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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
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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
nanofibers, provide high surface area for the deposition of conducting polymer/metal oxide that
facilitates the efficient ion diffusion phenomenon and contribute towards higher specific 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.
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properties as well as their unique structural features.20 Structural - Fast charge–discharge phenomenon.
features and morphology of the carbon-based materials are - Reasonably low self-discharging.
crucial for effective permeation of the electrolyte.21 In the current In order to resist the self-discharging, a high time constant
review, we focus on the electrochemical performance of gra- value is required. The stored energy (E) and the power density
phene, and CNT-based materials as well as their composites with (P) in a supercapacitor are calculated using the following
conducting polymers and various metal oxides for use as super- expressions:
capacitor electrodes. Specific capacitance values of different
carbon-based materials for supercapacitor application have been E ¼ 1/2CV2
summarized in Table 1.
A supercapacitor consists of two electrodes immersed in elec- where, C(F g1) is the total capacitance of the cell, V is the cell
trolyte solution, with a voltage potential across the current voltage, and Rs is the equivalent series resistance (ESR). To
collector. A dielectric separator between the two electrodes achieve a supercapacitor with high performance, the indispens-
prevents charge propagation between the electrodes (Fig. 1). able requirements, such as large SC, high cell voltage and
Supercapacitors can be explained via two types of mechanism: minimum ESR value should be achieved. The selection of elec-
(a) Electrical double layer capacitor (EDLC), where the energy trode material and electrolyte solution is the most crucial criteria
can be stored through ion adsorption. The charge transfer
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Specific capacitance
Types of materials (F g1) Reference
Graphene-based materials
RGO 347 40
CMG 135 41
99
PIL : RGO 127–187 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
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33.3 A g1 were 40 kW kg1 and 40 Wh kg1, respectively. The the pseudocapacitive behavior. Deviation from the rectangular
electrophoretic deposition (EPD) method was employed to shape was attributed to adsorption or desorption of positively
deposit a graphene nanosheet on Ni foam as electrode material.34 charged ions in a negative potential. The retention of the initial
The CV curve showed a non-rectangular shape which reflected capacitance value of the graphene based electrode was 60% at
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770 | J. Mater. Chem., 2012, 22, 767–784 This journal is ª The Royal Society of Chemistry 2012
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Fig. 2 CV (left) and Nyquist (right) plots of CMG material with KOH electrolyte (top), TEA–BF4 in propylene carbonate (middle) and TEA–BF4 in
acetonitrile (bottom) (adapted from ref. 41).
materials with respect to the current collectors resulted in utilized as an electrode for a supercapacitor.47 The pristine gra-
incomplete utilization of the electrochemical surface area. The phene exhibited an SP value of 101 F g1, while the SP of KOH-
electrolyte ions did not penetrate inside the graphitic planes. treated graphene was 136 F g1 at a scan rate of 10 mV s1. The
Alternatively, owing to improved interaction between the elec- energy density value of KOH-treated graphene was 18.9 Wh
trolyte ions with the graphitic layers in the ‘in-plane’ design, the kg1. The increased capacitance value might be attributed to the
high surface area of the graphene layers was fully utilized and edge defects and the oxygen containing groups introduced upon
henceforth exhibited a substantially high value of SC (247.3 F KOH modification, which led to enhancement of the pseudoca-
g1). A mild solvothermal method was employed to prepare pacitive properties. Functionalized graphene sheets (FGS) were
functionalized graphene.46 This process did not involve any prepared by a low-temperature thermal exfoliation procedure.48
strong reducing agent, which allowed retention of oxygen-con- The first kind of FGS was obtained by thermal exfoliation of GO
taining groups as a source of pseudocapacitance. A specific at low temperature in air. The second kind was prepared by the
capacitance up to 276 F g1 was achieved at a current density of carbonization of the first kind of FGS at a higher temperature in
0.1 A g1. The CV shape remained almost undistorted upon N2. The SP value of the first kind of FGS was 230 F g1,
increasing the scan rate from 10 mV s1 to 100 mV s1, indicating compared to 100 F g1 for second kind of FGS. However, the
excellent wetting and easy access of ions to the graphene surface. second kind of FGS demonstrated a higher capacitance retention
Specific energies of functionalized graphene were 20 and 14.5 Wh at high current density because of good conductive behaviors.
kg1, respectively, at specific powers of 34.5 and 1.69 103 W Highly conductive graphene hydrogels were prepared by
kg1. Potassium hydroxide (KOH) modified graphene was hydrothermal reduction of GO dispersion.49 The supercapacitor
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Fig. 5 Cyclic voltammograms of (A) G-paper and (B) GPCP, recorded from 2 to 20 mV s1 in 1 M H2SO4. (C) Nyquist plots of the G-paper and GPCP
60 s/300 s/900 s. (D) Cycling stability measured at 50 mV s1 (adapted from ref. 54).
involving pyrrole monomer in the presence of graphene under electrochemical performance of the composite was examined by
acidic conditions.58 The SC of the PPy/GNS composite was as Bose et al. The SPs of the nanocomposite were 417 and 267 F g1
high as 482 F g1 at a current density of 0.5 A g1. After 1000 at scan rates of 10 and 100 mV s1, respectively. The energy
cycles, the attenuation of the SC was much less (5%), indicating density and power density values of the nanocomposite were
excellent cyclic stability of the composite. The high value of SP 94.93 Wh kg1 and 3.797 kW kg1, respectively. Retention of
and enhanced rate capability of the composite material was 90% of the SP after 500 cycles highlighted the excellent electro-
attributed to the higher conductivity and smaller particle sizes of chemical cyclic stability of the nanocomposite.62 Composite films
composite, which in turn shorten ion diffusion length and of sulfonated graphene and PPy were electrochemically depos-
resulted in higher materials utilization. A sulfonated graphene/ ited from the aqueous solution of pyrrole monomer, sulfonated
PANI nanocomposite (SGEP) was fabricated by a novel graphene sheets, and DBSA.63 Introduction of sulfonated gra-
morphology-controlled strategy using liquid/liquid interfacial phene sheets improved the conductivity and reduced the IR drop
polymerization.59 The SGEP nanocomposite exhibited an SC of value. The composite films showed a high value of SP (285 F g1)
763 F g1 with 96% retention of SC after 100 cycles. Stable at a discharge rate of 0.5 A g1. They also demonstrated highly
aqueous dispersion of composite films based upon CMG and improved electrochemical cyclic stability and rate capabilities.
PANI nanofibers (PANI-NFs) were prepared by vacuum filtra- The charge–discharge shape of the PPy/sulfonated graphene
tion of mixed dispersions.60 In this method, the PANI-NFs were composite demonstrated a combination of EDL and pseudoca-
sandwiched between CCG layers. A high SC value (214 F g1) of pacitance. EDL capacitance was due to formation of a porous
the composite film indicated the synergistic effect between the structure and pseudocapacitance was from the highly conducting
PANI-NFs and CMG. Incorporation of PANI-NFs into CMG sulfonated graphene components.
played a significant role in the improvement of capacitance of the
composite film through the formation of a porous structure.
4.3 Graphene/metal oxide composites
Redox transitions of PANI-NFs were facilitated by the highly
conducting CMG materials. Mini et al. reported the high Hydrous ruthenium dioxide (RuO2) was exploited to fabricate
supercapacitive behavior of graphene/PPy composite.61 Firstly, RuO2/graphene sheet composite (ROGSCs) via the combination
the graphene was deposited on titanium metal substrate by EPD of sol–gel and low-temperature annealing processes.64 A
method. PPy was electropolymerized on the graphene surface to maximum SC of 570 F g1 was achieved for ROGSCs at 38.3 wt
develop the graphene/PPy composite. The electrode exhibited an % Ru loading, as compared to 148 F g1 for pure graphene. The
area capacitance of 151 mF cm2, volume capacitance of 151 F capacitance of the ROGSCs slowly decreased to 98.2% during
cm3 and an SP of 1510 F g1 was achieved at a scan rate of 10 the first 170 charge–discharge cycles, and then became quite
mV s1 (polymerization time 1500 s). The calculated energy stable. After 100 cycles, 97.9% of the initial capacitance was
density and power density values were 5.7 Wh kg1 and 3.0 kW retained. The energy density obtained for ROGSCs was 20.1 Wh
kg1, respectively. Graphene nanosheet (GNS)/PPy nano- kg1, while the corresponding power density value was 50 W kg1
composites were prepared by in situ polymerization and the at a current density of 0.1 A g1. A graphene–ZnO composite film
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as a supercapacitor electrode was reported by Zhang et al. electrode, the shorter discharge time was governed by EDLC,
Graphene was synthesized through an oxidation–reduction while, for the graphene–Bi2O3 electrode, the dual effect of EDLC
process using hydrazine as reducing agent. ZnO was deposited on and faradaic capacitance was responsible for the longer
graphene by ultrasonic spray pyrolysis (USP). The ITO–G–ZnO discharge duration. SC values were 71 and 255 F g1 for graphene
electrode exhibited an SC of 11.3 F g1.65 The composite elec- and graphene–Bi2O3 electrodes, respectively, at a current density
trode showed an excellent charge/discharge stability with typical of 0.1 A g1. The CV of the graphene–Bi2O3 composite at
supercapacitor behavior. The higher SP value was due to the different scan rates and the variation in discharge time for the
contribution of both EDLC from graphene and pseudo-capaci- graphene and graphene–Bi2O3 composite is shown in Fig. 7.
tance from ZnO. Li and co-workers developed a novel idea of Graphene/SnO2 nanocomposites as electrochemical super-
constructing multilayer films by electrostatic layer-by-layer self- capacitor demonstrated a capacitance value of 43.7 F g1
assembly, using poly(sodium 4-styrenesulfonate) modified gra- compared to 20.7 and 0.62 F g1 for CCG and GO.68 The
phene sheets (PSS–GS), MnO2, and PDDA as building block impedance curve for the nanocomposite in the high frequency
units.66 The CV curve area and the current response of ITO/
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region was nearly parallel to the real axis, indicating the low
(PDDA/PSS–GS/PDDA/MnO2) electrode were much larger contact resistance of the nanocomposite. However, in the low
than those of both the ITO/(PDDA/MnO2) and (ITO/PDDA/ frequency region, the imaginary part of the impedance curve was
PSS–GS) electrodes, indicating that the improved electro- vertical, corroborating a capacitive-type behavior. A polymer
chemical performance of the ITO/(PDDA/PSS–GS/PDDA/ assisted chemical reduction method for the fabrication of MnO2/
MnO2) electrode resulted from the synergistic effect between the graphene composite and the utilization of the same electrode
PSS–GS and MnO2 sheets in the multilayer system. The SC of material for supercapacitor was examined.69 A reasonably high
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ITO/(PDDA/PSS–GS/PDDA/MnO2) electrode was calculated value of SC was achieved (324 F g1) with excellent cyclic
to be 263 F g1 at a current density of 0.283 A g1. With stability (a decrease of only 3.2% in the SC was observed after
increasing current density, the capacitance of the electrode 1000 cycles). The composite exhibited an outstanding electro-
decreased from 263 to 154 F g1, which might be due to the chemical property as supercapacitor electrode, owing to elec-
diffusion effect of ions within the multilayer films. After 1000 trochemical activities of the embedded MnO2 nanoparticles and
cycles, 90% of the initial SC of this electrode was retained, activated graphene open network with increased specific surface
corroborating the long-term cyclic stability of the multilayer film. area. Based on the low cost, environmentally friendly nature and
The electrochemical performance of the multilayer film as elec- excellent capacitive properties, the MnO2/graphene composite
trode is shown in Fig. 6. Facile solvothermal synthesis of gra- was considered to be a promising electrode material for super-
phene nanosheet–bismuth oxide (Bi2O3) composite was reported capacitors. ZnO/RGO composites were prepared using a two-
by Wang et al.67 CV analysis of the graphene–Bi2O3 composite step method and electrochemical performance of the composite
confirmed the appearance of a pair of redox peaks compared to was evaluated.70 The composite showed an ideal capacitive
the rectangular shape for pure graphene. For the graphene-based behavior with an SC of 308 F g1 at a current density of 1 A g1,
Fig. 6 (a) CV curves of ITO/(PDDA/PSS–GS/PDDA/MnO2) electrode at different scan rates. (b) Charge–discharge behavior of the electrode at
different current densities. (c) Variation of specific capacitances with current density. (d) Specific capacitance and Coulombic efficiency change of the
electrode vs. number of charge/discharge cycles at a current density of 1.41 A g1 (adapted from ref. 66).
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Published on 16 November 2011 on http://pubs.rsc.org | doi:10.1039/C1JM14468E
Fig. 7 (a) CV curve of graphene–Bi2O3 composite at different scan rates. (b) Discharge curves of graphene and graphene–Bi2O3 composite in the
potential range from 0.9 to 0.1 V at a specific current of 1 A g1 (adapted from ref. 67).
much higher than those of ZnO (135 F g1) and RGO (157 F g1). Fe3O4-functionalized graphene nanocomposites, respectively, at
The unique 3D morphology of RGO-coated ZnO facilitated the a scan rate of 10 mV s1. The RuO2-functionalized graphene
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fast electron transfer between the active materials and current nanocomposite demonstrated the best performance among all of
collector. At a specific current of 4 A g1, an SC of 180 F g1 was the studied metal oxide-based nanocomposites, attributing to the
achieved, implying that the composite exhibited an impressive better electrical conductivity and fast faradaic reactions for
rate capability at high specific current. Wang et al. adopted RuO2 nanoparticles compared to other metal oxides. At a higher
a green route to synthesize a graphene/ZnO composite and scan rate, the SP value decreased to an extent for each sample.
utilized it as a supercapacitor electrode.71 Glucose and exfoliated An approximate 10–16% reduction in SP was observed for each
GO were used as reducing agent and precursor, respectively. studied nanocomposite, suggesting the high degree of sustain-
ZnO was directly grown on the graphene surface. CV loops were ability of capacitance even at a higher scan rate. A CeO2 nano-
quasi-rectangular in nature with no obvious redox peaks. An particles/graphene nanocomposite was fabricated by depositing
increase in the current output with increasing scan rate demon- CeO2 nanoparticles onto three-dimensional graphene material
strated the excellent rate capability of the material. The and its supercapacitor performance was further investigated.75
composite showed an SP of 62.2 F g1 with power density of 8.1 The calculated SP values of graphene, CeO2 and CeO2 nano-
kW kg1. A composite material composed of MnO2 and func- particles/graphene nanocomposite were 81, 57 and 191 F g1,
tionalized graphene was utilized as supercapacitor electrode.72 respectively. The synergistic effect between CeO2 with graphene
Functionalized graphene was prepared by reducing functional- led to boost the SP of the nanocomposite. The nanocomposite
ized GO with PDDA. MnO2 was deposited on the graphene also demonstrated excellent cyclic stability even after 1000 cycles.
surface via the electrostatic co-precipitation method. An SP of Yu et al. investigated the electrochemical performance of solu-
188 F g1 was achieved for the MnO2/functionalized graphene tion-processed graphene/MnO2 nanostructured textiles.76 The
composite at a current density of 0.25 A g1. Additionally, over as-mentioned nanocomposite exhibited an SP of 315 F g1 with
89% of the original capacitance was retained after 1000 cycles, a maximum power density and energy density of 110 kW kg1and
indicating a good cycle stability of the composite materials. Chen 12.5 Wh kg1, respectively. The supreme performance of the
et al. adopted a facile soft chemical approach to fabricate gra- graphene/MnO2 nanostructured textiles could be attributed to
phene–Co(OH)2 nanocomposites in a water–isopropanol system, the following factors:
followed by analysis of their electrochemical properties.73 The 3D porous microstructures of the polyester textiles allowing
nanocomposite demonstrated an SP of 972.5 F g1. The conformal coating of graphene nanosheets.
substantially high value of SP could be ascribed from the faradic Incorporation of MnO2 facilitated easy access of electrolyte
reactions of nanoscale Co(OH)2. The combination of Co(OH)2 to electrode surfaces.
and graphene may result in synergistic performance, which in Graphene nanosheets provided high surface area and
turn resulted in enhanced electrochemical performance. Elec- conductive paths for the deposition of MnO2 and thereby
trochemical properties of metal oxide (RuO2, TiO2, and Fe3O4) allowed fast electron transport.
decorated functionalized graphene were demonstrated by Mishra Nano-flower architectures of electrodeposited MnO2 helped
et al.74 The CV shape of functionalized graphene, RuO2-func- to reduce ion diffusion length during the charge/discharge
tionalized graphene, and TiO2-functionalized graphene nano- process.
composites were found to be almost rectangular in 1 M H2SO4 Moreover, retention of 95% capacitance after 5000 cycles
solution, suggesting the capacitive behavior of nanocomposites. corroborated its excellent cycling performance. Wu et al. devel-
Alternatively, Fe3O4-functionalized graphene nanocomposites oped a high-voltage asymmetric electrochemical capacitor based
showed a better rectangular shape for 1 M Na2SO4 as an elec- on graphene as the negative electrode and an MnO2 nanowire/
trolyte solution. SP values with 1 M H2SO4, were found to be graphene composite as the positive electrode in a neutral aqueous
125, 265, 60, and 180 F g1, for functionalized graphene, RuO2- Na2SO4 solution as electrolyte.77 The capacitance value was
functionalized graphene, and TiO2-functionalized graphene, and observed to be 31 F g1. However, after 1000 cycles, the
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CNTs. CNTs. (d) Electrochemical test system of the film (adapted from ref. 87).
II. Formation of open mesoporous network through the
entanglement of nanotubes allows fast and efficient migration of
the ions to the active surfaces of the composite components. scan rate, the penetration of ions into the porous films was
III. CNTs are characterized by high resiliency and thus the progressively reduced causing decrement in SC.91 The maximum
composite electrodes can easily adapt to the volumetric changes energy density and power density values were 43.7 Wh kg1 and
during the charge and discharge process which in turn improves 197.3 kW kg1, respectively. Du et al. utilized the EPD method to
the cycling performance. fabricate a MWCNT film to be used as a high power density
In this section of the review, we will focus on the recent supercapacitor electrode.92 The advantageous features of the
progress on the use of CNT and CNT-based composite materials EPD method involves short formation time, simple apparatus,
as supercapacitor electrodes. 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
5.1 CNT-based materials
fast diffusion of the electrolyte. The power density of the con-
Nanoporous current collectors for supercapacitors were fabri- cerned materials was 20 kW kg1. Carboxylic acid- and ester-
cated using cross-stacking super aligned CNT (SACNT) films as functionalized SWCNTs and MWCNTs were deposited on the
an ideal replacement for heavy conventional metallic current polymer substrate via the spray deposition technique for super-
collectors.87 The CNT-based current collectors showed excellent capacitor application.93 A rectangular CV shape of the ester-
conducting properties along with outstanding electrochemical functionalized CNT (E-MWCNT/E-SWCNT) demonstrated an
stability. The schematic drawing of the CNT-based film prepa- EDLC capacitance; alternatively, the CV of the acid-modified
ration and the construction of the respective cell is shown in CNT (A-MWCNT/A-SWCNT) was composed of a pair of redox
Fig. 8. peaks, corroborating the pseudocapacitance behavior. The
A facile and efficient way of preparing supercapacitor elec- charge–discharge curves of the pure CNTs (P-MWCNT/P-
trodes based on CNTs was reported by Shi et al. CNTs were SWCNT) and ester-functionalized CNT films (E-MWCNT/E-
grown directly on Ni-foam by chemical vapor deposition (CVD). SWCNT) were nearly symmetrical. The SCs of the A-MWCNT
The electrochemical performance of the Ni-foam-based CNTs and A-SWCNT were 77 and 155 F g1 at a scan rate of 100 mV
was superior compared to conventional CNT-based super- s1, compared to 23 and 38 F g1 for P-MWCNT or P-SWCNT,
capacitors due to the hierarchical porous structure and robust respectively. The impedance spectra of the CNT films exhibited
CNT–metal contact. Ni-foam-based CNTs retained almost 72% semi-circles at frequencies above 1 Hz and nearly vertical straight
of the initial capacitance at a high current density.88 lines at frequencies below 1 Hz. The galvanostatic charge–
Compact-designed supercapacitors were fabricated using discharge behavior, and the impedance spectroscopy of the CNT
large-scale freestanding and flexible SWCNT films as electrode films are shown in Fig. 9. Yu et al. proposed the concept of
materials.89 The SWCNT films were prepared by floating CVD stretchable supercapacitors based on buckled SWCNT macro-
method.90 The advantageous feature of this method is that the films.94 The fabrication procedure of buckled SWCNT macro-
directly grown film can be tailored into the desired shape and size films on a PDMS substrate is shown in Fig. 10. The initial SCs of
depending upon the required application. The SC of the SWCNT the stretchable supercapacitor were 54 F g1 (without applied
film-based supercapacitor was 34 F g1 at a scan rate of 20 mV strain) and 52 F g1 (30% applied strain). However, the SCs of
s1. The high value of SC at lower scan rate compared to that at stretchable supercapacitors with or without applied strain did
higher scan rate was due to the efficient diffusion of the ions from not vary even up to 1000 charge–discharge cycles, thus demon-
the electrolyte through the SWCNTs pores. However, at higher strating excellent electrochemical stability.
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Published on 16 November 2011 on http://pubs.rsc.org | doi:10.1039/C1JM14468E
Fig. 9 (a) Galvanostatic charging/discharging behaviour of CNT films. (b) AC impedance spectra of CNT films after 50 cycles (adapted from ref. 93).
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Fig. 11 (a) CV curves of PEDOT and PEDOT/F-SWNTs at scan rate of 10 mV s1. (b) Nyquist plots as a function of frequency. (c) Cyclic stability and
discharge efficiency of the composite (adapted from ref. 98).
However, both pure PPy and SWCNT/PPy nanocomposite Zhang et al.,101 and obtained the SC values of 34, 234 and
electrodes showed a gradual decrease in the SC with an 485 F g1 for SWCNTs, pure PANI and PANI/SWCNT
increase in discharge current density due to large internal composite, respectively, at a current density of 5 mA cm2.
electrode resistance. However, for the as-grown SWCNTs, the Functionalization of the CNTs was performed using a micro-
reverse phenomenon was true which might be due to the wave hydrothermal strategy with a thorn-like organometallic
porous structure of the SWCNTs. Pores with a small diameter methyl orange–iron(III) chloride (MO–FeCl3) complex.103 The
acted as a platform for ion diffusion from the electrolyte. The complex served as an oxidant, and PPy nanoparticles were
supercapacitor application of highly flexible and all-solid-state directionally attached onto the CNTs through the polymeri-
paper-like materials based upon PANI and CNT was investi- zation of pyrrole in the absence of any extra oxidants. Gal-
gated by Meng et al.100 The electrochemical performance was vanostatic charge/discharge for the PPy/CNT composite was
evaluated using H2SO4–polyvinyl alcohol (PVA) solution as performed with an applied current density of 1.0 mA cm2 in
electrolyte. The all-solid-state based material as an electrode the potential range between 0.5 to 0.5 V. The resulting curve
showed nearly an identical CV curve as observed in the case of was not an ideal straight line, indicating pseudocapacitance
the 0.5 M H2SO4 solution, where the redox peaks were due to behavior.104 The maximum capacitance value of PPy/CNT
the pseudocapacitance of PANI. SC of the material under composite was 304 F g1. The high SC could be attributed to
consideration was 332 F g1 at a current density of 1.0 A g1. the large electrolyte-accessible surface area of the functional-
The energy density and power density values were 7.1 Wh kg1 ized CNTs, facilitating the effective utilization of PPy for the
and 2189 W kg1, respectively. Reasonably high cyclic stability redox reaction.105 The electrochemical redox reaction between
was attributed from the decrement of only 8.1% SC after 1000 the electrode and electrolyte is shown below:
cycles. MWCNT/PANI composite films were prepared
via in situ electrochemical polymerization of aniline solution
with varying MWCNT contents. MWCNT/PANI composites [PPy0] + Cl / [PPy+]Cl + e
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
[PPy+]Cl + e / [PPy0] + Cl
0.2, 0.4, and 0.8 wt% MWCNT loading were 434, 481 and
500 F g1, respectively, at a current density of 5 mA cm2.
Shortening of the diameter of the semicircles with the incor-
5.3 CNT/metal oxide composite
poration of MWCNT into the PANI matrix indicated the
reduced charge-transfer complex resistance of the MWCNT/ A spray deposition technique had been adopted to fabricate
PANI composite.101 Gupta et al.102 prepared SWCNT/PANI a flexible nanostructured hybrid supercapacitor based on
composite adopting a similar method as demonstrated by hematite (a-Fe2O3)/MWNT composite anode. The composite as
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anode material showed a very high specific energy density of 50 variation of SC was evident. The electrochemical performance of
Wh kg1 at a specific power density of 1.0 kW kg1 over In2O3 nanowire/CNT film is shown in Fig. 12. Intertwined CNT/
a potential range of 0–2.8 V.106 The superior electrochemical vanadium pentoxide (V2O5) nanowire nanocomposites were also
performance of the hybrid supercapacitor arrangement was employed as high performance supercapacitors.115 The V2O5
attributed to the decrement of internal resistance and an nanowire showed two pairs of broad and well-separated redox
improvement in both the ion diffusion behaviour as well as the peaks, indicating sluggish lithium ion insertion/deinsertion
integrity of the a-Fe2O3 containing films. The potential of the kinetics. Alternatively, the nanocomposite demonstrated two
CNT/RuO2 nanocomposite supercapacitor electrode was exam- distinct and well defined redox peaks with improved kinetic
ined by Park et al.107 The SC of this nanocomposite (13 wt% properties. The hybrid composite of MnO2/MWCNTs showed
RuO2 loading) was 70 F g1 at a scan rate of 20 mV s1, which an SC of 56 F g1 at a current density of 1 mA cm2 which was far
was much higher than pristine CNT (6 F g1). The microporous better than that of the MWCNT-based electrode.116 The
structure of the CNTs provided a suitable environment for the MWCNTs-based electrode showed a perfect linear discharge
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deposition of RuO2 nanoparticles. RuO2 particles behaved as curve indicating EDLC behavior, while the hybrid composite-
individual nanoscale reactors and thus facilitate the possibilities based electrode stored the energy primarily through pseudoca-
of faradaic reactions. CNT–ZnO assemblies were utilized as an pacitance, exhibiting quasi-linear discharge curve. The hybrid
electrode for a supercapacitor with gel polymer as electrolyte capacitor combined both the non-faradic and faradic processes
solution.108 The CNT film was fabricated using screen-printing for energy storage.117,118 Reddy et al. introduced Au–MnO2/CNT
and ZnO was deposited on the film by USP for different time hybrid coaxial arrays for high-power supercapacitor applica-
periods. The SC of the CNT-based electrode was 92.7 F g1. tions.119 The fabrication procedure of Au–MnO2/CNT hybrid
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However for CNT–ZnO-5 (composite with ZnO deposition for 5 coaxial arrays is shown in Fig. 13. The lack of symmetry in the
min), the value of SC increased to the apparent maximum of CV curves of the coaxial nanotube electrodes was indicative of
126.3 F g1. However, with a deposition time greater than 10 the dual contribution of EDL and pseudocapacitance. However,
min, a dramatic reduction in SC was observed. With increasing increased area of the CV curve of Au–MnO2/CNT coaxial elec-
deposition time, the CNT surface was totally covered by ZnO trodes prompted the enhancement of the SC to 68 F g1 for Au–
which had a high resistance and thus lowered the capacitance of MnO2/CNT hybrid coaxial arrays. The absence of ohmic drop in
the electrodes. Furthermore, the accumulation of ZnO destroyed the discharge curve for the Au–MnO2/CNT electrode clearly
the network formation of CNTs and in the process hampered the corroborated the improved contact between the electrode and
adsorption of protons or electrons on the electrode surface. current collector, and the material showed reasonable cyclic
Zhang et al.109 also investigated ZnO deposition for 5 min over stability up to 1000 charge–discharge cycles. Electrochemical
CNT electrode demonstrated lowest internal resistance with very impedance spectroscopy (EIS) analysis of the Au–MnO2/CNT
high SC value (323.9 F g1). CNT–ZnO-5 exhibited excellent electrode demonstrated that the impedance curve was parallel to
reversibility after 100 cycles by recovering almost 83% of the the imaginary axis at lower frequency, suggesting the capacitive
initial capacitance value. Flexible paper-based supercapacitors behavior of the electrode, where a semicircular loop at higher
were fabricated using CNTs and MnO2.110 CNTs were synthe- frequencies was due to charge-transfer resistance of the electrode.
sized via a water-assisted CVD method and dispersed in water The Au–MnO2/CNT coaxial array electrodes revealed
using sodium dodecyl benzene sulfonate (SDBS) as surfactant. a maximum power density of 33 kW kg1 with an energy density
CNT papers were prepared by drop–dry method and MnO2 was of 4.5 Wh kg1, higher than that of original the MnO/MnO2 cell
electrochemically deposited on CNT papers. The MnO2/CNT- (3.3 Wh kg1).120 Improvement in power density and energy
paper supercapacitors showed a very high SC of 540 F g1. The density for Au–MnO2/CNT coaxial array electrodes compared
specific energy and power densities were 20 Wh kg1 and 1.5 kW to MnO2/CNT coaxial array electrodes could be attributed to
kg1, respectively, at a current density of 5 A g1 in 0.1 M Na2SO4 low contact resistance between the electrode and current
aqueous solution. The CV curve exhibited a nearly rectangular collector. Each coaxial nanotube was assumed to be electrically
shape indicating EDLC behavior with fast current response. The connected to the current collector. Details of the electrochemical
charge storage mechanism was explained on the basis of inter- performance is shown in Fig. 14. MnO2 nanowire/SWNT hybrid
calation of H+ or Na+ in the bulk of MnO2 and adsorption of Na+ films and ITO nanowire/SWNT hybrid films were utilized as the
on the surface of MnO2.111 Charge storage near the MnO2 positive and negative electrodes in an ASC.121 The hybrid
surface contributed towards the enhancement of effective surface nanostructured ASCs exhibited superior device performance
area of MnO2 which may have caused the significant improve- with SC of 184 F g1 and energy density value of 25.5 Wh kg1. In
ment in SC. Flexible and transparent supercapacitor based on addition, the ASCs revealed an impressive power density of 50.3
indium trioxide (In2O3) nanowire/CNT composite films was kW kg1 with a Coulombic efficiency of 90%. A thin film was
fabricated by Chen et al.112 The In2O3 nanowire/CNT film developed through combining MWCNTs and iridium dioxide
supercapacitor showed higher SC (64 F g1) compared to the nanotubes (IrO2NT) for supercapacitor applications.122 The
CNT film and PEDOT : CNT film supercapacitors which might growth of IrO2NT on MWCNTs is shown in Fig. 15. Incorpo-
be due to pseudocapacitance behavior exhibited by the In2O3 ration of IrO2NT resulted in an increase in SC of the MWCNTs.
nanowire.113,114 The specific energy density and power density The capacitance values of IrO2NT/MWCNT on stainless steel
values were 1.29 Wh kg1 and 7.48 kW kg1, respectively. Vari- substrate were estimated as 74, 70, 66, and 66 F g1 at the
ation in SC as a function of cycle number was exhibited to respective scan rates of 10, 30, 50, and 100 mV s1, which were
determine the stability of the material. After the first 100 cycles, significantly higher than those of 23, 17, 15, and 13 F g1 for
the SC decreased from 64 to 53 F g1 and after 500 cycles, a slight MWCNT on stainless steel substrate at the corresponding sweep
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Fig. 12 (a) Cyclic voltammograms of a CNT film supercapacitor, a PEDOT : CNT film supercapacitor, and In2O3 nanowires/CNT film super-
capacitors. (b) Charge–discharge behavior of In2O3 nanowires/CNT film supercapacitors. (c) Cyclic stability of In2O3 nanowires/CNT film capacitor
(adapted from ref. 112).
rates. The contact resistance reduced from 90 to 60 U for Ru oxide/a-MWCNT composites were 213 16 F g1 and 184
IrO2NT/MWCNT on stainless steel substrate. The unique 11 F g1, respectively. The capacitance value after the
structure provided high surface area for electrical charge storage 20 000thcycle was higher than that observed during the first 300
which in turn helped to improve the electrochemical performance cycles, demonstrating excellent long-term stability of the device.
of the nanocomposite. Liu et al. carried out the spontaneous Capacitive properties of V2O5 on the CNTs were also investi-
reduction of Ru(VI) and Ru(VII) for the deposition of Ru-oxide gated.124 Bare V2O5 showed a very low value of SC due to the
on MWCNT.123 Both unmodified and acid modified MWCNTs poor conductivity of V2O5, and its dense two-dimensional
were employed to fabricate Ru-oxide/MWCNT composite as structure. The low capacitance value for pristine CNTs was due
supercapacitor electrodes. SCs of the Ru-oxide/p-MWCNT and to the presence of micropores on the CNTs. However, the
Fig. 13 Schematic diagram showing the fabrication of Au–MnO2/CNT hybrid coaxial nanotube arrays using a combination of electrodeposition,
vacuum infiltration, 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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Fig. 14 (a) Cyclic voltammograms of a supercapacitor cell having MnO2/CNT and Au–MnO2/CNT hybrid coaxial nanotube electrodes, at a scan rate
of 10 mV s1. (b) Galvanostatic charge–discharge 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).
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reviewed in this article. The carbon based materials and their PVA Polyvinyl alcohol
composites demonstrate impressive energy density values and RGO Reduced graphite oxide
maintain long term stability. RuO2 Ruthenium oxide
One of the lacunas in developing supercapacitor devices is the SACNT Super aligned carbon nanotube
cost factor. Hence future research should be concentrated in the SC Specific capacitance
direction of fabricating carbon based supercapacitor devices with SDBS Sodium dodecyl benzene sulfonate
long term stability and high capacity in a cost effective way. A SnO2 Tin oxide
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one-step synthesis process for high density carbon-based mate- SWCNT Single-walled carbon nanotube
rials will be beneficial to design high power energy sources. TEA–BF4 Tetraethylammonium tetrafluoroborate
Adequate attention is required for the selection of electrolyte USP Ultrasonic spray pyrolysis
solution which is another imperative factor in deciding the V2O5 Vanadium pentoxide
performance of the supercapacitor. A new generation of super- ZnO Zinc oxide
capacitors is expected to replace batteries in certain applications
where high efficiency, high power, and a high level of reliability is
required. High performance supercapacitors are promising
candidates for future energy and power storage devices.
Acknowledgements
Acronyms This study was supported by the Human Resource Training
Project for Regional Innovation, the Converging Research
Center Program (2011K000776), and the World Class University
AN Acrylo nitrile (WCU) program (R31-20029) through the National Research
ASC Flexible asymmetric supercapacitor Foundation (NRF) funded by the Ministry of Education,
Bi2O3 Bismuth trioxide Science, and Technology (MEST) of Korea.
BMIPF6 1-Butyl-3-methylimidazolium
hexafluorophosphate
Notes and references
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