Energy 78 (2014) 298e303

Contents lists available at ScienceDirect

Energy
journal homepage: www.elsevier.com/locate/energy

Activated carbon nanotubes/polyaniline composites as supercapacitor

electrodes
Seul-Yi Lee, Ji-Il Kim, Soo-Jin Park*
Department of Chemistry, Inha University, 100 Inharo, Incheon 402-751, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Chemically A-MWCNT (activated multiwalled carbon nanotube)/PANI (polyaniline) composites produced
Received 28 March 2014 via ultrasonic polymerization of an aniline monomer in the presence of A-MWCNTs were investigated as
Received in revised form potential electrode materials for supercapacitors. These composites were compared to pristine MWCNTs
15 September 2014
and MWCNT/PANI composites. The influence of the pore structure, which developed because of the
Accepted 4 October 2014
polymerization process, was investigated by measuring N2 adsorption/desorption isotherms at 77 K. The
Available online 11 November 2014
electrochemical properties of the materials were determined by cyclic voltammetry and galvanostatic
chargeedischarge cycling measurements in 1 M NaNO3 electrolyte solution, using a three-electrode
Keywords:
Activated multi-walled carbon nanotubes
system at room temperature. The results suggested that the pore structure of the A-MWCNTs could
Supercapacitors effectively promote the homogenous-dispersion of aniline and consequently result in excellent cycling
Polyaniline performance. Furthermore, interaction between the p-conjugated structure of carbon and the quinoid
Nanocomposites ring of the PANI matrix can lead to enhancement in the charge transfer process.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction attaining-increased capacitance [6,7]. Additionally, when transition

Supercapacitors are energy storage devices that possess high
power density and excellent cycling performance, and have
attracted considerable attention because of their potential appli-
cations in a wide range of technologies such as hybrid electric ve-
hicles, cellular phones, and portable devices [1,2]. Supercapacitors
can also be used in hybrid electric vehicles as an auxiliary power
source in combination with lithium ion secondary batteries. The
electrode materials for supercapacitors are generally highly
developed porous carbon materials such as activated carbons,
carbon nanofibers, and mesoporous carbons [3e5]. However,
supercapacitors with electrodes composed of carbon materials
cannot provide as much energy density as faradaic pseudo-
capacitors, which indeed is the principal obstacle to their wide-
spread application.
Recently, most of the research on supercapacitors has been
focused on a pseudo-capacitive behavior and higher power/energy
densities. Thus, incorporation of heteroatoms such as nitrogen and
oxygen onto the carbon surface enhances the performance of the
supercapacitor electrodes, suppresses destruction of the surface
structure, and has proved to be an effective approach toward
* Corresponding author. Tel.: þ82 32 876 7234; fax: þ82 32 867 5604.
E-mail address: sjpark@inha.ac.kr (S.-J. Park).
metal oxides such as RuO2 and MnO2 are incorporated in the
electrode materials, supercapacitors exhibit markedly increased
capacitance properties and show pseudo capacitive behavior
(<1300 F/g) [8,9]. Conducting polymers have various advantages,
namely high conductivity, high doping/undoping rate during
cycling processes, excellent energy storage performance through
their redox processes, and facile synthesis through chemical
methods [10e14].
Among the various conducting polymers, PANI (polyaniline) is
frequently used as an electrode material, not only because of its
excellent specific capacitance but also because of its many advan-
tages for practical applications, such as inexpensive preparation,
ease of polymerization in aqueous media, and high stability in air
[13,14]. However, the main drawback of using conducting polymers
as supercapacitor electrodes is their poor stability during cycling
owing to the huge volumetric change that occurs during the
doping/undoping process.
Thus, the suitability of materials with high stability, high
porosity parameters, and excellent capacitive behavior for use as
fillers has been studied in order to solve the problem of poor sta-
bility of conducting polymers. MWCNTs (Multiwalled carbon
nanotubes) have unique structural and electrochemical properties
and high stability, and therefore, they have tremendous potential
for application as filler materials for conducting polymer elec-
trodes. Introduction of MWCNTs into the PANI matrix improves the

http://dx.doi.org/10.1016/j.energy.2014.10.011
0360-5442/© 2014 Elsevier Ltd. All rights reserved.
 S.-Y. Lee et al. / Energy 78 (2014) 298e303
stability during cycling as well as the textural properties of the
pristine polymer [15e18]. Effective utilization of MWCNTs can be
achieved by their homogeneous dispersal within the matrix as well
as by the developed porous structure, which could be optimized by
the preparation of chemically activated MWCNTs (A-MWCNTs)
[19,20]. The strong chemical etching effect resulting from activation
using KOH significantly increases the specific surface area of the
MWCNTs and their specific capacitance. In order to further study
the effects of introducing MWCNTs into a PANI matrix, some
MWCNT-containing samples were additionally activated by KOH
before the preparation of PANI composites.
In this work, we focus on the competitive effects of the porous
structures and capacitive performance of A-MWCNTs used as the
filler materials of a conducting polymer matrix. The A-MWCNT/
PANI composites were fabricated by the polymerization of an ani-
line monomer in the presence of A-MWCNTs. Since the formation
of the pore structure and its influence on the electrochemical
performance of A-MWCNT/PANI composites are relevant to the
application of these composites in supercapacitors, these factors
are discussed in detail in comparison to the MWCNT/PANI case.
2. Experimental details
2.1. Materials and sample preparation
MWCNTs (purity: 90%), manufactured by CVD (chemical vapor
deposition), were purchased from Nano Solution Co. Ltd (Korea).
Prior to use, the pristine MWCNTs were purified by treatment with
5 M HNO3 for 5 h at room temperature. Subsequently, these were
washed with distilled water, and then dried in a vacuum oven for
24 h at 120  C. To develop the pore structure, A-MWCNTs were
prepared by heating a KOH/MWCNT [3:1 (w/w)] mixture at 5  C/
min rate to 900  C in a tubular furnace under N2 flow and then kept
at that temperature for 1 h. A-MWCNTs were then obtained after
washing with HCl and distilled water to remove the residual
organic species (Kþ ions).
The A-MWCNT/PANI composites were synthesized by an in situ
chemical polymerization method [18], whereby 3 mL of aniline as
the precursor of PANI and 2.5 g of APS (ammonium persulfate) as
the oxidizing agent for polymerization were dissolved in 30 mL of
1 M HCl. Then, 0.3 g of A-MWCNTs was added to the above solution;
the resulting mixture was sonicated for 24 h at room temperature.
The APS solution was slowly dripped into the A-MWCNT-contain-
ing aniline solution to initiate the polymerization reaction and then
placed in an ice bath (0e5  C) for 24 h. A dark-green suspension was
obtained by filtering and washing to remove the residues this
mixture with distilled water were in the form of A-MWCNT/PANI
composites. Finally, the composites were treated by stirring for 3 h
in a 2.0 M HCl solution, and then filtered and washed with distilled
water and methanol to remove the excess acid. For comparison,
pristine MWCNT/PANI composites were also polymerized under
the same conditions.
2.2. Characterization
SEM (Scanning electron microscopy; Hitachi Co., S-4200) was
used to observe the morphologies of the prepared samples. The
textural properties were recorded from nitrogen adsorption/
desorption isotherms at 77 K (BEL Co., BEL-SORP). The specific
surface area, mesopore volume, and micropore volume were
calculated using the BET equation, BJH method, and HeK method,
respectively. The total pore volumes were estimated to be the liquid
volume of N2 adsorbed at a relative pressure (P/P0) of 0.99. The
working electrodes for supercapacitors were prepared by first
mixing 90 wt% of active materials with 10 wt% of carbon black and
299
10 wt% of the binder PVDF (polyvinylidenefluoride). A small
amount of NMP (N-methylpyrrolidone) was then added to the
composites to make a homogeneous mixture. The mixture was
finally cast onto a 1 cm2 Ni-foam current collector in order to
produce a working electrode. Electrochemical measurements (HS
Technology Co., Iviumstat electrochemical analyzer) were per-
formed at 25  C with the conventional three-electrode system in
1.0 M NaNO3 electrolyte solution. A Pt wire and Ag/AgCl electrode
were used as the counter and reference electrodes, respectively. CV
(Cyclic voltammograms) were measured at scan rates of 2 and
10 mV/s from 0.2e0.8 V. Charge-discharge cycling performance
tests were performed at different current densities, with cutoff
potentials varying from 0.2e0.8 V.
3. Results and discussion
3.1. Morphologies
SEM images of the MWCNT, MWCNT/PANI, and A-MWCNT/PANI
composites are illustrated in Fig. 1. The MWCNTs [Fig. 1(a)] are
shown to be randomly oriented, and are present in a bundled form.
After introducing PANI into the MWCNTs, the MWNT/PANI com-
posites (Fig. 1b) assume thick bundled shapes, which is consistent
with an earlier study [21]. The A-MWCNT/PANI has a homogeneous
structure and resembles tree branches when compared with
MWCNT/PANI. Moreover, their homogenous morphology becomes
more complex on the introduction of PANI because of the well-
dispersed A-MWCNT.
3.2. Textural properties
Fig. 2 shows the N2 adsorption/desorption isotherms of all
samples at 77 K. The behavior of the isotherms for the materials
containing MWCNTs was between type II and type IV, indicating
the maintenance of mesoporous structures. However, the isotherm
of A-MWCNTs showed a significantly increased uptake at low
relative pressures (<0.1), indicating the development of micro-
pores. Before the activation process, the micropore structures of the
MWCNTs were not detected. It is suggested that the adsorbed pore
volumes of MWCNT/PANI are significantly decreased as compared
with that of A-MWCNT/PANI. The pore volumes of the MWCNTs
decreased upon the introduction of PANI, because the pore struc-
tures of the MWCNTs were blocked. The results suggest that the
porosity parameter of A-MWCNT/PANI has a lower value than that
of MWCNT/PANI, which may be attributed to the enhanced
adsorption volume caused by chemical activation.
The details of the structural parameters of the pores are sum-
marized in Table 1. The MWCNTs had a specific surface area of
211 m2/g and a total pore volume of 0.810 cm3/g; the corresponding
values for the A-MWCNTs were 581 m2/g and 1.571 cm3/g,
respectively. After the introduction of PANI into MWCNTs and A-
MWCNTs, the specific surface area and total pore volume decreased
because of the pore blocking effect. The specific surface area and
total pore volume of A-MWCNT/PANI were higher than that of
MWCNT/PANI, which could be attributed to the well-dispersed
MWCNT particles as fillers in PANI composites.
Fig. 3 shows the micropore size distribution of all samples
calculated by the HeK method. After producing A-MWCNTs by the
activation process, the pore volumes significantly increase due to
the increased micropore content; however, after introducing PANI,
both the pore volumes and pore diameters decrease significantly
because of the blocking of the MWCNT pore structure. The A-
MWCNT/PANI composites have larger pore volumes (0.7e1.2 nm)
than does MWCNT/PANI. The relationship between the capacitive
300 S.-Y. Lee et al. / Energy 78 (2014) 298e303

Fig. 1. SEM images of MWCNTs (a), MWCNT/PANI (b), and A-MWCNT/PANI (c) (scale bar: 100 nm).

performance and the pore sizes (~1 nm) of carbon material elec-
trodes can be verified by the following Equation (1) [22,23]:
εA
C¼
d symmetric in these cases, which suggests the high efficiency of the
where C is the capacitance, A is the electrode surface area accessible
to electrolyte ions, ε is the electrolyte dielectric constant, and d is
the separation between the carbon and electrolyte ions.
A sharp increase in the capacitance is observed as the pore size
decreases below 1 nm. A-MWCNT/PANI appears to have a larger
number of pores with volumes less than 1 nm; this might have a
beneficial effect on its capacitive performance.
3.3. Electrochemical properties
Fig. 4 shows the CV (cyclic voltammograms) of all sample
electrodes between 0.2 and 0.8 V, recorded at scan rates of 2 and
10 mV/s, using 1.0 M NaNO3 as an electrolyte. The distortion of the
current response at the switching potential caused by the electro-
lyte and electrode resistance is usually dependent on the scan rate
[24], as indeed is the case in this study. As shown in Fig. 4, the CV
curves are nearly rectangular particularly at low scan rates, and
(1)
capacitive performance or the electrode and electrolyte. However,
at higher scan rates, the CV curves deviate from the rectangular
shape, indicating that chargeedischarge reversibility occurs be-
tween the electrode and the electrolyte interface. No visible redox
peaks of A-MWCNT/PANI composite electrodes are observed in the
entire potential range, implying that the electrolyte is stable.
Moreover, as PANI is introduced, there is a remarkable increase in
the current density, and the CV shape changes. The change in the
shape of the CV curve is more marked for PANI, which is attributed
to limited ion diffusion-migration in the polymer bulk and to the
ohmic drop in the thick polymer layer [25]. The capacitive perfor-
mance of A-MWCNT/PANI composites shows almost rectangular
and symmetric I-E responses of the ideal capacitive behavior in
neutral electrolyte solutions. In addition, the output current density
of A-MWCNT/PANI is higher than that of MWCNT/PANI. These re-
sults could be owing to the improved porosity of A-MWCNTs as
compared to that of MWCNTs.
Fig. 5A and B shows the chargeedischarge curves of all elec-
trodes at a constant current density of 0.5 A/g and that of A-
MWCNT/PANI with current densities varying from 0.25 to 5 A/g,
respectively. The chargeedischarge profiles of MWCNT/PANI and A-
MWCNT/PANI are nearly triangular, demonstrating their excellent
capacitive performances due to the introduction of PANI [26].
Moreover, there is a sharper potential drop for A-MWCNT/PANI as
compared to that of MWCNT/PANI, indicating that the highly

Fig. 2. Nitrogen adsorption/desorption isotherms of all samples.

Table 1
Porosity parameters of all samples.

Specimens SBETa Vmicb Vmec Vtd

MWCNT 211 0.021 0.810 0.831

A-MWCNT 581 0.142 1.429 1.571
MWCNT/PANI 48 0.015 0.147 0.162
A-MWCNT/PANI 112 0.021 0.334 0.355
a
Specific surface area (m2/g).
b
Micropore volume (cm3/g).
c
Mesopore volume (cm3/g).
d
Total pore volume (cm3/g). Fig. 3. Micropore size distribution of all samples.
 S.-Y. Lee et al. / Energy 78 (2014) 298e303
Fig. 4. Cyclic voltammograms of MWCNTs (a), A-MWCNTs (b), MWCNT/PANI (c), and
A-MWCNT/PANI (d) at scan rates of 2 and 10 mV/s.
accessible surface area improved the pore structure, and that well-
dispersed polymerization in A-MWCNT/PANI could improve the ion
transfer behaviors and reduce the contact resistance of the elec-
trodes [27].
The galvanostatic chargeedischarge cycling performance of all
electrodes was measured from 0.2e0.8 V in 1.0 M NaNO3 at
different current densities. The average specific capacitance (C) of
these electrodes in the supercapacitors can be calculated from the
chargeedischarge profiles according to the following Equation (2):
I  Dt
C¼
DV  m
where C is the capacitance of the cell in F, I is the discharge current
in A, Dt is the time of discharge corresponding to the voltage dif-
ference (DV), and m is the mass of active materials on the
electrodes.
Based on Equation (2), the specific capacitance for MWCNT is
21 F/g at a current density of 0.5 A/g; for the A-MWCNT, it is 42 F/g;
and for the MWCNT/PANI composites, it is 176.5 F/g. It is observed
that the A-MWCNT/PANI composites have a higher specific capac-
itance (201 F/g) than the MWCNT/PANI composites. The three
dimensional network structure of an MWCNT enables a greater
degree of contact between the PANI and the electrolyte, which can
result in more active sites in the composites [21]. Moreover, the
more porous structure of A-MWCNTs when used as the filler into
301
Fig. 5. Charge-discharge curves of all electrodes at the current density of 0.5 A/g (A)
and chargeedischarge curves of A-MWCNT/PANI with various current densities (B) in
1.0 M NaNO3 as an electrolyte solution.
PANI can provide a complementary effect to further improve the
capacitive performance [28].
Some researchers have investigated the modification of
MWCNT/PANI composites as electrode materials for super-
capacitors. Frackowiak et al. reported a specific capacitance of
250 F/g or even lower (at 0.3 A/g) for MWCNT/PANI composites
with different operating voltages from 0.4 to 0.8 V [15]. Das et al.
prepared ternary composites of Cu-bridged MWCNT and PANI,
which showed a higher specific capacitance of 264 F/g (at 1.5 A/g)
(2) than that of the binary composites (Cu-bridged MWCNT; 125 F/g)
[29]. Kim et al. synthesized the leucoemeraldine, emeraldine, and
pernigraniline forms of PANI/MWCNT composites. They have
investigated the different pseudocapacitive properties depending
on the oxidation state of PANI in the MWCNT composites. It was
observed that the PANI/MWCNT nanocomposites showed specific
capacitance values of 217 F/g, 328 F/g, and 139 F/g for leucoemer-
aldine base, emeraldine salt, and pernigraniline base, respectively
[30]. Wu et al. synthesized SA (sodium alginate)-modified MWCNT/
PANI composites with coaxial tubular morphology. The introduc-
tion of SA resulted in a higher specific capacitance of 442 F/g (at 0.5
A/g) for the SA-MWCNT/PANI composites as compared to that for
the MWCNT/PANI composites (334 F/g) [31].
In addition, the chargeedischarge curves of A-MWCNT/PANI
composites with various current densities in their optimal potential
302
range were measured (Fig. 5B). The A-MWCNT/PANI composites
showed almost triangular curves with a small discharge decrease
caused by the internal resistance, throughout the current density
range of 0.25e5 A/g. When the applied current density was
increased from 0.25 to 5 A/g, the specific capacitances of A-
MWCNT/PANI composites remain at about 40%.
Variation of the specific capacitance with the current density is
shown in Fig. 6 for all samples. A-MWCNT/PANI and MWCNT/PANI
have considerably higher specific capacitances than those of
pristine MWCNTs and A-MWCNT. PANI shows remarkable
enhancement in the capacitance of the MWCNTs, which originates
from its multiple reduction and oxidation states, resulting in
improved pseudo capacitive behavior of the electrode materials
[32]. It is well known that MWCNTs comprise sp2 hybridized
carbon atoms surrounded by a p electron cloud. These p electrons
undergo p- p stacking interactions with the quinoid ring of the
PANI matrix without disturbing the graphitized plane of the
MWCNTs [29].
Although the rate of capacitance decreases with the increasing
current density of the A-MWCNT/PANI composites, it is still
higher than that of the other fillers. The specific capacitance in-
creases by about 20% and 84% for these composites as compared
to the values for MWCNT/PANI and A-MWCNTs, respectively. The
high specific capacitance of the A-MWCNT/PANI composites can
be attributed to the porous structures of the A-MWCNTs after
chemical activation, which results in greater interpenetration of
the PANI network onto the A-MWCNT surfaces. The charge
accumulation and faradaic oxidationereduction properties are
also enhanced because of the developed pore structure and
specific surface area, resulting in improved capacitance of the
electrode materials.
4. Conclusions
A-MWCNT/PANI composites were fabricated by the in situ
polymerization of an aniline monomer containing A-MWCNTs for
application as electrode materials in supercapacitors. The A-
MWCNT/PANI electrodes exhibited better specific capacitance,
porous parameter, and cycling performance than did the MWCNT/
PANI electrodes. The obtained results could be employed to obtain
the desired specific capacitance by controlling the pore structure of
the MWCNT/PANI composites. This study has shown that the
MWCNT/PANI composites are more effective as capacitors if PANI is
Fig. 6. Specific capacitances of all electrodes as a function of current density.
S.-Y. Lee et al. / Energy 78 (2014) 298e303
polymerized over A-MWCNTs. Remarkably, A-MWCNTs can lead to
a 20% increase (from 200 to 248 F/g) in the capacitance over that of
pristine MWCNTs.
Acknowledgments
This work was supported by the Carbon Valley Project by
Ministry of Trade, Industry and Energy, Korea.
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