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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta
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
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
546
Fig. 1. Cyclic voltammograms recorded in 0.100 M H2SO4 solution for 0.3 mg cm2 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.
Fig. 2. FTIR spectra of PPy coatings (a) in the absence, (b) in the presence of TA and
(c) pure tartaric acid.
547
Fig. 3. Cyclic voltammograms recorded in 0.100 M H2SO4 solution for 0.3 mg cm2 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 cm2. 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
Fig. 4. Cyclic voltammograms recorded in 0.1 M H2SO4 solution for 0.3 mg cm2 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.
548
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 s1. The mass of coatings on each electrode was
0.3 mg cm2.
Electrode
Chronopotentiometric
Condition
Step
I:
Step
II:
Step
III:
Pt
Passivated
316Ti SS
PG
25 s
14 mA cm2
40 s
12 mA cm2
14 s
10 mA cm2
20 s
28 mA cm2
15 s
19 mA cm2
20 s
1.3 mA cm2
50 s
13 mA cm2
100 s
9.4 mA cm2
119 s
6.3 mA cm2
Coating
Polymerization Solution
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
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.
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 g1 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 s1 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 g1, 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
550
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).
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 cm2.
Coated Electrode
Rs/V.cm2
Q1/F cm2
4
R1/V.cm2
W/Vs1/2 cm2
Q2/F cm2
321
11.9
11.2
2.8
2.5
2.0
5.95 103
53.5 103
59.8 103
PPy/Pt
PPy-TA/Pt
PPy-TA-TX100/Pt
1.75
1.72
1.67
0.87 10
1.07 104
1.38 104
PPy/316Ti SS
PPy-TA/316Ti SS
PPy-TA-TX100/316Ti SS
0.82
0.72
0.71
2.71 104
7.53 104
7.64 104
1.42
0.93
0.82
3.67
3.44
0.54
25.5 103
33.3 103
34.9 103
PPy/PG
PPy-TA/PG
PPy-TA-TX100/PG
0.98
0.90
0.66
103 104
397 104
400 104
0.30
0.23
0.21
3.60
3.56
0.67
59.6 103
62.2 103
66.7 103
Fig. 9. Variations of the specic and areal capacitances of 0.3 mg cm2 of PPyTA
TX100 on (a) Pt (b) passivated 316Ti SS (c) PG electrodes as a function of scan rate.
552
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 cm2) for passivated 316Ti SS and 984458 F g1 (295137 mF cm2) 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].
Fig. 10. Galvanostatic chargedischarge curves recorded at 5 mA cm-2 for 0.3 mg cm2 of (a) PPy, (b) PPyTA and (c) PPyTATX100 coatings prepared on (A) Pt, (B) passivated
316Ti SS and (C) PG electrodes.
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)
I Dt
DV
553
[24] Eq. 2
C DV2
2m
[24] Eq. 3
I DV
2m
[24] Eq. 4
Table 4
Variation of energy and power densities with increasing current densities for 0.3 mg cm2 of PPyTATX100 coatings. on Pt, passivated 316Ti SS and PG electrodes by using
galvanostatic chargedischarge cycling.
E/Wh kg1
J/mA cm
1.0
3.0
5.0
10
15
2
P/kW kg1
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
Fig. 11. Ragon plots of PPyTATX100 coatings prepared on (a) Pt, (b) passivated
316Ti SS and (c) PG electrodes at various current densities.
Table 5
Specic capacitances, energy densities and power densities of supercapacitor materials.
Supercapacitor Electrode Material
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