Electrochimica Acta 147 (2014) 545556

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Galvanostatic deposition of polypyrrole in the presence of tartaric acid

for electrochemical supercapacitor
Erhan Karaca, Nuran ziek Pekmez *, Kadir Pekmez
Hacettepe University, Department of Chemistry, 06800 Ankara, Turkey

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 14 June 2014
Received in revised form 20 August 2014
Accepted 27 September 2014
Available online 2 October 2014

Galvanostatic deposition of tartratedoped polypyrrole (PPy) is carried out on platinum foil in

acetonitrile solution with tartaric acid, tetrabutylammonium tetrauoroborate and Triton-X 100 for
supercapacitor studies. The effect of substrate is studied by comparing the results obtained by using
platinum, stainless steel and pencil graphite electrodes. The capacitive performance of the coatings are
evaluated in an H2SO4/water medium by cyclic voltammetry, electrochemical impedance spectroscopy
and galvanostatic chargedischarge methods. Based on the chargedischarge results obtained, the
tartratedoped PPy coatings represent a high specic capacitance of 794 F g
1 (areal capacitance of
238 mF cm-2) and a high energy density of 105 Wh kg-1 on pencil graphite electrode, and a high power
density of 36.3 kW kg-1 on 316Ti stainless steel electrode. High values may be attributed to the
incorporation of tartaric acid via hydrogen bonding, and/or tartrate anion as dopant together with the
tetrauoroborate anion. Besides, Triton X100 provides high porosity and therefore high surface area.
2014 Elsevier Ltd. All rights reserved.

Keywords:
Supercapacitor
Electrodeposition
Polypyrrole
Tartaric acid
Pencil graphite

1. Introduction
Supercapacitors are being developed as an alternative to
batteries and capacitors. They have much higher power density,
lower energy density and longer cycle life than batteries [1].
Generally, supercapacitors can operate over a wide range of
temperatures and their coulombic efciencies are as high as 99%.
The equivalent series resistance in supercapacitors is extremely
low, so they can be charged with a very high current, which is not
possible in energy storage devices like batteries.
Due to the pseudocapacitive properties of polyaniline, polypyrrole, polythiophene and their derivatives, they are studied as
electrode materials for redox capacitors. Polypyrrole (PPy) offers a
higher specic capacitance and a greater degree of exibility in
electrochemical processing than most conducting polymers, and
consequently the material has been the subject of much research
as a supercapacitor or battery electrode. The specic capacitance of
PPy coated electrodes has been reported over a range of 179 F/g to
506 F/g at a scan rate of 10.0 mV s-1 [24]. These capacitances are
much higher than those of the electrodes based on commercial
activated carbons (<200 F/g at 1 mV s-1) [5], but lower than those
fabricated with expensive, rare metals, such as ruthenium oxide
(1170 F/g at 10.0 mV s-1) [6]. However, PPy could have as high

* Corresponding author. Fax: +90 312 299 2163.

E-mail address: npekmez@hacettepe.edu.tr (N.. Pekmez).
http://dx.doi.org/10.1016/j.electacta.2014.09.136
0013-4686/ 2014 Elsevier Ltd. All rights reserved.

specic capacitances as metal oxides when electrosynthesized in

the presence of various dopants based on organic acid such as
oxalic acid (480 F g
1 at 10 mV s-1 on Ti foil) [2], ptoluene
sulphonic acid (200 F g
1 at 0.8 mA cm-2 on stainless steel) [7],
2,7Bis(2sulfophenylazo) chromotropic acid (about 200 F g
1 at
20 mV s
1 on Ni foam) [8], chromotropic acid (343 F g
1 at 2 mV s
1
on stainless steel) [9], 5sulfosalicylic acid (545 F g
1 at 2 mV s
1
on stainless steel) [10], sulfanilic acid (5.43 F cm
2 at 2 mV s
1 on
Ni foam) [11] and in the presence of various surfactants such as
sodium dodecyl benzene sulfonate (95 mF cm-2 at 50 mV s
1 on Pt
electrode) [12]. PPy lmcoated stainless steel electrode, studied
by Zhang et. al., was prepared by pulse galvanostatic method in
aqueous solution containing ptoluene sulphonic acid and
determined as 403 F g-1 at 0.5 mA cm-2 of the specic capacitance
[13]. Generally, organic acids improve the properties of conducting
polymers as not only capacitance but also stability [14]. Also,
surfactants provide enhancement in the specic area of coating.
Polythiophene and polyaniline were also prepared for supercapacitor studies in the presence of various organic acids [14,15] as
well as cationic, anionic, nonionic surfactants [16,17]. Gnanakan
et al. investigated that polythiophene prepared with tartaric acid
exhibited higher specic capacitance of 156 F g-1 at 5.00 mVs
1 on
stainless steel [14]. Senthilkumar et al. studied the chemical
oxidative polymerization of polythiophene in aqueous medium
using such surfactants as Cetyl trimethylammonium bromide,
Sodium dodecyl sulfate and Triton X100 (TX100) [16]. The
polythiophene prepared with TX100 exhibited higher specic

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E. Karaca et al. / Electrochimica Acta 147 (2014) 545556

Fig. 1. Cyclic voltammograms recorded in 0.100 M H2SO4 solution for 0.3 mg cm
2 of PPy prepared on Pt electrode in an acetonitrile solution containing (a) pyrrole and TBABF4
(b) pyrrole, TBABF4 and TA/T
(c) pyrrole, TBABF4, TA/T
and TX100, and (Pt) for bare Pt electrode. .Cpyrrole: 50.0 mM, CTBABF4: 25.0 mM, CTA: 25.0 mM, CTBAT: 25.0 mM, CTX100:
25.0 mM, v = 100 mV s-1.

capacitance of 117 F g-1 compared with that of surfactant free

polythiophene (78.0 F g
1 at 5.00 mVs
1) on graphite. A similar
type of enhanced specic capacitance was reported by Girija et al.
[15] for the case of polyaniline when TX100 was used as the
surfactant (805 F g
1 at 3 mA cm
2 on stainless steel).
Martins et al. studied the electrochemical polymerization of
PPy with tartaric acid on aluminum for corrosion studies [18]. This
bilayer Al2O3/PPy showed high corrosion resistance of 38 k V in 3%
NaCl medium, and also high specic capacitance of 1.62 mF cm
2
according to synthesis conditions. There has been no report on the
synthesis of PPy on platinum foil (Pt), 316Ti stainless steel (316Ti
SS) and disposable pencil graphite (PG) electrodes in the presence
of both tartaric acid (TA) and TX100 for supercapacitor studies.
Hence, in this study, polypyrrole lms are galvanostatically
deposited on these electrode surfaces from acetonitrile solutions
containing pyrrole as monomer, tartrate and tetrauoroborate ions
as dopant, TX100 as surfactant, applying different current density,
including multistep currents. It is expected that TA and/or T- ions
immobilize in polymer, due to the ability of construction of
hydrogen bonds byNcenter in the pyrrole ring [19]. The
tetraalkylammonium cation is preferred for preparing tartrate
salt due to fact that the tetraalkylammonium salts promotes the
formation of the hydrogen-bonded chains from the compounds
that can form hydrogen bonds [2022]. Polymerization solution is

Fig. 2. FTIR spectra of PPy coatings (a) in the absence, (b) in the presence of TA and
(c) pure tartaric acid.

prepared by adding pyrrole, TA, TBAOH, TBABF4 and TX100. TA and

TBAOH are reacted to yield tetrabutylammonium tartrate (TBAT).
Thus, the polymerization solution consists of pyrrole, TA + TBAT
(TA/T
), TBABF4 and TX100. The obtained coatings were characterized by cyclic voltammetry and EDX methods. Their capacitive
properties were investigated in aqueous H2SO4 solution by using
cyclic voltammetry, electrochemical impedance spectroscopy (EIS)
and galvanostatic chargedischarge studies.
2. Experimental
Pyrrole (Py, Fluka) was distilled under the protection of high
purity nitrogen (Linde) and then kept in refrigerator before use.
Triton X100 (Sigma), acetonitrile (HPLCgrade, Sigma), sulfuric
acid (H2SO4, Fluka), dextrotartaric acid (Laboratory BDH Reagent),
tetrabutylammonium hydroxide (TBAOH, Aldrich) and tetrabutylammonium tetrauoroborate (TBABF4, Aldrich) were analytical
grades and were used without any further purication.
Electrochemical measurements were carried out under nitrogen atmosphere in a threeelectrode type cell with separate
compartments for reference electrode [Ag, AgCl (sat) in acetonitrile
and saturated calomel reference electrode (SCE) in aqueous
solution] and counter electrode (Pt spiral). Pt foil (0.500 cm2)
was used as working electrode. The other working electrodes were
316Ti stainless steel disc electrode (0.00785 cm2) and pencil
graphite electrode (0.015 cm2). Geometric area of the electrode
was used to calculate current density and mass of PPy per unit
area [23].
The 316Ti stainless steel electrode had the following composition (wt.%): C 0.0100; Mn 1.91; Si 0.510; S 0.0300; P 0.0280; Cr 16.6;
Ni 10.8; Mo 2.06; Si 0.510; Ti 0.100; Fe 68.0, respectively. The
surface of stainless steel electrode was wet mechanically polished
successively with 800, 1000, 1200 and 2000 abrasive paper before
each electrochemical experiment. After this process, the electrode
was washed with distilled water, rinsed with acetonitrile and dried
at room temperature, respectively. Pencil graphite electrode is a
disposable electrode. The platinum foil electrodes were cleaned by
burning in a ame before each experiment. These electrodes were
washed with ultra pure water and then immersed for 3 min in an
acetonitrile solution. Ultimately, they were dried at room
temperature. The polymercoated electrodes were immersed in
acetonitrile to remove adsorbed electrolytes, monomers and the
soluble oligomers formed during electrosynthesis of the coating
before studies. Then, they were dried at room temperature.
Experiments involving the deposition of polymer and its
subsequent characterization by cyclic voltammetry, EIS and

E. Karaca et al. / Electrochimica Acta 147 (2014) 545556

547

Fig. 3. Cyclic voltammograms recorded in 0.100 M H2SO4 solution for 0.3 mg cm
2 of PPy prepared on prepassivated 316Ti SS electrode in an acetonitrile solution containing
(a) pyrrole and TBABF4 (b) pyrrole, TBABF4 and TA/T
(c) pyrrole, TBABF4, TA/T
and TX100, and (SS) for prepassivated 316Ti SS electrode. Cpyrrole:50.0 mM, CTBABF4:25.0 mM,
CTA:25.0 mM, CTBAT:25.0 mM, CTX100:25.0 mM. v = 100 mV s-1.

galvanostatic charging experiments were made using CH Instruments 6011D. EIS was performed in the frequency range of
1.00105 to 1.0010-2 Hz with amplitude of 5.00 mV at the EOCP of
substrates. Equivalent circuit models were formed by ZSimpWin
V3.50 software (Scribner Associates Inc., UK) based on EIS
measurements from the obtained data, and the parameters of
equivalent circuits were calculated using this software. Scanning
electron micrographs (SEM) of the polymer coatings were taken
with a Carl Zeiss EVO50.
3. Results and discussion
3.1. Galvanostatic synthesis of PPy in the presence of tartaric acid and
its characterization
3.1.1. Synthesis of PPy on Pt surface
Polymerization medium is an acetonitrile solution prepared by
adding 50 mM pyrrole, 50 mM tartaric acid (TA), 25 mM TBAOH and
25 mM TBABF4. TA and TBAOH are reacted to yield tetrabutylammonium tartrate (TBAT). Thus, the polymerization solution consists
of 50 mM pyrrole, 25 mM TA + 25 mM TBAT (TA/T
) and 25 mM
TBABF4. Electropolymerization of pyrrole was carried out at several
current densities by applying various steps (14) of galvanostatic
method vs. Ag/AgCl. The amount of PPy formed on Pt electrode
varied between 0.30 and 1.17 mg cm-2. The electrode surface was not
completely coated when the amount of PPy was smaller than
0.30 mg cm-2. The cyclic voltammograms of obtained coatings were
recorded in an aqueous H2SO4 solution by sweeping the potential
region between0.30 V and 0.65 V vs. SCE at a 100 mV s-1 scan rate.
The capacitance values were obtained by using these cyclic
voltammograms from the following equation.
C

la jlc j
2dV=dt

size, higher ionic concentration and higher mobility than nonaqueous electrolytes, facilitating high power operation. Besides,
they also have added advantages of low cost and enhanced safety
in operation. In literature, the higher energy density for the sample
tested with sulfuric acid electrolyte (instead of saline) conrms
that acid solutions result in higher capacitance and energy density
[28].
According to the result, the Cm values decreased with the
increase of mass. This is attributed to diffusion limitation of
electrolyte in the bulk of the lm [11]. The maximum Cm value was
368 F g-1 at total current density of 12.3 mA cm-2 in the depositing
condition which was step I: 25 s at 7.0 mA, step II: 40 s at 6.0 mA
and step III: 14 s at 5.0 mA. Also, the amount of PPy was
0.30 mg cm
2. Fig. S1b and Fig. 1b show the chronopotentiometric
curve recorded during the polymerization for latter PPy coating
and its cyclic voltammogram recorded in 0.100 M H2SO4 solution,
respectively. In order to investigate the effect of TA/T
on specic
capacitance, PPy coating was prepared in the absence of TA/T

(acetonitrile solution containing 50 mM pyrrole and 25 mM
TBABF4) under the same condition and its chronopotentiometric
curve and cyclic voltammogram are given in the same gures
(Fig. S1a and Fig. 1a) for comparison. The Cm value is determined as
215 F g-1. It is clear that an appreciable enhancement was obtained
solely on account of the polymerization in the presence of TA/T
. In
addition, the potential linearly increases to attain a maximum
value as seen in Fig. S1b when compared with the chronopotentiometric curves, which could indicate the adsorption of tartaric
acid on the Pt surface prior to electropolymerization.

[24] Eq.1

where C (F) is the capacitance of coating; Ia and Ic (A) are the

currents of anodic and cathodic voltammetric curves on positive
and negative sweeps, respectively, and dV/dt (V s
1) is the scan
rate. The specic capacitance, Cm, (F g
1) of the electrode is
obtained by dividing the capacitance by the mass of the PPy (g) and
the areal capacitance, Cs, (F cm
2) is calculated by dividing the
capacitance by the area of the electrode [25].
An aqueous H2SO4 solution is used as electrolyte for evaluating
the capacitive properties of coatings. Supercapacitors usually have
low capacitive and power capabilities because of limited ionic
concentration and conductivity in organic electrolytes [26,27]. On
the other hand, aqueous-based electrolytes offer ions of smaller

Fig. 4. Cyclic voltammograms recorded in 0.1 M H2SO4 solution for 0.3 mg cm
2 of
PPy prepared on PG electrode in an acetonitrile solution containing (a) pyrrole and
TBABF4 (b) pyrrole, TBABF4 and TA/T
(c) pyrrole, TBABF4, TA/T
and TX100, and
(PG) for bare PG electrode, Cpyrrole:50.0 mM, CTBABF4:25.0 mM, CTA:25.0 mM,
CTBAT:25.0 mM, CTX100:25.0 mM, v = 100 mV s-1.

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E. Karaca et al. / Electrochimica Acta 147 (2014) 545556

Table 1
Specic capacitances from cyclic voltammetry of PPy, PPyTA and PPyTA
TX100 on Pt, passivated 316Ti SS and PG electrodes to investigate the effect of TA TA/
T
and TX100, v= 100 mV s
1. The mass of coatings on each electrode was
0.3 mg cm
2.
Electrode
Chronopotentiometric
Condition

Step
I:
Step
II:
Step
III:

Pt

Passivated
316Ti SS

PG

25 s
14 mA cm
2
40 s
12 mA cm
2
14 s
10 mA cm
2

20 s
28 mA cm
2
15 s
19 mA cm
2
20 s
1.3 mA cm
2

50 s
13 mA cm
2
100 s
9.4 mA cm
2
119 s
6.3 mA cm
2

Coating

Polymerization Solution

Cm/F g
1 (Cs/mF cm
2)

PPy

50 mM Py
25 mM TBABF4

215 (64.5)

230 (69.0)

362 (109)

PPyTA

50 mM
50 mM
25 mM
25 mM

Py
TA
TBAOH
TBABF4

368 (110)

341 (102)

396 (119)

PPyTX100

50 mM Py
25 mM TBABF4
25 mM TX100

237 (71.1)

319 (95.7)

422 (127)

PPyTA-TX100

50 mM
50 mM
25 mM
25 mM
25 mM

379 (114)

367 (110)

458 (137)

Py
TA
TBAOH
TBABF4
TX100

The PPy coated electrodes were prepared in the polymerization

solution, which includes 50 mM pyrrole, 25 mM TBABF4, 25 mM
TBAOH and various concentrations of TA (37.5, 50.0, 62.5 mM) to
investigate the inuence of tartaric acid concentration. There is a
decrease in the specic capacitance from 368 F g-1 to 333 F g-1
when the concentration of TA is increased to 62.5 mM (i.e. 37.5 mM
TA and 25 mM TBAT). On the other hand, the electrode surface was
not completely coated at 37.5 mM TA (i.e. 12.5 mM TA and 25 mM
TBAT). It can be concluded that optimum ratio of TA to TBAOH is 2.

In other words, the polymerization solution must include 25 mM

TA and 25 mM TBAT (TA/T
).
PPy lms prepared in the absence and presence of TA/T
were
characterized by FTIR (Fig 2). In the spectrum of lm doped with
solely BF4
(Fig. 2a), the characteristic absorption band at 1549 cm1
and 1375 cm-1 was observed to originate from C=C stretching
of pyrrole ring [29]. The band at 1291 cm
1 belongs to C-N
stretching vibration. The bands at 1199 cm-1 and 918 cm-1 belong to
C-H in-plane and out-of-plane deformations, respectively. The
broad band at 1033 corresponds to the BF4anion [30]. When the
lm was prepared with TA/T
, the bands related to pyrrole ring
broadened and also shifted to lower wavenumber (1444 cm-1,
1362 cm-1, 1254 cm-1, 1124 cm-1, 993 cm-1) (Fig. 2b). The shifted
bands indicate the interaction between pyrrole ring and TA (and/
or T
ions) [31]. In addition to these bands, the tartaric acid doped
PPy has a stronger absorption band at 3353 cm
1 due to hydrogenbonded NH stretching vibration, similar to the study by Park et al.
[31]. The same broad band does not appear in the FTIR spectrum of
pure TA (Fig. 2c). This is an evidence of the presence of hydrogen
bonding between TA (and/or T
ions) andN center in the pyrrole
ring. Extra band observed at 1725 cm
1 corresponds to the
asymmetric stretching of C=O in TA and/or T
. [30]. The
appearance of the T
and/or TA peaks indicates that the T
and/
or TA enter the polymer as dopant anions together with BF4
and/
or via hydrogen bonding.
3.1.2. Synthesis of PPy on SS and PG surfaces
In order to investigate the effect of substrate, PPy lm was
deposited on stainless steel (316Ti SS) and pencil graphite (PG)
electrodes in the abovementioned polymerization solution
containing TA/T
by galvanostatic method. For the purpose of
comparison of specic capacitances, the optimum depositing
conditions of PPy on Pt electrode was applied for 316Ti SS and PG
electrodes, but the electrode surfaces were not completely coated.
Hence, electropolymerization of pyrrole was performed under
different galvanostatic conditions by keeping the amount of
polymer constant at about 0.3 mg cm-2. The coatings obtained in
the absence and presence of TA/T
were denoted as PPy/316Ti SS,
PPy/PG and PPyTA/316Ti SS, PPyTA/PG, respectively.

Fig. 5. SEM images (10,000 times magnicated) of coatings synthesized in an acetonitrile solution containing (a) pyrrole and TBABF4 (PPy) (b) pyrrole, TBABF4 and TA/T

(PPyTA) (c) pyrrole, TBABF4, TA/T
and TX100 (PPyTATX100) on Pt surfaces Cpyrrole:50.0 mM, CTBABF4:25.0 mM, CTA:25.0 mM, CTBAT:25.0 mM, CTX100:25.0 mM.

E. Karaca et al. / Electrochimica Acta 147 (2014) 545556

549

Fig. 6. SEM images (10,000 times magnicated) of coatings synthesized in an acetonitrile solution containing (a) pyrrole and TBABF 4 (PPy) (b) pyrrole,TBABF 4 and TA/T-(PPy
TA) (c) pyrrole, TBABF 4, TA/T-and TX100 (PPyTATX100) on PG surfaces. Cpyrrole :50.0 mM, CTBABF4 :25.0 mM, C TA :25.0 mM, CTBAT :25.0 mM, CTX100 :25.0 mM.

Various galvanostatic conditions were examined for electropolymerization of pyrrole on 316Ti SS surface. The cyclic
voltammograms of obtained coatings were recorded in an aqueous
H2SO4 solution by sweeping the potential region between
0.40 V
and 0.70 V vs. SCE at a 100 mV s-1 scan rate. When their cyclic
voltammograms were evaluated, the maximum value of Cm was
found to be 301 F g
1 at the total current density of 15.9 mA cm-2 in
the depositing conditions which were step I: 20 s at 220 mA, step II:
15 s at 150 mA and step III: 20 s at 10.0 mA. In the case where there
is SS as surface, the applied current was consumed for the
electropolymerization of monomer as well as passivation of
electrode. The passive oxide layer formed during electropolymerization condition may not be stable, which affects the specic
capacitance of coating. For this reason, a layer of passive lm was
formed on the steel surface even before electrodeposition process.
Also in literature, a number of studies exist on the protection of
metals by a thin passive oxide underneath the polymer coating
[3234]. The prepassivation process was performed between
0.00 V and 0.60 V vs. Ag/AgCl at a 20.0 mV s
1 scan rate by using the
Linear Sweep Voltammetry technique in the polymerization
solution (Py, TA/T
, TBABF4) and various monomerfree solutions
(solution I: TA/T
, TBABF4; solution II: TA/T
and solution III:
TBABF4) as prepassivation medium. After the prepassivation,
electropolymerization of monomers was initiated in the polymerization solution. As a result, the Cm values of PPyTA/316Ti SS
coatings were 330, 341, 239 and 257 F g
1, respectively. The most
stable passive oxide layers were obtained in the monomerfree
solution with TA/T
(i.e. the acetonitrile solution including TA/T
,
TBABF4). It could be concluded that iron tartrate together with iron
oxide formed during prepassivation process was a more stable
interface for electropolymerization than others. The electrode
surface was stabilized by an iron tartrate layer [9], which decreased
the dissolution of SS, and enabled the formation of polymer with
longer conjugated chains. Reports in the literature show that
longer conjugation length of PPy on Pt, Ni and glassy carbon
surfaces exhibited a higher electrical conductivity that may be the
reason for the increase in specic capacitance of PPy [3537].
Senthilkumar et all. also nd the similar result for polythiophene
on graphite[16]. The chronopotentiometric curves obtained in the
absence and presence of TA/T
for 316Ti SS and their cyclic

voltammograms recorded in 0.1 M H2SO4 solution are given in

Fig. S2 and Fig. 3, respectively.
In the case of the PG electrode, various galvanostatic conditions
were examined for the coating of PPy in the abovementioned
polymerization solution containing TA/T
. The maximum value of
Cm was 396 F g-1 at the total current density of 8.80 mA cm-2 in the
depositing conditions which were step I: 50 s at 85.0 mA, step II:
100 s at 60.0 mA and step III: 119 s at 40.0 mA (Fig. S3b). The
chronopotentiometric curves obtained in the absence and
presence of TA/T
and their cyclic voltammograms recorded in
0.100 M H2SO4 solution are given in Fig. S3 and Fig. 4, respectively.
When compared with the chronopotentiometric curves, unlike the
Pt electrode, the potential does not increase to attain a maximum
value in the presence of TA/T
as seen in Fig. 4b. This could indicate
the nonadsorption of tartaric acid on the PG surface prior to
electropolymerization.
The effect of surfactant on specic capacitances of PPy coatings
was also investigated. Structures of surfactants with nonpolar
hydrocarbon chains and ionic or neutral polar head groups play
an important role in electrosynthesis [38]. This is because they
can form micelle at solidliquid interfaces. In addition, the
concentration of the surfactant is an important factor in terms of
enough micelles formation at slightly above of critical concentration [38]. In the present study, TX100 was preferred as a
surfactant due to the fact that the physicochemical properties of
nonionic surfactants are not affected by electrolytes, contrary to
ionic surfactants [24]. PPy lms were prepared on Pt foil,
passivated 316Ti SS and PG electrodes in the abovementioned
polymerization solution, which includes TA/T
and various
concentrations of TX100 (12.5, 25.0, 37.5 mM). The maximum
values of specic capacitances were obtained in the presence of
25 mM TX100 for three electrodes. Also, these values were found
to be 430, 367 and 458 F g-1 for Pt foil, passivated 316 Ti SS and PG,
which were higher than those of PPy obtained in the absence of
TX100, respectively. This may be due to higher porosity and
therefore higher surface area, which enables more accessible ions
during the electrochemical process [39]. Figs. S1c, S2c. S3c and
Fig. 1c, 3c, 4c show the chronopotentiometric curves recorded
during the polymerization for latter coatings and their cyclic
voltammograms recorded in 0.1 M H2SO4 solution, respectively.

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E. Karaca et al. / Electrochimica Acta 147 (2014) 545556

Fig. 7. The Nyquist plots recorded in 0.100 M H2SO4 for the (a) PPy, (b) PPyTA and (c) PPyTATX100 prepared on (A) Pt, (B) passivated 316Ti SS and (C) PG electrodes (Their
Bode plots are also shown as inset).

When their cyclic voltammograms are compared, it can be

concluded that not only the highest current density but also the
highest symmetry of the voltammogram in anodic and cathodic
directions (i.e. rectangular form) are obtained for PG coating
(Fig. 4c), an indicator of an ideal capacitive nature.
To sum up, the capacitive behaviours of the coatings prepared
on Pt, passivated 316Ti SS and PG electrodes in the presence and
absence of TA/T
and TX100 are summarized as the specic and
areal capacitances for comparison in Table 1. Also they are denoted
as PPy, PPyTA, PPyTX100 and PPyTATX100. Considerable
attention is paid to ensure that the specic mass of PPy on each
electrode is about 0.3 mg cm
2. While the increase in capacitance
values are higher in the presence of TA/T
for coatings on Pt and
passivated 316Ti SS electrodes, it is higher in the presence of
TX100 for coating on PG electrode as seen in Table 1. The last but
not the least, the highest values are obtained for the polymers
carried out in the presence of both TA/T
and TX100. High
capacitances may be attributed to the formation of PPy with longer
conjugated length and higher surface area on the electrode surface
[16,40]. Generally, the longer conjugated length of the PPy exhibits
a higher electrical conductivity, which may be the reason for the
increase in specic capacitance [41].

3.1.3. SEM micrographs and EDX analysis

It is known that the electrochemical performance of PPy coating
is strongly inuenced by microstructure and porosity [9]. In this
study, SEM has been used to investigate the surface morphology of
polymercoated electrodes. The lms grown on Pt and 316Ti SS
surfaces have a globular structure, with the formation of
aggregates and a uniform surface morphology, often referred in
the literature as cauliower [42,43]. SEM images of PPy, PPyTA
and PPyTATX100 deposited on Pt substrate are shown in Fig. 5 a,
b,c, respectively. The PPy coatings exhibit an increasingly sponge
like and porous structure when TA/T
and TX100 are gradually
inserted in the polymer, leading to more access to the interior sites
of the polymer for dopant and/or electrolyte ions during the
electrochemical process [9]. This leads to the increase of

Fig. 8. Electrical equivalent circuit used to t impedance spectra.

E. Karaca et al. / Electrochimica Acta 147 (2014) 545556

551

Table 2
Impedance parameters obtained by tting the impedance spectra recorded in 0.1 M H2SO4 solution for PPy, PPyTA and PPyTATX100 coatings on Pt, 316Ti SS and PG
electrodes. The mass of coatings on each electrode was 0.3 mg cm
2.
Coated Electrode

Rs/V.cm2

Q1/F cm
2

4

R1/V.cm2

W/Vs
1/2 cm
2

Q2/F cm
2

321
11.9
11.2

2.8
2.5
2.0

5.95  10
3
53.5  10
3
59.8  10
3

PPy/Pt
PPy-TA/Pt
PPy-TA-TX100/Pt

1.75
1.72
1.67

0.87  10
1.07  10
4
1.38  10
4

PPy/316Ti SS
PPy-TA/316Ti SS
PPy-TA-TX100/316Ti SS

0.82
0.72
0.71

2.71 10
4
7.53  10
4
7.64  10
4

1.42
0.93
0.82

3.67
3.44
0.54

25.5  10
3
33.3  10
3
34.9  10
3

PPy/PG
PPy-TA/PG
PPy-TA-TX100/PG

0.98
0.90
0.66

103  10
4
397  10
4
400  10
4

0.30
0.23
0.21

3.60
3.56
0.67

59.6  10
3
62.2  10
3
66.7  10
3

capacitance, which is compatible with the results of cyclic

voltammetry.
The presence of ordered graphite layers on the bare PG
electrode surface can be observed in Fig. S4. When this surface
is covered with PPy in the presence and absence of TA/T
and/or
TX100, the lms grow a porous structure with brils (Fig. 6 a,b,c)
unlike those of the Pt and 316Ti SS electrodes. This type structure
provides easy access of ions to the electrode/electrolyte interface,
which is a very important factor for the faradaic reactions [44]. This
might enhance the electrochemical activity of polymer layers
benecial for the construction of high energy or high power energy
sources.
EDX analysis of the coatings was performed and it was found
that the atomic ratio of F/N were about 1.7, 0.91, 0.95 for the PPy,
PPyTA and PPyTATX100, and O/N were about 0.28, 0.37, 0.53,
respectively. In addition to TBABF4, TA/T
was added to the
polymerization solution, which caused the uorine content (F/N
ratio) to decrease and the amount of oxygen (O/N ratio) to increase.
F/N and O/N ratios indicate BF4 anion and TA/T
per pyrrole ring
during polymerization and doping, respectively. This indicates that
tartrate anions were present along with the BF4
anions in the
polymer. When TX100 was added to the polymerization solution
with the others, the most important difference was that the
amount of oxygen (O/N) increased signicantly.

because the semicircle is depressed, and Q2 was used because the

lowfrequency behavior is not ideal capacitive. The nonideal
nature of capacitances arises due to the nonhomogeneous nature
of the electrode [45]. It was found that the RS and Rct values of PPy
TATX100 coating are smaller than those of PPy, and PPyTA
coatings for three electrodes as revealed in Table 2, which are
primarily attributable to the improved wettability [24] and implies
that the cation insertion/extraction process into/from PPyTA
TX100 is more facile than in the case of the other coatings,
respectively [38]. And PPyTATX100 coating has the smallest
internal resistance, probably because of bigger conjugation length
similar to the study by Martini et al. [46]. The W values gradually
decrease for three electrodes when TA/T
and TX100 were inserted
in the polymer in succession. However, for Q values, the results are
vice versa. It can be concluded that the real surface area of PPy in
contact with solution increases by inserting TA/T
and TX100,
which improves the pseudocapacitances of PPy [38]. These
results are in concurrence with that of SEM. Among the PPyTA
TX100 coated electrodes, the PG electrode exhibits the best
capacitive behavior.
3.3. Effect of the scan rate
In order to investigate the inuence of scan rate on the
capacitance of PPyTATX100 coating, the cyclic voltammograms

3.2. EIS measurements

Fig. 7 shows the Nyquist plots recorded in 0.1 M H2SO4 solution
for the PPy, PPyTA and PPyTATX100 coatings on Pt foil,
passivated 316Ti SS and PG electrodes. The Bode plots of
impedance spectra are also given as an inset in these gures. In
the lowfrequency, the slopes of the impedance plots for PPy, PPy
TA and PPyTATX100 coatings gradually increase, respectively,
and PPyTATX100 coatings tend to become purely capacitive. In
Bode plots, the maximum phaseangle values gradually increase in
lowfrequency for three electrodes by inserting TA/T
and
TX100 in the polymer in succession. It is inferred that PPyTA
TX100 coating is the best capacitive material for each electrode.
The impedance data were subjected to ZSimpWin V3.50 tting
program and the impedance parameters were obtained by using
the electrical equivalent circuit shown in Fig. 8. The x2 tting
parameter is always less than 2  10
3. The best tting values for
the parameters corresponding to the circuit elements are listed in
Table 2. The circuit elements are explained as follows [38]: Rs
represents the electrolyte resistance (equivalent to the high
frequency intercept on the real axis), Rct is chargetransfer
resistance (equal to diameter of the semicircle), Q1 is constant
phase element (CPE) used in place of doublelayer capacitance
(Cdl), W is Warburg arising from a diffusioncontrolled process at
low frequency, and Q2 is CPE used in place of the pseudo
capacitance of the coating. The CPE, Q1, was used instead of Cdl

Fig. 9. Variations of the specic and areal capacitances of 0.3 mg cm
2 of PPyTA
TX100 on (a) Pt (b) passivated 316Ti SS (c) PG electrodes as a function of scan rate.

552

E. Karaca et al. / Electrochimica Acta 147 (2014) 545556

were recorded at scan rates of 5.00, 10.0, 20.0, 50.0 and 100 mV s-1
in 0.1 M H2SO4 solution vs. SCE. The specic (and also areal)
capacitances were obtained in range of 610379 F g-1 (183
114 mF cm-2) for Pt, 529367 F g-1 (159110 mF cm
2) for passivated 316Ti SS and 984458 F g
1 (295137 mF cm
2) for PG electrodes, respectively. Fig. 9 shows variations of the specic (and also
areal) capacitances of PPyTATX100 coatings on Pt, passivated
316Ti SS and PG electrodes with scan rate. The capacitance values
decrease with the increase in the scan rate as presented in Fig. 9,
which is typical for conducting polymerbased supercapacitor. It is
believed that the inner part of the surface of an electrode material
cannot contribute to the charging/discharging at high charging/
discharging rate, which decreases the specic (and also areal)
capacitance values [16].

3.4. Galvanostatic chargedischarge measurements

Capacitance behaviours of PPy, PPyTA and PPyTA
TX100 coatings on Pt foil, passivated 316Ti SS and PG electrodes
were compared by preparing these electrodes at the chronopotentiometric condition as mentioned above, subjecting them to
galvanostatic chargedischarge cycling. Chargedischarge experiments were performed from
0.40 to 0.7 V for 316Ti SS electrode
and
0.30 to 0.65 V for Pt and PG electrodes using several current
density values in the range of 1.015.0 mA cm
2. The potential
varied linearly with time of charge and discharge. Fig. 10 shows the
galvanostatic chargedischarge cycles of coatings on each electrode recorded at a current density of 5.0 mA cm
2 in 0.100 M
H2SO4 solution. Their capacitance values were obtained by using

Fig. 10. Galvanostatic chargedischarge curves recorded at 5 mA cm-2 for 0.3 mg cm
2 of (a) PPy, (b) PPyTA and (c) PPyTATX100 coatings prepared on (A) Pt, (B) passivated
316Ti SS and (C) PG electrodes.

E. Karaca et al. / Electrochimica Acta 147 (2014) 545556

Table 3
The specic capacitances of 0.3 mg cm
2 of PPyTATX100 on Pt, passivated 316Ti
SS and PG electrodes by using galvanostatic chargedischarge cycling at different
current densities.

electrode is due to coating only and PG substrate does not

contribute signicantly.
PPyTATX100 coatings on Pt, SS and PG electrodes were
subjected to a prolonged cyclelife test at a current density of
10 mA cm-2 up to 1000th cycles in a threeelectrode cell
conguration and the data are shown in Fig. S5. During the
initial cycles, the specic capacitances of 331, 300 and 455 Fg
1
are obtained, respectively. The specic capacitances of PPyTA
TX100 coatings on Pt and PG electrodes gradually decrease with
the increasing cycle up to 500 (258 and 364 Fg
1) and with the
increasing cycle up to 1000 (245 and 309 Fg
1), respectively. Also
their capacitance retentions are 78% and 80% at 500th cycle while
74% and 68% at 1000th cycle, respectively. There is a dramatic
decrease of coating on 316Ti SS to about 175 F g
1 in about
150 cycles, and thereafter it remains fairly constant up to
1000 chargedischarge cycles tested and its capacitance retention
is about 54%. In literature, the conducting polymerbased
electrochemically supercapacitor often is remarkably degraded
under less than a thousand cycles, as indicated in the following
studies. The electrochemical supercapacitor device formed with
PPy coated shed graphite plate electrode shows an initial
capacitance of 120 F g
1, which is degraded by 50.0% in the rst
1000 cycles at a constant current density of 2.0 mA cm
2 [1].
The capacitance of PPy coated nylon lycra fabric decreases
severely after 500 charge/discharge cycles, only about 12.5% of
the initial capacitance [48]. The specic capacitance of PPy/
modied graphite oxide, PPy/graphite oxide and PPy shows 16.2%,
34.3% and 41.4% degradation after as many as 1000 cycles at
1.00 A g
1 [49].

Cm/Fg-1 (Cs/mF cm-2

J/mA cm

2

Pt
497
427
395
331
286

1.0
3.0
5.0
10
15

(149)
(128)
(119)
(99.3)
(85.8)

Passivated 316Ti SS

PG

458
420
398
300
240

794
700
501
455
444

(137)
(126)
(119)
(90.0)
(72.0)

(238)
(210)
(150)
(137)
(133)

these chargedischarge curves from the following equation:

C

I  Dt
DV

553

[24] Eq. 2

where C (F) is the capacitance of coating; I (A) is the current used

for chargedischarge cycling, Dt (s) the discharge time and DV (V)
corresponds to potential window of cycling.
The specic capacitance, Cm, (F g
1) of the electrode is obtained
by dividing the capacitance by the mass of the PPy (g) and the areal
capacitance, Cs, (F cm
2) is calculated by dividing the capacitance
by the area of the electrode [25], as above.
The specic capacitances of PPy, PPyTA, PPyTATX100 were
obtained at a current density of 5.0 mA cm-2 as 118, 366, 395 F g-1
(35.4, 110, 119 mF cm
2) for Pt electrode, 199, 219, 398 F g
1 (59.7,
65.7 and 119 mF cm-2) for passivated 316Ti SS electrode and 382,
440, 501 F g
1 (115, 132 and 150 mF cm-2) for PG electrode,
respectively. Higher values were obtained for the polymers
synthesized in the presence of both TA and TX100 like the result
of cyclic voltammetry. However, these capacitance values are
different from the values obtained using cyclic voltammograms
(Table 1). It is anticipated that cyclic voltammetry and galvanostatic chargedischarge methods will not yield identical estimates
on account of different parameters measured in each case. The
sequence for capacitance values is the same, that is, 316Ti SS has
the minimum value and PG has the maximum.
Variations of the capacitances of PPyTATX100 on Pt,
passivated 316Ti SS and PG electrodes with current densities of
chargedischarge cycling are presented in Table 3. It is obvious that
the capacitance values of coatings on PG are fairly high at all
current densities of cycling, and there is a decrease in capacitances
with an increase of current density. This can be explained by the
fact that, at higher current densities, only the outer layers of active
materials can contribute to chargedischarges processes which, in
turn, will result in the decreased capacitance [47]. In order to
compare, a bare PG electrode (without coating) was also subjected
to chargedischarge cycling at 5 mA cm
2. The capacitance value
was only 2.21 F g
1 (0.66 mF cm
2). Therefore, the capacitance
(501 F g
1 (150 mF cm
2)) obtained from PPyTATX100/PG

3.5. Power and Energy densities

The power density (P) and energy density (E) are generally used
as important parameters to characterize the electrochemical
performance of supercapacitor materials. The P and E values of
PPyTATX100 coatings were calculated from the following
equations using the galvanostatic chargedischarge curves
recorded at several current densities:
E

C  DV2
2m

[24] Eq. 3

I  DV
2m

[24] Eq. 4

where C (F) is the capacitance of the coatings, I (A), DV (V), and m

(g) represent discharge current, the potential range of the charge
and discharge, the mass of the PPy, respectively. The energy
density is divided by a 3.6 factor to obtain the unit of Wh/kg (1 Wh/
kg = 3600 J/1000 g) [50]. Also, the power density is multiplied by
1000 to obtain the unit of W/kg.

Table 4
Variation of energy and power densities with increasing current densities for 0.3 mg cm
2 of PPyTATX100 coatings. on Pt, passivated 316Ti SS and PG electrodes by using
galvanostatic chargedischarge cycling.
E/Wh kg
1
J/mA cm
1.0
3.0
5.0
10
15

2

P/kW kg
1

Pt

Passivated 316Ti SS

PG

Pt

Passivated 316Ti SS

PG

65.6
56.3
52.1
43.7
37.7

70.0
64.2
60.8
45.8
36.7

105
92.4
66.1
60.0
58.6

0.680
2.04
3.40
6.81
10.2

2.41
7.25
12.0
24.1
36.3

0.651
1.95
3.25
6.51
9.77

554

E. Karaca et al. / Electrochimica Acta 147 (2014) 545556

exhibit higher capacitance which conrms the possibility of

utilizing the electrodes in electrochemical supercapacitors.
4. Conclusion

Fig. 11. Ragon plots of PPyTATX100 coatings prepared on (a) Pt, (b) passivated
316Ti SS and (c) PG electrodes at various current densities.

The P and E values of coatings are presented in Table 4, and

Fig. 11 shows their Ragon plots. The energy densities of all coatings
gradually decrease with the increase of the current density, while
the power densities increase in the same manner. PPyTATX100/
PG has the highest energy density at lowest current density, and
PPyTATX100/passivated 316Ti SS has the highest power density
at highest current density. These encouraging ndings can open up
the possibility of using these materials in supercapacitor studies
with high voltage, high energy, and high power densities. Some
examples of the conducting polymerbased supercapacitor
electrode materials and their electrochemical properties are given
in Table 5 for comparison. PPyTATX100 coatings in this study

Galvanostatic deposition of tartratedoped PPy was carried out

on Pt, passiviated SS and PG electrodes in acetonitrile solution
containing TA/T
and TX100 by galvanostatic method. When their
capacitive properties obtained from the galvanostatic charge
discharge method are compared with those prepared in the
solution without both TA/T
and TX100, it is found that the PPy
synthesized in the presence of both TA/T
and TX100 (PPyTA
TX100) has the highest capacitance for three electrodes. High
capacitances may be attributed to the incorporation of TA via
hydrogen bonding and/or A
as dopant anion together with BF4
.
Also TX100 provides high porosity, which enables the electrolyte to
access more easily into the polymer coating. Consequently, TA/T

and TX100 lead to the formation of PPy with longer conjugated
length and higher surface area on the electrode surface. The
capacitance value of PPyTATX100 coating on PG electrode is
fairly high (794 F g
1 (238 mF cm-2) at 1.0 mA cm-2) when compared with those on Pt and passivated SS electrodes (497 F g
1
(149 mF cm-2) and 458 F g
1 (137 mF cm-2)), respectively, and it has
also the highest energy density for all current densities (105 Wh
kg
1 at 1.0 mA cm-2). These results reveal that the bril structure of
polymer on PG plays an important role in the performance of
coating as it provides a porous surface area. The evaluation of
power densities shows that the PPyTATX100/passivated 316Ti SS
coating was three times as high (36.3 kW kg-1) as those of other
coatings at 15 mA cm-2. This could originate from the passive layer
between SS and tartratedoped PPy. The results suggest that the
tartratedoped PPy coatings are promising electrode materials to
be used in electrochemical supercapacitors.
Acknowledgements
The authors are grateful for the nancial support from the
Hacettepe University Scientic Research Unit (01301601001).

Table 5
Specic capacitances, energy densities and power densities of supercapacitor materials.
Supercapacitor Electrode Material

Current Density/ma cm
2

Specic Capacitance/F g
1

Energy Density/Wh kg
1

Power Density/W kg
1

References

CoSx/Nickel gauze

5.0
10.0
1.0
1.0
3.0
5.0
1.0
1.0
1.0
5.0
3.0
5.0
10.0
15.0
1.0
5.0
0.25
1.0
5.0
10.0
1.0
5.0
10.0
1.0
5.0
10.0

475
431
251
144
86.2
79.4
125
282
204
111
416
419
394
378
510
497
395
331
458
398
300
794
501
455

34.9
51.5
22.7
17.7
11.1
31.8
23.0
4.90
4.20
133
65.6
52.1
43.7
70.0
60.8
45.8
105
66.1
60.0

0.09  103
0.23  103
0.36  103
0.80  103
0.24  103
1.20  103
0.76  103
0.68  103
3.40  103
6.81 103
2.41 103
12.0  103
24.1 103
0.65  103
3.25  103
6.51 103

[51]

PEDOTcomp/SS
NMC/SS

PPy coated NLF/Cu

PPy nanowiresCTAB/Graphite groove
PPyCTAB/Graphite groove
PPyCNTMnO2/Ti
PPyPANI comp/Graphite

PPyPANI/Carbon paper
Nanostructure PPy/SS
PPyTATX100/Pt

PPyTATX100/316Ti SS

PPyTATX100/PG

[52]
[53]

[48]
[54]
[55]
[56]

[57]
[58]
This study

PEDOT: poly(3,4-ethylenedioxythiophene); NMC: nickel-doped mesoporous carbon comp.; CTAB: cetyl trimethyl ammonium bromide; NLF: nylon lycra fabric; Et4NBF4:
tetraethylammonium tetrauoroborate; CNT: carbon nanotubes; PANI: polyaniline.

E. Karaca et al. / Electrochimica Acta 147 (2014) 545556

Appendix A. Supplementary data

Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.electacta.2014.09.136.
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