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TUTORIAL REVIEW www.rsc.org/csr | Chemical Society Reviews
Carbon-based materials as supercapacitor electrodes
Li Li Zhang and X. S. Zhao*
Received 9th March 2009
First published as an Advance Article on the web 12th June 2009
DOI: 10.1039/b813846j
This tutorial review provides a brief summary of recent research progress on carbon-based
electrode materials for supercapacitors, as well as the importance of electrolytes in the
development of supercapacitor technology. The basic principles of supercapacitors, the
characteristics and performances of various nanostructured carbon-based electrode materials are
discussed. Aqueous and non-aqueous electrolyte solutions used in supercapacitors are compared.
Published on 12 June 2009 on http://pubs.rsc.org | doi:10.1039/B813846J
The trend on future development of high-power and high-energy supercapacitors is analyzed.
1. Introduction
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Climate change and the limited availability of fossil fuels
have greatly affected the world economy and ecology. With
a fast-growing market for portable electronic devices and the
development of hybrid electric vehicles, there has been an ever
increasing and urgent demand for environmentally friendly
high-power energy resources. Supercapacitors, also known as
electrochemical capacitors or ultracapacitors, have attracted
much attention because of their pulse power supply, long cycle
life (4100 000 cycles), simple principle, and high dynamic of
charge propagation.1–3 As illustrated in Fig. 1, where various
energy conversion and storage devices are compared and
presented in the simplified ‘Ragone plot’, supercapacitors
occupy an important position in terms of the specific energy
as well as the specific power. With a high power capability and
relatively large energy density compared to conventional
capacitors, supercapacitors offer a promising approach to
meet the increasing power demands of energy storage systems
in the twenty first century. Currently, supercapacitors are
Department of Chemical and Biomolecular Engineering, National
University of Singapore, 4 Engineering Drive 4, 117576, Singapore.
E-mail: chezxs@nus.edu.sg; Fax: +65-67791936; Tel: +65-65164727
Li Li Zhang received her
Bachelor’s degree in Chemical
and Biomolecular Engineering
(first class honours) from
the National University of
Singapore in 2004. After two
years of experience in industry,
she took up a PhD scholarship
to work under the supervision
of Professor X. S. Zhao. Her
research project deals with
designing novel carbon-based
electrode materials for electro-
chemical energy storage
Li Li Zhang applications.
2520 | Chem. Soc. Rev., 2009, 38, 2520–2531
widely used in consumer electronics, memory back-up systems
and industrial power and energy management.4 A more recent
application is the use of supercapacitors in emergency doors
on the Airbus A380, highlighting their safe and reliable
performance. One of the most promising applications is their
use in low-emission hybrid electric vehicles, and fuel cell
vehicles. In such cases, supercapacitors are coupled with
primary high-energy batteries or fuel cells to serve as a
temporary energy storage device with a high-power capability
to store energies when braking. Supercapacitors are likely to
show an equal importance to batteries for future energy
storage systems.
Generally, on the basis of the energy storage mechanism,
supercapacitors can be classified into two categories.5 One is
the electrical double layer capacitor (EDLC), where the
capacitance comes from the pure electrostatic charge accumu-
lated at the electrode/electrolyte interface, therefore it is
strongly dependent on the surface area of the electrode
materials that is accessible to the electrolyte ions. The other
category is the pseudo-capacitor, in which fast and reversible
faradic processes take place due to electro-active species.
These two mechanisms can function simultaneously depending
on the nature of the electrode materials. Progress towards
supercapacitor technologies can benefit from the continuous
X. S. Zhao received his PhD in
Chemical Engineering from
the University of Queensland
in 1999 under the supervision
of Professor Max Lu. After
two-years of postdoctoral
researching training at the
same university, he joined the
Department of Chemical and
Biomolecular Engineering,
National University of
Singapore, as an Assistant
Professor, and then later
became an Associate Professor.
X. S. Zhao His main research interest
focuses on template synthesis
of porous materials and the exploitation of their applications in
emerging areas.
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Fig. 1 Ragone plot showing the specific power against specific
energy for various electrical energy storage systems (r The Nature
Publishing Group, reprinted with permission).6
development of nanostructured materials. Readers can refer to
a number of recent reviews, which discuss the scientific and
technological improvements of supercapacitors of various
configurations and electrodes.1,2,5–8
Carbon-based materials ranging from activated carbons
(ACs) to carbon nanotubes (CNTs) are the most widely used
electrodes because of the often-cited desirable physical and
chemical properties. These properties include low cost, variety
of form (powders, fibers, aerogels, composites, sheets,
monoliths, tubes, etc.), ease of processability, relatively inert
electrochemistry, controllable porosity and electrocatalytic
active sites for a variety of redox reactions.9,10 In the
development of EDLCs, a proper control over the specific
surface area and the pore size adapted to an appropriate
type of electrolyte solution are crucial to ensure a good
performance of the supercapacitor in terms of both power
delivery rate and energy storage capacity. ACs are often
considered as EDLC electrode materials because of their high
surface area and somewhat controllable pore size, depending
on the method of activation (chemical or physical activation).
Since Knox and co-workers pioneered the template syn-
thesis of porous carbons,11 many porous carbon materials
with well controlled and uniform pore sizes have been
designed and synthesized.12 Templated porous carbons of
microporous, mesoporous and macroporous sizes with a
tailorable hierarchical structure hold a great promise as super-
capacitor electrode materials. On the other hand, CNTs are of
particular interest for the development of supercapacitor
electrodes because of their unique tubular porous structures
and superior electrical properties, which favor fast ion and
electron transportation. More recently, the rise of graphene,
which is a new class of two-dimensional carbon nanostructure,
having large specific surface area and exceptionally high
electronic qualities, is forecasted to have enticing potential in
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supercapacitor applications if large-scale production of
graphene sheets is possible.13
In developing high-capacitance supercapacitors, the pseudo-
capacitance due to the presence of foreign electro-active
species in the porous carbon framework is coupled with the
EDLC to enhance the overall capacitance of the electrode
materials. The most commonly studied species having quick
and reversible faradic reactions include oxygen- and nitrogen-
containing surface functional groups, electrically conducting
polymers, and transition metal oxides (e.g., RuO2, MnOx,
etc.). The capacitive performance and some physical properties
of various carbon and carbon-based electrode materials are
summarized in Table 1, which is based on a literature survey.
The use of high-capacitance materials (high surface area or
pseudo-active species) is a key factor to ensure high energy
density; whereas a high electrical conductivity (thus a fast
charge transportation) of the electrode materials as well as the
electrolyte solution is necessary for a high rate capability.
Hence, one of the most critical aspects in the development of
supercapacitors is to optimize the energy density without
deteriorating their high power capability as these two parameters
determine the ultimate performance of the supercapacitor. In
this tutorial review, we provide a brief summary of recent
research progress on carbon-based electrode materials and the
importance of the electrolyte solutions in the development of
supercapacitor technologies.
2. Principle of energy storage in supercapacitors
2.1 The energy storage mechanism
Supercapacitors are electrochemical energy storage devices.
The way that supercapacitors store energy is based, in principal,
on two types of capacitive behavior: the electrical double layer
(EDL) capacitance from the pure electrostatic charge
accumulation at the electrode interface, and the pseudo-capacitance
developed from fast and reversible surface redox processes at
characteristic potentials. It is more convenient to discuss the
two mechanisms separately, though they usually function
together in a supercapacitor.
2.1.1 The energy storage mechanism of EDLCs.
Conventional capacitors store little by way of energy, due to
the limited charge storage areas and geometric constrains of the
separation distance between the two charged plates. However,
supercapacitors based on the EDL mechanism can store much
more energy because of the large interfacial area and the
atomic range of charge separation distances. As schematically
illustrated in Fig. 2a, the concept of the EDL was first
described and modeled by von Helmholtz in the 19th century,
when he investigated the distribution of opposite charges at
the interface of colloidal particles.14 The Helmholtz double
layer model states that two layers of opposite charge form at
the electrode/electrolyte interface and are separated by an
atomic distance. The model is similar to that of two-plate
conventional capacitors. This simple Helmholtz EDL
model was further modified by Gouy and Chapman15,16 on
consideration of a continuous distribution of electrolyte ions
(both cations and anions) in the electrolyte solution, driven by
thermal motion, which is referred to as the diffuse layer
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Table 1 Properties and characteristics of various carbon and carbon-based materials as supercapacitors electrode materials

Aqueous electrolyte Organic electrolyte

1 3
Materials 2
Specific surface area/m g 1
Density/g cm 3
/F g /F cm /F g1 /F cm3
Carbon materials
Commercial activated carbons (ACs) 1000–3500 0.4–0.7 o 200 o 80 o 100 o 50
Particulate carbon from SiC/TiC 1000–2000 0.5–0.7 170–220 o 120 100–120 o 70
Functionalized porous carbons 300–2200 0.5–0.9 150–300 o 180 100–150 o 90
Carbon nanotube (CNT) 120–500 0.6 50–100 o 60 o 60 o 30
Templated porous carbons (TC) 500–3000 0.5–1 120–350 o 200 60–140 o 100
Activated carbon fibers (ACF) 1000–3000 0.3–0.8 120–370 o 150 80–200 o 120
Carbon cloth 2500 0.4 100–200 40–80 60–100 24–40
Carbon aerogels 400–1000 0.5–0.7 100–125 o 80 o 80 o 40
Carbon-based composite materials
TC–RuO2 composite 600 1 630 630 — —
CNT–MnO2 composite 234 1.5 199 300 — —
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AC–polyaniline composite 1000 — 300 — — —

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Fig. 2 Models of the electrical double layer at a positively charged surface: (a) the Helmholtz model, (b) the Gouy–Chapman model, and (c) the
Stern model, showing the inner Helmholtz plane (IHP) and outer Helmholtz plane (OHP). The IHP refers to the distance of closest approach of
specifically adsorbed ions (generally anions) and OHP refers to that of the non-specifically adsorbed ions. The OHP is also the plane where the
diffuse layer begins. d is the double layer distance described by the Helmholtz model. j0 and j are the potentials at the electrode surface and the
electrode/electrolyte interface, respectively.

(see Fig. 2b). However, the Gouy–Chapman model leads to an
overestimation of the EDL capacitance. The capacitance of two
separated arrays of charges increases inversely with their
separation distance, hence a very large capacitance value would
arise in the case of point charge ions close to the electrode
surface. Later, Stern17 combined the Helmholtz model with the
Gouy–Chapman model to explicitly recognize two regions of
ion distribution—the inner region called the compact layer or
Stern layer and the diffuse layer (see Fig. 2c). In the compact
layer, ions (very often hydrated) are strongly adsorbed by the
electrode, thus the name of compact layer. In addition, the
compact layer consists of specifically adsorbed ions (in most
cases they are anions irrespective of the charge nature of the
electrode) and non-specifically adsorbed counterions. The inner
Helmholtz plane (IHP) and outer Helmholtz plane (OHP) are
used to distinguish the two types of adsorbed ions. The diffuse
layer region is as what the Gouy–Chapman model defines.
The capacitance in the EDL (Cdl) can be treated as a
combination of the capacitances from two regions, the Stern
type of compact double layer capacitance (CH) and the
diffusion region capacitance (Cdiff). Thus, Cdl can be expressed
by the following equation:
1 1 1
¼ þ ð1Þ
Cdl CH Cdiff
The factors that determine the EDL behavior at a planar
electrode surface include the electrical field across the electrode,
the types of electrolyte ions, the solvent in which the

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electrolyte ions are dissolved, and the chemical affinity
between the adsorbed ions and the electrode surface. As the
electrode is usually a porous material with a high specific
surface area, the EDL behavior at the pore surface of the
porous electrode is more complex than that at an infinite
planar one as the ion transportation in a confined system
can be drastically affected by a number of parameters, such as
the tortuous mass transfer path, the space constrain inside the
pores, the ohmic resistance associated with the electrolyte, and
the wetting behavior of the pore surface by the electrolyte.
Fig. 3 schematically illustrates an EDLC made of porous
carbon electrode.
The capacitance estimation for an EDL-type supercapacitor
is generally assumed to follow that of a parallel-plate
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capacitor:9
er e0
C¼ A ð2Þ
d
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where er is the electrolyte dielectric constant, e0 is the
permittivity of a vacuum, A is the specific surface area of the
electrode accessible to the electrolyte ions, and d is the effective
thickness of the EDL (the Debye length). Based on eqn (2),
there should be a linear relationship between specific
capacitance (C) and specific surface area (A). However, some
experimental results have shown that this simple linear
relationship does not hold.18,19 Traditionally it was believed
Fig. 3 Schematic representation of an EDLC based on porous
electrode materials.
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that the submicropores of an electrode do not participate
in the formation of EDL due to the inaccessibility of the
submicropore surfaces to the large solvated ions. However,
Raymundo-Pinero and co-workers20 recently observed the
important contributions of micropores to the overall capacitance
and suggested that partial desolvation of hydrated ions
occurred, leading to an enhanced capacitance. Very recently,
Simon and Gogotsi6 reported an anomalous capacitance
increase in carbon electrodes with pore sizes less than 1 nm.
The authors observed the maximum EDL capacitance when
the electrode pore size was very close to the ion size. These
results further confirmed a capacitance contribution from
pores with sizes smaller than the solvated ion size.
However, these new experimental findings cannot be fully
interpreted by the EDL theory because in such confined
micropore spaces, there would be insufficient room to
accommodate both the compact layer and diffuse layer.
Recently, Huang and co-workers21 have reported a heuristic
approach to describing nanoporous carbon-based super-
capacitors. In their approach, the pore curvature is taken into
account and a different capacitive behavior was proposed
depending on the size of the pore. An electric double-cylinder
capacitor (EDCC) model is used for describing mesoporous
carbon electrodes, while an electric wire-in-cylinder capacitor
(EWCC) model is proposed for modelling microporous
carbon electrodes, as illustrated in Fig. 4. When the pores
are large enough so that the pore curvature is no longer
significant, the EDCC model can be reduced natually to the
traditional planar EDL model given in eqn (2). The capacitance
estimation for the two proposed models are given in eqn (3)
for the EDCC model and eqn (4) for the EWCC model,
respectively:
er e0
C¼ A ð3Þ
b ln½b=ðb  dÞ
er e0
C¼ A ð4Þ
b lnðb=a0 Þ
in which b is the pore radius, d is the distance of approaching
ions to the surface of the carbon electrode, and a0 is the
Fig. 4 Schematic diagrams (top views) of (a) a negatively charged
mesopore with solvated cations approaching the pore wall to form an
electric double-cylinder capacitor and (b) a negatively charged micro-
pore of radius b with cations lining up along the pore axis to form an
electric wire-in-cylinder capacitor (r Wiley InterScience, reprinted
with permission).21
Chem. Soc. Rev., 2009, 38, 2520–2531 | 2523

effective size of the counterions (that is, the extent of electron
density around the ions).
With these models, the authors were able to make good fits
of mathematical results obtained using eqn (3) and (4) to
experimental data, regardless of the types of carbon materials
and electrolytes employed. Both the anomalous increase in
capacitance for pores sizes below 1 nm, and the trend for
slightly increased capacitance with an increase in pore size
above 2 nm, can be explained by fitting with the proposed
EWCC and EDCC models, respectively. In addition, the
dielectric constant calculated from the fitting results using
eqn (4) is close to the vacuum value, which indicates that
desolvation of hydrated ions occurs before entering the
micropores.
Published on 12 June 2009 on http://pubs.rsc.org | doi:10.1039/B813846J
In spite of the recent experimental and theoretical advance-
ments, there still lacks of an in-depth understanding of the
EDL charge storage mechanism in the nano-confined spaces.
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More theoretical and fundamental studies on what happens
and how the charge is stored inside the micropores are desired
for future EDLC development.
2.1.2 The energy storage mechanism of pseudo-capacitance.
In contrast to EDL capacitance, pseudo-capacitance arises for
thermodynamics reasons and is due to charge acceptance (Dq) and
a change in potential (DV).5 The derivative C = d(Dq)/(dDV)
corresponds to a capacitance, which is referred to as the
pseudo-capacitance. The main difference between pseudo-
capacitance and EDL capacitance lies in the fact that
pseudo-capacitance is faradic in origin, involving fast and
reversible redox reactions between the electrolyte and
electro-active species on the electrode surface. The most
commonly known active species are ruthenium oxide,22
manganese oxide,23 vanadium nitride,24 electrically conducting
polymers such as polyaniline,25 and oxygen- or nitrogen-
containing surface functional groups.26 While pseudo-capacitance
can be higher than EDL capacitance, it suffers from the
drawbacks of a low power density (due to poor electrical
conductivity), and lack of stability during cycling.
A good example of a material providing a pseudo-capacitive
property is ruthenium oxide. Due to its intrinsic reversibility
for various surface redox couples5,27 and high conductivity,
the electrochemical behavior of both amorphous and crystal-
line forms of ruthenium oxide has been widely studied in acidic
electrolyte solution over the past few decades. It was shown
that amorphous hydrous ruthenium oxide (RuO2xH2O)
exhibited a much higher specific capacitance (720 F g1) than
anhydrous ruthenium oxide.28 This has been attributed to the
mixed proton–electron conductivity within RuO2xH2O, as
the superfacial redox transitions of ruthenium oxide involve
proton and electron double injection/expulsion according to
the following reaction:5,22
RuOx (OH)y + dH+ + de 3 RuOxd (OH)y+d (5)
where RuOx (OH)y and RuOxd (OH)y+d represent the inter-
facial oxyruthenium species at higher and lower oxidation
states. In a proton-rich electrolyte environment (e.g. H2SO4),
the faradic charges can be reversibly stored and delivered
through the redox transitions of the oxyruthenium groups,
i.e., Ru(IV)/Ru(III) and Ru(III)/Ru(II). Based on the mean
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electron transfer numbers, the theoretical specific capacitance
of RuO2xH2O is estimated to range from ca. 1300 to
2200 F g1.29 A very high specific capacitance of 1300 F g1
was reported for a pure bulk nanostructured RuO2xH2O
electrode.22 The superior electrochemical performance is
related to its tailored nanotubular arrayed porous architecture
with metallic conductivity as well as its hydrous nature. As
implied by eqn (5), the reversible redox transitions depend on
both proton exchange and electron-hopping processes. The
tubular arrayed porous structure and metallic conductivity
provided an effective pathway for electrolyte and electron
transportation. In addition, the hydrous nature of
RuO2xH2O ensures a high rate of proton exchange because
the surface of the hydrous oxide has been considered to be a
proton liquid.30 As a result, the designed nanostructure
demonstrated a promising electrode material for energy
storage. However, the cost of the precious metal oxide
and difficulties in large scale production limit its practical
applications.
2.2 The performance of supercapacitors
There are fundamental differences between batteries and
supercapacitors in terms of energy storage mechanism and
electrode materials. Therefore, the characteristic performance
of supercapacitors that sets them apart from batteries should
be maintained for any technology improvement.
The performance of supercapacitors is mainly evaluated
on the basis of the following criteria: (1) a power density
substantially greater than batteries with acceptably high
energy densities (4 10 Wh kg1); (2) an excellent cyclability
(more than 100 times that of batteries); (3) fast charge/
discharge processes within seconds; (4) low self-discharging;
(5) safe operation, and (6) low cost. The basic operation of a
single-cell supercapacitor consisting of two electrodes is
illustrated in Fig. 5 below in a simple equivalent RC circuit
representation. Ca and Cc are the capacitance of the anode and
cathode, respectively (the specific capacitance of a single
electrode reported in the literature is based on a three-
electrode cell configuration). Rs is the equivalent series
resistance (ESR) of the cell. RF is the resistance responsible
for the self-discharge of a single electrode and the notation for
anode and cathode are RFa and RFc, respectively. The total
capacitance of the cell (CT) is therefore calculated
according to:
1 1 1
¼ þ ð6Þ
CT Ca Cc
In an RC circuit, the time constant (t) expressed as resistance
(R)  capacitance (C) gives important information on the
characteristic of a capacitor. For example, the time constant
Fig. 5 A simple RC equivalent circuit representation illustrates the
basic operation of a single-cell supercapacitor.
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for the self-discharge of the anode is equal to RFaCa and
hence a larger value of RFa is desirable for smaller leakage of
the anode. The maximum energy stored (E) and power
delivered (P) for such a single cell supercapacitor are given
in eqn (7) and (8):
E = 12 CTV2 (7)
2 the capacitance of the ACs and their specific surface area.
V
P¼ ð8Þ
4Rs
where V is the cell voltage (in volts), CT is the total capacitance
of the cell (in farads) and Rs is the ESR (in ohms). Each
element inside the equivalent circuit is crucial to the final
performance of the supercapacitor. The capacitance of the cell
Published on 12 June 2009 on http://pubs.rsc.org | doi:10.1039/B813846J
depends extensively upon the electrode material. The cell
voltage is limited by the thermodynamic stability of the
electrolyte solution. ESR comes from various types of
resistance associated with the intrinsic electronic properties
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of the electrode matrix and electrolyte solution, mass transfer
resistance of the ions in the matrix, and contact resistance
between the current collector and the electrode. Hence,
for a supercapacitor to have a good performance, it must
simultaneously satisfy the requirements of having a large
capacitance value, high operating cell voltage and minimum
ESR. It is thus obvious that the development of both electrode
materials as well as the electrolyte solutions is required
in order to optimize the overall performance of the super-
capacitor.
With regard to the electrode materials, the development of
high surface area carbon electrodes with a defined pore size
distribution, and the incorporation of pseudo-active materials
to optimize the overall capacitance and conductivity without
destroying the stability, are currently hot research areas. High
density electrode materials will give a high volumetric energy
which is desirable for practical applications, especially for the
design of a highly compact energy and power source. On the
other hand, electrolyte development, especially non-aqueous
electrolytes with lower resistivity are highly desirable for their
higher power and energy density owing to higher operating
voltages (up to 3.5–4 V). In the following sections, an overview
of recent developments on carbon-based electrode materials as
well as electrolytes will be discussed.
3. Carbon-based electrode materials
3.1 Activated carbons (ACs)
ACs are the mostly widely used electrode materials due to their
large surface area, relatively good electrical properties and
moderate cost. ACs are generally produced from physical
(thermal) and/or chemical activation of various types of
carbonaceous materials (e.g. wood, coal, nutshell, etc.).
Physical activation usually refers to the treatment of carbon
precursors at high temperature (from 700 to 1200 1C) in the
presence of oxidizing gases such as steam, CO2 and air.
Chemical activation is usually carried out at lower temperatures
(from 400 to 700 1C) with activating agents like phosphoric
acid, potassium hydroxide, sodium hydroxide and zinc
chloride. Depending on the activation methods as well as the
carbon precursors used, ACs possessing various physicochemical
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properties with well developed surface areas as high as 3000 m2 g1
have been produced and their electrochemical properties have
been studied.18–20,31–34 It is well known that the porous
structure of ACs produced by activation processes have a
broad pore size distribution consisting of micropores
(o 2 nm), mesopores (2–50 nm) and macropores (450 nm).
Several researchers have pointed out the discrepancy between
With a high surface area up to 3000 m2 g1, only a relatively
small specific capacitance o 10 mF cm2 was obtained,
much smaller than the theoretical EDL capacitance
(15–25 mF cm2),5 indicating that not all pores are effective
in charge accumulation.32 Therefore, although the specific
surface area is an important parameter for the performance
of EDLC, some other aspects of the carbon materials such as
pore size distribution, pore shape and structure, electrical
conductivity and surface functionality can also influence their
electrochemical performance to a great extent. Furthermore,
excessive activation will lead to large pore volume,
which results in the drawbacks of low material density and
conductivity. These would in turn cause a low volumetric
energy density and loss of power capability. In addition, high
active surface areas may increase the risk of decomposition of
the electrolyte at the dangling bond positions.34 The presence
of the acidic functionalities and moisture on the surface
of ACs is responsible for the aging of the supercapacitor
electrodes in organic electrolytes.35
Efforts have been made to search for the relationship
between the nanoporous structure of ACs and their
capacitance performance in different electrolytes. In general,
the capacitance of ACs is higher in aqueous electrolytes
(ranging from 100 F g1 to 300 F g1) than in organic
electrolytes (less than 150 F g1). One reason for this is
believed to be the larger effective size of the electrolyte ions
in organic solutions when compared with those in water.
Organic electrolytes increase the number of pores that are
smaller than the ions, and therefore increase the number not
contributing to the charge storage. The wettability of the
carbon surface by the organic electrolyte, which is determined
by the chemical affinity between the two may be another
reason. Salitra and co-workers have concluded that a pore
size above 0.4 nm can be active in EDL charging in aqueous
solution.33 The studies by the Beguin group also concluded
that the optimal pore size for EDL capacitance is 0.7 nm in
aqueous media and 0.8 nm in organic electrolytes.20 All these
findings have shown the essential role of micropores that are
electrochemically accessible by the electrolyte ions on the
capacitance performance. Most recent studies by Largeot et al.
have clearly demonstrated the relationship between ion size
and pore size for an EDLC using carbide-derived-carbons
(CDCs) and concluded that the maximum EDL capacitance is
achieved when the pore size matches with the ion size.36 The
pore size-dependent capacitive behavior is shown in Fig. 6.
Besides the porous structure of ACs, the surface
functionalities also play important roles on the carbon
electrode performance, as they will affect the wettability of
the carbon surface by the electrolyte ions and give additional
pseudo-capacitance.10,26,34 An activated carbon containing a
high concentration of oxygen-functional groups with low
Chem. Soc. Rev., 2009, 38, 2520–2531 | 2525

Fig. 6 Normalized capacitance change as a function of pore size for
CDC samples prepared at different temperatures. Ionic liquid
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EMI–TFSI was used as the electrolyte and the maximum capacitance
was obtained at a pore size that matched the maximum ion dimension
(r The American Chemical Society, reprinted with permission).36
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porosity (BET specific surface area = 270 m2 g1) has been
prepared by one-step carbonization of an oxygen-rich carbon
precursor.34 The material showed a good electrochemical
performance with a high energy density of 10 Wh kg1 even
at high power densities close to 10 kW kg1 in acidic
electrolyte. Moreover, good capacitance values were still retained
after 10 000 cycles, indicating few catalytically active sites on
the carbon surface, probably due to the comparatively low
surface area. However, most commercial supercapacitors use
organic electrolytes because of the higher operating voltages,
which offer a higher energy density. Pandolfo and Hollenkamp
have given an overview of ACs with various types of
functional groups and pointed out that the presence of some
active surface oxides and a trace amount of water result in
instability of the electrode, an increase of series resistance and
the decomposition of the organic electrolyte.10 Some other
studies also showed the aging of AC electrodes in organic
electrolytes due to the active surface of carbon.35,37 Therefore,
surface functionality and porosity of ACs should be optimized
for improved long-term performance. Pure ACs without
heteroatoms and water might be better for use in an organic
electrolyte.
In short, ACs have been commercially used as super-
capacitor electrode materials. However, their applications
are still restricted to only certain niche markets due to the
limited energy storage and rate capability. Although activated
carbons provide a high surface area, the control of pore size
distribution and pore structure is still challenging. Therefore,
designing ACs to have narrow pore size distribution
(accessible to the electrolyte ions) with an interconnected pore
structure and short pore length together with controlled
surface chemistry would be beneficial for enhancing the energy
density of supercapacitors, without deteriorating their high
power density and cycle life.
3.2 Carbon nanotubes (CNTs)
The discovery of CNTs has significantly advanced the science
and engineering of carbon materials. Fig. 7 shows the atomic
structures of different types of carbon nanotubes. As discussed
previously, the major factor that determines the power density
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Fig. 7 Atomic structure of carbon nanotubes, (a) schematic diagram
showing how a graphene sheet is ‘rolled’ according to a pair of chiral
vectors to form different atomic structures of carbon nanotubes, (b) zig-zag
(n,0) (c) chiral (n,m) and (d) armchair (n,n) carbon nanotubes.
is the overall resistance of the components in a supercapacitor.
Carbon nanotubes, due to their unique pore structure, super-
ior electrical properties, and good mechanical and thermal
stability, have attracted a great deal of attention for super-
capacitor electrode applications.23,38–41 CNTs can be categorized
as single-walled carbon nanotubes (SWNTs) or multi-walled
carbon nanotubes (MWNTs), both of which have been widely
explored as energy storage electrode materials. CNTs are
usually regarded as the choice of a high-power electrode
material because of their good electrical conductivity and
readily accessible surface area. Moreover, their high mechanical
resilience and open tubular network make them a good
support for active materials. The energy density is, however,
a concern due to their relatively small specific surface area
(generally o 500 m2 g1) as compared to ACs. Of greater
importance is the difficulty in retaining the intrinsic properties
of individual CNTs on a macroscopic scale39 and the high
purity and electrolyte-dependent capacitance performance.40
Niu et al. have reported a MWNT-based supercapacitor
electrode showing a high specific capacitance of 102 F g1 with
surface area of 430 m2 g1 and a power density of 8 kW kg1
in an acidic electrolyte.38 It should be taken into account that
recent studies have shown that entangled CNTs are less
efficient in facilitating fast ionic transportation when compared
to aligned CNTs, due to the irregular pore structures and high
entanglement of the CNT structure in the former.42 Hence, the
use of aligned CNT seems to be more advantageous in terms
of power performance. Futaba and co-workers have presented
a method to fabricate a densely packed aligned SWNT solid
by using the zipping effect of liquids, which allowed the bulk
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materials to retain the intrinsic properties of the SWNTs.39

The energy density of the obtained SWNT solid was about
35 Wh kg1 (normalized to a cell consisting of two identical
electrode materials) in organic electrolyte, and the rate
capability was better than that of ACs. These studies showed
the importance of the aligned tubular structures and preserved
intrinsic CNT properties on the electrochemical performance
of the electrode materials.
Research has been undertaken to improve the energy
density of CNTs by increasing their specific surface area via
chemical activation (KOH activation).10 However, a proper
balance between the porosity and the conductivity must be
achieved in order to have both high capacitance and good rate
performance. Very recently, an interesting CNT–aerogel
Published on 12 June 2009 on http://pubs.rsc.org | doi:10.1039/B813846J

composite material was synthesized by uniformly dispersing

a carbon aerogel throughout the CNT host matrix without
destroying the integrity or reducing the aspect ratio of the
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CNT.41 A high specific surface area of 1059 m2 g1 and

extremely high specific capacitance of 524 F g1 were
obtained, but at the expense of a tedious preparation pathway.
Another way to enhance the specific capacitance is by
modification of CNTs with active materials to realize
pseudo-capacitance through faradic processes, which will be
described later.
In spite of having excellent properties, the limited surface
area of CNTs restricted their use as high energy performance
EDLCs. In addition, the present difficulty in purification and
high cost of production still hinder their practical applications.
3.3 Templated carbons
A templating method offers another effective way to produce
nanostructured carbons with well controlled narrow pore size
distributions, ordered pore structures, large specific surface
areas and an interconnected pore network, making them
promising candidates for supercapacitor electrode materials.
There has been remarkable progress in the synthesis of ordered
nanostructured carbons through templating techniques.43 In
general, the preparation procedure of templated carbons is
infiltration of a carbon precursor into the pores of the
template, followed by a carbonization treatment and finally
the removal of the template to leave behind a porous carbon
structure. The schematic representation in Fig. 8 shows the
general concept of the templating technique and the porous
carbons obtained from different templates.
Various carbon structures with well controlled micropores,
mesopores and/or macropores produced from different types
of template and carbon precursors have been studied for
supercapacitor applications.44–46,9 A functionalized micro-
porous carbon material was obtained by using zeolite Y as a
template and the resultant carbon material possessed a high
gravimetric capacitance of about 340 F g1 in aqueous
electrolyte with good cyclability (over 10 000 cycles).44
Compared to ACs, whose micropores are essentially disordered
and broad in pore-size distribution, the templated micro-
porous carbons with a narrow pore size distribution, well
adapted pore size to the electrolyte ions and the ordered
straight pore channels are better for use as high-energy-density
electrode materials. Moreover, the well controlled porous
Fig. 8 (a) Macroscopic representation showing the general concept of
the templating technique; microscopic synthesis of (b) macroporous
carbons using silica spheres as template, (c) mesoporous carbons using
SBA-15 as template and (d) microporous carbons using zeolite Y as
template.
structure facilitated an efficient use of pseudo-capacitance from
the nitrogenated and oxygenated functionalities of the carbon
materials.
It has been proposed that the presence of mesopores
(usually 2–8 nm) can accelerate the kinetic process of the ion
diffusion in the electrodes and improve the power performance
at high current densities, whereas micropores that are
accessible to the electrolyte ions are essential for high energy
storage.9,21,46 Wang and co-workers have reported a
3-dimensional (3D) hierarchical porous graphitic carbon
(HPGC) material with macroporous cores, mesoporous walls
and micropores for high rate supercapacitor applications.46 In
their designed hierarchical structure, macropores serve as ion-
buffering reservoirs; the graphitic mesopore walls provide
excellent electrical conductivity, capable of overcoming the
primary kinetic limits of electrochemical process in porous
electrodes. In addition, the presence of micropores can
enhance the charge storage. The schematic representation of
the 3D structure and the performance of the carbon materials
are shown in Fig. 9.
Yamada’s group have also synthesized ordered porous
carbons containing meso/macro/micropores with large surface
areas by a colloidal-crystal templating technique.47 A high
EDL capacitance of 200–350 F g1 was achieved in an acidic
electrolyte solution. Their investigation on pore-dependent
capacitance properties have revealed that the micropores

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Fig. 9 (a) Schematic representation of the 3D hierarchical porous
structure (HPGC) and (b) Ragone plot comparing the performance of
HPGC material with those of CMK-3, CMK-5, activated carbon
(Maxsob, Japan), ALG-C, PVA porous carbon, and small-pore EC.
The dotted lines show the current drain time (r Wiley InterScience,
reprinted with permission).46
adjacent to the open mouths of pores are effective in
charge storage, and larger pores that are interconnected are
important for smooth electrolyte transportation. Hence,
carbon materials having well controlled hierarchical porous
structures would be favorable for designing high performance
EDLC electrodes.
The templating method has been shown to be one of the
most suitable techniques to control the preparation of porous
materials, especially ordered porous solids.43 Through careful
selection of the template materials as well as the carbon
precursors, and with good control over the carbonization
process, nanoporous templated carbons with desirable
physical and chemical properties can be obtained. In view of
their relatively high cost of production, development of a
simple, economical and environmentally benign template
route would be advantageous for their future application.
Despite the cost, templated carbons are good materials to
study, which provide valuable information about the effect of
pore size, pore shape, channel structures and other parameters
on the ion diffusion and charge storage in the nanoconfined
system.
3.4 Other carbon structures
Other carbon structures such as activated carbon fibers
(ACFs), carbon aerogels (CAGs) and carbon onions have also
been studied for supercapacitor applications. The general rules
for the selection of supercapacitor electrode materials are a
high and accessible specific surface area with good electrical
conductivity. ACFs typically have high specific surface areas,
up to 3000 m2 g1, and a more or less controllable pore size
distribution.48 They are usually produced from the carbonization
of pre-formed fibrous carbon precursors followed by
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activation processes. A high capacitance value of 371 F g1
in KOH electrolyte solution was reported recently. However,
such a high specific surface area together with the presence of
surface functional groups may cause a long term stability
problem.6 In addition, the cost of ACF production is generally
higher than AC.
CAGs are another interesting material suitable for use as a
supercapacitor electrode. They are ultralight, highly porous
materials, predominantly with mesopores, and have the
possibility of usage without binding substances. CAGs are
typically fabricated through a sol–gel process with subsequent
pyrolysis of the organic aerogels. The special porosity of a
CAG is based on the interconnection of colloidal-like carbon
nanoparticles. Due to the dominance of mesopores (42 nm),
the EDL capacitance is not so effective in CAG-based
electrode materials. Hence, an additional activation process
was employed to further increase the specific surface area by
introducing microporosity. Despite a large increase in the total
surface area (from 592 to 2371 m2 g1), the improvement
on the charge storage capacity was relatively small, especially
at high discharge rates,49 which is primarily due to the
inaccessibility of the micropores produced during the activation
and the relatively high internal resistance of the CAG matrix.
Nevertheless, a new type of carbon nanotube aerogel electrode
material gave promising capacitive properties, despite the
difficulty in preparation.41
3.5 Carbon-based composites
Materials with pseudo-capacitive properties are of great inter-
est in the development of supercapacitors with enhanced
energy storage capacity. However, most of the pseudo-capacitance
comes from surface redox reactions and hence only a very thin
surface layer is active in the faradic processes. In addition, the
poor electrical conductivity of pure transition metal oxides
such as MnO2, and the mechanical degradation of the
conducting polymers during faradic charging processes, hinder
their applications as electrode materials. Therefore, fabrication
of composites by using carbon as a support not only increases
the effective utilization of the active materials, but also
improve the electrical conductivity and mechanical strength
of the composite materials. Several studies have reported the
improved capacitive properties of the composite materials
using various types of carbons, such as carbon monolith,25
CNT23,50 and templated carbon51, as a support.
Hierarchically porous carbon monoliths were used as a support
for the electrodeposition of electroactive conducting polymers, i.e.
polyaniline (PANI) to prepare carbon–PANI composite electrode
materials.25 A high capacitance value about 300 F g1 was
obtained for the composite material and a very high capacitance
41000 F g1 was calculated based on the weight of PANI in
the carbon–PANI composite. A more interesting and important
finding is that the hierarchically porous carbon monolith served
as an effective support for electrodeposition of pseudo-active
material, leading not only to an enhanced capacitance value
with a high rate capability, but also good cyclability. The
improved stability and the high pseudo-capacitance value of
the PANI in the composite materials are of great interest for
supercapacitor electrode applications.
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Fig. 10 (a) Schematic representation of manganese oxide–CNTA
composite material and (b) specific capacitance of manganese
oxide–CNTA, manganese oxide–entangled CNT (ECNT), manganese
oxide–AC and CNTA versus discharge current density (r The
Published on 12 June 2009 on http://pubs.rsc.org | doi:10.1039/B813846J
American Chemical Society, reprinted with permission).23
It is known that CNTs serve as an effective support for
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transition metal oxides and conducting polymers due to their
open mesoporous tubular structure and superior electrical and
mechanical properties. Zhang and co-workers have reported
the use of a carbon nanotube array (CNTA), which is directly
connected to the current collector (Ta foil) as the support to
make composite electrodes with hierarchical porous
structures. Manganese oxide23 and PANI50 were selected as
pseudo-active materials to prepare manganese oxide–CNTA
and PANI–CNTA composite materials, respectively. The
electrochemical studies have shown that a very high specific
capacitance of about 1000 F g1 was obtained for the
PANI–CNTA composite material with a high rate capability
(95% capacity retention at 118 A g1) and good stability (up
to 5000 cycles test). The manganese oxide–CNTA composite
also possessed moderate specific capacitance of 101 F g1 at
high current density of 77 A g1 and with good cyclability. In
addition, the high density of the manganese oxide–CNTA
composite material leads to a high volumetric capacitance
which is suitable for compact electrode design. Fig. 10 shows
a schematic representation of the manganese oxide–CNTA
composite materials and their electrochemical performance at
different rates compared with other carbon substrates. The
high rate and energy performance of the composite materials
are due to the superior electrical properties of the substrate,
i.e. CNTA grown directly on the current collector, as well as
the pseudo-capacitive behavior of the active materials. Hence,
fine-tuning the structure of manganese oxide–CNTA and/or
investigation on the stability and capacitive properties of
PANI–CNTA in non-aqueous electrolytes may further
improve the performance of the composite electrode materials.
However, the high cost of making such sophisticated nano-
structures is of concern.
Templated ordered mesoporous carbon (OMC) was also
frequently used as a support for metal oxides such as RuO251
and MnO252 to prepare carbon–metal oxide composite
materials for supercapacitor applications. The OMC-based
composite materials not only improve the electrical conductivity
of the metal oxide (MnO2), but also increase the number of
active sites for pseudo-active species to achieve a high level
of utilization of pseudo-capacitance. In addition, the presence
of interconnected mesopores, ordered channel structures and a
relatively high specific surface area, simultaneously provide an
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efficient EDL capacitance, leading to an improved energy
performance. Dong and co-workers have prepared a
MnO2–OMC composite and they have shown that a high
capacitance value over 200 F g1 was obtained for the
composite material and 600 F g1 was calculated based on
MnO2 content in the composite.52 Li’s group have investigated
the electrochemical performance of RuO2–OMC composite
materials.51 They found out that by increasing the amount of
RuO2 (up to 30 wt%), the overall capacitance of the composite
material reached a value as high as 633 F g1. However, the
utilization rate of the precious metal oxide was decreased due
to the limited reaction of the large RuO2 particles. This also
highlights an important point that although metal oxides
possess high pseudo-capacitance values, their real contribution
to the total charge storage depends strongly on the surface
utilization of the active materials, which could be achieved by
dispersing nano-sized particles well onto highly ordered high-
surface carbon substrates. Simon and Gogotsi in their recent
review article proposed that, one possible strategy to improve
both energy and power densities for supercapacitors is to
achieve conformal deposition of pseudo-capacitive materials
onto highly ordered high-surface-area CNTs or ACs.6 Thus,
future research could be directed to enhance the surface
activity/interaction between the high-surface-area carbon
substrate with the thin or nano-sized active materials to
improve the faradic processes across the interface, so as to
achieve efficient pseudo-capacitance usage on top of the EDL
capacitance.
4. The electrolytes
The performance of a supercapacitor is not only dependent on
the electrode materials, but is also strongly affected by the
electrolytes employed. A high cell operating voltage provides
both high energy density and power density, but is limited by
the stability of the electrolyte in the applied potential. The
current trend in supercapacitor development involves the
switch from an aqueous electrolyte, which has a low operating
voltage of 1 V (due to the thermodynamic decomposition of
water) to a non-aqueous medium which allows a much higher
voltage window of about 2.5 V. The most recent super-
capacitors available in the market use electrolytes based on
aprotic solvents, typically acetonitrile or carbonate-based
solvents (i.e. propylene carbonate).3 Fig. 11 clearly shows
the advantages of a higher energy density when using aprotic
electrolyte rather than aqueous electrolyte.53 However, there
are other considerations on the use of non-aqueous electro-
lytes such as high cost, low conductivity compared to aqueous
electrolyte leading to power deterioration, low dielectric
constant resulting in smaller capacitance, complex purification
procedure as well as safety concerns due to the flammability
and toxicity of the organic solvent.
Ionic liquids (ILs), which are known as room temperature
molten salts, are under considerable research for use as next
generation electrolytes.54,55 They are attractive candidates for
electrolytes used in energy storage because of their good
chemical and physical properties, such as high thermal stability,
high electrochemical stability over a wide potential window
(43 V), non-toxicity, non-flammability, variety of combination
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Fig. 11 Ragone plots for comparison for the performance of various
types of carbon electrodes in aqueous electrolytes and aprotic electro-
lytes (r Science Direct, reprinted with permission).53
choices of cations and anions, acceptable conductivity at
elevated temperature, etc. ILs are liquids at ambient or even
lower temperatures and are composed entirely of ions, making
them attractive solvent free ‘green electrolytes’. But they are
typically high viscosity liquids and have low ionic conductivity
at room temperature, which inevitably affect their performance.
Fig. 12 shows the temperature dependent capacitive
performance of AC in one type of ionic liquid.9 Therefore,
designing an IL with high conductivity and a large voltage
window (44 V) for practical applications is still challenging.
Given that high purity ILs are of great importance for long
cycle lives of a supercapacitor, hydrophobic ILs are preferable
due to a more readily attainable high level of purity.
Balducci et al. reported that with the use of hydrophobic
N-butyl-N-methylpyrrolidinium bis(trifluromethanesulfonyl)imide
(PYR14TFSI) IL as electrolyte and AC as active material, the
cell voltage can be extended to 3.5 V at 60 1C with good
stability and a constant cell resistance (9 O cm2) over
40 000 cycles.55 The maximum energy density of 31 Wh kg1
with a cell voltage of 3.5 V can be obtained. Their recent study
showed that using carbide derived carbon as electrode material
and an EMI/TFSI IL (EMI = 1-ethyl-3-methylimidazolium)
as electrolyte, a high capacitance of 160 F g1 can be obtained
Fig. 12 Temperature-dependent capacitive behavior for AC in
trigeminal tricationic quat electrolyte (r Royal Society of Chemistry,
reprinted with permission).9
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at 60 1C with a cell voltage of 3 V. However, due to the
relatively low conductivity of the ILs, the power density is
smaller than that in an aprotic electrolyte.
It is worth noting that two principal factors are involved in
the conductivity of the electrolyte system: (1) the ability of the
salt dissociation to give out free charge carriers like cations
and anions; and (2) the mobility of the dissociated ions in the
electrolyte system. Hence, further research could be carried
out to design ILs with a combination of ions having high
dissociation constants, low molecular weight and with a wide
electrochemical stability window. Although, with the currently
available technology, ILs still fail to meet the requirements for
practical applications, its future development will be of great
significance in achieving high performance safe and ‘green’
energy storage systems.
5. Summary and future perspectives
Carbon materials with various microtextures and wide
availabilities represent very attractive materials for energy
storage. The key factors that dictate the selection of carbon
materials for supercapacitor electrodes include high surface
area, interconnected pore structure, controlled pore size
matching to the electrolyte ions, high electrical conductivity,
good wettability towards the electrolyte and the presence of
electrochemically stable surface functionalities. Improved
energy storage could be achieved by designing electrode
materials to combine EDL capacitance together with fast
and highly reversible pseudo-capacitance, utilizing ionic liquids
with an electrochemical stability window 44 V or hybrid
systems to optimize the potential range for each electrode so as
to widen the overall cell voltage. It must be kept in mind
that with improvements to energy densities, the principal
advantages of supercapacitors, which are a high rate capability
and long cycle life, must not be sacrificed.
One of the great challenges in the development of super-
capacitor technology is the relatively high cost when compared
to other energy devices. Thus, future research should be
directed towards the development of carbon materials with
high charge capacity and minimum ESR in a cost effective
way. One-step synthesis without an additional activation
process to obtain high density carbon or composite materials
would be beneficial for the compact design of high power
energy sources.
On the other hand, widening the cell operating voltage by
using alternative electrolyte solutions, e.g. ionic liquid, is a
very effective way to enhance both energy density and power
density owing to the V2 relation to both E (energy) and
P (power). In addition, higher cell voltage also reduces the
number of cells that must be used in series for a required
power system, which would potentially reduce the burden on
external voltage- balance circuits, as well as improve the
reliability of the device.
In conclusion, a new generation of supercapacitors are
expected to complement or replace batteries in certain applications
where high efficiency, high power, and high level of reliability
is required. High performance supercapacitors with safe
operation and ‘green chemistry’ are promising electrochemical
systems for future energy and power storage devices.
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Acknowledgements 30 J. W. Long, K. E. Swider, C. I. Merzbacher and D. R. Rolison,

Financial support from Ministry of Education Tier 2 Grant
(Project number MOE2008-T2-1-004) is greatly appreciated.
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