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Synthesis and characterization of ZnCo2O4 nanomaterial for symmetric supercapacitor applications

Synthesis and characterization of ZnCo2O4 nanomaterial for symmetric supercapacitor applications

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05/09/2014

 
Synthesis and characterization of ZnCo
2
O
4
nanomaterialfor symmetric supercapacitor applications
K. Karthikeyan
&
D. Kalpana
&
N. G. Renganathan
Received: 29 May 2007 /Revised: 8 April 2008 /Accepted: 11 April 2008
#
Springer-Verlag 2008
Abstract
ZnCo
2
O
4
nanomaterial was prepared by co- precipitation method and characterized by X-ray diffraction(XRD), scanning electron microscope (SEM), transmissionelectron microscopy (TEM), cyclic voltammetry (CV), andgalvanostatic charge
 – 
discharge tests at various currendensities. It is shown that the crystal structure and surfacemorphology play an important role in the enhancement of the specific capacitance. The TEM results clearly indicatethat the prepared material shows aggregated particles. The particle size powder was about 50 nm, and SEM picturesindicate a porous morphology. The electrochemical behav-ior of ZnCo
2
O
4
was characterized by mixing equal proportion of carbon nanofoam (CNF). From CV, it isconcluded that the combination of redox and pseudo-capacitance increases the specific capacitance up to77 F g
1
at 5 mV s
1
scan rate. The ZnCo
2
O
4
-basedsupercapacitor cell has good cyclic stability and highcoulombic efficiency.
Keywords
Supercapacitor .Zincoxide.Carbonnanofoam.Specificcapacitance
Introduction
With increasing demand for alternative energy sources,electrochemical capacitors with high power densitiescompared to batteries and high energy density comparedto dielectric capacitors are in big demand. They haveseveral advantages like long cycle life, short charge
 – 
discharge time and safety. Practical applications are seenfor electric vehicles and as memory back up for computers[1,2]. The basic electrode material used for electrochemicalcapacitors are (1) Carbon (aerogel, nanofoam, nanotube,etc.) [3] (2) Metal oxides (RuO
2
, IrO
2
)[4], and (3) Conducting polymers [5]. Among the metal oxides, oxideof Ru exhibit very high specific capacitance, but its wideacceptance is reduced due to high cost. Hence, a cheapmaterial with equivalent performance is required. Transitionmetal oxides [6,7] have been considered as promising materials for supercapacitors.ZnCo
2
O
4
is a spinel, where Zn ions occupy thetetrahedral sites in the cubic spinel structure, and thetrivalent Co ions occupy the octahedral sites. When nano-size particles of ZnCo
2
O
4
are electrochemically discharged,it will occupy the three-dimensional network carbon withinthe electrode toparticipate inthe formation ofelectrochemicaldouble layer. Energy is stored in these porous electrodes byaccumulation of ionic charge in the double layer at theelectrode
 – 
electrolyte interface.To our knowledge, there is no report, so far, on theapplication of ZnCo
2
O
4
for supercapacitor. Recently,Kalpana et al. have prepared ZnO nanoparticles by thesol
 – 
gel method and used this material for supercapacitor applications [8].In the present study, we have prepared ZnCo
2
O
4
by co- precipitation because of its high purity, atomic levelhomogeneous mixing of the constituent metal ions, andgood control of stoichiometry [9].
IonicsDOI 10.1007/s11581-008-0227-yK. Karthikeyan
:
D. Kalpana (
*
)
:
N. G. RenganathanCentral Electrochemical Research Institute,Karaikudi 630 006, Indiae-mail: dkalps@rediffmail.com
 
Experimental
Synthesis and fabrication of ZnCo
2
O
4
Stoichiometric quantities of ZnCl
2
and CoCl
2
were dis-solved in triple distilled water. A 6-M KOH solution wasadded slowly at a rate of five drops with an interval of 15 min into the solution. The solution was constantly stirredwell at 80 °C until the precipitate was formed. Then, it wasfiltered and washed with distilled water followed byethanol. The precursor was kept in an oven at 200 °C for 3 h. Electrodes for the symmetric electrochemical capacitor were prepared by mixing an equal proportion of ZnCo
2
O
4
and carbon nanofoam of 1,500 m
2
g
-1
surface area bondedwith N-methyl pyrolidine. The slurry was pasted on thestainless steel current collector of 1 cm
2
geometrical areaand dried in an oven at 200 °C for 30 min and slowlycooled down to room temperature. The cell was fabricated by sandwiching the electrodes between a polypropyleneseparator using 6 M KOH as electrolyte. For cyclicvoltammetry (CV), an Electrochemical Analyzer (BAS100B, USA) was used. The crystalline structure of ZnCo
2
O
4
nanoparticles was examined by XRD with CuK 
α 
radiation (
 l
=1.54056 Å). The morphology of the sampleswas investigated by a scanning electron microscope(HITACHI, S-3000H). The impedance properties of thecells were measured by a PARSTAT 2263, USA. Thecharge
 – 
discharge cycling properties of the cells wereevaluated by using Won-A-Tech Battery Cycler (WBCS3000).
Results and discussions
X-ray analysisX-ray powder diffraction analysis was performed usingCuK 
α 
radiation (
 l
=1.5405 Å) at a scanning rate of 2
0
min
1
, and the XRD pattern was identified by comparisonwith the JCPD standard. The crystalline size
D
c
, wasdetermined by using the Scherrer equation,
 D
c
¼
0
:
9
 l
=
B cos
θ
ð Þ
where,
l
is the corrected wavelength of the X-radiation, Bthe full width at half-maximum corrected for instrumental broadening, and
θ
is the Bragg angle of the diffraction peak.The mean grain size of as prepared ZnCo
2
O
4
was 50 nm.Figure1shows the XRD pattern of ZnCo
2
O
4
powder.The peaks are shaped, well-defined, and reveal theformation of the cubic spinel structure. The XRD patternsexhibited the characteristic peaks at 2
θ
=31.45, 36.96,45.00, 55.65, and 77.49
°
of the spinel type ZnCo
2
O
4
(JCPS23-1390).
2030405060708005010020406080050100
JCPS 23 - 1390
position (
°
2 theta)
XRD of ZnCo2O4
   (   5   3   3   )   (   6   2   0   )   (   4   4   0   )   (   5   1   1   )   (   4   2   2   )   (   3   3   1   )   (   4   0   0   )   (   2   2   2   )   (   3   1   1   )   (   2   2   0   )   (   1   1   1   )
   i  n   t  e  n  s   i   t  y   (   %   )
Fig. 1
XRD pattern of ZnCo
2
O
4
nanoparticle
 
a
b
 
b
Fig. 2
SEM and TEM photo-graph of ZnCo
2
O
4
nanoparticle.
a
SEM and
b
TEMIonics
 
SEM analysisFigure2shows the SEM and TEM images of ZnCo
2
O
4
. Nano-size particles with spherical shape reveal that the co- precipitation method enables to form well crystallineZnCo
2
O
4
powder. The TEM result clearly indicates that the prepared material has aggregated particles consisting of average particle size of 40
 – 
50 nm. The ZnCo
2
O
4
powder are smooth, porous with submicron crystallite formation,which will contribute to higher capacitance and lowimpedance.Electrochemical impedance analysisFigure3shows the electrochemical impedance results of the ZnCo
2
O
4
nanomaterial. As shown in the figure, thereare two distinct regions depending on the frequency range.The complex plane plot consists of a small semicircle at high frequencies with a transition to a linear part at lowfrequencies corresponding to a capacitive behavior. Theelectrolyte solution resistance of 0.2
Ω
is determined fromthe intersecting point of the semicircle with the real axis.The intermediate frequency region is the 45
°
line, which ischaracteristic of diffusion into the electrode. The more closeto the vertical spike the higher will be the supercapacitive behavior. The charge transfer resistance
R
ct 
of the electrodewas estimated to about 4.6
Ω
from the point of intercept with the real axis in the high frequency range. It is obviousthat ZnCo
2
O
4
with the carbon nanofoam enhanced theconductivity by reducing the internal resistance.Electrochemical analysisFigure4shows the CV results of the ZnCo
2
O
4/ 
CNFcomposite electrode recorded at 5, 10, 20, and 50 mV s
1
01020304050010203040506070
   Z
   i  m
   (  o   h  m   )
Z
re
(ohm)
Fig. 3
Nyquist plot of ZnCo
2
O
4
/CNF-based supercapacitor cell
-1200-1000-800-600-400-2000200400-0.010-0.008-0.006-0.004-0.0020.0000.0020.0040.006
   C  u  r  r  e  n   t   (   A   )
Potential (mV)5 mV/s10 mV/s20 mV/s50 mV/s
Fig. 4
Cyclic voltammogram of ZnCo
2
O
4
/CNF-based supercapacitor cell at various scan rates
Table 1
Specific capacitance of ZnCo
2
O
4
/CNF based supercapacitor cell at various scan ratesScan rate (mV/s) Specific capacitance of ZnCo
4
O
2
/CNF (F/g)5 7710 6420 4850 42
5006007008000.00.20.40.60.81.01.2
   V  o   l   t  a  g  e   (   V   )
Time (s)
Fig. 5
Charge
 – 
discharge profile of ZnCo
2
O
4
/CNF composite-basedsupercapacitor cell at 2 mA/cm
2
Ionics

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