Journal of Power Sources 276 (2015) 262e270

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Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

High performance supercapacitor based on graphene-silver

nanoparticles-polypyrrole nanocomposite coated on glassy carbon
electrode
Pramod K. Kalambate a, Riyaz A. Dar a, Shashi P. Karna b, Ashwini K. Srivastava a, *
a
Department of Chemistry, University of Mumbai, Vidyanagari, Santacruz (East), Mumbai, 400 098, India
b
U.S. Army Research Laboratory, Weapons and Materials Research Directorate, ATTN: RDRL-WM, Aberdeen Proving Ground, MD 21005-5069, USA

h i g h l i g h t s g r a p h i c a l a b s t r a c t

A supercapacitor with ternary com-

posite GNS/AgNPs/PPY is developed.

In situ oxidative polymerization of
PPY in presence of GNS and AgNPs.

High specic capacitance of 450 F g1
at 0.9 mA g1 for GNS/AgNPs/PPY.

Retention of 92% of its initial specic
capacitance after 1000 GCD cycles.

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

Article history: In the current study, we present a new hybrid material of double layer capacitive material graphene
Received 28 August 2014 (GNS), pseudo capacitive polypyrrole (PPY) and highly conducting silver nanoparticles (AgNPs). Gra-
Received in revised form phene/Silver nanoparticles/polypyrrole (GNS/AgNPs/PPY) composite has been synthesized by in situ
25 November 2014
oxidative polymerization of pyrrole in the presence of GNS and AgNPs. The different mass concentrations
Accepted 27 November 2014
Available online 28 November 2014
of AgNPs were utilized to improve the capacitive performance of supercapacitor. Characterization of the
electrode material has been carried out by X-ray diffraction, Raman spectroscopy, Thermal methods,
Scanning electron microscopy (SEM) and Transmission electron microscopy. SEM images showed that
Keywords:
Graphene
PPY nanoparticles uniformly coated on graphene sheets along with AgNPs. Electrochemical character-
Silver nanoparticles ization of the electrode surface has been carried out by means of cyclic voltammetry, galvanostatic
Polypyrrole charge/discharge and electrochemical impedance spectroscopy. Remarkably, GNS/AgNPs/PPY exhibits
Supercapacitor specic capacitance of 450 F g1 at current density of 0.9 mA g1, which is far better than GNS/PPY
Energy density (288 F g1), AgNPs/PPY (216 F g1) and PPY (153 F g1). Furthermore, GNS/AgNPs/PPY shows high charge
edischarge reversibility and retaining over 92.0% of its initial value after 1000 cycles. The cyclic stability
of the composite is improved due to the synergistic effect of GNS, AgNPs and PPY.
2014 Elsevier B.V. All rights reserved.

1. Introduction

Supercapacitors or ultracapacitors are a unique type of energy

* Corresponding author. storage devices being developed for a wide range of applications,
E-mail addresses: aksrivastava@chem.mu.ac.in, akschbu@yahoo.com including consumer electronics, memory backup systems, medical
(A.K. Srivastava).

http://dx.doi.org/10.1016/j.jpowsour.2014.11.130
0378-7753/ 2014 Elsevier B.V. All rights reserved.
 P.K. Kalambate et al. / Journal of Power Sources 276 (2015) 262e270
electronics, public transportation, various micro devices, and mil-
itary defense systems [1e3]. Supercapacitors, as energy storage
devices attract attention due to its superior properties including
high power density, rapid charge/discharge process, low cost, long
cycle life, and environmental friendly. [4e7]. However, energy
density, power density and cycle life of currently available super-
capacitors need to be improved to satisfy the rapidly increasing
energy demands and many other applications. To meet energy
demands low cost, environmentally friendly and more efcient
energy storage devices are essentially needed. Therefore, the
development of supercapacitor electrodes with superior properties
is of tremendous importance.
In general, supercapacitors are divided into three classes viz;
electrochemical double-layer capacitors (EDLC), pseudocapacitors,
and hybrid capacitors [8]. In each class mechanism of charge stor-
age is unique. EDLCs store charge by non-faradaic mechanism and
charges are distributed on the surfaces by physical processes. Car-
bon based materials (graphene, carbon nanotubes, activated car-
bon, nanodiamond etc.) are very popular to be employed as
electrode materials in EDLCs. Whereas, pseudocapacitors store
charge by faradaic process such as oxidationereduction reaction
and transfer of charge between electrode and electrolyte. Pseudo-
capacitors mainly use conducting polymers and metal oxide as
electrode material. Hybrid capacitors make use of both physical and
chemical charge storage mechanism together in a single electrode.
The main advantage of hybrid capacitors is superior cyclic stability
and high power density [9].
Graphene (GNS), a two-dimensional honeycomb lattice struc-
ture of graphite has triggered a new genre for the development of
supercapacitor electrode materials due to its large surface area,
very high electrical and thermal conductivity, great mechanical
strength and low manufacturing cost [10e14]. GNS has been used
for fabrication of energy storage devices, electronic devices, sensors
and composites. Conducting polymers have a relatively high spe-
cic capacitance, high conductivity and low cost compared to car-
bon based materials [15e18]. In recent years conducting polymers
such as polypyrrole (PPY) [19,20], polyaniline (PANI) [21,22], poly-
thiophenes (PTs) [23,24] and polyethylenedioxythiophene (PEDOT)
[25,26] have been successfully used as electrode materials in
electrochemical energy storage devices because of their high con-
ductivity and fast redox electroactivity. Among them, PPY is one of
the most promising supercapacitor material due to its high energy
density, low cost, simple preparation, and reversible doping/de-
doping electrochemistry. But the drawback associated with con-
ducting polymers is poor stability during charging/discharging
[27,28]. Therefore development of supercapacitor with good sta-
bility, high energy and power density is of great importance.
Addition of conducting polymers, metal and metal oxides to the
carbon based materials is a promising approach. This approach has
proven very successful in achieving high value of capacitance. The
superior performance of supercapacitors is due to increase in
polymer stability in the presence of carbon based material; the
porous network provides electrolyte permeation and enhancement
in conductivity and charging-discharging behavior of conducting
polymers.
In this article, we propose a simple method for fabrication of
GNS/AgNPs/PPY composite electrode with improved electro-
chemical performance. This is the rst instance wherein AgNPs
have been used along with graphene and PPY for supercapacitor.
There are few reports where silver nanoparticles are employed
with conducting polymers and metal oxides [29e33]. In the present
study AgNPs were incorporated into the conducting polymer i.e.,
polypyrrole. Presence of AgNPs reduces the electrical resistance of
the polymer and increase electrical conductivity and electro-
chemical storage capacity. Incorporation of AgNPs into polymeric
263
material results higher specic capacitance than polymeric mate-
rial itself. The surface characterization of the electrode has been
carried out by scanning electron microscopy (SEM), energy
dispersive x-ray spectroscopy (EDX), transmission electron micro-
scopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, Ther-
mogravimetric analysis (TGA) and differential thermal analysis
(DTA). The electrochemical characterization of the electrode has
been carried out by cyclic voltammetry (CV), galvanostatic char-
geedischarge (GCD) and electrochemical impedance spectroscopy
(EIS).
2. Experimental section
2.1. Chemicals and materials
Natural graphite (99.5% pure, particle size <50 mm) was ob-
tained from S. D ne Chem. Ltd. Pyrrole monomer (98% pure); silver
nanoparticles (particle size <100 nm, 99.5 trace metal basis) and
Iron (III) chloride hexahydrate (ACS reagent, 97%) were purchased
form Sigma Aldrich. Sulfuric acid (AR grade, 98%), potassium per-
manganate (AR grade, 99%), sodium nitrate (AR grade, 99.5%) were
obtained from S. D. ne Chem. Ltd. Hydrogen peroxide (30% w/w in
water), Sodium borohydride (99%) and hydrazine (98%) were pro-
cured from Sigma Aldrich. All the chemicals were used without any
further purication. Double distilled water was used throughout
analysis.
2.2. Synthesis of graphene
Graphite oxide was prepared form natural graphite by modied
Hummers method [34]. Briey, 2.0 g of graphite powder and 1.0 g
NaNO3 were mixed, and then put into 96.0 ml conc. H2SO4 in an ice
bath. Under vigorous stirring, 6.0 g KMnO4 was added gradually.
The temperature of the mixture was maintained bellow 20  C. The
ice bath was removed and mixture was stirred in a water bath for
2 h. To the brownish color pasty liquid 150 ml of water was added
and to maintain temperature bellow 50  C water was added
continuously till total volume of water was 240 ml. To the above
mixture 5 ml of 30% H2O2 was added and it is observed that the
solution color transformed into brilliant yellow along with
bubbling. The mixture was stirred for 2 h; it was ltered and
washed with 10% HCl aqueous solution, water, and ethanol. The
product obtained was dried under vaccume at 60  C. For the syn-
thesis of reduce graphene oxide, 100 mg of graphite oxide was
dispersed in water and sonicated for 1hr. In this step conversion of
graphite oxide to graphene oxide (brown dispersion) took place. To
the above dispersion 2.0 g hydrazine hydrate in 5 ml water was
added and the mixture was reux at 100  C for 24 h under magnetic
stirring. Finally, the mixture was ltered washed thoroughly with
water and dried at 60  C for 12 h.
2.3. Synthesis of GNS/AgNPs/PPY composite
Three composites of GNS/AgNPs/PPY were synthesized by
varying the ratio of silver nanoparticles and keeping the other
conditions the same for the evaluation of supercapacitor perfor-
mance. Graphene and AgNPs were taken in the different ratio viz;
100:10, 100:20, and 100: 30. Polypyrrole was synthesized by
chemical oxidative polymerization method using ferric chloride as
oxidizing agent. In a typical procedure, 0.1 g graphene, 20 mg silver
nanoparticles and 0.45 g freshly distilled pyrrole were mixed in
50 ml of de-ionized water and sonicated for 60 min. An equal
volume of ferric chloride (6 mM in 0.1 M HCl) was added slowly
with constant stirring at 0e5  C. The mixture was kept under
magnetic stirring at 0e5  C for 24 h. After reaction for 24 h, the
264 P.K. Kalambate et al. / Journal of Power Sources 276 (2015) 262e270
composite was thoroughly washed with water and then ethanol to
remove any impurities. The composite was ltered and dried in a
vacuum oven at 60  C for 12 h. For comparison, GNS/PPY, AgNPs/
PPY and PPY were prepared using same procedure. The illustration
of the preparation procedure for GNS/AgNPs/PPY nanocomposites
is shown in Scheme 1.
2.4. Characterization methods
Microstructure of the synthesized materials was characterized
by scanning electron microscopy (SEM) (FEI quanta-200 model
with an operating voltage of 30 kV). The TEM analysis was carried
out on PHILIPS-CM200 electron microscope with operating volt-
ages of 20e200 kv and resolution of 2.4 A . The crystallographic
studies of samples were carried out using X-ray diffraction (XRD)
technique (Shimadzu 7000S, Shimadzu Analytical, Japan) equipped
with CuKa radiation (l 0.154 nm). Raman spectra were recorded
using Renishaw micro-Raman spectrometer (RE-04) equipped with
solid state laser with the diode pumped at 514 nm. TG-DTA analysis
was carried out on Perkin Elmer Pyris Diamond analyzer. The pH
meter used during study was Elico LI 120. All electrochemical
measurement were performed using an Autolab PGSTATE 30
equipped with USB electrochemical interface using GPES software,
version 4.9.005 and frequency response analyzer, software version
2.0 respectively. The three electrode system employing modied
electrode was used as working electrode, platinum wire and Ag/
AgCl (sat. KCl) were used as counter and reference electrodes,
respectively in 1 M KCl. For electrochemical study 4.0 mg of active
material was dispersed in 2.0 ml of ethanol and 10 ml suspension
was deposited on glassy carbon electrode. The electrode was dried
under infra-red lamp and washed with water before electro-
chemical study.
3. Results and discussion
3.1. XRD, Raman and TG-DTA study
The XRD diffraction patterns of PPY, AgNPs/PPY, GNS/PPY and
GNS/AgNPs/PPY are shown in Fig. 1. It can be seen that polypyrrole
shows sharp diffraction peak at 25 indicating amorphous nature
and is due to the scattering from PPY chains at the interplaner
spacing. This result is matching well with the polypyrrole synthe-
sized by various methods reported in the literature [35]. The
average particle size of polypyrrole obtained using Scherrer's
equation was 13 nm. Similar peaks were observed in GNS/PPY,
AgNPs/PPY and GNS/AgNPs/PPY. In AgNPs/PPY composite AgNPs
Scheme 1. Illustration of the preparation procedure for
nanocomposites.
show ve diffraction peaks at 38.10 , 46.20 , 64.44 , 77.37 and
81.33 which correspond to (1 1 1), (2 0 0), (2 2 0), (3 1 1) and (2 2 2)
planes. While graphene shows only two peaks at 26 and 44
corresponding to its (0 0 2) and (1 1 1) reections. The results ob-
tained for graphene are comparable with the reported literature
[36]. In GNS/AgNPs/PPY composite the graphene peak at 44 is not
visible. The probable reason for this is graphene sheets are uni-
formly covered by PPY nanoparticles. Also some of the diffraction
peaks of silver are not visible in GNS/AgNPs/PPY composite elec-
trode. This is because AgNPs are completely dispersed in graphene
sheets.
Raman spectroscopy is the widely used technique to obtained
structural information especially for carbon based material. As
shown in Fig. 2(a) Raman spectra of PPY shows two wide bands at
1328 and 1552 cm1 corresponding to C]C backbone stretching
and the ring-stretching mode, respectively [37]. It is also seen that
graphene shows two prominent peaks around 1340 and 1584 cm1
that correspond to D and G bands, respectively. The D and G bands
of the graphene are due to the breathing vibrations of carbon atoms
of dangling bonds in plane termination of disordered and defected
graphite and the in-plane bond-stretching vibration of sp2 bonded
carbon atoms [38]. The PPY peaks are covered by the strong G and D
bands of graphene conrming successful polymerization of PPY.
The enhancement observed in GNS/AgNPs/PPY is due to AgNPs
display electrocatalytic role.
The thermal behavior of the composites has been studied in the
temperature range 30e1000  C at scan rate of 10  C/min in N2 at-
mosphere. As shown in Fig. 2(b), all the TGA curves show an initial
weight loss bellow 150  C due to vaporization of water molecules
adsorbed on the surface of materials. From 200 to 560  C, a major
weight loss is observed due to thermal decomposition of PPY [39].
It is seen that at 600  C, PPY showed 94.18 wt% loss, while at the
same temperature only 38.76 wt% weight loss has occurred for PPY
in GNS/AgNPs/PPY. The reasons for such difference in weight loss
are due to graphene in the composite is thermally stable at high
temperature and difference in globular structure of pure poly-
pyrrole and polypyrrole in composites. This observation implies
that the thermal stability of composites is enhanced by incorpo-
rating PPY to GNS and AgNPs. The onset decomposition tempera-
ture of composites is shifted towards higher side than PPY due to
the retardation effect of GNS, AgNPs as barrier for decomposition of
PPY [40]. The composites were further studied by DTA to check the
decomposition patterns which were found to be in agreement with
the TG results, conrming the thermal stability of these composites.
3.2. SEM, EDX and TEM study
Surface morphological studies of the electrode materials were
investigated using SEM and TEM images. Fig. 3 compares
morphological features of PPY, AgNPs/PPY, GNS/PPY and GNS/
AgNPs/PPY. As clearly seen from Fig. 3(a) that polypyrrole shows
typical globular morphology and particles are highly porous, which
helps in mass transport of electrolytes during charging and dis-
charging processes of the supercapacitor. Fig. 3(b) is the SEM image
for GNS/PPY composite showing polypyrrole globules on graphene
sheets. Fig. 3(c) shows AgNPs on polypyrrole clusters. Fig. 3(d) is
SEM image for GNS/AgNPs/PPY composite which shows Ag parti-
cles as tiny bright spots over PPY granules and PPY are embedded in
graphene sheets. This structure is benecial for supercapacitor
because, it reduces the diffusion resistance of electrolyte into
electrode matrix. EDX results of GNS/AgNPs/PPY composite (Fig. 4)
shows various elemental peaks for C at 0.24 KeV, N at 0.35 KeV, O at
0.52 KeV, Cl at 2.61 KeV and Ag at 3.13 KeV conrming the pres-
GNS/AgNPs/PPY ence of all the components of composite. It is interesting to note the
presence of Cl ions in the synthesized composite which acts as
 P.K. Kalambate et al. / Journal of Power Sources 276 (2015) 262e270 265

Fig. 1. XRD pattern of PPY, GNS/PPY, AgNPs/PPY and GNS/AgNPs/PPY.

Fig. 2. (a) Raman spectra of PPY, GNS/PPY, AgNPs/PPY and GNS/AgNPs/PPY; (b) TGA curves of PPY, GNS/PPY, AgNPs/PPY and GNS/AgNPs/PPY.

dopants thereby increasing the conductivity of the synthesized
composite as reported by earlier workers [41].
TEM image of PPY is shown in Fig. 3(e) which shows cluster as
well as granular morphology of PPY. Fig. 3(f) depicts thin akes-like
shapes of graphene on which polypyrrole is absorbed through -
interaction. Fig. 3(g) is TEM image of AgNPs/PPY composite
showing AgNPs along with PPY and it was found that AgNPs were
spherical in shape. TEM image of GNS/AgNPs/PPY composite
(Fig. 3h) shows that the PPY clusters are embedded in GNS sheets
along with AgNPs.
3.3. Electrochemical characterization
Electrochemical study was carried out in three-electrode system
consisting of GNS/AgNPs/PPY composite electrode as working
electrode, Ag/AgCl (sat. KCl) and Pt. wire as reference and counter
electrodes respectively. Cyclic voltammetry (CV) and galvanostatic
266 P.K. Kalambate et al. / Journal of Power Sources 276 (2015) 262e270
Fig. 3. SEM images of: a) PPY; b) GNS/PPY; c) AgNPs/PPY; d) GNS/AgNPs/PPY; TEM of: e) PPY; f) GNS/PPY; g) AgNPs/PPY; h) GNS/AgNPs/PPY.
chargeedischarge (GCD) study was carried out using three elec-
trodes in 1 M KCl electrolyte. Fig. 5(A) displays the comparison of
GNS/AgNPs/PPY electrodes with varying concentrations of silver
nanoparticles. It is notable from the CV study that 100:20 com-
posite shows the highest capacitive property and hence, was used
for further study. The reason for this observation can be explained
on the basis of the role of different components in the composite.
The presence of graphene in the composite not only serves as
highly conductive material, but also provides high surface area for
polymerization of PPY. The conducting polymer, polypyrrole, is
mainly used due to its high conductivity and consequential redox
properties associated with the chain heteroatoms. On the other
hand, silver nanoparticles reduce the electrical resistance of the
polymer and increase electrical conductivity and electrochemical
storage capacity. It is observed from CV study that increasing the
amount of silver nanoparticles in the composite from 20 to 30
(Fig. 5A) has resulted in lowering the value of specic capacitance.
This may be due to the excess of silver nanoparticles present in the
composite which may not be required to decrease the electrical
resistance of PPY but in turn blocks the action of GNS. Therefore, the
composition of graphene and silver nanoparticles containing
100:20 ratio in the composite was found to have maximum syn-
ergistic effect resulting in the highest capacitive property.
Fig. 5(B) shows comparison of cyclic voltammograms of
different electrode materials within potential range of 0.7 to 0.6 V
at the scan rate of 10 mV s1. As can be clearly seen that GNS/PPY
shows almost a rectangular CV loop which is characteristics of an
EDLC. However, a redox couple is observed for GNS/AgNPs/PPY
electrode which is attributed to the presence of AgNPs. A dominant
anodic peak at 0.062 V and another cathodic peak at 0.173 V
versus Ag/AgCl is obtained for the redox reaction of Ag/Ag. It is
also observed that the area under the CV loop of GNS/AgNP/PPY
composite is larger than that of GNS/PPY, AgNPs/PPY and PPY,
indicating its higher capacitance. The higher capacitance value of
GNS/AgNPs/PPY is attributed to the highly conducing AgNPs in the
composite which reduces electrical resistance of the composite and
increases the charge storage capacity. The presence of GNS in the
composite not only serve as highly conductive material, but also
provide high surface area for polymerization of PPY. CV curves of
GNS/AgNPs/PPY at different potential scan rates ranging from 5, 10,
20, 50, 100, 200, 300, 400, 500 mV s1 are shown in Fig. 5(C). It is
observed that the material exhibits excellent electrochemical
behavior in a wide range of potential scan rate. It is seen that
oxidation peak shifts positively and reduction peak shifts nega-
tively with increasing potential scan rate due to increase in resis-
tance at higher scan rate. As scan rate increases the area under the
curve increases with increase in redox peak current. The retention
of the redox peak current of the GNS/AgNPs/PPY electrode even at
higher scan rates shows the good rate ability and capacitive
behavior of the composite.
The specic capacitance of the electrode material was calculated
using cyclic voltammetry by using following equation.
Z
Idv
Csp (1)
DV$s$m
 P.K. Kalambate et al. / Journal of Power Sources 276 (2015) 262e270 267

Fig. 4. EDX of GNS/AgNPs/PPY.

Fig. 5. (A) Cyclic voltammograms of GNS/AgNPs/PPY with varying concentration of AgNPs; (B) Cyclic voltammograms of as prepared electrodes in 1 M KCl at a scan rate of
10 mV s1; (C) Cyclic voltammograms obtained at GNS/AgNPs/PPY in 1 M KCl, employing varying scan rates: 5.0e500 mV s1; (D) Specic capacitance vs. Scan rate ranging from 5 to
500 mV s1 of GNS/AgNPs/PPY electrode.
268 P.K. Kalambate et al. / Journal of Power Sources 276 (2015) 262e270
where Csp is the specic capacitance, Idv is the integrated area
under the CV curve, m is the mass of active material deposited on
electrode surface (g), DV (V) is the difference in potential, and s is
the potential scan rate [42,43]. The specic capacitance obtained
for GNS/AgNPs/PPY is much higher than that of GNS/PPY, AgNPs/
PPY and PPY at same scan rate. The maximum specic capacitance
obtained for GNS/AgNPs/PPY is 442 F g1 which is higher than
278 F g1 for GNS/PPY, 235 F g1 for AgNPs/PPY and 154 F g1 for
PPY at the scan rate of 10 mV s1.The variation of specic capaci-
tance with potential scan rate is shown in Fig. 5(D). The specic
capacitance decreases as potential scan increases because at low
scan rate electrolyte ions are completely diffused into the inner
active sites of material which undergo the redox transitions
completely. However, at higher scan rate electrolyte ions cannot
diffuse completely into the inner active sites of material as a result
it cannot make full use of inner surface area. Hence, there is a
decrease in specic capacitance at high potential scan rate. The
cyclic stability of the electrode was tested by performing CV for
1000 cycles at scan rate of 100 mV s1 as shown in Fig. 6. It is
observed that there is no degradation in the current of the CV loop
when comparing the 1000th and the 1st cycle conrming high
stability of GNS/AgNPs/PPY electrode. At 620 and 830 cycles slight
increase in specic capacitance observed, is due to the increase of
electrolyte temperature after continuous operation over time.
Further electrochemical performance of the electrodes was
tested by using chargeedischarge study which illustrates EDLC,
pseudo capacitance, and internal resistance of the material. Gal-
vanostatic charge/discharge is a very important method to evaluate
the electrochemical capacitance of the material under controlled
current conditions. Fig. 7(a) demonstrates the charge/discharge
behavior of different electrodes at current density of 0.9 mA g1.The
galvanostatic chargeedischarge proles of GNS/AgNPs/PPY, GNS/
PPY, AgNPs/PPY, and PPY show almost symmetrical char-
geedischarge curves indicating good capacitive behavior. The
observed deviation in linearity is mainly due to the presence of
pseudocapacitive PPY. Further, the plateaus corresponding to this
redox couple Ag/Ag1 are almost suppressed due to the high non-
Faradiac current caused due to electrical double layer formation
at GNS and PPY surfaces. The chargeedischarge curve of PPY has
similar shape of the GNS/AgNPs/PPY composite. The IR drop of the
PPY is higher than the composite electrode, indicating internal
resistance of PPY is higher than composites. Low internal resistance
Fig. 6. Cyclic stability of GNS/AgNPs/PPY electrode at100 mV s1, Inset shows the
comparison of 1000th CV cycle with 1st CV cycle at 100 mV s1.
is favorable in energy storage devices so that less energy will be
wasted to produce unwanted heat during chargeedischarge pro-
cess [44]. The GNS and AgNPs are highly conductive and hence,
they have very low internal resistance. The chargeedischarge time
increases in the order: PPY < AgNPs/PPY < GNS/PPY < GNS/AgNPs/
PPY, implying high specic capacitance of GNS/AgNPs/PPY. The
galvanostatic-charge discharge curves of GNS/AgNPs/PPY in 1 M
KCl at different current densities viz; 0.9 mA g1, 1.2 mA g1,
1.5 mA g1, 2.0 mA g1, 2.5 mA g1and 3.0 mA g1 are shown in
Fig. 7(b). As can be seen, the curves are highly symmetrical and
linear, which shows an ideal capacitive behavior and excellent
electrochemical reversibility. A good linear relation of the char-
geedischarge potential with time was observed, conrming rapid
IeV response and low equivalent series resistance. The specic
capacitance of the electrode was calculated by using the following
equation [45]:
I dt
Csp  (2)
m dv
where Csp is the specic capacitance (F g1), I (A g1), is the con-
stant current density, dt is the discharging time (s), m is the mass of
active material deposited on electrode surface (g) and dv is the
voltage change in chargeedischarge process. The specic capaci-
tance obtained from chargeedischarge curves of GNS/AgNPs/PPY,
GNS/PPY, GNS/PPY, AgNPs/PPY and PPY is 450 F g1, 288 F g1,
216 F g1 and 153 F g1, respectively at a constant current density of
0.9 mA g1. The results obtained by GCD are comparable with those
obtained by CV at scan rate of 10 mV s1. The energy and power
density values have been calculated from the following equations
[46]:
1
E Csp Vi2 (3)
2
E
P (4)
Dt
where E is the specic energy density (Wh kg1), Csp specic
capacitance (F g1), Vi refers to the maximum voltage (V); P rep-
resents the power density (kW kg1), and Dt stands for discharge
time (s).
The calculated energy and power density values of GNS/AgNP/
PPY electrode are 81.0 Wh kg1 and 10.13 kW kg1 respectively at a
current density of 0.9 mA g1
Electrochemical impedance spectroscopy (EIS) was performed
to compare faradaic resistance and capacitive traits of the electrode
material. The EIS spectrum has two parts semicircular parts and
linear parts. The semicircle at higher frequency corresponds to the
charge transfer resistance (Rct) caused by the faradaic reaction and
double layer capacitance (Cdl) at the interface between electrode
and electrolyte solution. The EIS study has been done in the fre-
quency range of 0.1 Hze106 Hz at open circuit potential with
amplitude of 5 mV. The Nyquist plots for PPY, GNS/PPY, AgNPs/PPY
and GNS/AgNPs/PPY are shown in Fig. 7(c). It is seen from Nyquist
plot that the diameter of semicircle goes on decreasing from PPY to
GNS/AgNPs/PPY suggesting low charge transfer and electrolyte
resistance of the later. The Rct values obtained for PPY, AgNPs/PPY,
GNS/PPY and GNS/AgNPs/PPY composites based electrodes are 0.9,
0.73, 0.68 and 0.32 K U, respectively. The Nyquist plot is a vertical
line for an ideal electrode material. The Nyquist plot vertical line for
GNS/AgNPs/PPY is almost parallel to imaginary axis compared to
PPY, GNS/PPY and AgNPs/PPY suggesting a good capacitive
behavior of composite electrode [10].
 P.K. Kalambate et al. / Journal of Power Sources 276 (2015) 262e270 269

Fig. 7. (a) Galvanostatic chargeedischarge curves of the GNS/AgNPs/PPY, GNS/PPY, AgNPs/PPY and PPY electrodes at 0.9 mA g1 current density; (b) Galvanostatic chargeedischarge
curves of GNS/AgNPs/PPY electrode at different current densities in 1 M KCl; (c) Electrochemical impedance spectra of the GNS/AgNPs/PPY, GNS/PPY, AgNPs/PPY and PPY; (d)
specic capacitance of the as prepared GNS/AgNPs/PPY, GNS/PPY, AgNPs/PPY and PPY electrodes at different current densities.

Fig. 7(d) presents relationship between the specic capacitance
and chargeedischarge density. It is observed that there is a
decrease in specic capacitance as the current density increases.
GNS/AgNPs/PPY not only exhibits higher specic capacitance but
also retains better rate capacity with specic capacitance retention
of 78.0% (0.9e3.0 mA g1), superior to PPY (62.9% from 0.9 to
3.0 mA g1). The cyclic stability of the GNS/AgNPs/PPY, GNS/PPY,
AgNPs/PPY, and PPY was studied by repeating constant current
chargeedischarge test for 1000 cycles in 1 M KCl electrolyte at a
current density of 0.9 mA g1 as shown in Fig. 8(a). The specic
capacitance of GNS/AgNPs/PPY is 450 F g1 at rst cycle and de-
creases to 414 F g1 after 1000 cycles, with retention of 92.0%
specic capacitance. Whereas, the specic capacitance of GNS/PPY,
AgNPs/PPY, and PPY in the rst cycle were 288 F g1 (85.41%
retention after 1000 cycles), 216 F g1 (81.10% retention after 1000
cycles, 153 F g1 (69.28% retention after 1000 cycles respectively. It
is found that, after 1000 cycles, GNS/AgNPs/PPY based super-
capacitor retains 92.0% of its initial capacitance, which demonstrate

Fig. 8. (a) Capacitance cycling performance of the as-prepared GNS/AgNPs/PPY, GNS/PPY, AgNPs/PPY and PPY electrodes at a current density of 0.9 mA g1; (b) First ve char-
geedischarge cycles for GNS/AgNPs/PPY electrode.
270 P.K. Kalambate et al. / Journal of Power Sources 276 (2015) 262e270
good electrochemical stability of electrode during cyclic test.
Fig. 8(b) shows rst ve chargeedischarge curves of GNS/AgNPs/
PPY composite at a current density of 0.9 mA g1. The decrease in
specic capacitance of the composite electrode is due to insertion
and de-insertion of ions in the matrix of conducting polymer which
involves volumetric changes causing cyclic degradation during
cyclic test [47]. However in case of GNS and AgNP the volumetric
changes are greatly reduced because nanoparticles allows effective
charge transport and reduces the charge trapping inside the elec-
trode material at great extent. Generally for a nanocomposite based
supercapacitor, a 10% decrease in specic capacitance is considered
to have a good stability [48].
4. Conclusions
GNS/AgNPs/PPY nanocomposites have been synthesized by in
situ polymerization method. The insertion of GNS in the composite
provides a large surface area for dispersing PPY and Ag reduces the
electrical resistance of the polymer and increase electrical con-
ductivity, and electrochemical storage capacity. Controlling the
ratio of AgNPs to GNS is very important to obtain good electro-
chemical performance. SEM analysis reveals that PPY nanoparticles
are uniformly coated on graphene sheets along with silver nano-
particles. XRD analysis shows that PPY is amorphous in nature and
have average particles size of 13 nm. TGA analysis conrmed
composite material has better thermal stability than PPY alone. The
maximum specic capacitance obtained is 442 F g1 at a current
density of 0.9 mA g1 in 1 M KCl electrolyte. The composite elec-
trode showed very good stability even after 1000 chargeedischarge
cycles. After 1000 chargeedischarge cycling test, electrode main-
tains 92.0% of its initial specic capacitance value. The enhanced
specic capacitance of the material is due to the synergistic effect of
three components viz; GNS, AgNPs and PPY. These results suggest
that GNS/AgNPs/PPY composite electrode is quite suitable and a
promising electrode material for high performance supercapacitor.
Acknowledgment
This research was funded by the US Army International Tech-
nology Center, Pacic Asia Countries, Tokyo, Japan through contract
number FA2386-12-1-4086.
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