See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/312183766

Hydrothermal Synthesis of CoWO4 as Active Material for Supercapacitor

Electrode

Conference Paper · November 2016

DOI: 10.14257/astl.2016.139.81

CITATIONS READS

4 1,348

2 authors, including:

Vaibhav Lokhande
Chonnam National University
51 PUBLICATIONS 1,307 CITATIONS

SEE PROFILE

All content following this page was uploaded by Vaibhav Lokhande on 14 September 2017.

The user has requested enhancement of the downloaded file.

 Advanced Science and Technology Letters
Vol.139 (EEC 2016), pp.409-413
http://dx.doi.org/10.14257/astl.2016.139.81

Hydrothermal Synthesis of CoWO4 as Active Material for

Supercapacitor Electrode

Vaibhav Lokhande1, Taeksoo Ji1*

1Department of Electronics and Computer Engineering,
Chonnam National University, Korea

Abstract. Cobalt tungstate was synthesized by facile one step hydrothermal

process and deposited on the carbon cloth to obtain a binder free electrode for
supercapacitor. The as prepared electrode exhibited specific capacitance of
1372 F/g at 5 mV scan rate and stability over 95% after 4000 cycles.

Keywords: Cobalt Tungstate, hydrothermal, supercapacitor, capacitance,

stability.

1 Introduction

Over the past decades, much of the research has been directed towards the development of
energy storage system to satisfy the increasing energy demands. Owing to the fast charging-
discharging capability, high power density, higher life span than batteries and low cost,
supercapacitors have received much attention in recent years. Supercapacitors can be
categorized in two types namely EDLC (electrochemical double layer capacitors) and
pseudocapacitors. EDLC devices are mainly carbon based devices having higher power density
and higher cyclic life. Pseudocapacitors are redox reactions based devices comprising of metal
oxides, conducting polymers and other such materials. They boast higher energy density but the
cyclic life is considerably lower. Constant efforts are being made to increase the energy density
while maintaining higher power density and cyclic life.
Among the many transitional metal oxides studied as an electrode material for
supercapacitor, Ruthenium oxide has shown best performance only to be marred by the high
cost and limited availability of Ruthenium. Many other metals are being investigated for this
purpose. Recent studies are directed towards binary metal oxides such as NiCo2O4, MnMoO4
etc. due to their low cost and abundant availability. The pseudocapacitive performance of these
materials has been quiet encouraging. Cobalt tungstate is a similar binary metal oxide. A p-type
semiconductor material having wide application in catalysis, magnetism and sensing. CoWO4
has good electrochemical performance but has been scarcely reported.
Many reports on metal oxide electrodes have used slurry coating method to fabricate the
electrode. The metal oxide powder is mixed with the binder and then pasted onto the current
collector. This method has inherent problems due to the use of binder and non-contact of active
material with the current collector. To improve this, binder free electrode has been fabricated
by directly depositing the active material on the current collector. This minimizes the resistance
due to the binder material and enables effective utilization of the active material. Chen et.al
have reported specific capacitance of 1127.6 F/g at 1 A/g for cobalt tungstate [1]. Adib et.al
have synthesized cobalt tungstate by chemical precipitation reaction. It exhibited specific
capacitance of 378 F/g at 2mV scan rate [2].

ISSN: 2287-1233 ASTL

Copyright © 2016 SERSC
Advanced Science and Technology Letters
Vol.139 (EEC 2016)

In this report, Cobalt tungstate has been prepared and deposited on carbon cloth by facile
one step hydrothermal process. The as prepared material showed better electrochemical
performance than the previous reports. The material exhibited specific capacitance of 1372 F/g
at 5mV scan rate and stability of 96% over 4000 cycles. On the basis of the findings, cobalt
tungstate can be a good candidate as an active material for supercapacitor electrode.

2 Experimental Method

The chemicals used in the experiment were obtained from Sigma Aldrich and were used as
received without purification.

2.1 Synthesis and Deposition on Carbon cloth.

Carbon cloth was cut into 2 cm* 2 cm sized piece. It was then dipped for several minutes in 6
M HCl to remove any impurities. In a typical synthesis, 5 mmol of K 2WO4 and 5mmol of
Co(NO3)2 were dissolved in 50 ml DI water. The solution was magnetically stirred for about 15
mins at room temperature. The solution was transferred into a 100ml Teflon-lined stainless
steel autoclave. The piece of carbon cloth was dropped in the solution before sealing it and
heating it in an oven for 18 h at 160 C. The autoclaves were allowed to cool down to room
temperature naturally. Then carbon cloth substrate and the precipitate powder were collected
and washed thoroughly several times ultrasonically with DI water. They were dried for 24 h at
60 C in an oven.

3 Characterization

The X-ray diffraction analysis was done using Ultima3. The surface morphology of the thin
films were characterized using field emission scanning electron microscopy (FE-SEM, Model:
JSM-6700F, Japan). The electrochemical characterization was done using Wonatech
WBCS3000S. The cyclic voltammetry characterization was done using three electrode system,
Ag/AgCl as reference electrode, Pt as counter and 3 M KOH electrolyte was used. The potential
was scanned between -0.2 V to 0.4 V at various scan rates.

4 Results and Discussion

Cobalt tungstate (CoWO4) was synthesized through the reaction of Na2WO4, 2H2O and CoCl2,
6H2O. The two aqueous solutions were mixed together and subjected to hydrothermal
processing to get the CoWO4 precipitate according to equation 3
Na2WO4, 2H2O 2Na+ (aq) + Wo42-(aq) + 2H2O … (1)

CoCl2, 6H2O Co2+ (aq) + 2Cl-(aq) + 6H2O … (2)

410 Copyright © 2016 SERSC

 Advanced Science and Technology Letters
Vol.139 (EEC 2016)

2Na+ (aq) + Wo42-(aq) + 2H2O + Co2+ (aq) + 2Cl-(aq) + 6H2O CoWO4 + 2Na+ +2Cl- +
8H2O … (3)

The crystalline structure of the CoWO4 was characterized using the powder XRD patterns.
Fig 1 shows the XRD pattern of the cobalt tungstate and reference XRD pattern of CoWO4
JCPDS # 00-15-0867.

Fig 1. XRD pattern

a b

Fig.2. SEM images a) carbon cloth coated with CoWO4.b, c) high magnification images of
carbon cloth fiber.

The micro structure and morphology were investigated by SEM. The figure 2 shows the
SEM images of cobalt tungstate on carbon cloth. Carbon cloth was selected as the substrate
because of high electrical conductivity and its ability to withstand harsh environment during
hydrothermal process. The top view image of the carbon cloth figure 2a confirms that the active
material has completely covered the cloth surface. Figures 2b,c show a single fiber of the cloth
with higher magnification. Cobalt tungstate seems to form small spheres. Also the morphology
seems to be very dense without any other significant structures being formed.

Copyright © 2016 SERSC 411

Advanced Science and Technology Letters
Vol.139 (EEC 2016)

0.07
0.06
0.05
0.04
0.03
0.02
Current (A)

0.01
0.00
-0.01
-0.02 50mV scan rate
-0.03 100 mV scan rate
-0.04 200 mV scan rate
-0.05
20 mV scan rate
10 mV scan rate
-0.06
5 mV scan rate
-0.07
-0.2 -0.1 0.0 0.1 0.2 0.3 0.4
Voltage (V)

Fig. 3. CV-graphs at different scan rates.

The cyclic voltammetry studies were conducted over the potential range of -0.2 V to 0.4 V
giving an effective potential window of 0.6 V. The CV graphs are shown in the fig 3. The
weight of the active material was found out to be 1.015 mg by recording the weight difference
of the carbon cloth before and after the deposition process. The capacitance was calculated
from the following formula:
… (4)
Where, m is the mass of active material.
v is the scan rate and
P is the potential window.
Capacitance (F/g)

1400

1200

1000
Capacitance (F/g)

800

600

400

200

0 50 100 150 200

Scan Rate(mV)

Fig.4. Rate stability of the sample at different scan rates.

412 Copyright © 2016 SERSC

 Advanced Science and Technology Letters
Vol.139 (EEC 2016)

0.04

0.03
st
1 cycle
th
0.02 4000 cycle
Current

0.01

0.00

-0.01

-0.02

-0.2 -0.1 0.0 0.1 0.2 0.3 0.4

Voltage

Fig.5. Cyclic stability after 4000 cycles.

Fig 4 shows the rate capability of the electrode. There is a significant drop in the capacitance
of the electrode at higher scan rates. The rate capability of 18% was observed at 200 mV scan
rate. The cyclic stability of the electrode is quite high. Fig 5 shows the graph at cycle number 1
and 4000. The capacitance retention is about 96 % which is high for a pseudocapacitive type
material.

5 Conclusion

Cobalt tungstate seems to be a promising candidate for electrochemical storage devices. The
binder free electrode prepared by facile one step hydrothermal process exhibited specific
capacitance of 1372 F/g at 5 mV scan rate. The cyclic stability of the electrode is also above
95% after 4000 cycles. Herein we report highest capacitance for cobalt tungstate recorded till
date to the best of our knowledge.

References

1. Chen, S., Yang, G., Jia, Y., Zheng, H.: Facile Synthesis of CoWO4 Nanosheet Arrays
Grown on Nickel Foam Substrates for Asymmetric Supercapacitors ChemElectroChem
Volume 3, Issue 9 September 2016, pp. 1490–1496
2. Adib, K., Rahimi-Nasrabadi, M., Rezvani, Z., Pourmortazavi, S.M., Ahmadi, F., Naderi,
H.R., Ganjali, M.R.: Facile chemical synthesis of cobalt tungstates nanoparticles as high
performance supercapacitor, Journal of Materials Science Materials in
Electronics, January 2016.

Copyright © 2016 SERSC 413

View publication stats