Journal of the Korean Physical Society, Vol. 59, No. 1, July 2011, pp.

145149

Supercapacitive Characteristics of Electrodeposited Polyaniline Thin Films

Grown on Indium-doped Tin-oxide Substrates

A. I. Inamdar, Young Sam Kim, Jae Sang Sohn and Hyunsik Im

Department of Semiconductor Science, Dongguk University, Seoul 100-715, Korea

Hyungsang Kim
Department of Physics, Dongguk University, Seoul 100-715, Korea

Dae-Young Kim
Department of Biological & Environmental Science, Dongguk University, Seoul 100-715, Korea

R. S. Kalubarme and ChanJin Park

Department of Materials Science and Engineering,
Chonnam National University, Gwangju 500-757, Korea

(Received 25 April 2011, in final form 20 May 2011)

Polyaniline (PANI) thin films were successfully synthesized using the electrodeposition (ED) tech-
nique from a mixed solution of 0.2M aniline and 0.2M H2 SO4 . PANI films with thicknesses of 220
and 250 nm were synthesized. The formation of compact and amorphous PANI films was confirmed
with scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements. The electro-
chemical supercapacitor properties of the PANI films were examined using cyclic voltammetry and
galvanostatic charge-discharge measurements. A specific capacitance of 473 Fg1 at 1 mAcm2
in a 0.5 M H2 SO4 electrolyte was obtained for the PANI electrodes. The electrochemical stability of
the PANI electrodes was investigated using cyclic voltammetry and charge-discharge measurements.
Both the films were quite stable with 16% capacitance loss after a few initial charge-discharge cycles.

PACS numbers: 84.32.Tt, 72.80.Le, 73.61.Ph

Keywords: Supercapacitor, Electrodeposition, Cyclic voltametry, Charge-discharge measurements, Polyani-
line
DOI: 10.3938/jkps.59.145

I. INTRODUCTION of metal oxides is limited due to the high cost of the

Electrochemical supercapacitors play an important
role in power source applications such as hybrid elec-
tric vehicles, computers, and short-term power sources
for mobile electronic devices [13]. They can be classified
into two types based on their charge storage mechanisms:
(i) electrical double-layer capacitors (EDLCs) and (ii) re-
dox supercapacitors [4]. Compared to the EDLC-based
capacitors, redox capacitors based on transition-metal
oxides or conducting polymers such as RuO2 [5], MnO2
[6], NiO [7], Co3 O4 [8], V2 O5 [9], and polyaniline [10,
11] may provide much higher specific capacitances up
to 1000 Fg1 of the active material. Metal oxides and
electrochemical conducting polymers are widely studied
materials and are used as pseudocapacitive electrode ma-
terials with remarkable performance. However, the use
E-mail: hyunsik7@dongguk.edu
-145-
materials. Thus, a key issue is to develop cost-effective
polymers for use in the fabrication of electrochemical su-
percapacitors.
Among the wide variety of conducting polymers,
polyaniline (PANI) has received considerable attention
due to its good redox reversibility and chemical sta-
bility [1217]. Various methods can be used to grow
PANI films, and PANI films prepared by different meth-
ods show dissimilar supercapacitive properties with re-
spective advantages and disadvantages. Polyaniline
nanofibers were synthesized by using interfacial polymer-
ization, and an electrochemical capacitance of 554 Fg1
was reported. However, in this case, the capacitance val-
ues decreased rapidly during electrochemical cycling. In
addition, efforts have been made to improve the stability
of PANI films by preparing composite PANI/CNT films
[18]. Girija and Sangaranarayanan studied the electro-
chemical polymerization of PANI by means of potential
-146-
Fig. 1. (Color online) Structural and morphological char-
acteristics of PANI films: (a) Chronoamperometric (CA)
curves for PANI film deposition for two time periods. The in-
sets show a photograph of the uniform PANI film and its scan-
ning electron micrograph (SEM) image. (b) X-ray diffraction
pattern of the amorphous PANI films.
cycling between -0.2 and 1.2 V at a scan rate of 300
mVs1 for 50 cycles and reported capacitance values in
the range of 346 to 404 Fg1 at different current densi-
ties [19]. In addition, PANI films coated and uncoated
with Naflon were studied, and their enhanced cycle life
was reported; however, the presented capacitance values
were too low [20].
In this study, electrodeposition (ED) is of particular
interest due to its low cost, environmental friendliness,
and the feasibility of low temperature growth. As an up-
date to previously studied PANI films, the goal of this
study was to test the applicability of the ED technique
for supercapacitor applications. We propose the synthe-
sis of PANI films using the ED technique, and we exam-
ined the supercapacitive properties of the films by using
cyclic voltametry and charge-discharge measurements.
II. EXPERIMENTS
PANI thin films were synthesized using the ED tech-
nique. The films were deposited on indium-doped tin-
oxide (ITO, 25 - 27 cm2 )-coated conducting glass
Journal of the Korean Physical Society, Vol. 59, No. 1, July 2011
substrates. Prior to the deposition, the ITO substrates
were ultrasonically cleaned consecutively in acetone,
methanol, and deionized water. The chemicals for the
synthesis of the PANI films were used as-received, with-
out further purification. The reaction bath for the PANI
film deposition contained 2M aniline and a 2M H2 SO4
(37%) solution. PANI films were electrodeposited using a
three-electrode electrochemical system in which the elec-
trodes were the ITO glass substrate as the working elec-
trode, graphite as the counter electrode, and a saturated
calomel electrode (SCE) as the reference electrode. ED
was carried out at 0.75 V (versus SCE) for 15 and 20 min
by using a chronoamperometry (CA) technique at room
temperature. Figure 1(a) shows the measured CA curves
for the PANI films. During the deposition, when the elec-
trode was polarized, the current decayed abruptly after
the initial surge due to the reduction of cations near the
electrodes. This led to the birth of nucleation centers
on the electrodes surface. As fresh cations diffused, the
current began to increase. In the CA curves, the cur-
rent started to increase steadily with time, suggesting
progressive nucleation and growth of the PANI film [21].
After the deposition, the films were immersed in deion-
ized water and dried in natural air. The films deposited
for 15 and 20 min were denoted PANI-1 and PANI-2,
respectively. The thicknesses of the PANI films were
measured using an alpha-step profiler and were found
to be 220 and 250 nm for PANI-1 and PANI-2, respec-
tively. The left inset of Fig. 1(a) shows a photograph
of the PANI-2 film with uniform coverage on the ITO
substrate.
The structural properties of the PANI films were
studied using high-resolution X-ray diffraction (XRD)
with Ni-filtered Cu K radiation (K = 1.54056 A)
(X pert PRO, Philips, Eindhoven, Netherlands). The
surface morphology was observed using field-emission
scanning electron microscopy (FE-SEM, Model: JSM-
6701F, JEOL, Japan). The supercapacitive properties of
the film were determined using cyclic voltammetry and
galvanostatic charge-discharge measurements. Cyclic
voltametry and chronoamperometry are used most of-
ten as diagnostic tools for elucidating electrode mech-
anisms. The supercapacitive properties of the mate-
rials are mainly based on the redox reactions at the
electrode-electrolyte interfaces. CV is an important tool
to measure the redox reaction in terms of the current
and the voltage by using computer controlled programs
that provide information on the supercapacitive behav-
ior of the electrode. The electrochemical measurements
(supercapacitive characteristics) of the PANI films were
performed on an electrochemical workstation by using
a three-electrode electrochemical cell containing 0.5M
H2 SO4 as the electrolyte, an SCE as the reference elec-
trode, and graphite as the counterelectrode. A multi-
channel potentiostat/glavanostat (model WMPG 1000)
interfaced with a computer was used in the galvanostatic
mode to record the charging and the discharging of the
supercapacitor thin films.
Supercapacitive Characteristics of Electrodeposited Polyaniline Thin Films
Fig. 2. (Color online) Electrochemical supercapacitive characteristics of PANI films. (a) CV curves of the PANI-1 film at
different scan rates. (b) CV curves of the PANI-2 film at different scan rates. (c) Specific capacitance versus scan rate for the
PANI-1 and the PANI-2 electrodes (calculated from the CV measurements).
III. RESULTS AND DISCUSSION
The compact nature of the PANI films was observed
using scanning electron microscopic (SEM) measure-
ments. The right inset of Fig. 1(a) shows an SEM im-
age of the PANI-2 film. The structural properties of
the PANI films were studied using XRD measurements.
Figure 1(b) shows the measured X-ray diffraction spec-
trum of a PANI film grown on an ITO substrate. The
peaks marked with exactly match the XRD peaks of
the ITO substrate. This indicates that the PANI film is
amorphous.
The electrochemical properties and supercapacitor
properties of the PANI electrodes were determined using
cyclic voltametry. The electrochemical measurements,
like cyclic voltammetry, were performed at room temper-
ature. Figure 2 shows measured cyclic voltammograms
(CVs) recorded in the H2 SO4 electrolyte for the PANI-
1 and PANI-2 films at four different scan rates (20, 50,
80, and 100 mVs1 ). The CVs were cycled between 1 V
(versus SCE) to -0.4 V (versus SCE). The CVs started
at 1 V, reversed at -0.4 V, and terminated at 1 V (versus
SCE). CVs provide valuable information on reduction-
oxidation (charge-discharge) behavior. Here, the capaci-
tance was mainly based on the redox reaction because the
shape of the CVs is distinguished from the shape of elec-
tric double-layer capacitance, which is normally close to
an ideal rectangle [4]. During the CV scans, two reduc-
tion and two oxidation peaks (marked with up and down
arrows, respectively) were observed, thus presenting an
exchange between the leucoemeraldine/emeraldine and
emeraldine/pernigraniline states of the PANI film [1].
As the scan rate was increased, the current response,
which is a measure of the capacitance, increased. The
relatively higher current density for the PANI-2 film in-
dicates good rate capability for supercapacitor applica-
tions. The similar shape of the CVs recorded at different
scan rates indicates excellent electrochemical reversibil-
ity of the PANI films. The specific capacitance of the
PANI electrode can be calculated from the CV curves
A. I. Inamdar et al. -147-
according to the following equation [4]:
i
Csp = , (1)
rm
where i is the average cathodic current, r is the scan rate,
and m is the mass of the active electrode. The specific
capacitance values were found to be 435 Fg1 and 460
Fg1 for the PANI-1 and the PANI-2 films, respectively,
at a scan rate of 20 mVs1 . The specific capacitance val-
ues at a scan rate of 100 mVs1 decreased to 320 Fg1
and 239 Fg1 for the PANI-1 and the PANI-2 films, re-
spectively because the utilization of active material de-
creased, leading to a decrease in capacitance [22].
Figure 2(c) shows the specific capacitance values cal-
culated from the CV measurements as a function of scan
rate. The decrease in the capacitance values is described
according by the Randle-Sevcik relationship, in which
the current (which is a measure of the supercapacitive
properties) of the electrochemical redox reaction is lin-
early proportional to the concentration of the electroac-
tive species and the square root of the scan rate.
Ip = Kn3/2 AD1/2 Hf 1/2 , (2)
where the constant K = 2.72 105 , n is the number
of moles of electrons transferred per mole of electroac-
tive species, A is the area of the electrode in cm2 , D
is the diffusion coefficient in cm2 /s, H is the solution
concentration in mole/L, and f is the scan rate of the
potential in volt/s. Here, the concentration of the elec-
troactive species is the same at different scan rates. If the
peak current increases linearly with the scan rate, then
it is reasonable to say that it is a diffusion-controlled (re-
versible) reaction. According to the inset of Fig. 2(c), the
reaction is an irreversible redox reaction at the electrode-
electrolyte interface. This irreversible nature of the elec-
trode reduces the charge-transfer processes at the inter-
face. We believe that this is a possible reason for the
decrease in the supercapacitive properties with the scan
rate.
Figure 3 shows charging-discharging curves recorded
in the voltage range from -0.6 V to 0.1 V (versus
-148-
Fig. 3. (Color online) Electrochemical supercapacitive characteristics of the PANI films. (a), (b) Charge-discharge curves
for the PANI-1 film and the PANI-2 film, respectively, at a constant current of 1 mAcm2 in a 0.5M H2 SO4 electrolyte within
the potential window of -0.6 V to 0.1 V versus the SCE. (c) Specific capacitance versus number of cycles for the PANI-1 and
the PANI-2 electrodes (calculated from the charge-discharge measurements). The inset shows the charge-discharge curve of the
PANI-2 film for 100 cycles.
Fig. 4. (Color online) Electrochemical cycling stability
measurement. (a), (b) CV curves of the PANI-1 and the
PANI-2 films, respectively, after 100 cycles in a 0.5M H2 SO4
electrolyte at a scan rate of 100 mVs1 .
SCE) at an applied current density of 1 mAcm2 . The
charge/discharge curves exhibit reversible characteristics
without apparent deviation in each cycle. This sug-
gests good electrochemical stability for the PANI elec-
trodes. The specific capacitances were calculated from
the charge-discharge curves by using the following equa-
tion [1]:
Journal of the Korean Physical Society, Vol. 59, No. 1, July 2011
it
Csp = , (3)
V m
where i is the charge-discharge current, t is the dis-
charge time, V is the electrochemical potential window
and m is the mass of the active material. The specific ca-
pacitance values were found to be 446 Fg1 and 473 Fg1
for the PANI-1 and the PANI-2 films, respectively. The
specific capacitance values of the cells determined us-
ing this galvanostatic charge-discharge method followed
the trend determined by the CV measurements. These
specific capacitance values are in agreement with those
reported in the literature for pure PANI films [1820,23].
The specific capacitance of PANI-based electrochemi-
cal capacitors depends on many factors, such as the mass
of the active electrode, the conductivity of the active
electrode, the concentration of the electrolyte, and the
morphology of the electrode. Electrochemical stability
is one of the important indicators of device quality. To
test the stability of the devices, the films were charged-
discharged repeatedly for 100 cycles in a 5M H2 SO4 elec-
trolyte at a constant current density of 1 mAcm2 . Fig-
ure 3(c) shows the measured specific capacitances of the
PANI-1 and the PANI-2 films for 100 cycles. The capac-
itance values were initially found to decrease after tens
of cycles and to subsequently become stable. A 16% ca-
pacitance loss occurred during the initial cycles. Even
after 100 cycles, the charge-discharge curve appears sim-
ilar, with only a negligible change in capacitance values.
These results suggest that PANI films synthesized using
the ED technique are suitable for supercapacitor appli-
cations. The inset shows the measured charge-discharge
curve of the PANI-2 film.
The fast charge-discharge and electrochemical stabil-
ity of the PANI electrodes was also examined using a
CV test. Figures 4(a) and (b) show CVs of PANI-1 and
PANI-2 electrodes after 100 reduction-oxidation cycles
in 0.5M H2 SO4 electrolyte, respectively. As the number
Supercapacitive Characteristics of Electrodeposited Polyaniline Thin Films
of cycles increased, the capacitance current decreased
for both the PANI-1 and the PANI-2 films. This de-
crease is attributed to the degradation of polyaniline due
to mechanical doping/dedoping by the acid [20]. The
shape of the CV is one of the important factors used to
judge the electrochemical stability of the electrode dur-
ing charge-discharge cycling. The shape of the measured
CVs for the PANI-2 film remained relatively unchanged
compared to that of the PANI-1 film. This indicates
that the PANI-2 film is electrochemically more stable.
The noticeable change in the CV shape of the PANI-1
film is presumably due to a degradation of the electrodes
surface during the doping/de-doping process.
IV. CONCLUSION
PANI thin films with different thicknesses were suc-
cessfully synthesized onto ITO substrates by using an
electrodeposition technique for electrochemical super-
capacitor applications. SEM and XRD measurements
showed that the PANI films were compact and amor-
phous. The electrochemical supercapacitor measure-
ments were performed in a 0.5M H2 SO4 electrolyte by
using cyclic voltametry and charge-discharge techniques
in the galvanostatic mode. The highest supercapacitance
values were found to be 473 Fg1 for 250nm thick PANI
film (PANI-1) and 446 Fg1 for 220nm-thick PANI film
(PANI-2). The capacitance values were almost the same
as those calculated from CV measurements. According
to electrochemical stability measurements, the thicker
PANI film (PANI-2) was electrochemically more stable
than the thinner film (PANI-1).
ACKNOWLEDGMENTS
This project was supported by the National Research
Foundation (NRF) of Korea (Grant Nos. K20901000002-
09E0100-00210 and 2009-0076332).
REFERENCES
[1] J. Liu, M. Zhou, L. Z. Fan, P. Li and X. Qu, Electrochim.
Acta 55, 5819 (2010).
A. I. Inamdar et al. -149-
[2] Y. G. Wang, Z. D. Wang and Y. Y. Xia, Electrochim.
Acta 50, 5641 (2005).
[3] B. Z. Chen, Y. Qin, D. Weng, Q. Xiao, Y. Peng, X.
Wang, H. Li, F. Wei and Y. Lu, Adv. Funct. Mater. 19,
3420 (2009).
[4] A. I. Inamdar, Y. S. Kim, S. M. Pawar, J. H. Kim, H.
Im and H. Kim, J. Power Sources 196, 2393 (2011).
[5] C. C. Wang and C. C. Hu, Electrochim. Acta 50, 2573
(2005).
[6] M. Nakayama, T. Kanaya and R. Inoue, Electrochem.
Commun. 9, 1154 (2007).
[7] J. W. Lang, L. B. Kong, W. J. Wu, Y. C. Luo and L.
Kang, Chem. Commun. 35, 4213 (2008).
[8] C. Lin, J. A. Ritter and B. N. Popov, J. Electrochem.
Soc. 145, 4097 (1998).
[9] R. N. Reddy and R. G. Reddy, J. Power Sources 156,
700 (2006).
[10] Y. G. Wang, H. Q. Li and Y. Y. Xia, Adv. Mater. 18,
2619 (2006).
[11] S. R. Silvakumar, W. J. Kim, J. A. Choi, D. R. Mac-
Farlance, M. Forsyth and D. W. Kim, J. Power Sources
171, 1062 (2007).
[12] P. Sivaraman, R. K. Kushwaha, K. Shashidhara, V. R.
Hande, A. P. Thakur, A. B. Samui and M. M. Khand-
pekar, Electrochim. Acta 55, 2451 (2010).
[13] S. R. Sivakkumar and R. Saraswathi, J. Power Sources
137, 322 (2004).
[14] K. S. Ryu, K. M. Kim, N. G. Park, Y. J. Park and S. H.
Chang, J. Power Sources 103, 305 (2002).
[15] P. J. Kulesza, M. Skunik, B. Baranowska, K.
Miecznikowski, M. Chojak, K. Karnicka, E. Frackowiak,
F. Beguin, A. Kuhn, M. H. Delville, B. Starobrzynska
and A. Ernst, Electrochim. Acta 51, 2373 (2006).
[16] A. M. P. Hussain, A. Kumar, F. Singh and D. K. Avasthi,
J. Phys. D: Appl. Phys. 39, 750 (2006).
[17] A. M. P. Hussain and A. Kumar, Eur. Phys. J. Appl.
Phys. 36, 105 (2006).
[18] S. R. Sivakkumar, W. J. Kim, J. A. Choi, D. R. Mac-
Farlane, M. Forsyth and D. W. Kim, J. Power Sources
171, 1062 (2007).
[19] T. C. Girija and M. V. Sangaranarayanan, J. Power
Sources 156, 705 (2006).
[20] B. C. Kim, J. S. Kwon, J. M. Ko, J. H. Park, C. O. Too
and G. G. Wallace, Synth. Met. 160, 94 (2010).
[21] A. I. Inamdar, S. H. Mujawar, S. B. Sadale, A. C. Son-
avane, M. B. Shelar, P. S. Shinde and P. S. Patil, Sol.
Energy Mater. Sol. Cells 91, 864 (2007).
[22] C. H. Liang and C. S. Hwang, J. Alloys Compd. 500,
102 (2010).
[23] G. A. Snook, P. Kao and A. S. Best, J. Power Sources
196, 1 (2011).