. Zheng, S. A. Long, X. Y. Zhang,
Carbon 2010, 48, 1662.
[154] M. P. Bichat, E. Raymundo-Pinero, F. Beguin, Carbon 2010, 48,
4351.
[155] E. Raymundo-Pinero, M. Cadek, F. Beguin, Adv. Funct. Mater. 2009,
19, 1032.
[156] F. C. Wu, R. L. Tseng, C. C. Hu, C. C. Wang, J. Power Sources 2004,
138, 351.
[157] G. Dobele, T. Dizhbite, M. V. Gil, A. Volperts, T. A. Centeno,
Biomass Bioenergy 2012, 46, 145.
[158] V. Subramanian, C. Luo, A. M. Stephan, K. S. Nahm, S. Thomas,
B. Q. Wei, J. Phys. Chem. C 2007, 111, 7527.
[159] L. Wei, G. Yushin, J. Power Sources 2011, 196, 4072.
[160] T. E. Rufford, D. Hulicova-Jurcakova, E. Fiset, Z. H. Zhu, G. Q. Lu,
Electrochem. Commun. 2009, 11, 974.
[161] G. H. Sun, K. X. Li, L. J. Xie, J. L. Wang, Y. Q. Li, Microporous
Mesoporous Mater. 2012, 151, 282.
[162] Z. J. Zheng, Q. M. Gao, J. Power Sources 2011, 196, 1615.
[163] S.-J. Han, Y.-H. Kim, K.-S. Kim, S.-J. Park, Curr. Appl. Phys. 2012, 12,
1039.
[164] V. Ruiz, A. G. Pandolfo, J. Power Sources 2011, 196, 7816.
[165] B. Xu, F. Wu, D. B. Mu, L. L. Dai, G. P. Cao, H. Zhang, S. Chen,
Y. S. Yang, Int. J. Hydrogen Energy 2010, 35, 632.
[166] G. Hasegawa, M. Aoki, K. Kanamori, K. Nakanishi, T. Hanada,
K. Tadanaga, J. Mater. Chem. 2011, 21, 2060.
[167] D.-W. Wang, F. Li, L.-C. Yin, X. Lu, Z.-G. Chen, I. R. Gentle,
G. Q. Lu, H.-M. Cheng, Chem. Eur. J. 2012, 18, 5345.
[168] C. O. Ania, V. Khomenko, E. Raymundo-Piero, J. B. Parra,
F. Bguin, Adv. Funct. Mater. 2007, 17, 1828.
[169] Z. Chen, J. Wen, C. Yan, L. Rice, H. Sohn, M. Shen, M. Cai,
B. Dunn, Y. Lu, Adv. Energy Mater. 2011, 1, 551.
1300816 (38 of 43)
[170] Y. Y. Liang, M. G. Schwab, L. J. Zhi, E. Mugnaioli, U. Kolb,

X. L. Feng, K. Mullen, J. Am. Chem. Soc. 2010, 132, 15030.
[171] L. C. Sang, A. Vinu, M. O. Coppens, J. Mater. Chem. 2011, 21,
7410.
[172] B. Xu, L. Peng, G. Wang, G. Cao, F. Wu, Carbon 2010, 48, 2377.
[173] Q. Li, R. R. Jiang, Y. Q. Dou, Z. X. Wu, T. Huang, D. Feng, J. P. Yang,
A. S. Yu, D. Y. Zhao, Carbon 2011, 49, 1248.
[174] N. Liu, H. H. Song, X. H. Chen, J. Mater. Chem. 2011, 21, 5345.
[175] Y. Meng, D. Gu, F. Q. Zhang, Y. F. Shi, L. Cheng, D. Feng,
Z. X. Wu, Z. X. Chen, Y. Wan, A. Stein, D. Y. Zhao, Chem. Mater.
2006, 18, 4447.
[176] Y. R. Liang, F. X. Liang, D. C. Wu, Z. H. Li, F. Xu, R. W. Fu, Phys.
Chem. Chem. Phys. 2011, 13, 8852.
[177] Z. Wu, W. Li, Y. Xia, P. Webley, D. Zhao, J. Mater. Chem. 2012, 22,
8835.
[178] H. Lu, W. Dai, M. Zheng, N. Li, J. Cao, J. Power Sources 2012, 209,
243.
[179] C.-H. Huang, Q. Zhang, T.-C. Chou, C.-M. Chen, D. S. Su,
R.-A. Doong, ChemSusChem 2012, 5, 563.
[180] D. W. Wang, F. Li, M. Liu, G. Q. Lu, H. M. Cheng, Angew. Chem.
Int. Ed. 2008, 47, 373.
[181] T. Kwon, H. Nishihara, H. Itoi, Q.-H. Yang, T. Kyotani, Langmuir
2009, 25, 11961.
[182] R. Ryoo, S. H. Joo, S. Jun, J. Phys. Chem. B 1999, 103, 7743.
[183] W. F. Zhang, Z. H. Huang, G. P. Cao, F. Y. Kang, Y. S. Yang,
[184] M. Lazzari, F. Soavi, M. Mastragostino, Fuel Cells 2010, 10, 840.
[185] X. F. Qian, Y. Y. Lv, W. Li, Y. Y. Xia, D. Y. Zhao, J. Mater. Chem. 2011,
21, 13025.
[186] B. Liu, H. Shioyama, T. Akita, Q. Xu, J. Am. Chem. Soc. 2008, 130,
5390.
[187] B. Liu, H. Shioyama, H. L. Jiang, X. B. Zhang, Q. Xu, Carbon 2010,
48, 456.
[188] W. Chaikittisilp, M. Hu, H. Wang, H.-S. Huang, T. Fujita,
K. C. W. Wu, L.-C. Chen, Y. Yamauchi, K. Ariga, Chem. Commun.
2012, 48, 7259.
[189] H. J. Liu, X. M. Wang, W. J. Cui, Y. Q. Dou, D. Y. Zhao, Y. Y. Xia,
J. Mater. Chem. 2010, 20, 4223.
[190] P. F. Fulvio, R. T. Mayes, X. Q. Wang, S. M. Mahurin, J. C. Bauer,
V. Presser, J. McDonough, Y. Gogotsi, S. Dai, Adv. Funct. Mater.
2011, 21, 2208.
[191] M. Zhong, E. K. Kim, J. P. McGann, S.-E. Chun, J. F. Whitacre,
M. Jaroniec, K. Matyjaszewski, T. Kowalewski, J. Am. Chem. Soc.
2012, 134, 14846.
[192] X. Zhang, X. Wang, L. Jiang, H. Wu, C. Wu, J. Su, J. Power Sources
2012, 216, 290.
[193] Y. Han, X. Dong, C. Zhang, S. Liu, J. Power Sources 2012, 211, 92.
[194] C. R. Prez, S.-H. Yeon, J. Sgalini, V. Presser, P.-L. Taberna,
P. Simon, Y. Gogotsi, Adv. Funct. Mater. 2013, 23, 1081.
[195] Y. Gao, V. Presser, L. F. Zhang, J. J. Niu, J. K. McDonough,
C. R. Perez, H. B. Lin, H. Fong, Y. Gogotsi, J. Power Sources 2012,
201, 368.
[196] M. Heon, S. Lofland, J. Applegate, R. Nolte, E. Cortes,
J. D. Hettinger, P.-L. Taberna, P. Simon, P. Huang, M. Brunet,
Y. Gogotsi, Energy Environ. Sci. 2011, 4, 135.
[197] Y. Korenblit, M. Rose, E. Kockrick, L. Borchardt, A. Kvit, S. Kaskel,
G. Yushin, ACS Nano 2010, 4, 1337.
[198] M. Rose, E. Kockrick, I. Senkovska, S. Kaskel, Carbon 2010, 48, 403.
[199] D. D. Zhou, H. J. Liu, Y. G. Wang, C. X. Wang, Y. Y. Xia, J. Mater.
Chem. 2012, 22, 1937.
[200] M. Rose, Y. Korenblit, E. Kockrick, L. Borchardt, M. Oschatz,
S. Kaskel, G. Yushin, Small 2011, 7, 1108.
[201] H. Kurig, A. Janes, E. Lust, J. Electrochem. Soc. 2010, 157, A272.
[202] F. Bguin, E. Frackowiak, Carbons for electrochemical energy storage
and conversion systems, CRC Press, Boca Raton 2009.
www.advenergymat.de
[236] D. Li, M. B. Muller, S. Gilje, R. B. Kaner, G. G. Wallace, Nat. Nanotechnol. 2008, 3, 101.
[237] S. Park, R. S. Ruoff, Nat. Nanotechnol. 2009, 4, 217.
[238] W. Gao, L. B. Alemany, L. Ci, P. M. Ajayan, Nat. Chem. 2009, 1,
403.
[239] Y. Wang, Z. Q. Shi, Y. Huang, Y. F. Ma, C. Y. Wang, M. M. Chen,
Y. S. Chen, J. Phys. Chem. C 2009, 113, 13103.
[240] A. P. Yu, I. Roes, A. Davies, Z. W. Chen, Appl. Phys. Lett. 2010, 96.
[241] Z. Lei, L. Lu, X. S. Zhao, Energy Environ. Sci. 2012, 5, 6391.
[242] Y. Chen, X. Zhang, D. Zhang, P. Yu, Y. Ma, Carbon 2011, 49, 573.
[243] D. R. Dreyer, S. Murali, Y. W. Zhu, R. S. Ruoff, C. W. Bielawski,
J. Mater. Chem. 2011, 21, 3443.
[244] Y. Z. Liu, Y. F. Li, M. Zhong, Y. G. Yang, Y. F. Wen, M. Z. Wang,
J. Mater. Chem. 2011, 21, 15449.
[245] X. T. Zhang, Z. Y. Sui, B. Xu, S. F. Yue, Y. J. Luo, W. C. Zhan, B. Liu,
J. Mater. Chem. 2011, 21, 6494.
[246] D. Zhang, X. Zhang, Y. Chen, C. Wang, Y. Ma, Electrochim. Acta
2012, 69, 364.
[247] W. Lv, D.-M. Tang, Y.-B. He, C.-H. You, Z.-Q. Shi, X.-C. Chen,
C.-M. Chen, P.-X. Hou, C. Liu, Q.-H. Yang, ACS Nano 2009, 3,
3730.
[248] Y. W. Zhu, S. Murali, M. D. Stoller, A. Velamakanni, R. D. Piner,
R. S. Ruoff, Carbon 2010, 48, 2118.
[249] X. A. Du, P. Guo, H. H. Song, X. H. Chen, Electrochim. Acta 2010,
55, 4812.
[250] Y. Xu, K. Sheng, C. Li, G. Shi, ACS Nano 2010, 4, 4324.
[251] L. F. Lai, L. W. Chen, D. Zhan, L. Sun, J. P. Liu, S. H. Lim, C. K. Poh,
Z. X. Shen, J. Y. Lin, Carbon 2011, 49, 3250.
[252] Y. Y. Shao, J. Wang, M. Engelhard, C. M. Wang, Y. H. Lin, J. Mater.
Chem. 2010, 20, 743.
[253] H.-C. Huang, C.-W. Huang, C.-T. Hsieh, P.-L. Kuo, J.-M. Ting,
H. Teng, J. Phys. Chem. C 2011, 115, 20689.
[254] L. F. Lai, H. P. Yang, L. Wang, B. K. Teh, J. Q. Zhong, H. Chou,
L. W. Chen, W. Chen, Z. X. Shen, R. S. Ruoff, J. Y. Lin, ACS Nano
2012, 6, 5941.
[255] Z.-J. Fan, K. Wang, J. Yan, T. Wei, L.-J. Zhi, J. Feng, Y.-m. Ren,
L.-P. Song, F. Wei, ACS Nano 2011, 5, 191.
[256] Z. J. Fan, K. Wang, T. Wei, J. Yan, L. P. Song, B. Shao, Carbon 2010,
48, 1686.
[257] S. R. C. Vivekchand, C. S. Rout, K. S. Subrahmanyam,
A. Govindaraj, C. N. R. Rao, J. Chem. Sci. 2008, 120, 9.
[258] Z. Y. Lin, Y. Liu, Y. G. Yao, O. J. Hildreth, Z. Li, K. Moon, C. P. Wong,
J. Phys. Chem. C 2011, 115, 7120.
[259] Y. W. Zhu, M. D. Stoller, W. W. Cai, A. Velamakanni, R. D. Piner,
D. Chen, R. S. Ruoff, ACS Nano 2010, 4, 1227.
[260] T. F. Yeh, J. M. Syu, C. Cheng, T. H. Chang, H. S. Teng, Adv. Funct.
Mater. 2010, 20, 2255.
[261] V. Eswaraiah, S. S. J. Aravind, S. Ramaprabhu, J. Mater. Chem.
2011, 21, 6800.
[262] Q. Wu, Y. Sun, H. Bai, G. Shi, Phys. Chem. Chem. Phys. 2011, 13,
11193.
[263] Y. Sun, Q. Wu, G. Shi, Phys. Chem. Chem. Phys. 2011, 13, 17249.
[264] J. L. Xia, F. Chen, J. H. Li, N. J. Tao, Nat. Nanotechnol. 2009, 4, 505.
[265] Y. C. Si, E. T. Samulski, Chem. Mater. 2008, 20, 6792.
[266] L. Buglione, A. Bonanni, A. Ambrosi, M. Pumera, ChemPlusChem
2012, 77, 71.
[267] W. H. Shi, J. X. Zhu, D. H. Sim, Y. Y. Tay, Z. Y. Lu, X. J. Zhang,
Y. Sharma, M. Srinivasan, H. Zhang, H. H. Hng, Q. Y. Yan,
J. Mater. Chem. 2011, 21, 3422.
[268] W. Lv, F. Sun, D.-M. Tang, H.-T. Fang, C. Liu, Q.-H. Yang,
H.-M. Cheng, J. Mater. Chem. 2011, 21, 9014.
[269] Q. Qu, S. Yang, X. Feng, Adv. Mater. 2011, 23, 5574.
[270] H. Wang, H. S. Casalongue, Y. Liang, H. Dai, J. Am. Chem. Soc.
2010, 132, 7472.
[271] X. Yang, J. Zhu, L. Qiu, D. Li, Adv. Mater. 2011, 23, 2833.
(39 of 43) 1300816
REVIEW
[203] G. Yushin, R. Dash, J. Jagiello, J. E. Fischer, Y. Gogotsi, Adv. Funct.

Mater. 2006, 16, 2288.
[204] Y. Gogotsi, Carbon Nanomaterials, CRC Press, Boca Raton 2006.
[205] C. Portet, G. Yushin, Y. Gogotsi, J. Electrochem. Soc. 2008, 155,
A531.
[206] D. N. Futaba, K. Hata, T. Yamada, T. Hiraoka, Y. Hayamizu,
Y. Kakudate, O. Tanaike, H. Hatori, M. Yumura, S. Iijima, Nat.
Mater. 2006, 5, 987.
[207] H. Zheng, J. Wang, Y. Jia, C. a. Ma, J. Power Sources 2012, 216, 508.
[208] C. M. Niu, E. K. Sichel, R. Hoch, D. Moy, H. Tennent, Appl. Phys.
Lett. 1997, 70, 1480.
[209] K. H. An, W. S. Kim, Y. S. Park, Y. C. Choi, S. M. Lee, D. C. Chung,
D. J. Bae, S. C. Lim, Y. H. Lee, Adv. Mater. 2001, 13, 497.
[210] Y. Fu, X. Cai, H. Wu, Z. Lv, S. Hou, M. Peng, X. Yu, D. Zou, Adv.
Mater. 2012, 24, 5713.
[211] F. Meng, Y. Ding, Adv. Mater. 2011, 23, 4098.
[212] Z. Q. Niu, W. Y. Zhou, J. Chen, G. X. Feng, H. Li, W. J. Ma, J. Z. Li,
H. B. Dong, Y. Ren, D. A. Zhao, S. S. Xie, Energy Environ. Sci. 2011,
4, 1440.
[213] M. Kaempgen, C. K. Chan, J. Ma, Y. Cui, G. Gruner, Nano Lett.
2009, 9, 1872.
[214] L. B. Hu, M. Pasta, F. La Mantia, L. F. Cui, S. Jeong, H. D. Deshazer,
J. W. Choi, S. M. Han, Y. Cui, Nano Lett. 2010, 10, 708.
[215] L. B. Hu, H. Wu, Y. Cui, Appl. Phys. Lett. 2010, 96, 183502.
[216] W. Lu, L. T. Qu, K. Henry, L. M. Dai, J. Power Sources 2009, 189,
1270.
[217] S. W. Lee, N. Yabuuchi, B. M. Gallant, S. Chen, B.-S. Kim,
P. T. Hammond, Y. Shao-Horn, Nat. Nanotechnol. 2010, 5, 531.
[218] S. W. Lee, B. S. Kim, S. Chen, Y. Shao-Horn, P. T. Hammond,
J. Am. Chem. Soc. 2009, 131, 671.
[219] C. S. Du, N. Pan, J. Power Sources 2006, 160, 1487.
[220] C. S. Du, N. Pan, Nanotechnology 2006, 17, 5314.
[221] J. H. Chen, W. Z. Li, D. Z. Wang, S. X. Yang, J. G. Wen, Z. F. Ren,
Carbon 2002, 40, 1193.
[222] C. Portet, P. L. Taberna, P. Simon, E. Flahaut, J. Electrochem. Soc.
2006, 153, A649.
[223] C. Portet, P. L. Taberna, P. Simon, E. Flahaut, C. Laberty-Robert,
[224] K. H. An, W. S. Kim, Y. S. Park, J. M. Moon, D. J. Bae, S. C. Lim,
Y. S. Lee, Y. H. Lee, Adv. Funct. Mater. 2001, 11, 387.
[225] C. Emmenegger, P. Mauron, P. Sudan, P. Wenger, V. Hermann,
R. Gallay, A. Zuttel, J. Power Sources 2003, 124, 321.
[226] C. Emmenegger, P. Mauron, A. Zuttel, C. Nutzenadel,
A. Schneuwly, R. Gallay, L. Schlapbach, Appl. Surf. Sci. 2000, 162,
452.
[227] M. M. Shaijumon, F. S. Ou, L. J. Ci, P. M. Ajayan, Chem. Commun.
2008, 2373.
[228] S. Talapatra, S. Kar, S. K. Pal, R. Vajtai, L. Ci, P. Victor,
M. M. Shaijumon, S. Kaur, O. Nalamasu, P. M. Ajayan, Nat. Nanotechnol. 2006, 1, 112.
[229] L. J. Gao, A. P. Peng, Z. Y. Wang, H. Zhang, Z. J. Shi, Z. N. Gu,
G. P. Cao, B. Z. Ding, Solid State Commun. 2008, 146, 380.
[230] E. Frackowiak, S. Delpeux, K. Jurewicz, K. Szostak, D. CazorlaAmoros, F. Beguin, Chem. Phys. Lett. 2002, 361, 35.
[231] Q. Jiang, M. Z. Qu, G. M. Zhou, B. L. Zhang, Z. L. Yu, Mater. Lett.
2002, 57, 988.
[232] B. J. Yoon, S. H. Jeong, K. H. Lee, H. S. Kim, C. G. Park, J. H. Han,
Chem. Phys. Lett. 2004, 388, 170.
[233] L. Yan, Y. B. Zheng, F. Zhao, S. Li, X. Gao, B. Xu, P. S. Weiss,
Y. Zhao, Chem. Soc. Rev. 2012, 41, 97.
[234] K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang,
S. V. Dubonos, I. V. Grigorieva, A. A. Firsov, Science 2004, 306, 666.
[235] S. Stankovich, D. A. Dikin, G. H. B. Dommett, K. M. Kohlhaas,
E. J. Zimney, E. A. Stach, R. D. Piner, S. T. Nguyen, R. S. Ruoff,
Nature 2006, 442, 282.
www.advenergymat.de
REVIEW
[272] D. W. Wang, F. Li, J. P. Zhao, W. C. Ren, Z. G. Chen, J. Tan,
Z. S. Wu, I. Gentle, G. Q. Lu, H. M. Cheng, ACS Nano 2009, 3,
1745.
[273] J. Yan, T. Wei, B. Shao, Z. J. Fan, W. Z. Qian, M. L. Zhang, F. Wei,
Carbon 2010, 48, 487.
[274] P. A. Mini, A. Balakrishnan, S. V. Nair, K. R. V. Subramanian, Chem.
Commun. 2011, 47, 5753.
[275] Z. Fan, J. Yan, L. Zhi, Q. Zhang, T. Wei, J. Feng, M. Zhang, W. Qian,
F. Wei, Adv. Mater. 2010, 22, 3723.
[276] J. Yan, T. Wei, B. Shao, F. Ma, Z. Fan, M. Zhang, C. Zheng,
Y. Shang, W. Qian, F. Wei, Carbon 2010, 48, 1731.
[277] S. Y. Yang, K. H. Chang, H. W. Tien, Y. F. Lee, S. M. Li, Y. S. Wang,
J. Y. Wang, C. C. M. Ma, C. C. Hu, J. Mater. Chem. 2011, 21, 2374.
[278] X. Lu, H. Dou, B. Gao, C. Yuan, S. Yang, L. Hao, L. Shen, X. Zhang,
[279] D. Yu, L. Dai, J. Phys. Chem. Lett. 2010, 1, 467.
[280] Y. Wang, Y. Wu, Y. Huang, F. Zhang, X. Yang, Y. Ma, Y. Chen,
J. Phys. Chem. C 2011, 115, 23192.
[281] M.-Q. Zhao, Q. Zhang, J.-Q. Huang, G.-L. Tian, T.-C. Chen,
W.-Z. Qian, F. Wei, Carbon 2013, 54, 403.
[282] Z. Fan, Q. Zhao, T. Li, J. Yan, Y. Ren, J. Feng, T. Wei, Carbon 2012,
50, 1699.
[283] G. Ning, Z. Fan, G. Wang, J. Gao, W. Qian, F. Wei, Chem. Commun.
2011, 47, 5976.
[284] B. G. Choi, M. Yang, W. H. Hong, J. W. Choi, Y. S. Huh, ACS Nano
2012, 6, 4020.
[285] C.-M. Chen, Q. Zhang, C.-H. Huang, X.-C. Zhao, B.-S. Zhang,
Q.-Q. Kong, M.-Z. Wang, Y.-G. Yang, R. Cai, D.-S. Su, Chem.
Commun. 2012, 48, 7149.
[286] J. Yan, J. Liu, Z. Fan, T. Wei, L. Zhang, Carbon 2012, 50, 2179.
[287] C. G. Liu, Z. N. Yu, D. Neff, A. Zhamu, B. Z. Jang, Nano Lett. 2010,
10, 4863.
[288] F. Du, D. Yu, L. Dai, S. Ganguli, V. Varshney, A. K. Roy, Chem.
Mater. 2011, 23, 4810.
[289] J. Yan, Y. Xiao, G. Ning, T. Wei, Z. Fan, RSC Adv. 2013, 3, 2566.
[290] J. J. Yoo, K. Balakrishnan, J. S. Huang, V. Meunier, B. G. Sumpter,
A. Srivastava, M. Conway, A. L. M. Reddy, J. Yu, R. Vajtai,
P. M. Ajayan, Nano Lett. 2011, 11, 1423.
[291] D. Hulicova-Jurcakova, M. Seredych, G. Q. Lu, T. J. Bandosz, Adv.
Funct. Mater. 2009, 19, 438.
[292] J. Han, L. L. Zhang, S. Lee, J. Oh, K.-S. Lee, J. R. Potts, J. Ji, X. Zhao,
R. S. Ruoff, S. Park, ACS Nano 2013, 7, 19.
[293] Z.-S. Wu, A. Winter, L. Chen, Y. Sun, A. Turchanin, X. Feng,
K. Mllen, Adv. Mater. 2012, 24, 5130.
[294] L.-F. Chen, X.-D. Zhang, H.-W. Liang, M. Kong, Q.-F. Guan,
P. Chen, Z.-Y. Wu, S.-H. Yu, ACS Nano 2012, 6, 7092.
[295] X. Zhao, Q. Zhang, C.-M. Chen, B. Zhang, S. Reiche, A. Wang,
T. Zhang, R. Schlgl, D. Sheng Su, Nano Energy 2012, 1, 624.
[296] X. C. Zhao, Q. Zhang, B. S. Zhang, C. M. Chen, A. Q. Wang,
T. Zhang, D. S. Su, J. Mater. Chem. 2012, 22, 4963.
[297] M. J. Bleda-Martinez, J. A. Macia-Agullo, D. Lozano-Castello,
E. Morallon, D. Cazorla-Amoros, A. Linares-Solano, Carbon 2005,
43, 2677.
[298] H. Oda, A. Yamashita, S. Minoura, M. Okamoto, T. Morimoto,
J. Power Sources 2006, 158, 1510.
[299] C. T. Hsieh, H. Teng, Carbon 2002, 40, 667.
[300] K. Okajima, K. Ohta, M. Sudoh, Electrochim. Acta 2005, 50, 2227.
[301] B. Fang, Y. Z. Wei, K. Suzuki, A. Kumagai, Electrochim. Acta 2005,
50, 3616.
[302] C. Wu, X. Wang, B. Ju, L. Jiang, H. Wu, Q. Zhao, L. Yi, J. Power
Sources 2013, 227, 1.
[303] D. Hulicova-Jurcakova, M. Kodama, S. Shiraishi, H. Hatori,
Z. H. Zhu, G. Q. Lu, Adv. Funct. Mater. 2009, 19, 1800.
[304] Y. J. Kim, Y. Abe, T. Yanagiura, K. C. Park, M. Shimizu, T. Iwazaki,
S. Nakagawa, M. Endo, M. S. Dresselhaus, Carbon 2007, 45, 2116.
1300816 (40 of 43)
[305] L. L. Zhang, X. Zhao, H. X. Ji, M. D. Stoller, L. F. Lai, S. Murali,

S. McDonnell, B. Cleveger, R. M. Wallace, R. S. Ruoff, Energy
Environ. Sci. 2012, 5, 9618.
[306] X. Q. Yang, D. C. Wu, X. M. Chen, R. W. Fu, J. Phys. Chem. C 2010,
114, 8581.
[307] Z. Li, L. Zhang, B. S. Amirkhiz, X. Tan, Z. Xu, H. Wang, B. C. Olsen,
C. M. B. Holt, D. Mitlin, Adv. Energy Mater. 2012, 2, 431.
[308] W. Shen, W. Fan, J. Mater. Chem. A 2013, 1, 999.
[309] C.-M. Chen, Q. Zhang, X.-C. Zhao, B. Zhang, Q.-Q. Kong,
M.-G. Yang, Q.-H. Yang, M.-Z. Wang, Y.-G. Yang, R. Schlogl,
D. S. Su, J. Mater. Chem. 2012, 22, 14076.
[310] E. J. Ra, E. Raymundo-Piero, Y. H. Lee, F. Bguin, Carbon 2009,
47, 2984.
[311] W. Kim, M. Y. Kang, J. B. Joo, N. D. Kim, I. K. Song, P. Kim,
J. R. Yoon, J. Yi, J. Power Sources 2010, 195, 2125.
[312] H. L. Wang, Q. M. Gao, J. Hu, Microporous Mesoporous Mater.
2010, 131, 89.
[313] K. Y. Lee, Y. S. Lin, Y. M. Chen, Y. S. Huang, Phys. E 2010, 42, 2799.
[314] D. W. Wang, F. Li, Z. G. Chen, G. Q. Lu, H. M. Cheng, Chem.
Mater. 2008, 20, 7195.
[315] Z.-S. Wu, W. Ren, L. Xu, F. Li, H.-M. Cheng, ACS Nano 2011, 5,
5463.
[316] C. H. Choi, S. H. Park, S. I. Woo, ACS Nano 2012, 6, 7084.
[317] T. Tsubota, T. Yamaguchi, C. Wang, Y. Miyauchi, N. Murakami,
T. Ohno, J. Power Sources 2013, 227, 24.
[318] B.-H. Kim, K. Seung Yang, H.-G. Woo, Mater. Lett. 2013, 93, 190.
[319] T. Tomko, R. Rajagopalan, P. Aksoy, H. C. Foley, Electrochim. Acta
2011, 56, 5369.
[320] X. C. Zhao, A. Q. Wang, J. W. Yan, G. Q. Sun, L. X. Sun, T. Zhang,
Chem. Mater. 2010, 22, 5463.
[321] N. Soin, S. S. Roy, S. K. Mitra, T. Thundat, J. A. McLaughlin,
J. Mater. Chem. 2012, 22, 14944.
[322] Y. Cheng, S. Lu, H. Zhang, C. V. Varanasi, J. Liu, Nano Lett. 2012,
12, 4206.
[323] G. Yu, L. Hu, N. Liu, H. Wang, M. Vosgueritchian, Y. Yang, Y. Cui,
Z. Bao, Nano Lett. 2011, 11, 4438.
[324] C. Yuan, L. Yang, L. Hou, L. Shen, X. Zhang, X. W. Lou, Energy
Environ. Sci. 2012, 5, 7883.
[325] B. Wang, J. S. Chen, Z. Wang, S. Madhavi, X. W. Lou, Adv. Energy
Mater. 2012, 2, 1188.
[326] T. Xue, X. Wang, J. M. Lee, J. Power Sources 2012, 201, 382.
[327] J. Jiang, J. Liu, R. Ding, J. Zhu, Y. Li, A. Hu, X. Li, X. Huang,
ACS Appl. Mater. Interfaces 2011, 3, 99.
[328] H.-W. Park, T. Kim, J. Huh, M. Kang, J. E. Lee, H. Yoon, ACS Nano
2012, 6, 7624.
[329] Q. Qu, Y. Zhu, X. Gao, Y. Wu, Adv. Energy Mater. 2012, 2, 950.
[330] Q. Lu, Y. K. Zhou, J. Power Sources 2011, 196, 4088.
[331] J. Zhang, J. Jiang, H. Li, X. S. Zhao, Energy Environ. Sci. 2011, 4,
4009.
[332] H. Wang, Y. Liang, T. Mirfakhrai, Z. Chen, H. S. Casalongue,
H. Dai, Nano Res. 2011, 4, 729.
[333] Z. S. Wu, D. W. Wang, W. Ren, J. Zhao, G. Zhou, F. Li, H. M. Cheng,
Adv. Funct. Mater. 2010, 20, 3595.
[334] C. Sassoye, C. Laberty, H. Le Khanh, S. Cassaignon, C. Boissiere,
M. Antonietti, C. Sanchez, Adv. Funct. Mater. 2009, 19, 1922.
[335] Y. F. Ke, D. S. Tsai, Y. S. Huang, J. Mater. Chem. 2005, 15, 2122.
[336] W. Sugimoto, H. Iwata, Y. Yasunaga, Y. Murakami, Y. Takasu,
Angew. Chem. Int. Ed. 2003, 42, 4092.
[337] C.-C. Hu, K.-H. Chang, M.-C. Lin, Y.-T. Wu, Nano Lett. 2006, 6,
2690.
[338] Y. T. Kim, K. Tadai, T. Mitani, J. Mater. Chem. 2005, 15, 4914.
[339] W. Sugimoto, S. Makino, R. Mukai, Y. Tatsumi, K. Fukuda,
Y. Takasu, Y. Yamauchi, J. Power Sources 2012, 204, 244.
[340] V. D. Patake, S. M. Pawar, V. R. Shinde, T. P. Gujar, C. D. Lokhande,
Curr. Appl. Phys. 2010, 10, 99.
www.advenergymat.de
[376] X. L. Wang, A. B. Yuan, Y. Q. Wang, J. Power Sources 2007, 172,

1007.
[377] P. Yu, X. Zhang, Y. Chen, Y. W. Ma, Mater. Lett. 2010, 64, 61.
[378] Y. Zhang, G.-y. Li, Y. Lv, L.-z. Wang, A.-q. Zhang, Y.-h. Song,
B.-l. Huang, Int. J. Hydrogen Energy 2011, 36, 11760.
[379] S. K. Meher, G. R. Rao, J. Power Sources 2012, 215, 317.
[380] Z. J. Fan, Z. W. Qie, T. Wei, J. Yan, S. S. Wang, Mater. Lett. 2008, 62,
3345.
[381] H. Liu, B. Lu, S. Wei, M. Bao, Y. Wen, F. Wang, Solid State Sci.
2012, 14, 789.
[382] T. Brousse, M. Toupin, R. Dugas, L. Athouel, O. Crosnier,
D. Belanger, J. Electrochem. Soc. 2006, 153, A2171.
[383] R. Liu, S. B. Lee, J. Am. Chem. Soc. 2008, 130, 2942.
[384] W. Yan, T. Ayvazian, J. Kim, Y. Liu, K. C. Donavan, W. Xing, Y. Yang,
J. C. Hemminger, R. M. Penner, ACS Nano 2011, 5, 8275.
[385] X. H. Tang, Z. H. Liu, C. X. Zhang, Z. P. Yang, Z. L. Wang, J. Power
Sources 2009, 193, 939.
[386] J. Q. Yuan, Z. H. Liu, S. F. Qiao, X. R. Ma, N. C. Xu, J. Power
Sources 2009, 189, 1278.
[387] X. Lang, A. Hirata, T. Fujita, M. Chen, Nat. Nanotechnol. 2011, 6,
232.
[388] J. P. Liu, J. Jiang, C. W. Cheng, H. X. Li, J. X. Zhang, H. Gong,
H. J. Fan, Adv. Mater. 2011, 23, 2076.
[389] W. B. Yan, J. Y. Kim, W. D. Xing, K. C. Donavan, T. Ayvazian,
R. M. Penner, Chem. Mater. 2012, 24, 2382.
[390] Q. Li, Z.-L. Wang, G.-R. Li, R. Guo, L.-X. Ding, Y.-X. Tong, Nano
Lett. 2012, 12, 3803.
[391] A. L. M. Reddy, M. M. Shaijumon, S. R. Gowda, P. M. Ajayan,
J. Phys. Chem. C 2010, 114, 658.
[392] G. N. Zhang, L. Zheng, M. Zhang, S. H. Guo, Z. H. Liu, Z. P. Yang,
Z. L. Wang, Energy Fuels 2012, 26, 618.
[393] D. F. Yang, J. Power Sources 2012, 198, 416.
[394] J. A. Yan, E. Khoo, A. Sumboja, P. S. Lee, ACS Nano 2010, 4, 4247.
[395] H. N. Yoo, D. H. Park, S. J. Hwang, J. Power Sources 2008, 185,
1374.
[396] X. Zhao, L. Zhang, S. Murali, M. D. Stoller, Q. Zhang, Y. Zhu,
R. S. Ruoff, ACS Nano 2012, 6, 5404.
[397] H. Zhang, G. P. Cao, Z. Y. Wang, Y. S. Yang, Z. J. Shi, Z. N. Gu,
Nano Lett. 2008, 8, 2664.
[398] J. Yan, Z. J. Fan, T. Wei, W. Z. Qian, M. L. Zhang, F. Wei, Carbon
2009, 47, 3371.
[399] A. E. Fischer, K. A. Pettigrew, D. R. Rolison, R. M. Stroud,
J. W. Long, Nano Lett. 2007, 7, 281.
[400] J. Yan, Z. J. Fan, T. Wei, J. Cheng, B. Shao, K. Wang, L. P. Song,
M. L. Zhang, J. Power Sources 2009, 194, 1202.
[401] W. Chen, R. B. Rakhi, L. Hu, X. Xie, Y. Cui, H. N. Alshareef, Nano
Lett. 2011, 11, 5165.
[402] J. H. Kim, K. H. Lee, L. J. Overzet, G. S. Lee, Nano Lett. 2011, 11,
2611.
[403] X. P. Dong, W. H. Shen, J. L. Gu, L. M. Xiong, Y. F. Zhu, Z. Li,
J. L. Shi, J. Phys. Chem. B 2006, 110, 6015.
[404] M. Zhi, A. Manivannan, F. Meng, N. Wu, J. Power Sources 2012,
208, 345.
[405] J. Li, X. Y. Wang, Q. H. Huang, S. Gamboa, P. J. Sebastian, J. Power
Sources 2006, 160, 1501.
[406] S. M. Zhu, H. A. Zhou, M. Hibino, I. Honma, M. Ichihara, Adv.
Funct. Mater. 2005, 15, 381.
[407] H. Jiang, J. Ma, C. Li, J. Mater. Chem. 2012, 22, 16939.
[408] J. Wang, Y. Yang, Z.-H. Huang, F. Kang, J. Mater. Chem. 2012, 22,
16943.
[409] R. K. Sharma, A. C. Rastogi, S. B. Desu, Electrochim. Acta 2008, 53,
7690.
[410] R. Liu, J. Duay, S. B. Lee, ACS Nano 2010, 4, 4299.
[411] Y. Yan, Q. Cheng, V. Pavlinek, P. Saha, C. Li, Electrochim. Acta 2012,
71, 27.
(41 of 43) 1300816
REVIEW
[341] J. W. Long, K. E. Swider, C. I. Merzbacher, D. R. Rolison, Langmuir

1999, 15, 780.
[342] N. L. Wu, S. L. Kuo, M. H. Lee, J. Power Sources 2002, 104, 62.
[343] Y. S. Lin, K. Y. Lee, K. Y. Chen, Y. S. Huang, Appl. Surf. Sci. 2009,
256, 1042.
[344] Y. H. Li, K. L. Huang, D. M. Zeng, S. Q. Liu, Z. F. Yao, J. Solid State
Electron. 2010, 14, 1205.
[345] J. G. Wen, X. Y. Ruan, Z. T. Zhou, J. Phys. Chem. Solids 2009, 70, 816.
[346] T. F. Hsieh, C. C. Chuang, W. J. Chen, J. H. Huang, W. T. Chen,
C. M. Shu, Carbon 2012, 50, 1740.
[347] H. Lee, M. S. Cho, I. H. Kim, J. D. Nam, Y. Lee, Synth. Met. 2010,
160, 1055.
[348] T. S. Hyun, J. E. Kang, H. G. Kim, J. M. Hong, I. D. Kim, Electrochem. Solid-State Lett. 2009, 12, A225.
[349] F. Pico, J. Ibanez, T. A. Centeno, C. Pecharroman, R. M. Rojas,
J. M. Amarilla, J. M. Rojo, Electrochim. Acta 2006, 51, 4693.
[350] C. C. Hu, Y. L. Yang, T. C. Lee, Electrochem. Solid-State Lett. 2010,
13, A173.
[351] C. C. Hu, C. C. Wang, K. H. Chang, Electrochim. Acta 2007, 52,
2691.
[352] B. C. Kim, G. G. Wallace, Y. I. Yoon, J. M. Ko, C. O. Too, Synth. Met.
2009, 159, 1389.
[353] M. T. Brumbach, T. M. Alam, R. H. Nilson, P. G. Kotula,
B. B. McKenzie, R. G. Tissot, B. C. Bunker, Mater. Chem. Phys.
2010, 124, 359.
[354] K. Naoi, S. Ishimoto, N. Ogihara, Y. Nakagawa, S. Hatta, J. Electrochem. Soc. 2009, 156, A52.
[355] X. Li, W. Gan, F. Zheng, L. Li, N. Zhu, X. Huang, Synth. Met. 2012,
162, 953.
[356] S. Sopcic, M. K. Rokovic, Z. Mandic, G. Inzelt, J. Solid State
Electron. 2010, 14, 2021.
[357] C. R. K. Rao, M. Vijayan, Synth. Met. 2008, 158, 516.
[358] R. Y. Song, J. H. Park, S. R. Sivakkumar, S. H. Kim, J. M. Ko,
D. Y. Park, S. M. Jo, D. Y. Kim, J. Power Sources 2007, 166, 297.
[359] J. F. Zang, S. J. Bao, C. M. Li, H. J. Bian, X. Q. Cui, Q. L. Bao,
C. Q. Sun, J. Guo, K. R. Lian, J. Phys. Chem. C 2008, 112, 14843.
[360] R. Liu, J. Duay, T. Lane, S. B. Lee, Phys. Chem. Chem. Phys. 2010,
12, 4309.
[361] L. Chen, C. Z. Yuan, B. Gao, S. Y. Chen, X. G. Zhang, J. Solid State
Electron. 2009, 13, 1925.
[362] L. M. Huang, H. Z. Lin, T. C. Wen, A. Gopalan, Electrochim. Acta
2006, 52, 1058.
[363] J. Yan, Z. J. Fan, T. Wei, Z. W. Qie, S. S. Wang, M. L. Zhang, Mater.
Sci. Eng. B 2008, 151, 174.
[364] M. Toupin, T. Brousse, D. Belanger, Chem. Mater. 2004, 16, 3184.
[365] P. Yu, X. Zhang, D. L. Wang, L. Wang, Y. W. Ma, Cryst. Growth Des.
2009, 9, 528.
[366] V. Subramanian, H. W. Zhu, R. Vajtai, P. M. Ajayan, B. Q. Wei,
J. Phys. Chem. B 2005, 109, 20207.
[367] H. Jiang, T. Sun, C. Z. Li, J. Ma, J. Mater. Chem. 2012, 22, 2751.
[368] X. X. He, M. Y. Yang, P. Ni, Y. Li, Z. H. Liu, Colloids Surf. A 2010,
363, 64.
[369] J. Yan, T. Wei, J. Cheng, Z. J. Fan, M. L. Zhang, Mater. Res. Bull.
2010, 45, 210.
[370] H. Jiang, T. Zhao, J. Ma, C. Y. Yan, C. Z. Li, Chem. Commun. 2011,
47, 1264.
[371] J. Zhu, W. Shi, N. Xiao, X. Rui, H. Tan, X. Lu, H. H. Hng, J. Ma,
Q. Yan, ACS Appl. Mater. Interfaces 2012, 4, 2769.
[372] S. Chen, J. Zhu, X. Wang, ACS Nano 2010, 4, 6212.
[373] Y. Wang, S. F. Yu, C. Y. Sun, T. J. Zhu, H. Y. Yang, J. Mater. Chem.
2012, 22, 17584.
[374] A. Zolfaghari, F. Ataherian, M. Ghaemi, A. Gholami, Electrochim.
Acta 2007, 52, 2806.
[375] D. Zhai, B. Li, H. Du, G. Gao, L. Gan, Y. He, Q. Yang, F. Kang,
Carbon 2012, 50, 5034.
www.advenergymat.de
REVIEW
[412] Y. Hou, Y. W. Cheng, T. Hobson, J. Liu, Nano Lett. 2010, 10, 2727.
[413] M.-K. Song, S. Cheng, H. Chen, W. Qin, K.-W. Nam, S. Xu,
X.-Q. Yang, A. Bongiorno, J. Lee, J. Bai, T. A. Tyson, J. Cho, M. Liu,
Nano Lett. 2012, 12, 3483.
[414] H. Cheng, Z. G. Lu, J. Q. Deng, C. Y. Chung, K. L. Zhang, Y. Y. Li,
Nano Res. 2010, 3, 895.
[415] J. A. Xu, L. Gao, J. Y. Cao, W. C. Wang, Z. D. Chen, Electrochim.
Acta 2010, 56, 732.
[416] F. Zhang, C. Z. Yuan, X. J. Lu, L. J. Zhang, Q. Che, X. G. Zhang,
[417] J. W. Lang, X. B. Yan, Q. J. Xue, J. Power Sources 2011, 196, 7841.
[418] X.-C. Dong, H. Xu, X. Wang, Y. Huang, M. B. Chan-Park, H. Zhang,
L.-H. Huang, W. Huang, P. Chen, ACS Nano 2012, 6, 3206.
[419] C. Yuan, L. Yang, L. Hou, J. Li, Y. Sun, X. Zhang, L. Shen, X. Lu,
S. Xiong, X. W. Lou, Adv. Funct. Mater. 2012, 22, 2560.
[420] M. Y. Cheng, Y. S. Ye, J. H. Cheng, Y. J. Yeh, B. H. Chen, B. J. Hwang,
J. Mater. Chem. 2012, 22, 14722.
[421] A. D. Jagadale, V. S. Jamadade, S. N. Pusawale, C. D. Lokhande,
[422] G. X. Pan, X. Xia, F. Cao, P. S. Tang, H. F. Chen, Electrochim. Acta
2012, 63, 335.
[423] C. Z. Yuan, X. G. Zhang, L. R. Hou, L. F. Shen, D. K. Li, F. Zhang,
C. G. Fan, J. M. Li, J. Mater. Chem. 2010, 20, 10809.
[424] H. J. Ahn, W. B. Kim, T. Y. Seong, Electrochem. Commun. 2008, 10,
1284.
[425] S. Chen, J. W. Zhu, X. Wang, J. Phys. Chem. C 2010, 114, 11829.
[426] H. A. Pang, Q. Y. Lu, Y. Z. Zhang, Y. C. Li, F. Gao, Nanoscale 2010,
2, 920.
[427] Z. Y. Lu, Z. Chang, J. F. Liu, X. M. Sun, Nano Res. 2011, 4, 658.
[428] C. Yuan, J. Li, L. Hou, L. Yang, L. Shen, X. Zhang, Electrochim. Acta
2012, 78, 532.
[429] C. Y. Cao, W. Guo, Z. M. Cui, W. G. Song, W. Cai, J. Mater. Chem.
2011, 21, 3204.
[430] X. Xia, J. Tu, Y. Zhang, X. Wang, C. Gu, X.-B. Zhao, H. J. Fan, ACS
Nano 2012, 6, 5531.
[431] Q. Lu, M. W. Lattanzi, Y. Chen, X. Kou, W. Li, X. Fan, K. M. Unruh,
J. G. Chen, J. Q. Xiao, Angew. Chem. Int. Ed. 2011, 50, 6847.
[432] X. Cao, Y. Shi, W. Shi, G. Lu, X. Huang, Q. Yan, Q. Zhang,
H. Zhang, Small 2011, 7, 3163.
[433] B. Gao, C. Z. Yuan, L. H. Su, S. Y. Chen, X. G. Zhang, Electrochim.
Acta 2009, 54, 3561.
[434] H. Jiang, T. Zhao, C. Z. Li, J. Ma, J. Mater. Chem. 2011, 21, 3818.
[435] L. L. Zhang, Z. Xiong, X. S. Zhao, J. Power Sources 2013, 222, 326.
[436] Y. M. Wang, D. D. Zhao, Y. Q. Zhao, C. L. Xu, H. L. Li, RSC Adv.
2012, 2, 1074.
[437] S. Chen, J. W. Zhu, H. Zhou, X. Wang, RSC Adv. 2011, 1, 484.
[438] G. Zhang, W. Li, K. Xie, F. Yu, H. Huang, Adv. Funct. Mater. 2013,
23, 3675.
[439] K. Y. Xie, J. Li, Y. Q. Lai, W. Lu, Z. A. Zhang, Y. X. Liu, L. M. Zhou,
H. T. Huang, Electrochem. Commun. 2011, 13, 657.
[440] M. Zhu, Y. Wang, D. Meng, X. Qin, G. Diao, J. Phys. Chem. C 2012,
116, 16276.
[441] X. F. Xia, Q. L. Hao, W. Lei, W. J. Wang, D. P. Sun, X. Wang,
J. Mater. Chem. 2012, 22, 16844.
[442] Y. H. Kim, S. J. Park, Curr. Appl. Phys. 2011, 11, 462.
[443] X. Zhao, C. Johnston, A. Crossley, P. S. Grant, J. Mater. Chem.
2010, 20, 7637.
[444] J. Zhu, M. Chen, H. Qu, Z. Luo, S. Wu, H. A. Colorado, S. Wei,
Z. Guo, Energy Environ. Sci. 2013, 6, 194.
[445] M. Xue, F. Li, J. Zhu, H. Song, M. Zhang, T. Cao, Adv. Funct. Mater.
2012, 22, 1284.
[446] X. Lang, L. Zhang, T. Fujita, Y. Ding, M. Chen, J. Power Sources
2012, 197, 325.
[447] X. M. Feng, R. M. Li, Y. W. Ma, R. F. Chen, N. E. Shi, Q. L. Fan,
W. Huang, Adv. Funct. Mater. 2011, 21, 2989.
1300816 (42 of 43)
[448] J. Yan, T. Wei, Z. J. Fan, W. Z. Qian, M. L. Zhang, X. D. Shen, F. Wei,

J. Power Sources 2010, 195, 3041.
[449] C. H. Xu, J. Sun, L. Gao, J. Mater. Chem. 2011, 21, 11253.
[450] J. J. Xu, K. Wang, S. Z. Zu, B. H. Han, Z. X. Wei, ACS Nano 2010, 4,
5019.
[451] H. S. Fan, H. Wang, N. Zhao, X. L. Zhang, J. Xu, J. Mater. Chem.
2012, 22, 2774.
[452] Y. G. Wang, H. Q. Li, Y. Y. Xia, Adv. Mater. 2006, 18, 2619.
[453] H. Wang, Q. Hao, X. Yang, L. Lu, X. Wang, Electrochem. Commun.
2009, 11, 1158.
[454] Y. Hu, Y. Zhao, Y. Li, H. Li, H. Shao, L. Qu, Electrochim. Acta 2012,
66, 279.
[455] L. Z. Fan, Y. S. Hu, J. Maier, P. Adelhelm, B. Smarsly, M. Antonietti,
Adv. Funct. Mater. 2007, 17, 3083.
[456] Z. Lei, Z. Chen, X. S. Zhao, J. Phys. Chem. C 2010, 114, 19867.
[457] X. B. Yan, Z. X. Tai, J. T. Chen, Q. J. Xue, Nanoscale 2011, 3,
212.
[458] D. S. Patil, J. shaikh, S. A. Pawar, R. S. Devan, Y.-R. Ma,
A. V. Moholkar, J. H. Kim, R. S. Kalubarme, C. J. Park, P. S. Patil,
Phys. Chem. Chem. Phys. 2012, 14, 11886.
[459] K. Xie, J. Li, Y. Lai, Z. a. Zhang, Y. Liu, G. Zhang, H. Huang,
Nanoscale 2011, 3, 2202.
[460] Q. Gao, L. Demarconnay, E. Raymundo-Piero, F. Bguin, Energy
Environ. Sci. 2012, 5, 9611.
[461] K. Fic, G. Lota, M. Meller, E. Frackowiak, Energy Environ. Sci. 2012,
5, 5842.
[462] Z. Weng, F. Li, D.-W. Wang, L. Wen, H.-M. Cheng, Angew. Chem.
Int. Ed. 2013, 52, 3722.
[463] D. B. Zhao, M. Wu, Y. Kou, E. Min, Catal. Today 2002, 74, 157.
[464] P. J. Hall, M. Mirzaeian, S. I. Fletcher, F. B. Sillars, A. J. R. Rennie,
G. O. Shitta-Bey, G. Wilson, A. Cruden, R. Carter, Energy Environ.
Sci. 2010, 3, 1238.
[465] G. Lota, E. Frackowiak, Electrochem. Commun. 2009, 11, 87.
[466] S. Roldn, C. Blanco, M. Granda, R. Menndez, R. Santamara,
Angew. Chem. Int. Ed. 2011, 50, 1699.
[467] E. Frackowiak, K. Fic, M. Meller, G. Lota, ChemSusChem 2012, 5,
1181.
[468] F. Beguin, E. Frackowiak, Supercapacitors: Materials, Systems
and Applications, Vol. 1, Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim 2013.
[469] R. B. Rakhi, W. Chen, D. Cha, H. N. Alshareef, Adv. Energy Mater.
2012, 2, 381.
[470] Q. T. Qu, P. Zhang, B. Wang, Y. H. Chen, S. Tian, Y. P. Wu,
R. Holze, J. Phys. Chem. C 2009, 113, 14020.
[471] T. Tomko, R. Rajagopalan, M. Lanagan, H. C. Foley, J. Power
Sources 2011, 196, 2380.
[472] T. Brousse, M. Toupin, D. Belanger, J. Electrochem. Soc. 2004, 151,
A614.
[473] T. Brousse, P. L. Taberna, O. Crosnier, R. Dugas, P. Guillemet,
Y. Scudeller, Y. Zhou, F. Favier, D. Belanger, P. Simon, J. Power
Sources 2007, 173, 633.
[474] H. A. Mosqueda, O. Crosnier, L. Athouel, Y. Dandeville, Y. Scudeller,
P. Guillemet, D. M. Schleich, T. Brousse, Electrochim. Acta 2010,
55, 7479.
[475] H. Q. Wang, Z. S. Li, Y. G. Huang, Q. Y. Li, X. Y. Wang, J. Mater.
Chem. 2010, 20, 3883.
[476] Z.-H. Gao, H. Zhang, G.-P. Cao, M.-F. Han, Y.-S. Yang, Electrochim.
Acta 2013, 87, 375.
[477] Z. Chen, Y. Qin, D. Weng, Q. Xiao, Y. Peng, X. Wang, H. Li, F. Wei,
Y. Lu, Adv. Funct. Mater. 2009, 19, 3420.
[478] X. Xiao, T. Ding, L. Yuan, Y. Shen, Q. Zhong, X. Zhang, Y. Cao,
B. Hu, T. Zhai, L. Gong, J. Chen, Y. Tong, J. Zhou, Z. L. Wang, Adv.
Energy Mater. 2012, 2, 1328.
[479] H. R. Ghenaatian, M. F. Mousavi, M. S. Rahmanifar, Electrochim.
Acta 2012, 78, 212.
www.advenergymat.de
[488] H. S. Choi, T. Kim, J. H. Im, C. R. Park, Nanotechnology 2011, 22,

405402.
[489] Y. G. Wang, Y. Y. Xia, Electrochem. Commun. 2005, 7, 1138.
[490] S. B. Ma, K. W. Nam, W. S. Yoon, X. Q. Yang, K. Y. Ahn, K. H. Oh,
K. B. Kim, Electrochem. Commun. 2007, 9, 2807.
[491] J. Y. Luo, Y. Y. Xia, J. Power Sources 2009, 186, 224.
[492] H. Y. Wang, M. Yoshio, A. K. Thapa, H. Nakamura, J. Power Sources
2007, 169, 375.
[493] V. Khomenko, E. Raymundo-Pinero, F. Beguin, J. Power Sources
2008, 177, 643.
[494] V. Khomenko, E. Raymundo-Pinero, F. Beguin, J. Power Sources
2010, 195, 4234.
[495] S. R. Sivakkumar, A. G. Pandolfo, Electrochim. Acta 2012, 65, 280.
(43 of 43) 1300816
REVIEW
[480] P. J. Hung, K. H. Chang, Y. F. Lee, C. C. Hu, K. M. Lin, Electrochim.

Acta 2010, 55, 6015.
[481] P. Perret, Z. Khani, T. Brousse, D. Blanger, D. Guay, Electrochim.
Acta 2011, 56, 8122.
[482] W. Tang, L. L. Liu, S. Tian, L. Li, Y. B. Yue, Y. P. Wu, K. Zhu, Chem.
Commun. 2011, 47, 10058.
[483] X. Zhao, C. Johnston, P. S. Grant, J. Mater. Chem. 2009, 19, 8755.
[484] J. Zhang, X. S. Zhao, ChemSusChem 2012, 5, 818.
[485] Y. P. Lin, N. L. Wu, J. Power Sources 2011, 196, 851.
[486] H. S. Choi, J. H. Im, T. Kim, J. H. Park, C. R. Park, J. Mater. Chem.
2012, 22, 16986.
[487] H.-G. Jung, N. Venugopal, B. Scrosati, Y.-K. Sun, J. Power Sources
2013, 221, 266.

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Recent Advances in Design and Fabrication of

Figure 1. Specific power against specific energy, also called a Ragone

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 2. Trends in the number of publications on supercapacitors (data

have triggered an explosion of interest for a wide and growing

Jun Yan received his PhD

Zhuangjun Fan received

around the world. Therefore, it is imperative and important

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Energy Mater. 2014, 4, 1300816

literature are highlighted. However, we do not claim that this

2. Important Parameters for High Energy Density

Adv. Energy Mater. 2014, 4, 1300816

Figure 3. Schematic illustration of different approaches to improve

is of critical significance for it to simultaneously possess high

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

3. Electrode Materials with High SC

Figure 5. a) Schematic illustration of an EDLC in its charged state.

store charge electrostatically through reversible adsorption of

3.1. Porous Carbon Materials

where r (a dimensionless constant) is the relative dielectric

Figure 4. Capacitive performance of various electrode materials reported

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Energy Mater. 2014, 4, 1300816

3.1.1. Activated Carbon

Adv. Energy Mater. 2014, 4, 1300816

Figure 6. a) Specific surface capacitance vs. average pore size shows a

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Coal tar pitch

Green needle coke

Camellia oleifera shell

Argan seed shells

Sugar cane bagasse

Sunflower seed shell

Rubber wood saw

can be accumulated at the electrode/electrolyte interface.

capacitance and stored energy density due to the increase in

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Energy Mater. 2014, 4, 1300816

Figure 7. a) Scanning electron microscopy (SEM) image, b) pore size

Adv. Energy Mater. 2014, 4, 1300816

voltage and saturates at high voltages both theoretically and

Figure 8. a) Transmission electron microscopy (TEM) image and b) SC

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

seaweeds for symmetric supercapacitors exhibited a SC of

Figure 9. Schematic representation of templating synthesis of various

macroporous carbons with different structures can be prepared

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Energy Mater. 2014, 4, 1300816

Adv. Energy Mater. 2014, 4, 1300816

Figure 10. Schematic representation of the highly ordered MCNAs.

co-workers demonstrated the facile synthesis of highly ordered

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 11. a) Schematic representation of the 3D hierarchical porous

impressive performances are believed to be attributed to its

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Figure 12. a) Illustration of the synthetic routes to 3D HOPC through

MC(s) M(g) + C(s)

The as-synthesized CDCs possess a narrow and tunable

2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Energy Mater. 2014, 4, 1300816

Adv. Energy Mater. 2014, 4, 1300816

CNTs have attracted increasing interest for supercapacitor