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Journal of Power Sources 276 (2015) 262e270

Contents lists available at ScienceDirect

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 263

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

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-
Scheme 1. Illustration of the preparation procedure for GNS/AgNPs/PPY ence of all the components of composite. It is interesting to note the
nanocomposites. 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 (Fig. 3h) shows that the PPY clusters are embedded in GNS sheets
composite as reported by earlier workers [41]. along with AgNPs.
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 3.3. Electrochemical characterization
shapes of graphene on which polypyrrole is absorbed through -
interaction. Fig. 3(g) is TEM image of AgNPs/PPY composite Electrochemical study was carried out in three-electrode system
showing AgNPs along with PPY and it was found that AgNPs were consisting of GNS/AgNPs/PPY composite electrode as working
spherical in shape. TEM image of GNS/AgNPs/PPY composite 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- anodic peak at 0.062 V and another cathodic peak at 0.173 V
trodes in 1 M KCl electrolyte. Fig. 5(A) displays the comparison of versus Ag/AgCl is obtained for the redox reaction of Ag/Ag. It is
GNS/AgNPs/PPY electrodes with varying concentrations of silver also observed that the area under the CV loop of GNS/AgNP/PPY
nanoparticles. It is notable from the CV study that 100:20 com- composite is larger than that of GNS/PPY, AgNPs/PPY and PPY,
posite shows the highest capacitive property and hence, was used indicating its higher capacitance. The higher capacitance value of
for further study. The reason for this observation can be explained GNS/AgNPs/PPY is attributed to the highly conducing AgNPs in the
on the basis of the role of different components in the composite. composite which reduces electrical resistance of the composite and
The presence of graphene in the composite not only serves as increases the charge storage capacity. The presence of GNS in the
highly conductive material, but also provides high surface area for composite not only serve as highly conductive material, but also
polymerization of PPY. The conducting polymer, polypyrrole, is provide high surface area for polymerization of PPY. CV curves of
mainly used due to its high conductivity and consequential redox GNS/AgNPs/PPY at different potential scan rates ranging from 5, 10,
properties associated with the chain heteroatoms. On the other 20, 50, 100, 200, 300, 400, 500 mV s1 are shown in Fig. 5(C). It is
hand, silver nanoparticles reduce the electrical resistance of the observed that the material exhibits excellent electrochemical
polymer and increase electrical conductivity and electrochemical behavior in a wide range of potential scan rate. It is seen that
storage capacity. It is observed from CV study that increasing the oxidation peak shifts positively and reduction peak shifts nega-
amount of silver nanoparticles in the composite from 20 to 30 tively with increasing potential scan rate due to increase in resis-
(Fig. 5A) has resulted in lowering the value of specic capacitance. tance at higher scan rate. As scan rate increases the area under the
This may be due to the excess of silver nanoparticles present in the curve increases with increase in redox peak current. The retention
composite which may not be required to decrease the electrical of the redox peak current of the GNS/AgNPs/PPY electrode even at
resistance of PPY but in turn blocks the action of GNS. Therefore, the higher scan rates shows the good rate ability and capacitive
composition of graphene and silver nanoparticles containing behavior of the composite.
100:20 ratio in the composite was found to have maximum syn- The specic capacitance of the electrode material was calculated
ergistic effect resulting in the highest capacitive property. using cyclic voltammetry by using following equation.
Fig. 5(B) shows comparison of cyclic voltammograms of
different electrode materials within potential range of 0.7 to 0.6 V Z
at the scan rate of 10 mV s1. As can be clearly seen that GNS/PPY Idv
shows almost a rectangular CV loop which is characteristics of an Csp (1)
EDLC. However, a redox couple is observed for GNS/AgNPs/PPY DV$s$m
electrode which is attributed to the presence of AgNPs. A dominant
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 is favorable in energy storage devices so that less energy will be
under the CV curve, m is the mass of active material deposited on wasted to produce unwanted heat during chargeedischarge pro-
electrode surface (g), DV (V) is the difference in potential, and s is cess [44]. The GNS and AgNPs are highly conductive and hence,
the potential scan rate [42,43]. The specic capacitance obtained they have very low internal resistance. The chargeedischarge time
for GNS/AgNPs/PPY is much higher than that of GNS/PPY, AgNPs/ increases in the order: PPY < AgNPs/PPY < GNS/PPY < GNS/AgNPs/
PPY and PPY at same scan rate. The maximum specic capacitance PPY, implying high specic capacitance of GNS/AgNPs/PPY. The
obtained for GNS/AgNPs/PPY is 442 F g1 which is higher than galvanostatic-charge discharge curves of GNS/AgNPs/PPY in 1 M
278 F g1 for GNS/PPY, 235 F g1 for AgNPs/PPY and 154 F g1 for KCl at different current densities viz; 0.9 mA g1, 1.2 mA g1,
PPY at the scan rate of 10 mV s1.The variation of specic capaci- 1.5 mA g1, 2.0 mA g1, 2.5 mA g1and 3.0 mA g1 are shown in
tance with potential scan rate is shown in Fig. 5(D). The specic Fig. 7(b). As can be seen, the curves are highly symmetrical and
capacitance decreases as potential scan increases because at low linear, which shows an ideal capacitive behavior and excellent
scan rate electrolyte ions are completely diffused into the inner electrochemical reversibility. A good linear relation of the char-
active sites of material which undergo the redox transitions geedischarge potential with time was observed, conrming rapid
completely. However, at higher scan rate electrolyte ions cannot IeV response and low equivalent series resistance. The specic
diffuse completely into the inner active sites of material as a result capacitance of the electrode was calculated by using the following
it cannot make full use of inner surface area. Hence, there is a equation [45]:
decrease in specic capacitance at high potential scan rate. The
cyclic stability of the electrode was tested by performing CV for I dt
1000 cycles at scan rate of 100 mV s1 as shown in Fig. 6. It is Csp  (2)
m dv
observed that there is no degradation in the current of the CV loop
when comparing the 1000th and the 1st cycle conrming high where Csp is the specic capacitance (F g1), I (A g1), is the con-
stability of GNS/AgNPs/PPY electrode. At 620 and 830 cycles slight stant current density, dt is the discharging time (s), m is the mass of
increase in specic capacitance observed, is due to the increase of active material deposited on electrode surface (g) and dv is the
electrolyte temperature after continuous operation over time. voltage change in chargeedischarge process. The specic capaci-
Further electrochemical performance of the electrodes was tance obtained from chargeedischarge curves of GNS/AgNPs/PPY,
tested by using chargeedischarge study which illustrates EDLC, GNS/PPY, GNS/PPY, AgNPs/PPY and PPY is 450 F g1, 288 F g1,
pseudo capacitance, and internal resistance of the material. Gal- 216 F g1 and 153 F g1, respectively at a constant current density of
vanostatic charge/discharge is a very important method to evaluate 0.9 mA g1. The results obtained by GCD are comparable with those
the electrochemical capacitance of the material under controlled obtained by CV at scan rate of 10 mV s1. The energy and power
current conditions. Fig. 7(a) demonstrates the charge/discharge density values have been calculated from the following equations
behavior of different electrodes at current density of 0.9 mA g1.The [46]:
galvanostatic chargeedischarge proles of GNS/AgNPs/PPY, GNS/
PPY, AgNPs/PPY, and PPY show almost symmetrical char-
1
geedischarge curves indicating good capacitive behavior. The E Csp Vi2 (3)
observed deviation in linearity is mainly due to the presence of 2
pseudocapacitive PPY. Further, the plateaus corresponding to this
redox couple Ag/Ag1 are almost suppressed due to the high non- E
Faradiac current caused due to electrical double layer formation P (4)
Dt
at GNS and PPY surfaces. The chargeedischarge curve of PPY has
similar shape of the GNS/AgNPs/PPY composite. The IR drop of the where E is the specic energy density (Wh kg1), Csp specic
PPY is higher than the composite electrode, indicating internal capacitance (F g1), Vi refers to the maximum voltage (V); P rep-
resistance of PPY is higher than composites. Low internal resistance 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
Fig. 6. Cyclic stability of GNS/AgNPs/PPY electrode at100 mV s1, Inset shows the PPY, GNS/PPY and AgNPs/PPY suggesting a good capacitive
comparison of 1000th CV cycle with 1st CV cycle at 100 mV s1. 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 current density of 0.9 mA g1 as shown in Fig. 8(a). The specic
and chargeedischarge density. It is observed that there is a capacitance of GNS/AgNPs/PPY is 450 F g1 at rst cycle and de-
decrease in specic capacitance as the current density increases. creases to 414 F g1 after 1000 cycles, with retention of 92.0%
GNS/AgNPs/PPY not only exhibits higher specic capacitance but specic capacitance. Whereas, the specic capacitance of GNS/PPY,
also retains better rate capacity with specic capacitance retention AgNPs/PPY, and PPY in the rst cycle were 288 F g1 (85.41%
of 78.0% (0.9e3.0 mA g1), superior to PPY (62.9% from 0.9 to retention after 1000 cycles), 216 F g1 (81.10% retention after 1000
3.0 mA g1). The cyclic stability of the GNS/AgNPs/PPY, GNS/PPY, cycles, 153 F g1 (69.28% retention after 1000 cycles respectively. It
AgNPs/PPY, and PPY was studied by repeating constant current is found that, after 1000 cycles, GNS/AgNPs/PPY based super-
chargeedischarge test for 1000 cycles in 1 M KCl electrolyte at a 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

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