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Electrochimica Acta
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A R T I C L E I N F O
A B S T R A C T
Article history:
Received 5 February 2016
Received in revised form 8 March 2016
Accepted 9 March 2016
Available online 10 March 2016
ZnFe2O4 thin lm has been synthesized by a simple and low cost successive ionic layer adsorption and
reaction (SILAR) method without the use of surfactant or template. The nanoplate composed of
nanoparticles with porous surface morphology has been revealed which is benecial towards
supercapacitor application. Formed ZnFe2O4 thin lm has been tested as an electrode material for
supercapacitor through electrochemical analysis. First attempt for SILAR synthesized ZnFe2O4 thin lm
exhibited a specic capacitance of 471 Fg1 at a scan rate of 5 mVs1 in 1 M NaOH aqueous solution.
Further, ZnFe2O4 solid-state symmetric (SSS) supercapacitor device demonstrated voltage window of
1.0 V with specic capacitance of 32 Fg1, energy density of 4.47 Whkg1 and power density of 277 Wkg1
at 1 Ag1 current density. Such high performance capacitive behavior indicates ZnFe2O4 thin lm is
promising and low cost electrode material towards energy storage devices for various portable electronic
systems.
2016 Elsevier Ltd. All rights reserved.
Keywords:
Mixed transition metal oxides (MTMO)
SILAR
solid-state symmetric (SSS) supercapacitor
1. Introduction
Among the various energy storage systems, supercapacitors are
important source of energy storage devices and power outputs.
Typically, supercapacitor shows reasonable energy with high
power density and long cycle life. There are growing demands for
the next generation exible and lightweight energy storage devices
with high power density and high energy density, as their special
features and potential applications in variety of portable electronic
devices such as smart sensors, mobiles, exible touch screen and
electronic newspaper etc [1]. Nanostructure electrode materials
have been extensively studied in supercapacitor due to their high
surface area which results in higher electrode-electrolyte contact
area, short path length for cation transport and high power
performance [2]. Currently, variety of electrode materials have
potential candidates for supercapacitor which store/deliver energy
with different working principles [3]. Activated carbon, carbon
204
OH
Fig. 1. Schematic presentation for the synthesis of ZnFe2O4 thin lm by using SILAR method. FE-SEM image shows formed ZnFe2O4 thin lm on SS substrate.
205
Id T d
DV m
Fig. 2. (a) XRD patterns of as-deposited and annealed (573 K and 773 K) ZnFe2O4
thin lms on SS substrate, (b) FT-IR spectra of as-deposited and annealed (573 K)
ZnFe2O4 scratch powder sample. (c) Raman spectra of annealed (573 K) ZnFe2O4
scratched powder sample.
206
V tdt
3:6m
E 3600
Td
Fig. 3. FE-SEM images of (a) SS substrate and (b) ZnFe2O4 thin lm. (c) Cross-sectional SEM image of ZnFe2O4 thin lm. (d) EDAX pattern of ZnFe2O4 scratched powder.
Fig. 4. (a) TEM image of ZnFe2O4 (inset is electron diffraction pattern of ZnFe2O4)
and (b) HR-TEM image of ZnFe2O4.
207
208
Fig. 5. Cyclic voltammetry (CV) curves of ZnFe2O4 thin lm electrode in (a) different SILAR cycle deposited lms (b) different electrolyte concentration at 5 mVs1 scan rate.
(c) CV curves of ZnFe2O4 thin lm electrode at different scan rate in 1 M NaOH electrolyte, and (d) Variation of the specic capacitance for ZnFe2O4 thin lm electrode as a
function of scan rate.
Fig. 6. (a) Constant current charge-discharge curve of ZnFe2O4 thin lm at different current density in 1 M NaOH electrolyte. (b) The energy density vs. power density of
ZnFe2O4 thin lm in Ragone plot. (c) Variation of capacity retention of ZnFe2O4 thin lm electrode with the number of cycles (inset is CV curves of ZnFe2O4 thin lm for
different number of cycles at a 50 mVs1 scan rate). (d) Nyquist plots of ZnFe2O4 thin lm with AC voltage amplitude of 10 mV.
209
Fig. 7. (a) CV curves of ZnFe2O4-SSS supercapacitor device at different scan rate. (b) Variation of the specic capacitance for ZnFe2O4-SSS supercapacitor device as a function of
scan rate.
Fig. 8. (a) Constant current charge-discharge curve of ZnFe2O4-SSS supercapacitor device at different current density. (b) The energy density vs. power density of ZnFe2O4-SSS
supercapacitor device in Ragone plot. (Inset is the photoimage of glow up of light emitting diode (LED)) (c) Variation of capacity retention of ZnFe2O4-SSS supercapacitor
device with the number of cycles (inset is CV curves of ZnFe2O4-SSS supercapacitor device for different number of cycles at a 50 mVs1 scan rate). (d) Nyquist plots of ZnFe2O4
SSS supercapacitor device with AC voltage amplitude of 10 mV.
210
Table 1
The calculated values of specic capacitance, energy density and power density at different current density of ZnFe2O4SSS supercapacitor device.
Sr. no
1
2
3
4
1
1.5
2
2.5
32.22
24.16
12.22
8.33
4.47
3.36
1.7
1.15
277.78
416.67
555.56
694.44
Table 2
Comparison of electrochemical properties of symmetric supercapacitor device (liquid (L)/solid).
Compounds
Electrolyte
Ref.
NiO/MWNT
Co(OH)2
Fe3O4
MnO2
Carbon
ZnFe2O4
PVA/LiClO4
L-1 M KOH
L-1 M H2SO4
L-LiPF6
L-KOH
PVA-LiClO4
0.6 to 0.6
0 to 1.2
0 to 1
0 to 1
0 to 1
0 to +1
24 at 5 mV s1
44 at 5 mV s1
15 at 0.25 A g1
32.22 at 1 A g1
3.96
12.4
3.4
7.4
4.5
42(kW kg1)
370
200
277
[41]
[42]
[43]
[44]
[45]
Present work
frequency spike. The Rs and Rct values of the tted EIS spectra of
ZnFe2O4 thin lm electrode are 0.8 V cm2 and 1.05 V cm2,
respectively.
3.4. Electrochemical properties of solid-state symmetric (SSS)
supercapacitor device
Solid-state symmetric (SSS) supercapacitor device was fabricated by using ZnFe2O4 thin lms as a exible electrode
(2.3 2 cm2) sandwiched by polyvinyl alcohol (PVA) LiClO4 gel
electrolyte. The cyclic voltammograms (CV) of the exible
ZnFe2O4-SSS device within the potential windows of 0 to +1.0 V
at different scan rates (2 to 100 mVs1) are demonstrated in
Fig. 7(a). The CV curves maintain their shape and current under the
CV curves increases with the scan rate which reveals the capacitive
performance of ZnFe2O4-SSS device.
The variation of specic capacitance with scan rate is shown in
Fig. 7(b). The maximum specic capacitance of the ZnFe2O4-SSS
supercapacitor device is found to be 26 Fg1 at 2 mVs1 scan rate
based on the total mass (1.80 mg) of active material in two
electrodes. The estimated values of specic capacitance are found
to be decreases from 26 to 10 Fg1 with increase in scan rate (2
100 mVs1).
The galvanostatic charge-discharge of ZnFe2O4-SSS supercapacitor device at different current density was studied in order
to nd out the energy density, power density and device
performance [Fig. 8 (a)]. The Ragone plot relating to energy
density and power density is shown in Fig. 8 (b). ZnFe2O4-SSS
supercapacitor device exhibited a maximum specic capacitance
of 32 Fg1, high energy density of 4.47 Whkg1 with power density
of 277 Wkg1 at 1 Ag1 current density. Table 1 provides the values
of specic capacitance, energy density, power density at different
current density of ZnFe2O4-SSS supercapacitor device. The
obtained energy density 4.47 Whkg1 is higher than previously
reported symmetric supercapacitor based on graphene @ carbon
cloth (1.64 Whkg1) [40]. Inset Fig. 8(b) shows the photoimage of
glow up of light emitting diode (LED) by using series combination
of two ZnFe2O4-SSS supercapacitor device. Table 2 summarizes
some of the results that have been reported with symmetric
supercapacitor device [4145]. In order to check the stability of
ZnFe2O4-SSS supercapacitor device, CV cycling is repeated for
1000 times at a scan rate of 100 mVs1 within potential windows of
0 to 1.0 V and as shown in inset of Fig. 8 (c). The plot of capacitance
retention with cycle number shows 66% capacitance retention over
1000CV cycles [Fig. 8 (c)]. The loss of capacitance during cycling
211
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