X-Ray Absorption Spectroscopy Studies of Nickel Oxide Thin Film Electrodes For Supercapacitors
X-Ray Absorption Spectroscopy Studies of Nickel Oxide Thin Film Electrodes For Supercapacitors
X-Ray Absorption Spectroscopy Studies of Nickel Oxide Thin Film Electrodes For Supercapacitors
1
to show the contribution of each
bond pair on the FT peak. The experimental Fourier-
filtered k
3
x(k) spectra were obtained from the inverse
Fourier transformation with the hanning window func-
tion in the r space range between 1.0 and 6.0 A
. The
curve fitting analysis of the EXAFS data was performed
using a UWXAFS 3.0 program package which uses
multiple scattering calculations with FEFF6.01 [16,17].
The amplitude reduction factor S
0
2
was scaled to a fixed
value of 0.8 after preliminary refinements. The coordi-
nation numbers (N) were also fixed to the crystal-
lographic values since the N value is highly correlated
with the Debye/Waller factor in the amplitude of
EXAFS spectra. The thickness of the sample was also
adjusted to a value close to mx/1.0 at the edge jump.
The experimental k
3
x(k) spectra were fitted with
possible scattering paths showing the substantial ampli-
tude for the corresponding FT peak. In that case, only
two structural parameters of the bond distance and the
Debye/Waller factor could be used as adjustable
parameters on the fitting process for the EXAFS
spectra.
K.-W. Nam et al. / Electrochimica Acta 47 (2002) 3201/3209 3202
3. Results and discussion
The effects of the heating temperature on the crystal-
line structure of the nickel oxides obtained by heating
the electrodeposited Ni(OH)
2
are shown in Fig. 1 in
terms of the XRD patterns. XRD pattern of as-
deposited Ni(OH)
2
corresponds to the a-Ni(OH)
2
struc-
ture [18]. Nickel oxide heated to 200 8C sustained the a-
Ni(OH)
2
structure but its (001) peak shifted slightly to
higher angles, resulting in a decrease of the c spacing of
the unit cell. This is due to water removal from planes
perpendicular to the c axis of nickel hydroxide crystals
[19]. At temperatures higher than 250 8C, the XRD
patterns exhibited the characteristic peaks of rock salt
NiO at 2u/37, 43 and 638, which first appeared at
250 8C. Therefore, when heated at or above 250 8C,
the Ni(OH)
2
is converted into nickel oxide with a
crystalline NiO structure. The XRD results shows that
heating temperature of 250 8C can be considered as the
critical temperature for the transformation of Ni(OH)
2
to oxide.
Fig. 2 shows the cyclic voltammograms of the
Ni(OH)
2
and nickel oxide films heated at various
temperatures. The Ni(OH)
2
and nickel oxide films
were cycled between /0.1 and 0.5 V
SCE
in 1 M KOH
solution. In Fig. 2(a), the cyclic voltammogram of the
as-deposited Ni(OH)
2
film shows an anodic current
peak and a cathodic current peak at 0.368 and 0.203
V
SCE
, respectively, and they are responsible for
Ni(OH)
2
/NiOOH redox reaction [18]. As shown in Fig.
2(a), heat-treatment of the Ni(OH)
2
film at 200 8C does
not significantly affect the electrochemical response of
the material, as is expected from the XRD results. In the
case of the film heated at 250 8C, cyclic voltammogram
is somewhat different in its current response and shape
from those of the films heated at temperatures lower
than 250 8C but it still contains visible anodic/cathodic
peaks. When the film is heated at 300 8C or above, the
peaks disappear and the anodic and cathodic current
responses are relatively symmetric about the current
axis, indicating the capacitive behavior. It can be
inferred from the XRD patterns in Fig. 1 and the cyclic
voltammograms in Fig. 2 that the capacitive behavior is
originated from the nickel oxide phase formed by
heating the electrodeposited Ni(OH)
2
at temperatures
higher than 250 8C. It should be noted that the cyclic
voltammogram of the film heated at 250 8C contains
characteristic peaks of Ni(OH)
2
/NiOOH redox reaction
although it shows the NiO structure in the XRD
pattern. This implies that Ni(OH)
2
is not completely
converted into the nickel oxide at 250 8C. Therefore,
the nickel oxide film heated at 250 8C can be considered
as an intermediate state of Ni(OH)
2
and oxide.
Fig. 1. XRD patterns for as-deposited Ni(OH)
2
and oxides heated at
different temperatures. The arrows in the XRD patterns for the as-
deposited Ni(OH)
2
and oxide heated at 200 8C correspond to the
(001) peak of a-Ni(OH)
2
structure.
Fig. 2. Cyclic voltammograms of as-deposited Ni(OH)
2
and oxide
lms heated at different temperatures in 1 M KOH solution. Potential
window: /0.1 to 0.5 V
SCE
, scan rate: 20 mV s
1
.
K.-W. Nam et al. / Electrochimica Acta 47 (2002) 3201/3209 3203
As-deposited Ni(OH)
2
and nickel oxide films were
cycled in the narrower potential range of /0.1 and 0.25
V
SCE
to observe changes in the specific capacitance as a
function of heating temperature without complications
associated with the Ni(OH)
2
/NiOOH redox reaction as
shown in Fig. 3. The current responses of as-deposited
Ni(OH)
2
and the film heated at 200 8C were very small
compared with those heated at temperatures higher than
250 8C. The cyclic voltammogram of the film heated at
250 8C exhibited somewhat distorted and asymmetric
current response as compared with those for the nickel
oxides heated at 300 8C or above. The average specific
capacitance is calculated using half the integrated area
between the curves of the cyclic voltammograms within
the potential range /0.1 to 0.25 V
SCE
and then dividing
by mass of the nickel oxide films and potential window
[10,11]. As shown in the Fig. 4. the specific capacitance
reaches a maximum at 300 8C, and then decreases on
further heating above 300 8C. Similar observations
were reported by Srinivasan et al. for the nickel oxide
films prepared by heating the electrodeposited Ni(OH)
2
at various temperatures [8,9]. Assuming stoichiometric
nickel oxide, they correlated the specific capacitance of
the nickel oxide films with heat-treatment and explained
this phenomenon due to the change in surface area of
chemically prepared Ni(OH)
2
powders with varying
temperature. In this study, non-stoichiometric nature
of nickel oxide was examined using XAS and efforts
were made to explain the change in the specific
capacitance in terms of non-stoichiometric nature of
nickel oxide.
The local structures around Ni atom in nickel oxides
have been investigated with the normalized Ni K-edge
k
3
x(k) spectra as a function of the heat-treatment
temperature. Since the EXAFS spectral change with
the heat-treatment temperature is indicative of the local
structural variation around Ni atom, it is of interest to
investigate quantitatively the variation of each Debye/
Waller factor and interatomic distance with the heat-
treatment temperature. Fig. 5 shows Fourier transform
magnitudes of the Ni K-edge EXAFS spectra for as-
deposited Ni(OH)
2
and nickel oxides heated at various
temperatures. In the structure of pure NiO, the A, B, C,
D, and E peaks (shells) in Fig. 5 should correspond to
six O atoms, 12 Ni atoms, six Ni atoms, 24 Ni atoms,
and 12 Ni atoms, respectively. In these EXAFS spectra,
scatterings with O atom in the region of r B/3 A
are not
resolved well since the backscattering amplitude of the
photoelectron with the oxygen is very weak compared
with Ni.
The fourth shell (C peak), corresponding to six Ni
neighbors at 4.16 A
, are
particularly prominent compared with the sixth shell
(D peak) which corresponds to 24 Ni neighbors at 5.12
A
)
a
s
2
( 10
3
)
a
DE (eV)
Ni
1x
O at 250 8C O 6 2.082 8.6 7.8
Ni 12 2.975 7.8 6.6
O 8 3.505 8.9 5.9
Ni 6 4.191 8.8 4.4
O 24 4.967 13.0 3.8
Ni 24 5.143 9.8 6.1
Ni 12 5.918 7.8 3.3
Ni
1x
O at 300 8C O 6 2.081 6.8 9.6
Ni 12 2.968 7.0 7.2
O 8 3.504 14.2 9.6
Ni 6 4.193 7.5 6.9
O 24 4.958 10.2 1.0
Ni 24 5.145 9.8 7.6
Ni 12 5.914 6.1 1.0
Ni
1x
O at 400 8O 6 2.083 6.5 9.2
Ni 12 2.961 6.6 7.5
O 8 3.532 13.7 11.1
Ni 6 4.191 7.2 9.6
O 24 4.969 7.5 0.5
Ni 24 5.139 8.7 7.8
Ni 12 5.910 5.7 0.1
Ni
1x
O at 500 8C O 6 2.087 6.1 9.2
Ni 12 2.957 6.2 7.6
O 8 3.526 12.6 10.2
Ni 6 4.187 6.8 11.0
O 24 4.976 5.9 1.6
Ni 24 5.131 7.9 7.2
Ni 12 5.914 6.0 0.9
Ni
1x
O at 600 8C O 6 2.085 6.4 9.0
Ni 12 2.958 6.2 7.8
O 8 3.553 12.9 11.6
Ni 6 4.182 6.6 11.2
O 24 4.979 7.2 1.4
Ni 24 5.127 7.9 7.3
Ni 12 5.909 5.6 0.9
a
The estimated errors are within 90.02 A
for the interatomic distance and about 20% for the Debye/Waller factor.
K.-W. Nam et al. / Electrochimica Acta 47 (2002) 3201/3209 3207
non-stoichiometric nature of the nickel oxide is strongly
related to its pseudocapacitance, which could be con-
trolled by the heat-treatment temperature. The defective
nature of the nickel oxide could be utilized to improve
its specific capacitance for supercapacitor application.
Acknowledgements
This study was supported by Korea Science and
Engineering Foundation (KOSEF) Research Project
(no. 2001-6-301-07-2) and the Brain Korea 21 Project.
The authors are grateful to authorities at the Pohang
Light Sources for X-ray absorption spectroscopic mea-
surements.
Fig. 7. Variations in the Debye/Waller factor of the major coordina-
tion shells for the nickel oxides heated at various temperatures.
Fig. 8. Normalized Ni K-edge XANES spectra for as-deposited
Ni(OH)
2
and nickel oxides heated at various temperatures.
Fig. 9. The second derivative curves of the normalized Ni K-edge
XANES spectra for the nickel oxides heated at various temperatures.
Fig. 10. Variations of edge positions in the XANES spectra for the
nickel oxides heated at various temperatures. These Ni K-edge energies
were measured at the energy at which the normalized absorption was
0.5, i.e. the absorption at the half-height of the edge step.
K.-W. Nam et al. / Electrochimica Acta 47 (2002) 3201/3209 3208
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