X-ray absorption spectroscopy studies of nickel oxide thin lm

electrodes for supercapacitors

Kyung-Wan Nam, Won-Sub Yoon, Kwang-Bum Kim*
Division of Material Science and Engineering, Yonsei University, 134 Shinchon-dong, Seodaemoon-gu, Seoul, South Korea
Received 9 July 2001; received in revised form 4 April 2002
Abstract
Nickel oxide films were synthesized by electrochemical precipitation of Ni(OH)
2
followed by heat-treatment in air at various
temperatures (200/600 8C). Their structure and electrochemical properties were studied by cyclic voltammetry, X-ray diffraction
(XRD) and X-ray absorption spectroscopy (XAS). XRD results showed that the nickel oxide obtained at 250 8C or above has a
crystalline NiO structure. The specific capacitance of the oxide depends on the heat-treatment temperature, showing a maximum
value at 300 8C. XAS results revealed that the non-stoichiometric nickel oxide (Ni
1x
O) approached the stoichiometric NiO
structure with increasing heat-treatment temperature due to the defect healing effect. The defective nature of the nickel oxide could
be utilized to improve its specific capacitance for supercapacitor application. # 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Supercapacitor; Pseudocapacitance; Nickel oxide; X-ray absorption spectroscopy; Non-stoichiometry
1. Introduction
Electrochemical capacitor has received considerable
amount of attention over the last few years because of
their use in high power energy storage devices. The
capacitance in an electrochemical capacitor can arise
from the charging or discharging of the electrical double
layers (electrical double layer capacitance) or from
Faradaic redox reactions (pseudocapacitance). Carbon
materials with very high-surface area are widely used for
double layer capacitors [1]. Subsequently, conducting
polymers [2] and transition metal oxides with relatively
high-surface-area, such as hydrous RuO
2
[3], nickel
oxide [4/11], CoO
x
[12] and MnO
2
[13,14] have been
identified as possible electrode materials for super-
capacitors (pseudocapacitors).
Nickel oxide is being considered as one of the
promising potential electrode materials for supercapa-
citors as well as for many other applications such as
catalyst, electrochromic films, fuel cell electrodes, and
gas sensors. Nickel oxide films for supercapacitors can
be prepared by thermal treatment of electrodeposited
Ni(OH)
2
(electrochemical route) [7/9,11], sol /gel
method [4/6] and electrostatic spray deposition techni-
que [10]. In the case of nickel oxide films prepared by the
electrochemical route, the specific capacitance was
observed to be from 200 to 278 F g
1
(from a single
electrode) in 1 M KOH within 0.5V potential window
comparable to those synthesized by other methods.
Our previous study revealed that the preparation
condition of Ni(OH)
2
films had a great effect on the
specific capacitance of nickel oxide films [11], Assuming
stoichiometric nickel oxide, Srinivasan et al. reported
that the heating time and temperature of Ni(OH)
2
also
had a remarkable effect on the specific capacitance of
nickel oxide films [8,9]. However, to the best of our
knowledge, there has been no structural investigation of
nickel oxide for supercapacitors using X-ray absorption
spectroscopy (XAS) as a function of heating tempera-
ture in order to explain the electrochemical properties of
this material for supercapacitors.
Structural properties are strongly related to the
electrochemical properties of nickel oxide for super-
capacitors. The powder X-ray diffraction (XRD) tech-
nique can be used for this reason, but a local structure
analysis of interesting atoms cannot be made only with
the XRD technique because it provides an average
structure for the crystalline phases with long-range
* Corresponding author. Fax: /82-2-312-5375
E-mail address: kbkim@yonsei.ac.kr (K.-B. Kim).
Electrochimica Acta 47 (2002) 3201/3209
www.elsevier.com/locate/electacta
0013-4686/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 3 - 4 6 8 6 ( 0 2 ) 0 0 2 4 0 - 2
structural order. XAS is a technique that is atom specific
and capable of probing the short to medium range
structure around an interesting atom. Conventionally,
X-ray absorption spectroscopic structure is divided into
two regions: the X-ray absorption near edge structure
(XANES) and the extended X-ray absorption fine
structure (EXAFS). Analysis of EXAFS spectra pro-
vides many quantitative structural characterizations
including coordination number, interatomic distance,
and the Debye/Waller factor of the coordination atoms
for the interesting atom. XANES can also provide some
useful structural information about the oxidation state
of an interesting atom and site symmetry.
In the present study, nickel oxide films were synthe-
sized by electrochemical precipitation of Ni(OH)
2
films
followed by heat-treatment in air at various tempera-
tures. Their structure and electrochemical properties
were studied by cyclic voltammetry, XRD, and XAS.
Especially, the variations in the local structures with
heat-treatment temperature were systematically investi-
gated on the basis of XAS. The XAS analysis gives a
better understanding of the relationship between the
pseudocapacitance and heat-treatment temperature of
nickel oxide.
2. Experimental
Ni(OH)
2
films were deposited on gold foils with
apparent area of 1.0 cm
2
by cathodic precipitation
from 0.1 M Ni(NO
3
)
2
solution. All depositions were
conducted in a three-electrode system. Pt foil and
saturated calomel electrode (SCE) were used as the
counter and reference electrode, respectively. Gold foils
were cleaned electrochemically prior to deposition by
passing anodic, cathodic and then anodic current at 1
mA cm
2
for 1 min in 1 M KOH. A cathodic current
density of 1.0 mA cm
2
was applied for 240 s, which
according to our previous deposition studies [11,15]
should result in /140 mg films of Ni(OH)
2
. Formation
of nickel oxide films on the substrates was tried by
heating the electrochemically deposited nickel hydroxide
films in air at desired temperatures (200/600 8C) for 1 h
with a rate of 5 8C min
1
. In the case of XRD and
XAS experiments, nickel oxide powders were obtained
by heat-treatment of the Ni(OH)
2
scraped from as-
deposited films.
Cyclic voltammetry was performed using a potentio-
stat/galvanostat (Solartron 1287) to determine the
electrochemical properties and specific capacitance of
nickel oxide films in 1 M KOH solution. The cyclic
voltammetric experiments were carried out in a three-
cell arrangement with platinum foil as the counter
electrode and SCE as reference electrode. Nickel oxide
films heated at different temperatures (200/500 8C)
were first cycled from /0.1 to 0.5 V
SCE
for 50 cycles in 1
M KOH and then further cycled in a narrower potential
window from /0.1 to 0.25 V
SCE
at a scan rate of 20 mV
s
1
.
XAS measurements were performed in transmission
mode at beamline 3C1 of Pohang Light Source (PLS)
using a Si(111) double-crystal monochromator detuned
to 80% of its original intensity to eliminate the high
order harmonics. The storage ring was operated with an
electron energy of 2.5 GeV and a current between 120
and 150 mA. Calibration was carried out using the first
inflection point of the spectrum of Ni foil, i.e. Ni K-
edge/8333 eV, as a reference. To remove an energy
shift problem, the X-ray absorption spectrum for Ni
metal foil was measured simultaneously in every mea-
surement as the metal foil was positioned in front of the
window of the third ion chamber.
The EXAFS data analysis was carried out by the
standard procedure. The measured absorption spectrum
below the pre-edge region was fitted to a straight line.
The background contribution above the post-edge
region, m
0
(E), was fitted to a fourth order polynomial
(cubic spline). The fitted polynomials were extrapolated
through the total energy region and subtracted from the
total absorption spectra. The background-subtracted
absorption spectra were normalized for the above
energy region, x(E)/{m(E)/m
0
(E)}/m
0
(E). The nor-
malized x(E) spectra were converted to x(k) in k space
by [8p
2
m(E/E
0
)/h
2
]
1/2
. The x(k) spectra were k
3
-
weighted to magnify the small signal in the higher k
space. The normalized k
3
-weighted EXAFS spectra,
k
3
x(k), were Fourier transformed (FT) in the k space
of 3.0 to 14.0 A

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

, and the seventh shell (E peak),

corresponding to 12 Ni neighbors at 5.91 A

, are
particularly prominent compared with the sixth shell
(D peak) which corresponds to 24 Ni neighbors at 5.12
A

. This is due to the well-known focusing effect [20]

which gives rise to very strong multiple scattering effects
for paths involving collinear atoms such as the one
involving the central Ni atoms, O in the first (A) shell
and Ni in fourth (C) shell, and the one involving the
central Ni atoms, Ni in second (B) shell and Ni in
seventh (E) shell.
Due to the importance of the FT peaks in the higher r
region, the curve fitting process has been carried out up
Fig. 3. 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 0.25 V
SCE
, scan rate: 20 mV s
1
.
Fig. 4. Specic capacitance of the nickel oxide lms heated at different
temperatures. The capacitances were calculated using the cyclic
voltammograms in Fig. 3. Non-linear curve t through the data points
is represented by solid line. Data points of the as-deposited Ni(OH)
2
and lm heated at 200 8C are given only to show the effects of heating
temperature on the current response.
K.-W. Nam et al. / Electrochimica Acta 47 (2002) 3201/3209 3204
to /6 A

. Usually, the higher multiple scattering paths

may be significant rather than the single scattering in the
higher r region. In the present EXAFS study, the
multiple scattering with only 1808 scattering angle has
been considered by the focusing effect where the multi-
ple scattering is enhanced as the scattering path
approaches a linear arrangement. The FT magnitude
at /4.16 A

includes three scattering paths which

correspond to a single scattering path of Ni 0/Ni(C), a
double scattering path of Ni 0/O(A) 0/Ni(C), and a
triple scattering path of Ni 0/O(A) 0/Ni(C) 0/O(A). The
FT magnitude at /5.91 A

also includes three scattering

paths which correspond to a single scattering path of
Ni 0/Ni(E), a double scattering path of Ni 0/Ni(B)0/
Ni(E), and a triple scattering path of Ni 0/Ni(B)0/
Ni(E)0/Ni(B).
The spectrum of the nickel oxide heated at 600 8C
has been fitted first, assuming the known fcc structure of
NiO. The bond lengths obtained are in excellent
agreement with those from crystallography [21]. Fig. 6
shows the experimental Fourier-filtered (solid line),
best-fitted (dotted line) k
3
x(k) spectra and Fourier
transforms for the nickel oxides heated at various
temperatures. The structural parameters obtained from
EXAFS refinement are listed in Table 1. In the FT peaks
for the nickel oxides heated at various temperatures, the
major variation has been observed in the magnitude of
the FT peak rather than in the interatomic distance of
each bond pair. The heat-treatment of nickel oxides
results in substantial increase of the FT magnitude for
each bond pair.
The coordination numbers and Debye/Waller factors
in disordered systems, which affect the magnitude of the
FT peak, are usually strongly correlated; thus the values
obtained by the least-squares fitting are a measure of the
disorder rather than precisely determined parameters.
For simplicity in the curve fitting process, therefore, the
coordination numbers (N) have been fixed to the
crystallographic values. The magnitude of the FT peak
is inversely related to the Debye/Waller factor that
corresponds to the mean square relative displacement of
interatomic distance for each bond pair due to static and
thermal vibrational disorders. Fig. 7 shows variations in
the Debye/Waller factor of the major coordination
shells for the nickel oxides heated at various tempera-
tures. As observed in Fig. 7. the Debye/Waller factors
of the major coordination shells for nickel oxides show
reducing trend with the increasing heat-treatment tem-
perature.
Natarajan et al. reported that when the electrochemi-
cally prepared Ni(OH)
2
is heated to /250 8C or above,
the Ni(OH)
2
is converted into the nickel oxide. Their
thermal and XPS analysis revealed that the Ni(OH)
2
film heat-treated at 450 8C is non-stoichiometric NiO
x
(x/1.079/0.1) [22]. K. Liu et al. also reported that the
nickel oxide film prepared by sol /gel process and heated
at 300 8C for 1 h is a non-stoichiometric nickel oxide
(Ni
x
O) and due to the presence of Ni vacancy, Ni
3
exists in the nickel oxide in order to balance the charge
[5].
For the Ni /O bond pair, a small decrease of the FT
magnitude is due to the disordered distribution of two
kinds of the first shell, Ni
2
/O and Ni
3
/O bonds.
The strong bond covalency by the increase of average
oxidation state is indicative of the decrease of thermal
vibrational disorder. Therefore, the decrease of FT
magnitudes results from the main contribution of static
disorder rather than thermal vibrational effect. In the
case of Ni /Ni bonds, the decrease of FT magnitudes for
the nickel oxides with a decrease in the heating
temperature is mainly associated with the static disorder
of two different oxidative Ni
2
and Ni
3
ions and also
Ni vacancies due to the non-stoichiometry of the nickel
oxides. The above results indicate that the non-stoichio-
metric nickel oxide (Ni
1x
O) is getting closer to the
stoichiometric NiO structure with increasing heat-treat-
ment temperature due to the defect healing effect. This is
confirmed by the present Ni K-edge XANES results for
the nickel oxides.
Fig. 8 shows normalized Ni K-edge XANES spectra
for Ni(OH)
2
and oxides heated at various temperatures.
Fig. 5. FT magnitudes of the Ni K-edge EXAFS spectra for as-
deposited Ni(OH)
2
and oxides heated at various temperatures.
K.-W. Nam et al. / Electrochimica Acta 47 (2002) 3201/3209 3205
The Ni K-edge XANES spectra originate from transi-
tions of the 1s core electron of the Ni metal to excited
vacant states of proper symmetry. Based on the previous
interpretations, each feature of XANES spectra can be
interpreted in terms of the local geometry and local
electronic structure [23/25]. The pre-edge absorption, A
peak, is the formally electric dipole-forbidden 1s0/3d
transition, which gains peak intensity from pure electric
quadrupole coupling and 3d/4p orbital mixing due to
the noncentrosymmetric environment of its slightly
distorted NiO
6
octahedral site. The first strong absorp-
tion, B peak, is assigned to a shakedown process
involving the 1s0/4p transition followed by ligand to
metal charge transfer. The strongest absorption, C peak,
is purely dipole-allowed 1s0/4p transition.
For the samples heat treated at 250 8C or above, the
second derivatives of XANES spectra are presented in
Fig. 9. The second derivative structure indicates that the
Ni K-edge XANES possesses considerable structure.
The absorption edge position shifts towards lower
energy side as the heating temperature increases, sug-
gesting a concomitant decrease in the nickel oxidation
state. The variations of edge positions in the XANES
spectra for nickel oxides heated at different tempera-
tures are shown in Fig. 10. As discussed above, the
nickel oxides obtained at modest heat-treatment condi-
tions are a non-stoichiometric nickel oxide (Ni
1x
O)
with some Ni vacancies which gives rise to the presence
of Ni
3
in the structure. A slight increase in the average
Ni /O bond distance is expected with an increase in
heat-treatment temperature because of the decrease in
Ni
3
ions in Ni
1x
O attributed to the defect healing
effect at high temperatures. However, the change in the
average Ni /O bond distance with heat-treatment tem-
perature is not much pronounced (Table 1) considering
the estimated errors of 9/0.02 A

for the interatomic

distance as compared with the edge positions in the
XANES spectra for nickel oxides heated at different
temperatures.
Heating the non-stoichiometric nickel oxide at higher
temperature heals the defects and lead to the corre-
sponding atomic rearrangement. Thus, highly defective
nickel oxide at lower temperature approaches stoichio-
metric nickel oxide as the heating temperature increases.
In the present study, Ni(OH)
2
prepared via the electro-
chemical route is converted to non-stoichiometric nickel
Fig. 6. (a) Experimental Fourier-ltered (solid line) and best-tted (dotted line) k
3
x(k) spectra and (b) Fourier transforms for the nickel oxides
heated at various temperatures.
K.-W. Nam et al. / Electrochimica Acta 47 (2002) 3201/3209 3206
oxide (Ni
1x
O) with Ni vacancies at temperatures over
250 8C. In all the nickel oxides except the one obtained
at 250 8C, the more defective the structure is, the larger
its specific capacitance is. The cyclic voltammogram of
the nickel oxide at 250 8C in Fig. 2 seems to be that of
an intermediate phase between nickel oxide and
Ni(OH)
2
. However, XRD and EXAFS data show that
the phase is much closer to the nickel oxide.
Heat-treatment of the electrochemically prepared
Ni(OH)
2
causes non-stoichiometric formation of nickel
oxide as well as changes in the surface area of the nickel
oxide. Extensive XAS investigation carried out by us
revealed that non-stoichiometric nature (or defective
nature) of nickel oxide is another important factor to be
considered in explaining the change in its specific
capacitance with heat-treatment temperature. Control
of non-stoichiometry of nickel oxide by heat-treatment
could be utilized to improve its specific capacitance for
supercapacitor application.
4. Conclusions
Nickel oxide films were synthesized by electrochemi-
cal precipitation of the Ni(OH)
2
films followed by heat-
treatment in air at various temperatures. XRD results
showed that the nickel oxides obtained at 250 8C or
above has a crystalline NiO structure. Cyclic voltammo-
grams, however, reveals that the Ni(OH)
2
is not
completely converted into the nickel oxide when heated
at 250 8C. The nickel oxide showed a maximum specific
capacitance at 300 8C and decreased capacitance with a
further increase in the heat-treatment temperature.
EXAFS results revealed that the non-stoichiometric
nickel oxide (Ni
1x
O) approached the stoichiometric
NiO structure with increasing heat-treatment tempera-
ture due to the defect healing effect. This is also
supported by XANES results. From the observation of
cyclic voltammograms and XAS results of the nickel
oxides at various temperatures, it is concluded that the
Table 1
Curve-tting results for the Fourier-ltered k
3
x(k) Ni K-edge EXAFS of the nickel oxides heated at various temperatures
Sample Atom N R (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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