Journal of Sol-Gel Science and Technology 31, 323–328, 2004

c 2004 Kluwer Academic Publishers. Manufactured in The United States.

Electrochemical and Electrochromic Properties of Ni Oxide Thin Films

Prepared by a Sol–Gel Method

JIN-YOUNG PARK, KWANG-SOON AHN, YOON-CHAE NAH AND HEE-SANG SHIM

Department of Materials Science and Engineering, Gwangju Institute of Science and Technology,
1 Oryong-dong, Buk-gu, Gwangju 500-712, S. Korea

YUNG-EUN SUNG∗
School of Chemical Engineering & Research Center for Energy Conversion and Storage, Seoul National
University, Seoul 151-744, S. Korea
ysung@snu.ac.kr

Abstract. Nickel oxide thin films, which are well known anodic coloration materials that are used in electrochromic
devices, were prepared by a sol–gel method, and their electrochemical and electrochromic properties were investi-
gated. The sol was prepared from Ni(OH)2 powder with an average size of 7 nm, in a mixture of ethylene glycol
and absolute ethanol. The films were coated on an ITO substrate using the powder, dispersed in the solution. When
additive materials, acetyl acetone and glycerol, were added to the sol its hardness and adhesion properties were
improved. The optimized thin film formed an amorphous, porous structure, and showed a large current density
during continuous potential and pulse potential cycling. The film also was transparent and had a high coloration
efficiency (33.5 cm2 /C) and a rapid response time (1.0–2.5 s) during the coloring/bleaching process.

Keywords: nickel oxide, electrochromism, sol–gel coating, nanoparticle synthesis, electrochemistry

1. Introduction oration materials due to its high electrochromic effi-

Electrochromism is a phenomenon in which a change
in optical properties occurs under an applied volt-
age [1–3]. Electrochromism is reversible when the
polarity of the voltage is changed. Because of their
low power consumption (<2 V), high coloration effi-
ciency, and memory effects under open circuit condi-
tions, electrochromic devices have a variety of poten-
tial applications in information displays, light shutters,
optical switching device, smart windows, and variable-
reflectance mirrors [4].
Typically, transition metal oxides are used in elec-
trochromic materials. Among these materials, nickel
oxide is an interesting material for use in anodic col-
ciency [5–7], large dynamic range, cyclic reversibility
and low material cost [8]. Nickel oxide is one of the
most widely used anodic electrochromic materials and
is able to change color from transparent in the reduced
state to brown black in the oxidized state. The mecha-
nism of the electrochromic phenomena for nickel oxide
in an aqueous electrolyte is not clear at present, but it
has been noted that the coloration reaction involves
a double intercalation of ions and electrons to the film
[1]. Therefore, the electrochromic reaction is generally
described by the scheme (1) shown as follows:
Ni(OH)2 ↔ NiOOH + H+ + e− (1)
(bleached) (colored)

A variety of methods are used to prepare elec-

∗ To whom all correspondence should be addressed. trochromic nickel oxide films, such as vacuum
324 Park et al.
evaporation, sputtering, chemical vapor deposition,
electrodeposition process, and sol–gel process [9–12].
The sol–gel process is widely used to prepare ceramic
films at low temperatures at atmospheric conditions and
requires a lower capital investment to deposit large area
of coating compared to the vacuum deposition process
[13]. Using this process, the microstructure of the films
can be easily controlled which, in turn, can affect col-
oration efficiency, durability, and the response time of
electrochromic films. Sol–gel processes consist of two
steps: hydrolysis and polymerization of the metal pre-
cursor. Metal alkoxides are the most commonly used
precursor but their cost is relatively high. In the recent
studies, however, acetate, chloride, nitrate, and sulphate
of metals have been used as precursors [14–19].
In this study, a different route was chosen to synthe-
size nickel oxide nanoparticles and then disperse these
nanoparticles in appropriate solvents at room tem-
perature. The coating solution was a hybrid organic-
inorganic sol containing nickel hydroxide nanoparti-
cles. The advantages of this method are that impurities
can be removed during the preparation of the nickel hy-
droxide sol and that nanoparticles can be readily dis-
persed in various solvents. The use of nanoparticles
would have an influence on a low light scattering and
on the high transparency of the coated films [20]. Sol–
gel nickel oxide films could undergo reversible change
during potential cycling and the films were stable in
the electrolytes with long cycling. The electrochemical
properties, coloration efficiency, and electrochromic
response were investigated whether the films were suit-
able for use as anodic electrochromic materials.
2. Experimental
2.1. Synthesis of Ni(OH)2 Nanoparticles
Ni(OH)2 nanoparticles were synthesized by a colloidal
method in a hydrous solvent under an ambient atmo-
sphere. 0.01 M NiCl2 ·6H2 O was dissolved in distilled
water at room temperature and this solution was stirred
for 1 h. After that, 1 M NaOH was added to the solution
until reaching at pH 9 and stirred for 1 h. The precipi-
tate, which was formed instantaneously as follows:
NiCl2 ·6H2 O + 2NaOH ⇒ Ni(OH)2 + 2NaCl. (2)
This precipitate was washed with distilled water several
times to remove NaCl and then freeze-dried.
2.2. Deposition of Ni(OH)2 Film
The powders were mechanically dispersed in absolute
ethanol. The solution was prepared with additive ma-
terials in an ethylene glycol (HOCH2 CH2 OH) and ab-
solute ethanol mixed solvent with continuous stirring
and sonication. The additive materials were added to
improve the hardness and adhesion of the films. The
additive materials were 10 wt% glycerol and 20 wt%
acetyl acetone (relative to the weight of Ni(OH)2 pow-
der), respectively.
Indium tin oxide (ITO, Samsung Corning Co, Ltd.)
coated glass was used as transparent conducting elec-
trodes. The thickness of the ITO layer was about
200 nm and the resistivity of the layer was about 8
/.
The ITO glasses were cleaned before use by sonica-
tion in methanol and distilled water, respectively, for
10 min. It was then rinsed with distilled water, and
blown dry with nitrogen. The prepared sols were coated
on the conductive side of the ITO substrates sized 2 ×
2 cm2 by spin coating, where the substrates were spun
at 2000 rpm for 35 s on a spinner. The coated films
were dried in air at room temperature, and were then
annealed at 330◦ C for 50 min in air. This process is
necessary in order to improve adhesion to the substrate
and to ensure structural stability during cycling in an
alkaline electrolyte. If the heat treatment temperature
is too high, the film has a lower electrochromic effect
and even becomes inactive [21]. In other words, op-
tical modulation and the maximum value of bleached
state of untreated films gradually decreased during the
cycling or the film became detached.
The thickness and morphology of all films were mea-
sured by field emission scanning electron microscopy
(FESEM, Hitachi S-4700). The morphology of the
nickel hydroxide particles was investigated by high
resolution transmission electron microscopy (HRTEM,
JEM-2010). The crystallographic structure of particles
and films were determined by X-ray diffraction (XRD)
using a Rigaku diffractometer operated with Cu Kα
radiation source radiation at 40 kV and 40 mA.
2.3. Electrochemical and Electrochromic Tests
All electrochemical tests were performed with a three-
electrode cell at room temperature. Nickel oxide films
were used as the working electrode. Pt and Ag/AgCl
(in saturated KCl) were used as the counter and refer-
ence electrodes, respectively. The electrolyte consisted
of 1 M NaOH solutions. Electrochemical experiments
 Electrochemical and Electrochromic Properties of Ni Oxide Thin Films
were performed with an Autolab PGSTAT30 Potentio-
stat/Galvanostat.
Continuous potential cycling was carried out for sev-
eral cycles in the range of −0.7 V to 0.5 V up to
30 cycles at a scan rate of 10 mV/s. The electrochromic
response time was then tested by applying a pulse po-
tential between -0.7 V and 0.5 V with a duration time
of 30 s. The optical transmittance was simultaneously
measured by means of an in-situ transmittance sys-
tem, using a He-Ne laser (633 nm, 10 mW), during all
experiments. The transmittance of the ITO/glass with
the electrolyte and the cell window was assumed to be
100%.
3. Results and Discussion
3.1. Powder Characterization
Figure 1(a) shows the XRD patterns of Ni(OH)2 pow-
der on glass plate, XRD patterns of which are shown in
Fig. 1(b). The difference between α-phase and β-phase
Ni(OH)2 is the location of the lowest 2θ diffraction
peaks. For the β-phase Ni(OH)2 , the (001) diffraction
peak appears at 2θ = 19.2◦ and the inter-sheet distance
(d) is c0 = 4.605 Å, while the lowest diffraction located
at 2θ = 11.0◦ corresponds to α-phase Ni(OH)2 [22].
As shown in Fig. 1, the presence of (001) diffraction at
2θ = 19.2◦ confirms that the as-synthesized powder is
β-phase Ni(OH)2 .
XRD also provides information concerning crystal-
lite size. The peak broadening is caused by the finite
Figure 1. XRD patterns of Ni(OH)2 nanoparticles: (a) Ni(OH)2
particles on glass and (b) a glass plate.
325
Figure 2. TEM image and diffraction pattern of Ni(OH)2 nanopar-
ticles.
size of the crystallites, about 0.1 µm (1,000 Å) [23].
Crystallite size can be determined by an analysis of
peak shapes for several diffraction orders, since the
crystallite size affects the peak width [24]. Crystallite
size can also be estimated from the peak width using
the Debye-Scherrer Eq. (3) [23]:
0.9λ 82.941
t= [ Å] = (3)
B cos θ B B × cos(θ/2)
In this formula, B denotes the full width at half maxi-
mum. To obtain this value, the diffraction peaks were
fitted to a Gaussian function. The average particle size
of the powder was 7 nm when the above formula is
used.
Figure 2 shows TEM image and diffraction pattern
of Ni(OH)2 particles. It was confirmed that the parti-
cle size was 6–7 nm from this image, which has good
agreement with the results of XRD analysis. Also, the
TEM image indicates the presence of (101) lattices
with 0.233 nm inter-sheet distances. Furthermore, the
diffused circular shape of the patterns in the inset in-
dicates that these nanosized particles are formed from
polycrystalline powder.
3.2. Film Characterization
Figure 3(a) and (b) are XRD patterns of NiO films
heat-treated at 420 and 330◦ C, respectively. It is well
326 Park et al.

Figure 3. XRD patterns of heat-treated films prepared by a sol with

acetyl acetone and glycerol in an absolute ethanol and ethylene glycol
mixed solvent at (a) 420◦ C and (b) 330◦ C.

known that the crystallization temperature of nickel

oxide is above 400◦ C [16]. As-deposited films were
transformed to NiO by a heat-treatment at 330◦ C. The
diffraction peaks arising from NiO appear at 2θ =
36.3◦ and 42.4◦ . However, in the XRD pattern, a NiO
peak does not appear in the case of the 330◦ C heat-
treated film, indicating that it has a short-range order
structure.
In the sol–gel method, although Ni(OH)2 is the elec-
trochromic active form, a heat treatment is necessary to
improve adhesion to the substrate and to ensure struc-
tural stability during cycling in an alkaline electrolyte
Figure 4. SEM images of films prepared by a sol process with acetyl
[25]. In addition, a more porous structured film is ob- acetone and glycerol in absolute ethanol and ethylene glycol mixed
tained by heat treatment. Figure 4 shows SEM im- solvent (a) as-deposited film and (b) heat-treated film at 330◦ C for
ages of as-deposited and heat-treated films. The ad- 50 min.
ditive materials (acetyl acetone, glycerol) could be
removed from the film during the heat treatment, af-
ter which, the film had a more porous structure com- ficiently move into the film. The comparison of current
pared to as-deposited film. The nickel hydroxide sol density at the first cycle with that at the last 30th cycle,
was prepared in absolute ethanol and ethylene glycol indicates that the gradual increase explains the increase
(HOCH2 CH2 OH) mixed solvent, which allows for the in protons incorporated into the film.
formation of a thicker film than that prepared in abso- Figure 5(b) and (c) show transmittance modulation
lute ethanol only. The thickness was about 200 nm con- during continuous potential cycling and pulse potential
firmed by SEM cross-section image (not shown here). cycling for this film. These data showed a stable color-
Figure 5(a) shows cyclic voltammetry curves of the ing/bleaching performance during cycling. The trans-
films annealed at 330◦ C. The choice of this voltage mittance modulation (T ) was gradually increased.
range is because electrochemical test should be stably This indicates that more amount of protons and elec-
performed without any side reaction such as oxygen trons are incorporated in the film as the cycling pro-
and hydrogen evolutions. The sizes of the curves were ceeds, which is consistent with the fact that current den-
gradually increased and large currents were obtained. sity increases during cycling as mentioned above. As
This indicates that a large amount of protons could ef- reported in previous studies, transmittance modulation
 Electrochemical and Electrochromic Properties of Ni Oxide Thin Films
Figure 5. (a) Cyclic voltammetry curves and in-situ transmittance
curve during (b) the continuous potential cycling, and (c) step po-
tential for the films prepared after annealing at 330◦ C for 50 min.
depends on film thickness [26, 27]. Therefore it is
important that sols have a suitable viscosity to per-
mit the formation of a film with the proper thickness.
The additive materials, glycerol and ethylene glycol,
were useful in that they provided a suitable mixture of
sols and improved the adherence of the films to sub-
327
strate, and resulted in thicker films. By optimizing the
amount of additive materials as shown in the experi-
ments, the film had the best electrochromic properties,
in which the transmittance modulation was 41.2% and
the coloration efficiency was 33.5 cm2 /C. Coloration
efficiency (η) is related to changes in optical density
(OD) and charge density (Q) per unit area as shown
in the equation below.
OD(λ)
η(λ) = [cm2 /C] (4)
Q
Tb
OD(λ) = log . (5)
Tc
From in-situ transmittance curves with pulse poten-
tial cycling, the response time, which is a key elec-
trochromic property, was calculated on the level of a
90% transmittance change [4]. The response time dur-
ing the coloring process was higher than that during
the bleaching process, due to differences in conduc-
tivity between Ni(OH)2 and NiOOH. The conductiv-
ity of Ni(OH)2 was lower than that of the NiOOH
[4, 28]. Therefore, it would be expected that the color-
ing process, which involves the transition of Ni(OH)2
to NiOOH, is slower than the bleaching process, which
involves the transition of NiOOH to Ni(OH)2 . The elec-
trochromic film prepared by sol–gel showed a response
time of 1.0–2.5 s during the coloring/bleaching process.
4. Conclusions
The electrochemical and electrochromic properties of
nickel oxide film prepared by a sol–gel method were
investigated. The synthesis of nickel hydroxide powder
from a precursor is different from the general sol–gel
method. In this work, β-phase Ni(OH)2 nanoparticles,
the average size of which was about 7 nm, as confirmed
by XRD and TEM, were synthesized. The sols were
prepared by suspending the synthesized particles in
an absolute ethanol and ethylene glycol mixed solvent
with acetyl acetone and glycerol as additives. Coated
films prepared by spin coating were dried at room
temperature and then heat-treated. The film treated at
330◦ C for 50 min showed better electrochromic proper-
ties than the film treated at 420◦ C due to its short-range
order structure. The film also had a porous structure
and good adherence to the substrate, and was thicker
when ethylene glycol was used. This film showed elec-
trochromic properties where the coloration efficiency
was 33.5 cm2 /C, as transmittance modulation of 41.2%,
328 Park et al.
and a response time of 1.0–2.5 s during the color-
ing/bleaching process. However, the modulation can
be improved by optimizing the film thickness, and cor-
responding investigations are currently underway.
Acknowledgment
The authors gratefully acknowledge the financial sup-
port of the Sol–Gel Innovation Project (SOLIP) funded
by Ministry of Commerce, Industry, and Energy
(MOCIE) in Korea and the KOSEF through the Re-
search Center for Energy Conversion and Storage.
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