Carbon-based nano materials for supercapacitor electrodes

Carbon-based nanostructured materials and their composites as
supercapacitor electrodes
Saswata Bose,
a
Tapas Kuila,
a
Ananta Kumar Mishra,
b
R. Rajasekar,
b
Nam Hoon Kim
c
and Joong Hee Lee
*
abc
Received 9th September 2011, Accepted 10th October 2011
DOI: 10.1039/c1jm14468e
This critical review provides an overview of current research on carbon-based nanostructured materials
and their composites for use as supercapacitor electrodes. Particular emphasis has been directed
towards basic principles of supercapacitors and various factors affecting their performance. The focus
of the review is the detailed discussion regarding the performance and stability of carbon-based
materials and their composites. Pseudo-active species, such as, conducting polymer/metal oxide have
been found to exhibit pseudo-capacitive behavior and carbon-based materials demonstrate electrical
double layer capacitance. Carbon-based materials, such as, graphene, carbon nanotubes, and carbon
nanobers, provide high surface area for the deposition of conducting polymer/metal oxide that
facilitates the efcient ion diffusion phenomenon and contribute towards higher specic capacitance of
the carbon based composite materials with excellent cyclic stability. However, further scope of research
still exists from the view point of developing high energy supercapacitor devices in a cost effective and
simple way. This review will be of value to researchers and emerging scientists dealing with or interested
in carbon chemistry.
1. Introduction
Energy storage technology is the key factor in harvesting kinetic
energy. In the past decade there has been an ever-increasing
demand for environmental friendly, high performance energy
storage systems. Supercapacitors, also known as ultracapacitors,
are the energy devices that store and release energy through
nanoscopic charge separation at the electrochemical interface
between a carbon electrode and a liquid electrolyte.
1,2
Super-
capacitors exhibit extremely high power density, reasonable
energy density, longer cycle life, and minimum charge separation
compared to those of conventional capacitors.
37
These
intriguing features have created a great interest towards the
application of supercapacitors in the eld of consumer elec-
tronics, heavy electric vehicles, and industrial power manage-
ment.
8
Batteries and fuel cells harvest the stored energy through
chemical processes, whereas supercapacitors utilize electrostatic
separation between electrolyte ions and high-surface area elec-
trodes for harvesting energy. Due to their substantially high
power capability and specic energy, supercapacitors can act as
a bridge between batteries and conventional capacitors.
However, an enormous amount of research still exists from the
perspective of increasing the energy efciency of supercapacitors,
so that they may nd their way into the market by replacing
batteries. Advancement of supercapacitor technologies can
benet from the development of nanostructured electrode
materials. Reasonably high surface area and optimum pore size
of the electrode materials for an appropriate electrolyte solution
play an important role in ensuring the excellent performance of
a supercapacitor in terms of power density and energy storage
capability.
9
Various carbon-based materials have been consid-
ered as electrode materials for supercapacitors aimed at high
specic capacitance (SC) coupled with high power and energy
density.
1015
The underlying reason behind the improvement of
performance of carbon-based electrode materials is due to the
unique combination of chemical and physical properties,
namely:
2,9,10,16,17
- Reasonably high conductivity.
- Relatively high surface-area.
- Excellent corrosion resistance.
- High thermal stability.
- Controlled pore size distribution.
- Satisfactory compatibility in composite materials.
- Cost effectiveness.
Activated carbons are the most widely used electrode materials
owing to their large surface area, low cost and easy process-
ability.
18,19
However, their applications are restricted by their
poor energy storage capacity and inferior rate capability.
Carbon-based materials such as, graphene and carbon nanotubes
(CNTs) can be exploited as potential candidates for electrode
materials due to their fascinating electrical and mechanical
a
Department of BIN Fusion Technology, Chonbuk National University,
Jeonju, Jeonbuk, 561-756, Republic of Korea
b
BIN Fusion Research Center, Department of Polymer and Nano
Engineering, Chonbuk National University, Jeonju, Jeonbuk, 561-756,
Republic of Korea
c
Department of Hydrogen and Fuel Cell Engineering, Chonbuk National
University, Jeonju, Jeonbuk, 561-756, Republic of Korea
This journal is The Royal Society of Chemistry 2012 J. Mater. Chem., 2012, 22, 767784 | 767
Dynamic Article Links
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www.rsc.org/materials FEATURE ARTICLE
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properties as well as their unique structural features.
20
Structural
features and morphology of the carbon-based materials are
crucial for effective permeation of the electrolyte.
21
In the current
review, we focus on the electrochemical performance of gra-
phene, and CNT-based materials as well as their composites with
conducting polymers and various metal oxides for use as super-
capacitor electrodes. Specic capacitance values of different
carbon-based materials for supercapacitor application have been
summarized in Table 1.
2. Principle and mechanism of supercapacitors
A supercapacitor consists of two electrodes immersed in elec-
trolyte solution, with a voltage potential across the current
collector. A dielectric separator between the two electrodes
prevents charge propagation between the electrodes (Fig. 1).
Supercapacitors can be explained via two types of mechanism:
(a) Electrical double layer capacitor (EDLC), where the energy
can be stored through ion adsorption. The charge transfer
process in EDLCs is non-faradic, i.e. electron transfer across the
electrodes does not occur and thus the accumulation of charge is
purely electrostatic.
9,22
(b) Pseudocapacitor, where the energy is stored through fast
redox reactions between the electrolyte and the electroactive
species on the electrode surface.
22,23
Electron transfer causes
charge accumulation in the pseudocapacitor and the charge
transfer process is faradic in nature.
SC of EDLC is measured using the following equation:
4
C
3
r
3
o
d
A
where, 3
r
is the relative permittivity and is a dimensionless
constant, 3
o
(F m
1
) is the permittivity of vacuum, A(m
2
g
1
) is the
specic surface area of the electrode, and d is the effective
thickness of the EDLC and is termed as the Debye length.
Alternatively, pseudocapacitance arises due to thermodynamic
consideration between the charge acceptance (Dq) and change in
voltage (Dv).
9
The derivative (dDq/dDv) corresponds to the
pseudocapacitance.
As discussed earlier, the foremost difference between EDLC
and the pseudocapacitor is that the EDLC utilizes a non-faradic
process to store energy, while the pseudocapacitors follow the
conventional faradic route involving fast and reversible redox
reactions between the electrolyte and electroactive species such
as, conducting polymers and metal oxides. The magnitude of
pseudocapacitance is higher as compared to EDLC, but pseu-
docapacitors suffer from the point of view of poor electro-
chemical cyclic stability, high resistance and low power density
values.
3. Factors affecting the performance of
supercapacitors
The performance of supercapacitors largely depends upon the
following factors:
-Power density of supercapacitors should be greater than that
of batteries and should be accompanied by acceptable energy
density.
- High electrochemical cyclic stability.
- Fast chargedischarge phenomenon.
- Reasonably low self-discharging.
In order to resist the self-discharging, a high time constant
value is required. The stored energy (E) and the power density
(P) in a supercapacitor are calculated using the following
expressions:
E 1/2CV
2
P V
2
/4R
s
where, C(F g
1
) is the total capacitance of the cell, V is the cell
voltage, and R
s
is the equivalent series resistance (ESR). To
achieve a supercapacitor with high performance, the indispens-
able requirements, such as large SC, high cell voltage and
minimum ESR value should be achieved. The selection of elec-
trode material and electrolyte solution is the most crucial criteria
to optimize the overall performance of the supercapacitor.
As previously discussed, the electrode material should possess
a large surface area and should be electrically conductive with
reasonably high electrochemical cyclic stability. Presence of
pseudo-active species in improving the capacitance value is also
very essential. The density of the electrode should be sufciently
high enough to cause a reasonably high volumetric energy
density. A non-aqueous electrolyte solution with reasonably high
conductivity is a useful candidate for designing high performance
supercapacitors as the non-aqueous electrolyte solution can be
operated at a high voltage.
4. Graphene and associated composites as
supercapacitor electrodes
Graphene, a one atom thick, two-dimensional honeycomb
nanostructure,
20,24
is emerging as a promising candidate for
electrochemical energy storage device applications owing to its
low mass density, excellent electronic conductivity, outstanding
intrinsic strength, reasonable chemical stability, superior thermal
conductivity, and high surface area.
2532
Herein, we will briey
summarize some recent advances concerning the application of
graphene and graphene-based composite materials in the eld of
supercapacitors.
4.1 Graphene based materials
Ku et al. described the function of noble metal lms in the
interlayer of graphene as electrode and Al foil as current
collector.
33
Graphene was prepared via chemical exfoliation and
mild thermal reduction (150

C) processes. The coating of the
synthesized graphene on Au or Pd was performed using a drop
dry method for the preparation of working electrodes for
supercapacitor application. A reasonably high value of SC (50 F
g
1
) was achieved at 300 mV s
1
. The rectangular CV shape
indicated excellent capacitive behavior of the graphene on the Au
surface. The shape remained almost undistorted even at a very
high scan rate of 3000 mV s
1
. Almost 82% of the initial SC was
retained after 1500 cycles, corroborating satisfactory electro-
chemical cyclic stability. Estimated power density and energy
density of the graphene based electrodes at a current density of
768 | J. Mater. Chem., 2012, 22, 767784 This journal is The Royal Society of Chemistry 2012
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33.3 A g
1
were 40 kW kg
1
and 40 Wh kg
1
, respectively. The
electrophoretic deposition (EPD) method was employed to
deposit a graphene nanosheet on Ni foam as electrode material.
34
The CV curve showed a non-rectangular shape which reected
the pseudocapacitive behavior. Deviation from the rectangular
shape was attributed to adsorption or desorption of positively
charged ions in a negative potential. The retention of the initial
capacitance value of the graphene based electrode was 60% at
Table 1 Specic capacitance values of different carbon-based materials for supercapacitors
Types of materials
Specic capacitance
(F g
1
) Reference
Graphene-based materials
RGO 347 40
CMG 135 41
99
PIL : RGO 127187 42
Low temperature exfoliated graphene 264 43
GMs 205 44
Functionalized grapheme (prepared by solvothermal method) 276 46
KOH-treated graphene 136 47
FGS (at low temperature in air) 230
FGS (at high temperature in nitrogen) 100 48
Hydrothermally reduced graphene 220 49
Non-covalently functionalized graphene using 9-anthracene carboxylic acid 148 50
Ultrathin, transparent graphene 135 51
KOH-activated graphene 166 52
Functionalized graphene using 1-pyrenecarboxylic acid 120 53
Graphene/conducting polymer composites
Graphene/PANI composite paper 233 54
Graphene/PANI composite by chemical precipitation technique 300500 55
Nanoarchitecture based on polypyrrole and graphene 165 56
GNS/PANI composite by in situ polymerization 978 57
PPy/GNS composite 482 58
Sulfonated graphene/PANI nanocomposite 763 59
PANINFs/CMG composite 214 60
Graphene/PPy composite 1510 61
GNS/PPy nanocomposite 417 62
PPy/sulfonated graphene composite 285 63
Graphene/metal oxide composites
RuO
2
/graphene sheet composite 570 64
ITO/(PDDA/PSSGS/PDDA/MnO
2
) 263 66
Graphene nanosheetbismuth oxide (Bi
2
O
3
) composite 255 67
Graphene/SnO
2
nanocomposite 43.7 68
MnO
2
/graphene composite 324 69
ZnO/RGO composites 308 70
Graphene/ZnO composite 62.2 71
MnO
2
/functionalized graphene composite 188 72
GrapheneCo(OH)
2
nanocomposite 972.5 73
CeO
2
nanoparticles/graphene nanocomposite 191 75
Graphene/MnO
2
315 76
MnO
2
nanowire/graphene composite 31 77
CNT-based materials
SWCNT lms 34 89
Acid-modied MWCNT 77 93
Buckled SWCNT macrolms 54 94
CNT/conducting polymer composites
PPy/SWCNTs 144
PPy/functionalized SWCNTs 200 95
PEDOT/F-SWCNT composite 210 98
PANI/CNT composite 332 100
MWCNT/PANI composites 434 101
PANI/SWCNT composite 485 102
PPy/functionalized CNT composite 304 103
CNT/conducting polymer composites
CNT/RuO
2
nanocomposite 70 107
CNTZnO-5 (composite with ZnO deposition for 5 min) 126.3 108
MnO
2
/CNTpaper 540 110
In
2
O
3
nanowire/CNT lm 64 112
AuMnO
2
/CNT hybrid coaxial arrays 68 119
IrO
2
NT/MWCNT 6674 122
RuO
2
/a-MWCNT composite 184 11 123
NiO/CNT composite 1329 126
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100 mV s
1
, which corresponds to 97 F g
1
; however, at 20 mV
s
1
, the capacitance retention was 89%. Poor electrical conduc-
tivity of graphene may be due to adsorption of oxidized product
of p-phenylenediamine (OPPD). Additionally, migration of ions
was too slow to cause efcient charge propagation due to lack of
pores in the graphene structure. However, the reasonably high
value of SC (100 F g
1
) at high current density (6 A g
1
) was likely
due to doping of nitrogen atoms of OPPD in the graphene.
35
Modication of graphene with nitrogen of OPPD strengthened
the wettability of the interface between the electrode and elec-
trolyte and also introduced a psedocapacitive behavior.
36,37
Vivekchand et al. prepared graphene in three different ways, (i)
thermal exfoliation of graphite oxide (GO), (ii) heating nano-
diamond at 1650

C in a helium atmosphere, and (iii) decom-
position of camphor over nickel nanoparticles. It was observed
that the graphene samples prepared through the rst two
processes exhibit high SC in aq. H
2
SO
4
and the value reached up
to 117 F g
1
with an appreciably high energy density value.
38
Graphene-based supercapacitor using an ionic liquid as electro-
lyte to achieve ultrahigh energy density at room temperature was
reported by Liu et al. A substantially high specic energy density
of 85.6 Wh kg
1
at 1.0 A g
1
was achieved at room temperature.
39
Graphene-based supercapacitors exceeded the specic energy of
21.442.8 Wh kg
1
, which was comparable to that of a modern
nickel metal hydride battery used in a hybrid vehicle. Substan-
tially high intrinsic capacitance and the exceptionally large
specic surface area held the responsibility for the graphene-
based supercapacitor to be utilized as high energy storage device.
The electrochemical properties of the partially reduced GO
(RGO) using hydrobromic acid as a reducing agent in the ionic
liquid electrolyte (BMIPF
6
) was investigated by Chen et al. A
maximum capacitance value of 348 F g
1
was achieved at
a current density of 0.2 A g
1
.
40
RGO facilitated the penetration
of aqueous electrolyte and in the process pseudocapacitive effects
were introduced. The residual oxygen functionality on the RGO
surface did have an effect on the lifetime and the capacitive
properties of the RGO-based supercapacitor. Surprisingly, the
capacitance of RGO did not degrade but increased continuously
until the 2000th cycle.
CMG was utilized as electrode materials for a supercapacitor
electrode. Stoller and co-workers achieved a substantially high
BET surface area (705 m
2
g
1
) for the CMG aggregates.
41
The
graphene sheets located within the agglomerated particles may
not be accessible by the electrolyte, but the sheets at the surface
can be accessed by the electrolyte solution. An aqueous electro-
lyte (5.5 M KOH) and two organic electrolyte systems (TEA
BF
4
in AN and in PC solvent) were utilized to inuence the
electrochemical performance. CMG demonstrated SC values of
135 and 99 F g
1
in aqueous and organic electrolytes, respec-
tively. CV and Nyquist plots of the CMG-based electrode
materials in the presence of different electrolytes are shown in
Fig. 2. Kim et al. explored the effectiveness of PIL-modied
RGO as electrodes for supercapacitor using EMIMNTf
2
as an
electrolyte.
42
The production of PIL-modied RGO electrode
materials was achieved through a thermal reduction of GO
suspension in propylene carbonate (PC) containing PIL; the SP
values ranged from 127 to 187 F g
1
. The high SP value was
attributed to the effective wetting of the electrodes by the func-
tional PIL molecules on the RGO surface. The supercapacitor
assembled with PIL : RGO electrode and EMIMNTf
2
electro-
lyte demonstrated a consistent electrochemical response up to an
operating voltage of 3.5 V and exhibited an energy density value
of 6.5 Wh kg
1
with a power density of 2.4 kW kg
1
. Vacuum
assisted low temperature exfoliation to generate graphene was
reported by Lv et al. The graphene materials showed a high
specic BET surface area of 400 m
2
g
1
and SC up to 264 F g
1
in
5.5 M KOH electrolyte solution.
43
The low-temperature exfoli-
ated samples were also characterized by excellent cycling
performance and until the 100th cycle, the capacitance was still
up to 256 F g
1
. Owing to the unique surface chemistry, the low-
temperature exfoliated graphenes demonstrated excellent energy
storage performance compared to that of the high-temperature
exfoliated ones. The low-temperature exfoliation process opened
up a dimension for the mass production of graphenes at low cost.
A gassolid reduction process was adopted to prepare the gra-
phene materials (GMs), and the GMs were utilized as electrode
materials to fabricate the supercapacitor devices.
44
The SC of this
device was 205 F g
1
with an impressive power density of 10 kW
kg
1
at an energy density of 28.5 Wh kg
1
. Meanwhile, the GMs-
based supercapacitor electrodes revealed excellent cycle life and
almost 90% SC was retained after 1200 cycle tests. Effective
adsorption of electrolyte ions was one of the keys to produce high
SP. The presence of heteroatoms and functional groups in GMs
contributed towards the pseudocapacitance. The near rectan-
gular CV shape reected lower contact resistance and excellent
capacitive behavior. An in-plane fabrication approach for the
preparation of an ultrathin capacitor comprised of pristine gra-
phene and multilayer RGO was reported by Yoo et al. The
schematic depiction of the conventional stacked geometry
versus the in-plane geometry is shown in Fig. 3.
45
In a stacked
geometry, the random orientation of the graphitic carbon-based
Fig. 1 Schematic representation of a supercapacitor cell.
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materials with respect to the current collectors resulted in
incomplete utilization of the electrochemical surface area. The
electrolyte ions did not penetrate inside the graphitic planes.
Alternatively, owing to improved interaction between the elec-
trolyte ions with the graphitic layers in the in-plane design, the
high surface area of the graphene layers was fully utilized and
henceforth exhibited a substantially high value of SC (247.3 F
g
1
). A mild solvothermal method was employed to prepare
functionalized graphene.
46
This process did not involve any
strong reducing agent, which allowed retention of oxygen-con-
taining groups as a source of pseudocapacitance. A specic
capacitance up to 276 F g
1
was achieved at a current density of
0.1 A g
1
. The CV shape remained almost undistorted upon
increasing the scan rate from 10 mV s
1
to 100 mV s
1
, indicating
excellent wetting and easy access of ions to the graphene surface.
Specic energies of functionalized graphene were 20 and 14.5 Wh
kg
1
, respectively, at specic powers of 34.5 and 1.69 10
3
W
kg
1
. Potassium hydroxide (KOH) modied graphene was
utilized as an electrode for a supercapacitor.
47
The pristine gra-
phene exhibited an SP value of 101 F g
1
, while the SP of KOH-
treated graphene was 136 F g
1
at a scan rate of 10 mV s
1
. The
energy density value of KOH-treated graphene was 18.9 Wh
kg
1
. The increased capacitance value might be attributed to the
edge defects and the oxygen containing groups introduced upon
KOH modication, which led to enhancement of the pseudoca-
pacitive properties. Functionalized graphene sheets (FGS) were
prepared by a low-temperature thermal exfoliation procedure.
48
The rst kind of FGS was obtained by thermal exfoliation of GO
at low temperature in air. The second kind was prepared by the
carbonization of the rst kind of FGS at a higher temperature in
N
2
. The SP value of the rst kind of FGS was 230 F g
1
,
compared to 100 F g
1
for second kind of FGS. However, the
second kind of FGS demonstrated a higher capacitance retention
at high current density because of good conductive behaviors.
Highly conductive graphene hydrogels were prepared by
hydrothermal reduction of GO dispersion.
49
The supercapacitor
Fig. 2 CV (left) and Nyquist (right) plots of CMG material with KOH electrolyte (top), TEABF
4
in propylene carbonate (middle) and TEABF
4
in
acetonitrile (bottom) (adapted from ref. 41).
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based on hydrothermally reduced graphene showed a SP of 220 F
g
1
at a current density of 1 A g
1
. The graphene-based super-
capacitor maintained an SP of 165 F g
1
even at a very discharge
rate of 100 A g
1
, justifying that the charge-transfer phenomenon
had been facilitated during the discharge process at high current
densities. Bose et al. prepared non-covalently functionalized
water dispersible graphene directly from graphite using 9-
anthracene carboxylic acid.
50
The molecule attached to the
surface of the graphite by pp* interaction and the dangling
COOH group of 9-ACA resulted in effective dispersion is
aqueous medium. The rectangular CV shape was indicative of
good charge propagation within the electrodes, and electrical
double layer capacitance (EDLC). The SP was calculated to be
148 F g
1
. Yu et al. reported the preparation of ultrathin,
transparent graphene lms to be used as supercapacitor.
51
The
CV curve showed a nearly rectangular shape indicating an ideal
EDLC behavior. The capacitance was measured to be 135 F g
1
for a lm of approximately 25 nm thickness. Even at the higher
scan rate of 200 mV s
1
, the graphene lms retained almost 75
80% of initial capacitance value suggesting excellent contact
between the electrolyte and the active material. The graphene
lm (thickness 25 nm) showed a high energy density of 15.4 Wh
kg
1
at 554 W kg
1
which gradually reduced to 10.0 Wh kg
1
at
7200 W kg
1
in 2 M KCl electrolyte. Zhu et al. employed acti-
vated graphene for supercapacitor electrode material. Firstly,
GO was exfoliated employing microwave treatment followed by
chemical activation of exfoliated GO using KOH to prepare
activated graphene.
52
The CV experiments showed rectangular
curves over a wide range of voltage scan rates. The values of SP
were 165, 166, and 166 F g
1
obtained at current densities of 1.4,
2.8, and 5.7 A g
1
, respectively. An et al. prepared graphene from
graphite and exploited their multi-functional high performance
application.
53
They utilized 1-pyrenecarboxylic acid to exfoliate
the layers of graphite. The ultracapacitors made from this kind of
graphene dispersion demonstrated an SP of 120 F g
1
with
substantially high power and energy densities of 105 kW kg
1
and 9.2 Wh kg
1
, respectively. Owing to its strong afnity toward
amphiphilic molecules, 1-pyrenecarboxylic acid-functionalized
graphene membrane had an inbuilt sensitivity toward alcohol
molecules. The entire process was performed at room tempera-
ture, and hence was extremely friendly for a number of tech-
nologies where temperature limitations exist.
4.2 Graphene/conducting polymer composite
Graphene/polyaniline (PANI) composite paper (GPCP) was
prepared via in situ anodic electropolymerization.
54
The pictorial
representation of the synthetic procedure is shown in Fig. 4.
GPCP demonstrated a high SC value of 233 F g
1
, which was
much larger than graphene paper (147 F g
1
). These intriguing
features of GPCP revealed its applicability as an electrode
material. The CV characteristics of G-paper and GPCPs along
with their cyclic stability and Nyquist plots are displayed in
Fig. 5. A chemical precipitation technique was adopted to
synthesize the graphene/PANI nanocomposite.
55
An SC of 300
500 F g
1
at a current density of 0.1 A g
1
was achieved for the
graphenePANI nanocomposite materials. The cyclability of the
graphenePANI nanocomposite as the electrode was evaluated
under long-term cycling over 100 cycles, demonstrating a good
cyclic performance and reversibility. Biswas et al. proposed
a novel nanoarchitecture consisting of nanostructured poly-
pyrrole (PPy) and highly electrically conductive graphene
nanosheets in a multilayered conguration to attain high SC and
low electronic resistance for supercapacitor electrode applica-
tions.
56
Strong van der Waals interaction between nano-
structured PPy and graphene basal planes was one of the reasons
for the improvement in electrochemical performance. The
multilayer composite electrode exhibited a high SC of 165 F g
1
with a nearly rectangular CV shape. Preparation of a GNS/PANI
composite via in situ polymerization was reported by Yan et al.
57
The CV shape of the GNS/PANI composite demonstrated
pseudocapacitance behavior attributed towards the redox tran-
sition of PANI. The substantially high capacitance value (978 F
g
1
) of the composite material was perhaps due to the homoge-
neous dispersion of PANI over the GNS sheets with large surface
area. The dispersion of PANI particles on GNS reduced the
diffusion and migration length of the electrolyte and in the
process the electrochemical utilization of PANI was improved.
PPy/GNS composite was prepared via in situ polymerization
Fig. 3 Schematic depiction of the conventional stacked geometry vs.
in-plane geometry (adapted from ref. 45).
Fig. 4 Anodic electropolymerization of aniline monomer on G-paper.
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involving pyrrole monomer in the presence of graphene under
acidic conditions.
58
The SC of the PPy/GNS composite was as
high as 482 F g
1
1
. After 1000
cycles, the attenuation of the SC was much less (5%), indicating
excellent cyclic stability of the composite. The high value of SP
and enhanced rate capability of the composite material was
attributed to the higher conductivity and smaller particle sizes of
composite, which in turn shorten ion diffusion length and
resulted in higher materials utilization. A sulfonated graphene/
PANI nanocomposite (SGEP) was fabricated by a novel
morphology-controlled strategy using liquid/liquid interfacial
polymerization.
59
The SGEP nanocomposite exhibited an SC of
763 F g
1
with 96% retention of SC after 100 cycles. Stable
aqueous dispersion of composite lms based upon CMG and
PANI nanobers (PANI-NFs) were prepared by vacuum ltra-
tion of mixed dispersions.
60
In this method, the PANI-NFs were
sandwiched between CCG layers. A high SC value (214 F g
1
) of
the composite lm indicated the synergistic effect between the
PANI-NFs and CMG. Incorporation of PANI-NFs into CMG
played a signicant role in the improvement of capacitance of the
composite lm through the formation of a porous structure.
Redox transitions of PANI-NFs were facilitated by the highly
conducting CMG materials. Mini et al. reported the high
supercapacitive behavior of graphene/PPy composite.
61
Firstly,
the graphene was deposited on titanium metal substrate by EPD
method. PPy was electropolymerized on the graphene surface to
develop the graphene/PPy composite. The electrode exhibited an
area capacitance of 151 mF cm
2
, volume capacitance of 151 F
cm
3
and an SP of 1510 F g
1
was achieved at a scan rate of 10
mV s
1
(polymerization time 1500 s). The calculated energy
density and power density values were 5.7 Wh kg
1
and 3.0 kW
kg
1
, respectively. Graphene nanosheet (GNS)/PPy nano-
composites were prepared by in situ polymerization and the
electrochemical performance of the composite was examined by
Bose et al. The SPs of the nanocomposite were 417 and 267 F g
1
at scan rates of 10 and 100 mV s
1
, respectively. The energy
density and power density values of the nanocomposite were
94.93 Wh kg
1
and 3.797 kW kg
1
, respectively. Retention of
90% of the SP after 500 cycles highlighted the excellent electro-
chemical cyclic stability of the nanocomposite.
62
Composite lms
of sulfonated graphene and PPy were electrochemically depos-
ited from the aqueous solution of pyrrole monomer, sulfonated
graphene sheets, and DBSA.
63
Introduction of sulfonated gra-
phene sheets improved the conductivity and reduced the IR drop
value. The composite lms showed a high value of SP (285 F g
1
)
at a discharge rate of 0.5 A g
1
. They also demonstrated highly
improved electrochemical cyclic stability and rate capabilities.
The chargedischarge shape of the PPy/sulfonated graphene
composite demonstrated a combination of EDL and pseudoca-
pacitance. EDL capacitance was due to formation of a porous
structure and pseudocapacitance was from the highly conducting
sulfonated graphene components.
4.3 Graphene/metal oxide composites
Hydrous ruthenium dioxide (RuO
2
) was exploited to fabricate
RuO
2
/graphene sheet composite (ROGSCs) via the combination
of solgel and low-temperature annealing processes.
64
A
maximum SC of 570 F g
1
was achieved for ROGSCs at 38.3 wt
% Ru loading, as compared to 148 F g
1
for pure graphene. The
capacitance of the ROGSCs slowly decreased to 98.2% during
the rst 170 chargedischarge cycles, and then became quite
stable. After 100 cycles, 97.9% of the initial capacitance was
retained. The energy density obtained for ROGSCs was 20.1 Wh
kg
1
, while the corresponding power density value was 50 W kg
1
1
. A grapheneZnO composite lm
Fig. 5 Cyclic voltammograms of (A) G-paper and (B) GPCP, recorded from 2 to 20 mV s
1
in 1 M H
2
SO
4
. (C) Nyquist plots of the G-paper and GPCP
60 s/300 s/900 s. (D) Cycling stability measured at 50 mV s
1
(adapted from ref. 54).
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as a supercapacitor electrode was reported by Zhang et al.
Graphene was synthesized through an oxidationreduction
process using hydrazine as reducing agent. ZnO was deposited on
graphene by ultrasonic spray pyrolysis (USP). The ITOGZnO
electrode exhibited an SC of 11.3 F g
1
.
65
The composite elec-
trode showed an excellent charge/discharge stability with typical
supercapacitor behavior. The higher SP value was due to the
contribution of both EDLC from graphene and pseudo-capaci-
tance from ZnO. Li and co-workers developed a novel idea of
constructing multilayer lms by electrostatic layer-by-layer self-
assembly, using poly(sodium 4-styrenesulfonate) modied gra-
phene sheets (PSSGS), MnO
2
, and PDDA as building block
units.
66
The CV curve area and the current response of ITO/
(PDDA/PSSGS/PDDA/MnO
2
) electrode were much larger
than those of both the ITO/(PDDA/MnO
2
) and (ITO/PDDA/
PSSGS) electrodes, indicating that the improved electro-
chemical performance of the ITO/(PDDA/PSSGS/PDDA/
MnO
2
) electrode resulted from the synergistic effect between the
PSSGS and MnO
2
sheets in the multilayer system. The SC of
ITO/(PDDA/PSSGS/PDDA/MnO
2
) electrode was calculated
to be 263 F g
1
1
. With
increasing current density, the capacitance of the electrode
decreased from 263 to 154 F g
1
, which might be due to the
diffusion effect of ions within the multilayer lms. After 1000
cycles, 90% of the initial SC of this electrode was retained,
corroborating the long-term cyclic stability of the multilayer lm.
The electrochemical performance of the multilayer lm as elec-
trode is shown in Fig. 6. Facile solvothermal synthesis of gra-
phene nanosheetbismuth oxide (Bi
2
O
3
) composite was reported
by Wang et al.
67
CV analysis of the grapheneBi
2
O
3
composite
conrmed the appearance of a pair of redox peaks compared to
the rectangular shape for pure graphene. For the graphene-based
electrode, the shorter discharge time was governed by EDLC,
while, for the grapheneBi
2
O
3
electrode, the dual effect of EDLC
and faradaic capacitance was responsible for the longer
discharge duration. SCvalues were 71 and 255 F g
1
for graphene
and grapheneBi
2
O
3
electrodes, respectively, at a current density
of 0.1 A g
1
. The CV of the grapheneBi
2
O
3
composite at
different scan rates and the variation in discharge time for the
graphene and grapheneBi
2
O
3
composite is shown in Fig. 7.
Graphene/SnO
2
nanocomposites as electrochemical super-
capacitor demonstrated a capacitance value of 43.7 F g
1
compared to 20.7 and 0.62 F g
1
for CCG and GO.
68
The
impedance curve for the nanocomposite in the high frequency
region was nearly parallel to the real axis, indicating the low
contact resistance of the nanocomposite. However, in the low
frequency region, the imaginary part of the impedance curve was
vertical, corroborating a capacitive-type behavior. A polymer
assisted chemical reduction method for the fabrication of MnO
2
/
graphene composite and the utilization of the same electrode
material for supercapacitor was examined.
69
A reasonably high
value of SC was achieved (324 F g
1
) with excellent cyclic
stability (a decrease of only 3.2% in the SC was observed after
1000 cycles). The composite exhibited an outstanding electro-
chemical property as supercapacitor electrode, owing to elec-
trochemical activities of the embedded MnO
2
nanoparticles and
activated graphene open network with increased specic surface
area. Based on the low cost, environmentally friendly nature and
excellent capacitive properties, the MnO
2
/graphene composite
was considered to be a promising electrode material for super-
capacitors. ZnO/RGO composites were prepared using a two-
step method and electrochemical performance of the composite
was evaluated.
70
The composite showed an ideal capacitive
behavior with an SC of 308 F g
1
at a current density of 1 A g
1
,
Fig. 6 (a) CV curves of ITO/(PDDA/PSSGS/PDDA/MnO
2
) electrode at different scan rates. (b) Chargedischarge behavior of the electrode at
different current densities. (c) Variation of specic capacitances with current density. (d) Specic capacitance and Coulombic efciency change of the
electrode vs. number of charge/discharge cycles at a current density of 1.41 A g
1
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much higher than those of ZnO (135 F g
1
) and RGO (157 F g
1
).
The unique 3D morphology of RGO-coated ZnO facilitated the
fast electron transfer between the active materials and current
collector. At a specic current of 4 A g
1
, an SC of 180 F g
1
was
achieved, implying that the composite exhibited an impressive
rate capability at high specic current. Wang et al. adopted
a green route to synthesize a graphene/ZnO composite and
utilized it as a supercapacitor electrode.
71
Glucose and exfoliated
GO were used as reducing agent and precursor, respectively.
ZnO was directly grown on the graphene surface. CV loops were
quasi-rectangular in nature with no obvious redox peaks. An
increase in the current output with increasing scan rate demon-
strated the excellent rate capability of the material. The
composite showed an SP of 62.2 F g
1
with power density of 8.1
kW kg
1
. A composite material composed of MnO
2
and func-
tionalized graphene was utilized as supercapacitor electrode.
72
Functionalized graphene was prepared by reducing functional-
ized GO with PDDA. MnO
2
was deposited on the graphene
surface via the electrostatic co-precipitation method. An SP of
188 F g
1
was achieved for the MnO
2
/functionalized graphene
composite at a current density of 0.25 A g
1
. Additionally, over
89% of the original capacitance was retained after 1000 cycles,
indicating a good cycle stability of the composite materials. Chen
et al. adopted a facile soft chemical approach to fabricate gra-
pheneCo(OH)
2
nanocomposites in a waterisopropanol system,
followed by analysis of their electrochemical properties.
73
The
nanocomposite demonstrated an SP of 972.5 F g
1
. The
substantially high value of SP could be ascribed from the faradic
reactions of nanoscale Co(OH)
2
. The combination of Co(OH)
2
and graphene may result in synergistic performance, which in
turn resulted in enhanced electrochemical performance. Elec-
trochemical properties of metal oxide (RuO
2
, TiO
2
, and Fe
3
O
4
)
decorated functionalized graphene were demonstrated by Mishra
et al.
74
The CV shape of functionalized graphene, RuO
2
-func-
tionalized graphene, and TiO
2
-functionalized graphene nano-
composites were found to be almost rectangular in 1 M H
2
SO
4
solution, suggesting the capacitive behavior of nanocomposites.
Alternatively, Fe
3
O
4
-functionalized graphene nanocomposites
showed a better rectangular shape for 1 M Na
2
SO
4
as an elec-
trolyte solution. SP values with 1 M H
2
SO
4
, were found to be
125, 265, 60, and 180 F g
1
, for functionalized graphene, RuO
2
-
functionalized graphene, and TiO
2
-functionalized graphene, and
Fe
3
O
4
-functionalized graphene nanocomposites, respectively, at
a scan rate of 10 mV s
1
. The RuO
2
-functionalized graphene
nanocomposite demonstrated the best performance among all of
the studied metal oxide-based nanocomposites, attributing to the
better electrical conductivity and fast faradaic reactions for
RuO
2
nanoparticles compared to other metal oxides. At a higher
scan rate, the SP value decreased to an extent for each sample.
An approximate 1016% reduction in SP was observed for each
studied nanocomposite, suggesting the high degree of sustain-
ability of capacitance even at a higher scan rate. A CeO
2
nano-
particles/graphene nanocomposite was fabricated by depositing
CeO
2
nanoparticles onto three-dimensional graphene material
and its supercapacitor performance was further investigated.
75
The calculated SP values of graphene, CeO
2
and CeO
2
nano-
particles/graphene nanocomposite were 81, 57 and 191 F g
1
,
respectively. The synergistic effect between CeO
2
with graphene
led to boost the SP of the nanocomposite. The nanocomposite
also demonstrated excellent cyclic stability even after 1000 cycles.
Yu et al. investigated the electrochemical performance of solu-
tion-processed graphene/MnO
2
nanostructured textiles.
76
The
as-mentioned nanocomposite exhibited an SP of 315 F g
1
with
a maximum power density and energy density of 110 kW kg
1
and
12.5 Wh kg
1
, respectively. The supreme performance of the
graphene/MnO
2
nanostructured textiles could be attributed to
the following factors:
3D porous microstructures of the polyester textiles allowing
conformal coating of graphene nanosheets.
Incorporation of MnO
2
facilitated easy access of electrolyte
to electrode surfaces.
Graphene nanosheets provided high surface area and
conductive paths for the deposition of MnO
2
and thereby
allowed fast electron transport.
Nano-ower architectures of electrodeposited MnO
2
helped
to reduce ion diffusion length during the charge/discharge
process.
Moreover, retention of 95% capacitance after 5000 cycles
corroborated its excellent cycling performance. Wu et al. devel-
oped a high-voltage asymmetric electrochemical capacitor based
on graphene as the negative electrode and an MnO
2
nanowire/
graphene composite as the positive electrode in a neutral aqueous
Na
2
SO
4
solution as electrolyte.
77
The capacitance value was
observed to be 31 F g
1
. However, after 1000 cycles, the
Fig. 7 (a) CV curve of grapheneBi
2
O
3
composite at different scan rates. (b) Discharge curves of graphene and grapheneBi
2
O
3
composite in the
potential range from 0.9 to 0.1 V at a specic current of 1 A g
1
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asymmetric capacitor retained 79% of the initial capacitance.
Such asymmetric electrochemical capacitor exhibited a superior
energy density of 30.4 Wh kg
1
.
5. CNT and associated composites as supercapacitor
electrodes
CNTs could be viewed as an attractive material to be used as
a supercapacitor electrode due to their remarkable properties,
such as, unique internal structures, high surface area, low mass
density, outstanding chemical stability and excellent electronic
conductivity.
7883
Individually single-walled carbon nanotubes
(SWCNTs) or multi-walled carbon nanotubes (MWCNTs) can
be utilized as electrode materials for supercapacitors. In addi-
tion, nanocomposites such as, CNT/polymer, and CNT/metal
oxides offer a new dimension in nanostructured carbon based
supercapacitor electrodes. The reasons behind the improved
performance of CNT-based nanocomposites are as follows:
8486
I. Excellent interaction of the electroactive materials with the
CNTs.
II. Formation of open mesoporous network through the
entanglement of nanotubes allows fast and efcient migration of
the ions to the active surfaces of the composite components.
III. CNTs are characterized by high resiliency and thus the
composite electrodes can easily adapt to the volumetric changes
during the charge and discharge process which in turn improves
the cycling performance.
In this section of the review, we will focus on the recent
progress on the use of CNT and CNT-based composite materials
as supercapacitor electrodes.
5.1 CNT-based materials
Nanoporous current collectors for supercapacitors were fabri-
cated using cross-stacking super aligned CNT (SACNT) lms as
an ideal replacement for heavy conventional metallic current
collectors.
87
The CNT-based current collectors showed excellent
conducting properties along with outstanding electrochemical
stability. The schematic drawing of the CNT-based lm prepa-
ration and the construction of the respective cell is shown in
Fig. 8.
A facile and efcient way of preparing supercapacitor elec-
trodes based on CNTs was reported by Shi et al. CNTs were
grown directly on Ni-foam by chemical vapor deposition (CVD).
The electrochemical performance of the Ni-foam-based CNTs
was superior compared to conventional CNT-based super-
capacitors due to the hierarchical porous structure and robust
CNTmetal contact. Ni-foam-based CNTs retained almost 72%
of the initial capacitance at a high current density.
88
Compact-designed supercapacitors were fabricated using
large-scale freestanding and exible SWCNT lms as electrode
materials.
89
The SWCNT lms were prepared by oating CVD
method.
90
The advantageous feature of this method is that the
directly grown lm can be tailored into the desired shape and size
depending upon the required application. The SC of the SWCNT
lm-based supercapacitor was 34 F g
1
at a scan rate of 20 mV
s
1
. The high value of SC at lower scan rate compared to that at
higher scan rate was due to the efcient diffusion of the ions from
the electrolyte through the SWCNTs pores. However, at higher
scan rate, the penetration of ions into the porous lms was
progressively reduced causing decrement in SC.
91
The maximum
energy density and power density values were 43.7 Wh kg
1
and
197.3 kW kg
1
, respectively. Du et al. utilized the EPD method to
fabricate a MWCNT lm to be used as a high power density
supercapacitor electrode.
92
The advantageous features of the
EPD method involves short formation time, simple apparatus,
improved adherence of electrophoretically deposited coatings,
and suitability for mass production. The rectangular CV shape
even at higher scan rate suggested a very small ESR value and
fast diffusion of the electrolyte. The power density of the con-
cerned materials was 20 kW kg
1
. Carboxylic acid- and ester-
functionalized SWCNTs and MWCNTs were deposited on the
polymer substrate via the spray deposition technique for super-
capacitor application.
93
A rectangular CV shape of the ester-
functionalized CNT (E-MWCNT/E-SWCNT) demonstrated an
EDLC capacitance; alternatively, the CV of the acid-modied
CNT (A-MWCNT/A-SWCNT) was composed of a pair of redox
peaks, corroborating the pseudocapacitance behavior. The
chargedischarge curves of the pure CNTs (P-MWCNT/P-
SWCNT) and ester-functionalized CNT lms (E-MWCNT/E-
SWCNT) were nearly symmetrical. The SCs of the A-MWCNT
and A-SWCNT were 77 and 155 F g
1
at a scan rate of 100 mV
s
1
, compared to 23 and 38 F g
1
for P-MWCNT or P-SWCNT,
respectively. The impedance spectra of the CNT lms exhibited
semi-circles at frequencies above 1 Hz and nearly vertical straight
lines at frequencies below 1 Hz. The galvanostatic charge
discharge behavior, and the impedance spectroscopy of the CNT
lms are shown in Fig. 9. Yu et al. proposed the concept of
stretchable supercapacitors based on buckled SWCNT macro-
lms.
94
The fabrication procedure of buckled SWCNT macro-
lms on a PDMS substrate is shown in Fig. 10. The initial SCs of
the stretchable supercapacitor were 54 F g
1
(without applied
strain) and 52 F g
1
(30% applied strain). However, the SCs of
stretchable supercapacitors with or without applied strain did
not vary even up to 1000 chargedischarge cycles, thus demon-
strating excellent electrochemical stability.
Fig. 8 (a) CNTs in a super-aligned CNT array. (b) CNTs drawn out and
cross-stacked into a CNT sheet. A nitrate salt dissolved in methanol is
used as the precursor for oxide formation and is directly dropped on the
sheet. (c) After annealing, the oxide nanoparticles are synthesized on the
CNTs. (d) Electrochemical test system of the lm (adapted from ref. 87).
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5.2 CNT/conducting polymer composite
The electrochemical capacitance properties of composite lms of
electrically conducting PPy and SWCNTs were investigated by
Wang et al.
95
The composite lms were electro-polymerized from
the homogenous mixture of pyrrole and SWCNTs. The SC
values of PPy/SWCNTs and PPy/functionalized SWCNTs were
144 F g
1
and 200 F g
1
, respectively, at a scan rate of 200 mV s
1
.
The high capacitance values of the nanocomposites compared to
those of PPy were attributed to the mesoporous structures of
SWCNTs. The unique structure facilitated the transfer of ions
from the electrolytes to the composite lms. Moreover, charge
discharge phenomena of the PPy/functionalized SWCNTs
composite lm were further improved as compared to those of
PPy/SWCNTs lm owing to better dispersion of CNTs
throughout the matrix. Pure PPy lms had a poor capacitance
value due to much larger resistance and reduced volume in the
discharging states. However, in the case of the composites, the
balancing behavior of cations diminished the ion-transfer
polarization in the discharging states. The supercapacitive
property of the electrochemically grown nanoporous composite
lm of MWCNTs and PPy was reported by Hughes et al.
96
CV
analysis highlighted that peak potentials of the composite were
approximately 200 mV more negative than those of the pure PPy
lm, corroborating the anionic dopant role of the MWCNTs.
97
In addition, the output current for the composite lm was twice
than that of the neat polymer implying that the capacitance value
of the composite was almost double that of PPy. Poly(3,4-eth-
ylenedioxythiophene)(PEDOT)/functionalized SWCNTs (F-
SWCNT) composite had been shown to have appreciable elec-
trochemical performance.
98
The CV curves of neat PEDOT and
the composite were nearly rectangular, corroborating the EDLC
capacitance of the material. The SC of the PEDOT/F-SWCNT
composite was 210 F g
1
as compared to 120 F g
1
for neat
PEDOT at a scan rate of 10 mV s
1
. The enhanced capacitance
value was due to the synergistic effect between PEDOT and F-
MWCNT. The composite retained 86% of the initial capacitance
as the scan rate varied from 10 mV s
1
to 200 mV s
1
. The
underlying reason behind the fast chargedischarge ability was
attributed to the presence of large amount of meso-tunnel in the
composite. The impedance analysis also revealed the ideal
capacitive behavior of the composite. In the low frequency
region, the impedance curve was nearly parallel to the imaginary
axis. After 1000 cycles, the composite retained 92% of the initial
capacitance value with a discharging capacity of almost 100%.
Electrochemical performance of the PEDOT/F-SWCNT
composite was displayed in Fig. 11. A SWCNT/PPy nano-
composite was also investigated as a supercapacitor electrode
material.
99
Improved electrochemical performance was due to
the uniform coating of PPy over SWCNTs via in situ polymeri-
zation. The as-grown SWCNTs showed EDLC, and faradic
redox reactions were obvious in the case of pure PPy. However,
the redox current of SWCNT/PPy nanocomposite was much
higher as compared to neat PPy. The remarkable improvement in
SC compared to those in PPy and SWCNTs was due to the
following reasons:
I. Pseudocapacitance aspects provided by PPy.
II. Increase in surface area provided by the SWCNT.
Fig. 9 (a) Galvanostatic charging/discharging behaviour of CNT lms. (b) AC impedance spectra of CNT lms after 50 cycles (adapted from ref. 93).
Fig. 10 Fabrication steps of a buckled SWNT macrolm on an elasto-
meric PDMS substrate (adapted from ref. 94).
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However, both pure PPy and SWCNT/PPy nanocomposite
electrodes showed a gradual decrease in the SC with an
increase in discharge current density due to large internal
electrode resistance. However, for the as-grown SWCNTs, the
reverse phenomenon was true which might be due to the
porous structure of the SWCNTs. Pores with a small diameter
acted as a platform for ion diffusion from the electrolyte. The
supercapacitor application of highly exible and all-solid-state
paper-like materials based upon PANI and CNT was investi-
gated by Meng et al.
100
The electrochemical performance was
evaluated using H
2
SO
4
polyvinyl alcohol (PVA) solution as
electrolyte. The all-solid-state based material as an electrode
showed nearly an identical CV curve as observed in the case of
the 0.5 M H
2
SO
4
solution, where the redox peaks were due to
the pseudocapacitance of PANI. SC of the material under
consideration was 332 F g
1
1
.
The energy density and power density values were 7.1 Wh kg
1
and 2189 W kg
1
, respectively. Reasonably high cyclic stability
was attributed from the decrement of only 8.1% SC after 1000
cycles. MWCNT/PANI composite lms were prepared
via in situ electrochemical polymerization of aniline solution
with varying MWCNT contents. MWCNT/PANI composites
demonstrated strong redox peaks indicating enhanced electro-
activity. A high value of SC was achieved for the composite
due to larger output current. SC values of the composite with
0.2, 0.4, and 0.8 wt% MWCNT loading were 434, 481 and
500 F g
1
, respectively, at a current density of 5 mA cm
2
.
Shortening of the diameter of the semicircles with the incor-
poration of MWCNT into the PANI matrix indicated the
reduced charge-transfer complex resistance of the MWCNT/
PANI composite.
101
Gupta et al.
102
prepared SWCNT/PANI
composite adopting a similar method as demonstrated by
Zhang et al.,
101
and obtained the SC values of 34, 234 and
485 F g
1
for SWCNTs, pure PANI and PANI/SWCNT
composite, respectively, at a current density of 5 mA cm
2
.
Functionalization of the CNTs was performed using a micro-
wave hydrothermal strategy with a thorn-like organometallic
methyl orangeiron(III) chloride (MOFeCl
3
) complex.
103
The
complex served as an oxidant, and PPy nanoparticles were
directionally attached onto the CNTs through the polymeri-
zation of pyrrole in the absence of any extra oxidants. Gal-
vanostatic charge/discharge for the PPy/CNT composite was
performed with an applied current density of 1.0 mA cm
2
in
the potential range between 0.5 to 0.5 V. The resulting curve
was not an ideal straight line, indicating pseudocapacitance
behavior.
104
The maximum capacitance value of PPy/CNT
composite was 304 F g
1
. The high SC could be attributed to
the large electrolyte-accessible surface area of the functional-
ized CNTs, facilitating the effective utilization of PPy for the
redox reaction.
105
The electrochemical redox reaction between
the electrode and electrolyte is shown below:
[PPy
0
] + Cl
/[PPy
+
]Cl
+ e
[PPy
+
]Cl
+ e
/[PPy
0
] + Cl
5.3 CNT/metal oxide composite

A spray deposition technique had been adopted to fabricate
a exible nanostructured hybrid supercapacitor based on
hematite (a-Fe
2
O
3
)/MWNT composite anode. The composite as
Fig. 11 (a) CV curves of PEDOT and PEDOT/F-SWNTs at scan rate of 10 mV s
1
. (b) Nyquist plots as a function of frequency. (c) Cyclic stability and
discharge efciency of the composite (adapted from ref. 98).
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anode material showed a very high specic energy density of 50
Wh kg
1
at a specic power density of 1.0 kW kg
1
over
a potential range of 02.8 V.
106
The superior electrochemical
performance of the hybrid supercapacitor arrangement was
attributed to the decrement of internal resistance and an
improvement in both the ion diffusion behaviour as well as the
integrity of the a-Fe
2
O
3
containing lms. The potential of the
CNT/RuO
2
nanocomposite supercapacitor electrode was exam-
ined by Park et al.
107
The SC of this nanocomposite (13 wt%
RuO
2
loading) was 70 F g
1
at a scan rate of 20 mV s
1
, which
was much higher than pristine CNT (6 F g
1
). The microporous
structure of the CNTs provided a suitable environment for the
deposition of RuO
2
nanoparticles. RuO
2
particles behaved as
individual nanoscale reactors and thus facilitate the possibilities
of faradaic reactions. CNTZnO assemblies were utilized as an
electrode for a supercapacitor with gel polymer as electrolyte
solution.
108
The CNT lm was fabricated using screen-printing
and ZnO was deposited on the lm by USP for different time
periods. The SC of the CNT-based electrode was 92.7 F g
1
.
However for CNTZnO-5 (composite with ZnO deposition for 5
min), the value of SC increased to the apparent maximum of
126.3 F g
1
. However, with a deposition time greater than 10
min, a dramatic reduction in SC was observed. With increasing
deposition time, the CNT surface was totally covered by ZnO
which had a high resistance and thus lowered the capacitance of
the electrodes. Furthermore, the accumulation of ZnO destroyed
the network formation of CNTs and in the process hampered the
adsorption of protons or electrons on the electrode surface.
Zhang et al.
109
also investigated ZnO deposition for 5 min over
CNT electrode demonstrated lowest internal resistance with very
high SC value (323.9 F g
1
). CNTZnO-5 exhibited excellent
reversibility after 100 cycles by recovering almost 83% of the
initial capacitance value. Flexible paper-based supercapacitors
were fabricated using CNTs and MnO
2
.
110
CNTs were synthe-
sized via a water-assisted CVD method and dispersed in water
using sodium dodecyl benzene sulfonate (SDBS) as surfactant.
CNT papers were prepared by dropdry method and MnO
2
was
electrochemically deposited on CNT papers. The MnO
2
/CNT-
paper supercapacitors showed a very high SC of 540 F g
1
. The
specic energy and power densities were 20 Wh kg
1
and 1.5 kW
kg
1
, respectively, at a current density of 5 A g
1
in 0.1 M Na
2
SO
4
aqueous solution. The CV curve exhibited a nearly rectangular
shape indicating EDLC behavior with fast current response. The
charge storage mechanism was explained on the basis of inter-
calation of H
+
or Na
+
in the bulk of MnO
2
and adsorption of Na
+
on the surface of MnO
2
.
111
Charge storage near the MnO
2
surface contributed towards the enhancement of effective surface
area of MnO
2
which may have caused the signicant improve-
ment in SC. Flexible and transparent supercapacitor based on
indium trioxide (In
2
O
3
) nanowire/CNT composite lms was
fabricated by Chen et al.
112
The In
2
O
3
nanowire/CNT lm
supercapacitor showed higher SC (64 F g
1
) compared to the
CNT lm and PEDOT : CNT lm supercapacitors which might
be due to pseudocapacitance behavior exhibited by the In
2
O
3
nanowire.
113,114
The specic energy density and power density
values were 1.29 Wh kg
1
and 7.48 kW kg
1
, respectively. Vari-
ation in SC as a function of cycle number was exhibited to
determine the stability of the material. After the rst 100 cycles,
the SC decreased from 64 to 53 F g
1
and after 500 cycles, a slight
variation of SC was evident. The electrochemical performance of
In
2
O
3
nanowire/CNT lm is shown in Fig. 12. Intertwined CNT/
vanadium pentoxide (V
2
O
5
) nanowire nanocomposites were also
employed as high performance supercapacitors.
115
The V
2
O
5
nanowire showed two pairs of broad and well-separated redox
peaks, indicating sluggish lithium ion insertion/deinsertion
kinetics. Alternatively, the nanocomposite demonstrated two
distinct and well dened redox peaks with improved kinetic
properties. The hybrid composite of MnO
2
/MWCNTs showed
an SC of 56 F g
1
at a current density of 1 mA cm
2
which was far
better than that of the MWCNT-based electrode.
116
The
MWCNTs-based electrode showed a perfect linear discharge
curve indicating EDLC behavior, while the hybrid composite-
based electrode stored the energy primarily through pseudoca-
pacitance, exhibiting quasi-linear discharge curve. The hybrid
capacitor combined both the non-faradic and faradic processes
for energy storage.
117,118
Reddy et al. introduced AuMnO
2
/CNT
hybrid coaxial arrays for high-power supercapacitor applica-
tions.
119
The fabrication procedure of AuMnO
2
/CNT hybrid
coaxial arrays is shown in Fig. 13. The lack of symmetry in the
CV curves of the coaxial nanotube electrodes was indicative of
the dual contribution of EDL and pseudocapacitance. However,
increased area of the CV curve of AuMnO
2
/CNT coaxial elec-
trodes prompted the enhancement of the SC to 68 F g
1
for Au
MnO
2
/CNT hybrid coaxial arrays. The absence of ohmic drop in
the discharge curve for the AuMnO
2
/CNT electrode clearly
corroborated the improved contact between the electrode and
current collector, and the material showed reasonable cyclic
stability up to 1000 chargedischarge cycles. Electrochemical
impedance spectroscopy (EIS) analysis of the AuMnO
2
/CNT
electrode demonstrated that the impedance curve was parallel to
the imaginary axis at lower frequency, suggesting the capacitive
behavior of the electrode, where a semicircular loop at higher
frequencies was due to charge-transfer resistance of the electrode.
The AuMnO
2
/CNT coaxial array electrodes revealed
a maximum power density of 33 kW kg
1
with an energy density
of 4.5 Wh kg
1
, higher than that of original the MnO/MnO
2
cell
(3.3 Wh kg
1
).
120
Improvement in power density and energy
density for AuMnO
2
/CNT coaxial array electrodes compared
to MnO
2
/CNT coaxial array electrodes could be attributed to
low contact resistance between the electrode and current
collector. Each coaxial nanotube was assumed to be electrically
connected to the current collector. Details of the electrochemical
performance is shown in Fig. 14. MnO
2
nanowire/SWNT hybrid
lms and ITO nanowire/SWNT hybrid lms were utilized as the
positive and negative electrodes in an ASC.
121
The hybrid
nanostructured ASCs exhibited superior device performance
with SC of 184 F g
1
and energy density value of 25.5 Wh kg
1
. In
addition, the ASCs revealed an impressive power density of 50.3
kW kg
1
with a Coulombic efciency of 90%. A thin lm was
developed through combining MWCNTs and iridium dioxide
nanotubes (IrO
2
NT) for supercapacitor applications.
122
The
growth of IrO
2
NT on MWCNTs is shown in Fig. 15. Incorpo-
ration of IrO
2
NT resulted in an increase in SC of the MWCNTs.
The capacitance values of IrO
2
NT/MWCNT on stainless steel
substrate were estimated as 74, 70, 66, and 66 F g
1
at the
respective scan rates of 10, 30, 50, and 100 mV s
1
, which were
signicantly higher than those of 23, 17, 15, and 13 F g
1
for
MWCNT on stainless steel substrate at the corresponding sweep
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rates. The contact resistance reduced from 90 to 60 U for
IrO
2
NT/MWCNT on stainless steel substrate. The unique
structure provided high surface area for electrical charge storage
which in turn helped to improve the electrochemical performance
of the nanocomposite. Liu et al. carried out the spontaneous
reduction of Ru(VI) and Ru(VII) for the deposition of Ru-oxide
on MWCNT.
123
Both unmodied and acid modied MWCNTs
were employed to fabricate Ru-oxide/MWCNT composite as
supercapacitor electrodes. SCs of the Ru-oxide/p-MWCNT and
Ru oxide/a-MWCNT composites were 213 16 F g
1
and 184
11 F g
1
, respectively. The capacitance value after the
20 000thcycle was higher than that observed during the rst 300
cycles, demonstrating excellent long-term stability of the device.
Capacitive properties of V
2
O
5
on the CNTs were also investi-
gated.
124
Bare V
2
O
5
showed a very low value of SC due to the
poor conductivity of V
2
O
5
, and its dense two-dimensional
structure. The low capacitance value for pristine CNTs was due
to the presence of micropores on the CNTs. However, the
Fig. 12 (a) Cyclic voltammograms of a CNT lm supercapacitor, a PEDOT : CNT lm supercapacitor, and In
2
O
3
nanowires/CNT lm super-
capacitors. (b) Chargedischarge behavior of In
2
O
3
nanowires/CNT lm supercapacitors. (c) Cyclic stability of In
2
O
3
nanowires/CNT lm capacitor
Fig. 13 Schematic diagram showing the fabrication of AuMnO
2
/CNT hybrid coaxial nanotube arrays using a combination of electrodeposition,
vacuum inltration, and CVD techniques. A thin layer of silver (100 nm) was sputter coated to act as the current collector for the electrodes (adapted
from ref. 119).
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capacitance value for the CNTV
2
O
5
composite was markedly
enhanced.
Long term cyclic stabilities of amorphous MnO
2
and SWCNT
composites were reported by Subramanian et al. SC of the
composites was higher as compared to pure MnO
2
at higher
current, which was mainly due to an increase in the electronic
conductivity of system. Enhancement of electrical conductivity
was due to the presence of the SWNTs and entanglement of
nanotubes. However, for pure MnO
2
, the SC declined to 10% of
the initial value after 500 cycles. Although pristine SWCNTs
showed a reasonably good cyclic stability at high current, their
initial SC value was much lower. However, composites showed
maximum retainment of SC after 500 cycles.
125
Lin et al.
proposed a simple hydrothermal approach for the synthesis of
NiO/CNT composite material as electrodes for
supercapacitors.
126
NiO showed a rectangular mirror image with
respect to the zero-current line, indicative of its capacitive
behavior.
127
However, the NiO/CNT composite material showed
distinguished redox peaks associated with Ni(OH)
2
/NiOOH
redox reaction.
128131
The composite demonstrated high SC value
with long-term cyclic stability. The dispersed NiO on the surface
of CNTs resulted in the highest SC of 1329 F g
1
at a current
density of 84 A g
1
. Reddy et al. presented the supercapacitor
behavior of TiO
2
/MWCNT, RuO
2
/MWCNT and SnO
2
/
MWCNT composites.
132
The CV curves of MWCNT/metal
oxide electrodes were deprived of symmetry, probably due to
contribution of both EDLC and pseudo capacitances. The area
of the curve was found to increase with TiO
2
, RuO
2
, and SnO
2
functionalization, indicating an enhancement of SP for these
electrodes. The average SPs measured of the pure MWCNT,
RuO
2
/MWCNT, TiO
2
/MWCNT, and SnO
2
/MWCNT nano-
composite electrodes were 67, 138, 160, and 93 F g
1
,
respectively.
7. Conclusions and future design concept
Supercapacitors, have been studied extensively in the past few
decades as energy storage devices. A supercapacitor electrode
should satisfy the basic requirements e.g., high SC, low internal
resistance and stability to achieve optimum performance. In
current research, carbon-based nanostructured materials and
their composites have been widely considered as electrode
materials for supercapacitors owing to their fascinating proper-
ties, such as high surface area, interconnected porous structure,
high electrical conductivity, excellent wettability towards the
Fig. 14 (a) Cyclic voltammograms of a supercapacitor cell having MnO
2
/CNT and AuMnO
2
/CNT hybrid coaxial nanotube electrodes, at a scan rate
of 10 mV s
1
. (b) Galvanostatic chargedischarge behavior at an applied constant current of 10 mA. (c) Complex-plane impedance spectra measured at
an AC amplitude of 10 mV (adapted from ref. 119).
Fig. 15 The SEM image of: (a) the top view of IrO
2
NT/MWCNT, (b)
the cross-sectional view of IrO
2
NT/MWCNT. The inset of (b) is
a magnied image of IrO
2
NT/MWCNT (adapted from ref. 122).
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electrolyte, and presence of electrochemically active surface
functionalities. Participation of both EDL capacitance and
pseudo-capacitance led to improve the overall SC of a material.
Pseudo-capacitance may be due to chemisorptions of anions with
a partial charge transfer, or due to redox processes. Electroactive
conducting polymers or metal oxide-based carbon composites
can be effectively utilized to achieve high SC value with
reasonable cyclic stability. Polymers/metal oxides can give rise to
the pseudo-capacitance aspects of the electrode and carbon-
based materials participate in EDL capacitance. A detailed
analysis of carbon based nanostructured materials and their
composites as supercapacitor electrodes have been critically
reviewed in this article. The carbon based materials and their
composites demonstrate impressive energy density values and
maintain long term stability.
One of the lacunas in developing supercapacitor devices is the
cost factor. Hence future research should be concentrated in the
direction of fabricating carbon based supercapacitor devices with
long term stability and high capacity in a cost effective way. A
one-step synthesis process for high density carbon-based mate-
rials will be benecial to design high power energy sources.
Adequate attention is required for the selection of electrolyte
solution which is another imperative factor in deciding the
performance of the supercapacitor. A new generation of super-
capacitors is expected to replace batteries in certain applications
where high efciency, high power, and a high level of reliability is
required. High performance supercapacitors are promising
candidates for future energy and power storage devices.
Acronyms
AN Acrylo nitrile
ASC Flexible asymmetric supercapacitor
Bi
2
O
3
Bismuth trioxide
BMIPF
6
1-Butyl-3-methylimidazolium
hexauorophosphate
CeO
2
Cerium oxide
CMG Chemically modied graphene
CNT Carbon nanotube
CNF Carbon nanober
Co(OH)
2
Cobalt hydroxide
CV Cyclic voltammetry
CVD Chemical vapor deposition
DBSA Dodecylbenzene sulfonic acid
EDLC Electric double layer capacitor
EIS Electrochemical impedance spectroscopy
EMIMNTf
2
1-Ethyl-3-methylimidazolium bis
(triuoromethylsulfonyl) amide
EPD Electrophoretic deposition
ESR Equivalent series resistance
FGS Functionalized graphene sheets
GO Graphite oxide
GNS Graphene nanosheet
In
2
O
3
Indium trioxide
IrO
2
Iridium dioxide
ITO Indium tin oxide
MOFeCl
3
Methyl orangeiron(III) chloride
MWCNT Multi-walled CNT
MnO
2
Manganese dioxide
NiO Nickel oxide
OPPD Oxidized p-phenylene diamine
PANI Polyaniline
PANI-NFs PANI nanobers
PC Polypropylene carbonate
PDDA Poly(diallyl dimethyl ammonium chloride)
PEDOT Poly(3,4-ethylenedioxythiophene)
PEI Polyether imide
PIL Poly(ionic liquid)
PPy Polypyrrole
PSS Poly(sodium 4-styrenesulfonate)
PVA Polyvinyl alcohol
RGO Reduced graphite oxide
RuO
2
Ruthenium oxide
SACNT Super aligned carbon nanotube
SC Specic capacitance
SDBS Sodium dodecyl benzene sulfonate
SnO
2
Tin oxide
SWCNT Single-walled carbon nanotube
TEABF
4
Tetraethylammonium tetrauoroborate
USP Ultrasonic spray pyrolysis
V
2
O
5
Vanadium pentoxide
ZnO Zinc oxide
Acknowledgements
This study was supported by the Human Resource Training
Project for Regional Innovation, the Converging Research
Center Program (2011K000776), and the World Class University
(WCU) program (R31-20029) through the National Research
Foundation (NRF) funded by the Ministry of Education,
Science, and Technology (MEST) of Korea.
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Carbon-based nano materials for supercapacitor electrodes

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Carbon-based nano materials for supercapacitor electrodes

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Carbon-based nanostructured materials and their composites as

5.3 CNT/metal oxide composite

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