International Journal of Hydrogen Energy 32 (2007) 4153 – 4159

www.elsevier.com/locate/ijhydene

Electrodeposition of nanoporous nickel oxide film for

electrochemical capacitors
Mao-Sung Wu ∗ , Yu-An Huang, Chung-Hsien Yang, Jiin-Jiang Jow
Department of Chemical and Material Engineering, National Kaohsiung University of Applied Sciences, Kaohsiung 807, Taiwan, ROC

Received 6 February 2007; received in revised form 3 June 2007; accepted 5 June 2007
Available online 24 July 2007

Abstract
Nanoporous nickel oxide film is electrochemically anodic deposited onto a stainless steel substrate by a plating bath of sodium acetate, nickel
sulfate, and sodium sulfate mixture at room temperature without any template or catalyst. The deposited film is highly porous and composed
of interconnected nanoflakes of thickness 12–16 nm after 300 ◦ C annealing. Specific capacitance of the deposited film depends on the applied
potential window significantly in 1 M KOH solution. Specific capacitance is much increased by increasing the upper limit potential due to
the contribution of redox reaction of nickel oxide to the measured capacitance. The deposited film shows a superior performance in high-
rate charge/discharge capability. Specific capacitance of the deposited electrode is 167.3 Fg−1 at 1 Ag−1 charge/discharge, and 156.6 Fg−1 at
16.5 Ag−1 . The film also shows a stable capacitance during cycling. After 5000 test cycles at current density of 4 Ag−1 , specific capacitance
of the film is 140 Fg−1 , approximately 87.5% of its maximum capacitance (160 Fg−1 ).
䉷 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Porous nickel oxide; Anodic deposition; Electrochemical capacitor

1. Introduction Nickel oxide is a promising candidate. In preparation, several

Nickel hydroxide oxide materials have been used as the
positive electrode in rechargeable alkaline batteries such as
nickel–cadmium and nickel–metal hydride batteries. Due to the
high power demand of portable electronic devices and electric
vehicles, electrochemical capacitors that deliver higher power
density than traditional batteries have been studied extensively
in recent years. Transition metal oxides such as ruthenium ox-
ide, manganese oxide, cobalt oxide, and nickel oxide are qual-
ified to be electrochemical capacitor materials. Among these
oxides, a hydrous form of ruthenium oxide in aqueous H2 SO4
possesses a high specific capacitance of 760 Fg−1 and an ex-
cellent cycle-life stability [1,2]. However, ruthenium oxide is
too expensive for commercialization. Most of the attention is,
therefore, focused on alternative electrode materials that are
inexpensive and exhibit capacitive behavior similar to that of
ruthenium oxide.
∗ Corresponding author. Fax: +886 9 45614423.
E-mail address: ms_wu@url.com.tw (M.-S. Wu).
0360-3199/$ - see front matter 䉷 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2007.06.001
techniques such as chemical precipitation [3], reactive radio-
frequency (rf) sputtering [4], calcining [5], electrochemical
cathodic deposition [6–11], and electrochemical anodic deposi-
tion [12] have been proposed. Among these synthetic methods,
electrochemical deposition technique has one advantage over
the others: weight and thickness of the metal oxide film may
be easily controlled by controlling the current, bath composi-
tion, and bath temperature [6]. On the other hand, electrode
composed of nanoparticles is more difficult to fabricate by the
traditional slurry coating method, because nanoparticles have
poor dispersibility in slurry (composed of solvent, nanoparti-
cles, polymer binder, and conducting agent, etc.). Thus, it is
more advantageous to have an electrode of nano-sized nickel
oxide fabricated by the electrochemical deposition directly onto
the substrates at room temperature without any template and/or
catalyst.
Nanostructured materials play an important role in electro-
chemical capacitors because they have high specific surface
area and fast redox reactions; electrochemical capacitance be-
havior is, therefore, enhanced by the material’s nanostructure.
4154 M.-S. Wu et al. / International Journal of Hydrogen Energy 32 (2007) 4153 – 4159
Most of the synthesized nickel oxides for electrochemical ca-
pacitors are nanopowders. Nanowhiskers or small nanowires
fabricated by template are also some of the alternative struc-
tures [5,12]. Crystallized nickel oxide nanoarrays with or-
dered mesoporous structure were synthesized by calcining
nickel nitrate at high temperature within a silica template [5];
three-dimensional nanowhiskers of nickel oxide were prepared
potentiodynamically by a plating bath of nickel chloride on
stainless steel (SS) and heating the hydroxide in air at 300 ◦ C
for 3 h [12]. In electrochemical preparation of nickel oxide film
electrodes, electrochemically cathodic deposition in nitrate-
based bath is generally used [6–11], but electrochemical anodic
deposition is rarely studied. Therefore, in this work, anodic de-
position is used to fabricate nanostructured nickel oxide films
by a plating bath of sodium acetate, nickel sulfate, and sodium
sulfate mixture at room temperature without any template or
catalyst, and the obtained films were analyzed in their capacitive
behavior.
2. Experimental
Nickel oxide film was deposited directly on both sides of
the SS foil (2 × 2 cm2 ) by applying an anodic current of
0.5 mA cm−2 in a solution bath of 0.13 M sodium acetate,
0.13 M nickel sulfate; and 0.1 M sodium sulfate mixture for
60 min at room temperature [13]. Prior to deposition, SS foil
was polished with emery paper, and washed in acetone and de-
ionized water, respectively. The plating solution was stirred by
a Teflon stir on a magnetic hot plate during the deposition. Af-
ter deposition, film was rinsed several times in de-ionized wa-
ter and dried at 300 ◦ C for 1 h in air. Amount of the deposited
nickel oxide was about 0.49 mg measured by a microbalance
(Ohaus G160, USA) with an accuracy of 0.01 mg. Note that
all experiments were carried out in a three-compartment cell.
A saturated Ag/AgCl electrode was used as the reference elec-
trode and a platinum foil with dimension of 2 × 2 cm2 was the
counter electrode.
Electrochemical characteristics of the electrodes were deter-
mined by cyclic voltammetry (CV) in a three-electrode cell
with a 1 M KOH electrolyte. The potential was cycled at dif-
ferent scan rates using a potentiostat (CH Instruments CHI
608, USA) in the range of −0.2–0.45 V vs Ag/AgCl refer-
ence electrode. Charge/discharge were performed by a poten-
tiostat (Princeton Applied Research EG&G 362, USA) in the
range of −0.2–0.45 V vs Ag/AgCl at different currents. Sur-
face morphology of the film was examined with a field emis-
sion electron microscope (SEM, JEOL-6330) with accelerating
voltage of 10 keV. Crystal structures of the deposited nickel
oxide were identified by a glance angle X-ray diffractometer
(GAXRD, Rigaku D/MAX2500, Japan) with a Cu K target
(wavelength = 1.54056 Å). Diffraction data were collected for
1 s at each 0.04◦ step width over 2, ranging from 20◦ to 80◦ .
3. Results and discussion
Using the anodic deposition method at constant current den-
sity of 0.5 mA cm−2 in a solution consisting of sodium acetate,
nickel sulfate, and sodium sulfate nitrate, a new nanostruc-
tured nickel oxide film composed of nanoflakes was obtained.
Fig. 1 shows the SEM image of the electrochemically anodic
deposited nickel oxide film in 25 000 magnifications (50 000 ×
is shown in the inset). Morphology of the deposited film is
highly porous and composed of interconnected nanoflakes with
thickness of 12–16 nm. Specific surface area of the chemical
precipitated nickel oxide/hydroxide powder is generally mea-
sured by means of BET technique using nitrogen gas to relate
the capacitance of the materials. However, in this work, it is
difficult to deposit electrochemically the requisite quantity of
material needed for BET analysis [7]. On the other hand, a
large specific surface of electrode materials does not always
guarantee high specific capacitance when used in aqueous or
nonaqueous electrochemical capacitors because not all BET
surface area is electrochemically accessible when immersed in
electrolyte.
In addition to the surface morphology of the oxide film,
crystal structure is determined by an X-ray diffraction. Fig. 2
shows the XRD pattern of the deposited nickel oxide film af-
ter 300 ◦ C annealing. The X-ray diffraction pattern resembles
NiO (nickel oxide, JCPDS 47-1049) closely. A characteristic
peak of deposited nickel oxide film at 2 = 37.2◦ is broad; such
a widening indicates a poor crystallinity. Generally, a poorly
crystalline-structured film (or amorphous film) has a larger spe-
cific surface area (smaller crystal size) than that of a highly
crystalline-structure film [14].
Fig. 3 shows the cyclic voltammogram of the deposited nickel
oxide film in 1 M KOH and 1 M Na2 SO4 solutions, respec-
tively, at a scan rate of 25 mVs−1 . Redox peaks are observed at
0.41 V (oxidation) and 0.32 V (reduction) vs Ag/AgCl reference
electrode in 1 M KOH solution. The redox couple in alkaline
solution is as follows [3,15,16]:
NiO + OH− ↔ NiOOH + e− . (1)
In addition to the redox peaks, CV result also shows that as the
film is cycled from 0 V towards the anodic direction, a purely
capacitive current is obtained between 0 and 0.3 V vs Ag/AgCl;
and the capacitance results from the electrical double-layer ca-
pacitance of the film rather than from the redox (faradaic) re-
action, as the peaks in Fig. 3 show. There exist no significant
peaks for the deposited nickel oxide film in 1 M Na2 SO4 so-
lution, because the solution has a much lower concentration of
OH− compared with 1 M KOH solution and hence no signif-
icantly electrochemical redox reaction (reaction 1) in acid so-
lution. Current response in acidic solution comes mainly from
the electrical double-layer capacitance of the deposited nickel
oxide film.
In general, CV is used to characterize capacitive behav-
ior of an electrode material. An ideal electrical double-layer
capacitor of smooth electrode surface has a current response
in CVs shapes like rectangular mirror image with respect to
the zero-current line; the CV also shows a rapid current re-
sponse at each reversal potential end [17,18]. Apart from instru-
mental response problem, electrical double-layer capacitance
is independent of the scan rate and the applied potential [18].
 M.-S. Wu et al. / International Journal of Hydrogen Energy 32 (2007) 4153 – 4159 4159

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