Accepted Manuscript

Title: Synthesis of Tin Oxide/Graphene (SnO2 /G)

nanocomposite and its Electrochemical Properties for
supercapacitor applications

Author: V. Velmurugan U. Srinivasarao R. Ramachandran M.

Saranya C. Santhosh Andrews Nirmala Grace

PII: S0025-5408(16)30318-X
DOI: http://dx.doi.org/doi:10.1016/j.materresbull.2016.07.015
Reference: MRB 8859

To appear in: MRB

Received date: 7-1-2016

Revised date: 9-7-2016
Accepted date: 13-7-2016

Please cite this article as: V.Velmurugan, U.Srinivasarao, R.Ramachandran, M.Saranya,

C.Santhosh, Andrews Nirmala Grace, Synthesis of Tin Oxide/Graphene (SnO2/G)
nanocomposite and its Electrochemical Properties for supercapacitor applications,
Materials Research Bulletin http://dx.doi.org/10.1016/j.materresbull.2016.07.015

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 Synthesis of Tin Oxide/Graphene (SnO2/G) nanocomposite and its

Electrochemical Properties for supercapacitor applications

V. Velmurugana,*, U. Srinivasaraoa , R. Ramachandrana, M. Saranyaa,

C.Santhosha and Andrews Nirmala Gracea

a
Centre for Nanotechnology Research, VIT University, Vellore-632014,TN, India

* To whom correspondence should be addressed:

E-mail: [email protected], [email protected]

Tel.: (+91) 416 2202412

1
Graphical Abstract

Cyclic voltammetry and TEM images of (a,c) SnO2 nanoparticles (b,d) SnO2/G-a
nanocomposites

2
Highlights
 SnO2/G nanocomposites were prepared through simple wet chemical route

 Electrochemical measurements were carried out in 6M KOH electrolyte.

 Cyclic voltammetry showed the excellent capacitive behavior of the composites.

 A specific capacitance of 818.6 F/g was observed for SnO2/G-a nanocomposites.

3
Abstract

Tin oxide/Graphene (SnO2/G) nanocomposites were prepared by a simple wet

chemical route and the as prepared nanocomposites were characterized by X-ray diffraction

(XRD), High Resolution Transmission Electron Microscopy (HRTEM) and Fourier transform

infrared spectra (FTIR). The characterized results showed the tetragonal structure of SnO2

nanostructures on uniform distribution on graphene sheets with a particle size of ~ 50 nm.

The reduction of graphene oxide to graphene during SnO2/G synthesis was confirmed from

FTIR analysis. HRTEM analysis showed that the individual SnO2 nanoparticles deposited on

graphene sheets. The electrochemical performances of SnO2/G nanocomposites towards

supercapacitors were studied in 6M KOH electrolyte. A maximum specific capacitance of

818.6 F/g was obtained for SnO2/G-a composite at 1 mV/s scan rate suggesting that the

presence of graphene matrix in SnO2 nanoparticles have enhanced the electrochemical

behaviour of SnO2. The galvanostatic charge/discharge studies confirmed the good cyclic

stability of the composite electrode. These excellent electrochemical properties suggested that

the SnO2/G nanocomposites could be used for high energy density supercapacitor electrode

materials.

Keywords: Supercapacitors; Nanocomposites; specific capacitance; SnO2, graphene, Energy

storage.

4
1. Introduction

In response to the global warming issue, energy storage has become a huge challenge to the

global power systems. Recently, a lot of efforts have been undertaken to develop new energy

storage devices like supercapacitors, which can provide high energy density than

conventional capacitors and high power density than batteries [1]. There are two energy

storage mechanisms for supercapacitors: (i). Electric double layer capacitors, wherein energy

storage arises mainly from the separation of ionic charges at the interfaces between electrodes

and electrolyte solution [2]. (ii). Pseudocapacitors uses transition metal oxides and

conducting polymers, which undergoes reversible faradic reactions [3]. As well known,

ruthenium oxide (RuO2) exhibits a high pseudocapacitance, but its high cost and

environmental harmfulness leads to the limit of its practical applications in supercapacitors

[4]. Hence the development of new materials at low cost for supercapacitors is still a

challenge and needs to be addressed. In recent days, considerable efforts have been devoted

by researchers to develop alternative electrode materials like MnO2 [5], NiO [6], Co3O4 [7]

and SnO2 [8], etc..

Among the various metal oxide nanomaterials, SnO2 based nanomaterials have

attracted a considerable attention as a promising electrode material for supercapacitors due to

its low cost and high power density. SnO2 has potential applications in various fields like

sensors [9] and solar cells [10]. Especially, SnO2 appears to be a promising electrode material

for energy storage devices like lithium ion batteries and supercapacitors due to its superior

electrochemical performance [11]. Though SnO2 gives better response towards specific

capacitance of supercapacitors, it is still limited to practicality due to the poor transportation

of the electrolyte ions within the SnO2 matrix and its poor electrical conductivity. Various

reports have demonstrated that the carbon based materials like carbon nanotube and graphene

5
enhance the electronic conductivity of metal oxides. In recent years, one atom-thick layered

crystalline with honeycomb structure of sp2-bonded carbon called graphene is a good

candidate for supercapacitor electrode material due to its superior electrical conductivity (~

106 S cm-2) [12], high surface area (2,630 m2 g-1) [13] and high thermal conductivity (5,000

Wm-1K-1) [14]. In addition, it can minimize the contact resistance between the electrode and

current collector, unlike the case of carbon nanotube [15]. Graphene is an ideal carbon

electrode material for electric double layer supercapacitors because it is capable of storing an

EDL capacitance value of up to 550 F/g, provided the entire surface area viz. 2630 m2/g is

fully utilized. Another advantage of graphene in a supercapacitor electrode is the notion that

both major surfaces of graphene sheets on exterior surfaces are readily accessible by

electrolyte. Many SnO2/graphene hybrids with various structures have been reported for

supercapacitor applications. Li et al., prepared SnO2/graphene using a one-pot synthesis

approach, which showed a specific capacitance of 34.6 F/g [16]. Wang and group worked

reported on the microwave assisted one-pot synthesis of SnO2/graphene, which gave rise to

the specific capacitance of 99.7 F/g [17]. Lim et al., reported solvothermal synthesis of

SnO2/graphene nanocomposites and achieved a maximum specific capacitance of 363.3 F/g

[8]. In view of these findings, more investigations need to be done to improve the specific

capacitance of the nanocomposites to meet the criteria for excellent supercapacitors.

In this report, a simple wet chemical route has been adopted for the synthesis of

SnO2/graphene nanocomposites and further extended to study its electrochemical behaviour

towards supercapacitor applications. During the preparation of graphene, the surface charge

of graphene oxide is highly negative when dispersed in ethylene glycol. After adding

SnCl2.2H2O into GO stable solution, positive charge of Sn2+ ions were anchored onto the

surface of GO sheets via electrostatic interaction especially along the edges of the nanosheets.

The GO sheets acted as an oxidizing agent, oxidizing Sn2+ to SnO2 on the surface of GO

6
sheets, while GO got simultaneously reduced to graphene by ethylene glycol. Afterwards,

high purity of SnO2 nanoparticles were obtained at 500oC under Ar atmosphere. The superior

electrochemical performance of SnO2/G composites could be ascribed to the synergistic

effect of graphene matric and SnO2 nanoparticles.

2. Experimental Methods

2.1. Materials

AR grade of Tin (II) chloride dehydrate (SnCl2.2H2O ), sodium nitrate (NaNO3), potassium

permanganate (KMnO4), sulphuric acid (H2SO4,99%), sodium borohydride (NaBH4),

hydrogen peroxide (H2O2, 30%), sodium hydroxide (NaOH), potassium hydroxide (KOH)

were purchased from Sigma-Aldrich. All the solutions were prepared by using Milli-Q water

(pH 7.2).

2.2. Preparation of SnO2/graphene (SnO2/G) nanocomposites:

Graphene oxide was synthesised using modified Hummer’s method according to our

previous report [19]. Briefly, 160 mg of GO was dispersed in 80 ml of ethylene glycol and

sonicated for 1 hr to form a stable GO solution. Then 80 ml of SnCl2 .2H2O (5 mM) aqueous

solution was added to GO suspension. Afterwards, the mixed solution was transferred into a

round bottom flask and refluxed at 190oC for 6 hrs. The resultant black colour product was

washed and centrifuged with de-ionized water and ethanol. Final product was dried at 60oC

for 12 hrs. The sample was named as SnO2/G-a. Similarly, other nanocomposites viz.

SnO2/G-b and SnO2/G-c were synthesized by a similar method, wherein b and c represents

different GO concentrations of 320 mg and 480 mg respectively so as to have a higher ration

of graphene concentration in the matrix.

2.3. Materials characterization:

X-ray diffraction system (BRUKER, D8 Advance, Germany) was used for the X-ray analysis

with Cu-Ka radiation (λ= 1.540 °A). Step scanning was done with 2 θ intervals from 10o to

7
65o. Fourier transform infrared spectra were recorded using Spectrum one: FTIR-

spectrometer in the range 450–4500 cm-1 to characterize the functional groups of the

composites. Transmission electron microscopy (TEM) images were captured with a

microscope (JEOL, 3010) at an acceleration voltage of 200 kV.

2.4. Electrochemical measurements:

All the electrochemical measurements were carried out in an electrochemical analyzer (CHI

600C work station, version 5.01) using a three electrode system in 6 M KOH as electrolyte

solution under ambient conditions. The potentials and current were measured with respect to

Ag/AgCl (sat.KCl) as the reference. Carbon paper (Purchased from Cabot, USA) and Pt wire

were used as the working and counter electrode respectively. The cyclic voltammetry

measurements were performed at various scan rates in the potential range from -0.4 to 1.0 V.

The working electrode was prepared as follows: In brief, a known amount of active material

was dispersed in 5 wt% of nafion and the mixture was coated on a carbon paper (3 cm x 1cm

x 0.1 cm). The total surface area of the active material coated was 0.5 cm2. The mass of the

active material on electrode was 2 mg/ cm2. Then, the electrode was dried for 3 h at room

temperature.

3. Results and Discussion

XRD pattern of graphene oxide, pure SnO2 and SnO2/G-a are shown in Fig.1. A sharp

diffraction peak at 2θ=10.6o in graphene oxide (inset picture) could be seen corresponding to

the interlayer distance of 8.1 Å. This expanded interlayer distance in comparison with that of

graphite (3.6 Å) indicating the presence of oxygen, carboxyl functional groups on GO sheets

during Hummer’s process [18]. The diffraction peaks of SnO2 nanoparticles at 26.5, 34.4,

52.1 and 64.1o are clearly distinguishable and could be indexed to (110), (101), (211) and

(301) planes of tetragonal structure (JCPDS 41-1445) [19]. Interestingly, no diffraction peaks

due to graphene could be observed in SnO2/G composite, which might be due to the

8
exfoliation of GO sheets at 190oC. During exfoliation, the regular stacks are destroyed and

thus disappearance or weak diffraction peaks could be observed in graphene [20]. In addition,

the attached SnO2 nanoparticles on graphene sheets prevent the aggregation and restacking of

graphene and due to the SnO2 nanoparticles in the composite, the diffraction of carbon atoms

in graphene is weakened. Thus, the SnO2 nanoparticles covering the graphene sheets gave a

strong diffraction of SnO2 only in the composite and the graphene peak at 26o was masked.

Reduction degree of GO in SnO2/G composite was determined by FTIR technique. The FTIR

spectrum of GO and SnO2/G-a composite is shown in Fig 2. In the GO sample, the

transmittance bands centered at 1093, 1400 and 1622 cm-1 correspond to the stretching

vibrations of C-O (C-O-C in epoxide), O-H stretching vibration (carboxyl) and C=O

stretching vibration (carboxyl or carbonyl) respectively [20, 21]. One characteristic peak was

observed at 3419 cm-1, which is attributed to the adsorbed bound water or hydroxyl groups

linked to the basic sites of the sample [22]. As revealed by the FTIR spectrum of SnO2/G-a

composite, most of C=O and C-O bands from oxygen functionalities of GO has disappeared,

demonstrating the conversion of GO into graphene during composite preparation [23].

The morphology of pure SnO2 and SnO2/G-a nanocomposite were further studied by

TEM observation. It can be seen from Fig 3(a&b) that the SnO2 nanoparticles with size of

less than 20 nm were aggregated due to Van der Waals force of attraction of the particles

[24]. As evidenced from Fig.3c&d, the SnO2 nanoparticles are well deposited on the surface

of wrinkled graphene nanosheets and this thin graphene layers can effectively improve the

electrical conductivity of the composite. Moreover, the individual SnO2 nanoparticles on

graphene sheets can facilitate the diffusion of the electrolyte from electrode. Restacking of

graphene layer makes the resulting material less porous and electrolyte infiltration more

difficult when the structures were used as electrochemical electrodes. The restacking of

graphene layers in composites could be inhibited by the attachment of SnO2 nanoparticles

9
[25]. Thus, the intercalation of SnO2 nanoparticles should facilitate the diffusion of

electrolyte ions into electrodes and hence improves the cyclic stability of the material, which

has been confirmed from electrochemical measurements.

Electrochemical performance of the prepared SnO2/G nanocomposites for

supercapacitors was estimated by cyclic voltammetry, galvanostatic charge/discharge and

electrochemical impedance measurements in 6M KOH electrolyte. Cyclic voltammetry

behaviour of pure SnO2 and SnO2/G composites are shown in Fig 4. As the evidence of the

figure, CV curves of all the electrodes are symmetrical in nature, characteristic of ideal

capacitive behaviour with quasi rectangular shape indicating the excellent capacitive

behaviour and a low contact resistance in the supercapacitor electrodes [26]. There are no

huge redox peaks at different scan rates in the potential range of -0.4 to 1 V, suggesting that

the electrodes were charged and discharged at pseudoconstant rate over the complete

voltammetric cycle [27,28]. From a close observation of CV curves of the composite

electrodes, more rectangular behaviour and relative increment of current level than pure SnO2

could be seen, which clearly evidenced that the overall specific capacitance of SnO2/G

composite electrodes are due to the combined contribution from EDLC and

pseudocapacitance behaviour of the composite, whereas the capacitance of pure SnO2

electrodes is from pseudocapacitance only. The faradic reactions of SnO2 nanoparticles, is

related to the following reversible process.

SnO2 + H 2 O + e -  SnOOH+ OH-

SnOOH+ e -  SnO + OH-

CV measurements were conducted at various scan rates and the relative current response in

curves with scan rates observed, which indicates the ideal capacitive behaviour. Further to

quantitatively find the charge storage capacity, the specific capacitance of the composites was

was determined by the expression Voltammetric charge/(potential window × composite

10
loading). As it was not a perfect mirror symmetry graph, the integral area of CV curve/ scan

rate method was used for the calculation of specific capacitance. The specific capacitance of

the composite is calculated from the following equation (1) [29, 30].

1

VA
C I (V ) dV (1)
m v (VC  VA ) VC

where, V2-V1 the potential window width, I+ is maximum current in the positive scan (A), I- is

maximum current in the negative scan (A), m is the mass of the active material (g) and υ is


VA
the scan rate (V/s), Vc and VA are the cutoff potentials in cyclic voltammetry. I (V ) dV is
VC

the total voltammetric charge obtained by integration of positive and negative sweep in cyclic

voltammograms. A plot of specific capacitance vs scan rates is given in Fig 5. As evidenced

from the figure, a maximum specific capacitance of 818.6 F/g was obtained for SnO2/G-a

composite at 1 mV/s scan rate, whereas at the same scan rate, pure SnO2 gave a maximum

specific capacitance of 470 F/g, which is lower than that of the composite electrodes. It is

believed that such a large capacitance difference is caused by the introduction of graphene

into SnO2 material. From the figure, it is evident that the specific capacitance decreased at

higher scan rates, which could be due to the approach of positive ions (K+) only at the outer

surface of the electrode, whereas at lower scan rates, positive ions could easily diffuse into all

the available spaces of electrodes and thus leading to sufficient insertion reaction to get a

high specific capacitance [31-36]. The capacitance retention property of pure SnO2 and

SnO2/G-a electrodes were investigated by repeating the CV measurement at 100 mV/s for

1000 cycles. As shown in Fig 6, 95.1% of capacitance retention was observed for SnO2/G-a

composite electrode even after 1000 cycles, whereas pure SnO2 electrode exhibited 92.1%

capacitance retention, indicating the high electrochemical cyclic stability of SnO2/G-a

composite electrodes. A comparison was made with the current material and those reported

11
(Table 1) and as seen from the table, SnO2/G-a reported in this paper has good activity and

could be used for supercapacitor applications.

Fig. 7 shows the typical charge/discharge curves of the electrodes at constant current

density. For SnO2/G composites, the charge/discharge curves were asymmetric and

charge/discharge duration was long, which showed typical pseudocapacitive performance

[37]. Therefore, it could be deduced that the specific capacitance of the SnO2/G composites

resulted from the faradic charge-transfer reaction of the composite materials. A sudden drop

in current at start of the discharge is due to the internal resistance of the electrode called “IR

drop”. The IR drop of the SnO2/G composite electrodes were much lower than that of pure

SnO2 electrode as clearly seen in the figure, which indicated the presence of

pseudocapacitance behaviour along with double layer capacitance [38]. To further confirm

the capacitance, the same was calculated from charge discharge curves by using the formula

as below:

it
C
m V (2)

where i is the charge-discharge current, ∆t is the discharge time, ∆V is the electrochemical

potential window and m is the mass of the active material. The specific capacitance as

calculated from eq.(2) was around 797 F/g for SnO2/G-a composites, which was almost

comparable with the CV results. The Coulombic efficiency of the electrode was calculated

according to the formula (3) [39],

td
 100 (3)
tc

Where, td is discharge duration and tc is charging duration. As seen in Fig. 8, the coulombic

efficiency of the electrodes gradually increased from 1st cycle to 1000th cycle. Notably, the

coulombic efficiency of SnO2/G-a composite electrode exhibited ~97.8% at 1000th cycle,

which is higher than the pure SnO2 suggesting the charge/discharge process of composite

12
electrode was highly reversible. The efficiency increases with cycle numbers, which indicates

the stability of the electrodes. As cycle increases coulombic efficiency increases, which

means that over cycles of usage, the discharge time over charging time is more. The reason

might be that the structure of the composite provides a relatively easy path for

electrode/electrolyte interface reactions and thus makes more redox Faradic reactions to

occur [40].

Electrochemical Impedance Spectroscopy (EIS) measurements were performed to

compare the internal resistance of the electrode material and the resistance between the

electrode and the electrolyte for pure SnO2 and SnO2/G nanocomposite. The impedance

behavior is generally dominated by three major process occurring in the high, medium and

low frequency region, respectively. A semicircle reflects the electrochemical reaction

impedance of the electrode and a smaller semicircle corresponds to a smaller charge transfer

resistance. The total impedance of a supercapacitor consists of electronic and ionic

interactions. The former is attributed to the intrinsic electronic resistance of the material and

the interfacial resistances between particles and the current collector. The latter is associated

with the electrolyte resistances in the pores and the ionic (diffusion) resistance of ions

moving in small pores. The Nyquist plots of the nanocomposites consist of a semicircle in the

high frequency range and a linear slope in the low frequency region. The semicircle is due to

the charge transfer process and the inclined line is attributed to the anomalous diffusion

region of species to the modified electrode. It is well known that a large semicircle indicates a

high interfacial charge transfer resistance, which probably results from the poor electrical

conductivity of the active materials, whereas a more vertical line at low frequencies indicates

that the electrode is closer to an ideal capacitor. From Fig 9, the depressed arc at high

frequency is attributed to the process occurring at the electrode/electrolyte interfaces. The

straight vertical 45o line shows the pure capacitive behavior of both electrodes [41]. The

13
intersection of curve at real axis in high frequency region gives the solution resistance (Rs)

which reflects the ionic conductivity of electrolyte system [25]. A semicircle region could not

be observed at high frequency in the electrodes, probably due to the low faradic charge-

transfer resistances [42]. As can be seen in the figure, the diameter of the semicircle for the

SnO2/G nanocomposite is much smaller than that for SnO2 in the high frequency region

because there is less charge transfer resistance in the composite, that is, the composite has a

higher conductivity than SnO2. The Inset in the figure shows the high frequency region of the

impedance plot and the fitting circuit for SnO2/G. In the fitting circuits, Rs and Rct are the

solution and charge transfer resistances respectively. Cdl is the double layer capacitance, Cp is

the pseudocapacitance, and M is the anomalous diffusion element. At high frequencies, the

intercept between the impedance plot and the real impedance (Z’) axis gives the solution

resistance (R) of the cell and the diameter of the semicircle gives the charge transfer

resistance (R) of the interface between the electrode and electrolyte. To calculate the absolute

values, the Nyquist plots were further investigated by using circuit fitting and it was found

that the Rct values of the SnO2/G composites are less than that of SnO2 alone. The Rs values

of SnO2/G and SnO2 are 22.5 and 27.9 Ω respectively. In general, solution resistance arises

due to the combination of many factors such as the ionic and electronic resistances, the

intrinsic resistance of the modified electrodes, and the diffusive and contact resistances at the

composite modified electrodes. Also, the Rct values of SnO2/G are smaller than SnO2 alone,

indicating that the electrochemical reaction on the electrode/electrolyte interface is more

facile for the former electrode. The EIS results suggest that the better capacitive behavior of

composite than pure SnO2.

4. Conclusion

SnO2/Graphene nanocomposites were synthesized successfully via a simple wet

chemical process. XRD analysis showed the reduction of GO into graphene and tetragonal

14
structure of SnO2 in the composite. Most of C=O and C-O bands from oxygen functionalities

of GO has disappeared in SnO2/G nanocomposite, which is confirmed from FTIR

measurement. HRTEM analysis showed the uniform distribution of SnO2 nanoparticles on

the wrinkled graphene nanosheets. The specific capacitive properties of composites were

analyzed through electrochemical measurements and the results showed that the presence of

graphene in SnO2 enhanced the electrochemical properties. A maximum specific capacitance

of 818.6 F/g was observed for SnO2/G-a nanocomposite with 95.1% of capacitance retention

for SnO2/G-a composite electrode even after 1000 cycles, which suggests that the prepared

SnO2/G nano composite could be used for high performance supercapacitor applications.

15
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20
Figure captions

Fig. 1 XRD pattern of (a) Pure SnO2 (b) SnO2/G-a nanocomposite and GO (Inset picture)

Fig. 2 FTIR spectrum of (a) GO and (b) SnO2/G-a nanocomposite

Fig. 3 HRTEM images (a and b) Pure SnO2 nanoparticles (c and d) SnO2/G-a nanocomposite

Fig. 4 Cyclic voltammetry response of (a) SnO2 nanoparticles (b) SnO2/G-a (c) SnO2/G-b

and (d) SnO2/G-c nanocomposites

Fig. 5 Plot of specific capacitance versus scan rate

Fig.6 Capacitance retention of pure SnO2 and SnO2/G-a composite electrodes as

function of cycle number measured at 100 mV/s scan rate

Fig.7 Galvanostatic charge/discharge behaviour of pure SnO2 and SnO2/G-a composite

at a current density 0.1 A g-1.

Fig.8 Coulombic efficiency of SnO2 and SnO2/G-a composite electrodes at constant current

density of 0.1 A g-1

Fig.9 Nyquist Plots of SnO2 and SnO2/G-a composite from the frequency range 0.1 Hz to 105

Hz

21
 C

(1 1 0)

Intensity (a.u.)
(1 0 1)
(2 1 1)

10 20 30 40 50 60 70 80
2θ (degree)
Intensity (a.u.)

(3 0 1)

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
2θ (degree)

Fig. 1 XRD pattern of (a) Pure SnO2 (b) SnO2/G-a nanocomposite and GO (Inset picture)

22
 b
% Transmittance (a.u.)

1000 2000 3000 4000

Wave Number (cm-1)
Fig. 2 FTIR spectrum of (a) GO and (b) SnO2/G-a nanocomposite

23
 a b

c d

Fig. 3 HRTEM images (a and b) Pure SnO2 nanoparticles (c and d) SnO2/G-a nanocomposite

24
 Potential (V) vs. Ag/AgCl
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
3.0x10-3
1.5x10-3 a 5 mV
10 mV b
20 mV 2.0x10-3
-3
1.0x10 50 mV
100 mV 1.0x10-3
-4
5.0x10
0.0
0.0
Current (A)

-1.0x10-3

Current (A)
-4
-5.0x10
-2.0x10-3
-3
-1.0x10
3.0x10 -3
3.0x10-3

c d
2.0x10-3 2.0x10-3

1.0x10-3
1.0x10-3

0.0
0.0

-1.0x10-3
-3
-1.0x10
-2.0x10-3
-3
-2.0x10
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 -0.6 -0.4 -0.2
1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2

Potential (V) vs. Ag/AgCl

Fig. 4 Cyclic voltammetry response of (a) SnO2 nanoparticles (b) SnO2/G-a (c) SnO2/G-b
and (d) SnO2/G-c nanocomposites

25
 900
SnO2/G-a
800 SnO2/G-b
Specific capacitance (F/g)

SnO2/G-c
700 SnO2

600

500

400

300

200

100

0
-10 0 10 20 30 40 50 60 70 80 90 100 110
Samples

Fig. 5 Plot of specific capacitance versus scan rate

26
 100 SnO2/G-a
98
Capacitance retention(%)
SnO2
96
94
92
90
88
86
84
82
80
0 200 400 600 800 1000
Cycle Number

Fig.6 Capacitance retention of pure SnO2 and SnO2/G-a composite electrodes as

function of cycle number measured at 100 mV/s scan rate

27
 1.2
SnO2/G-a
1.0
SnO2/G-b
Potential (V) vs. Ag/AgCl

0.8 SnO2/G-c
0.6 SnO2

0.4

0.2

0.0

-0.2

-0.4
0 2 4 6 8 10 12 14 16 18 20
Time (sec)
Fig.7 Galvanostatic charge/discharge behaviour of pure SnO2 and SnO2/G-a composite

at a current density 0.1 A g-1.

28
 100

95
Coulombic efficiency(%)

90

85 SnO2/G-a
SnO2
80

75

70

65

60
0 200 400 600 800 1000
Cycle Number

Fig.8 Coulombic efficiency of SnO2 and SnO2/G-a composite electrodes at constant current
density of 0.1 A g-

29
 1600

1400 SnO2/G-a
SnO2
1200

1000
Z” (Ω)

800

600

400

200

0 200 400 600 800 1000 1200 1400 1600 1800 2000
Z’ (Ω)
Fig.9 Nyquist Plots of SnO2 and SnO2/G-a composite from the frequency range 0.1 Hz to 105
Hz (Inset shows the enlargement of the Nyquist plots of SnO2/G in the high frequency region
and its equivalent circuit)

30
Table 1: Comparison of specific capacitance of various electrode materials towards the

supercapacitor applications.

Material Electrolyte Scan rate Specific capacitance Ref

(mV/s) (F/g)

SnO2/SWCNT 1 M Na2SO4 6 320 33

SnO2/Carbon 1 M KOH - 25.8 34

SnO2 1 M H2SO4 - 121 35

SnO2/Graphene 6 M KOH - 368 36

SnO2/Graphene 1 M Na2SO4 5 363.3 37

SnO2/Graphene 1 M H2SO4 1 43.4 38

SnO2 6 M KOH 5 470 This work

SnO2/G-a 6 M KOH 5 818.6 This work

SnO2/G-b 6 M KOH 5 610.5 This work

SnO2/G-c 6 M KOH 5 580.2 This work

31