SSRN Id4500318

Contruction of electrochromic porous NiO@Ni(OH)2
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hierarchical nanoarrays with ultra-large optical modulation
Shangzhi Yaoa,b, Yong Zhang*a,b, Jingyi Caia,b, Yong Hongc, Yan Wanga,b, Jiewu Cuia,b,
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Xia Shua,b, Jiaqin Liua,d, Hark Hoe Tane and Yucheng Wu*a,b
a. School of Materials Science and Engineering, Hefei University of Technology, Hefei,
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230009, China.
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b. Key Laboratory of Advanced Functional Materials and Devices of Anhui Province,
Hefei, 230009, China. er

c. School of Mechanical Engineering, Shanghai Dianji University, Shanghai 201306,
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China.
e. Department of Electronic Materials Engineering, Research School of Physics and
Engineering, The Australian National University, Canberra, ACT 2601, Australia.

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d. Institute of Industry & Equipment Technology, Hefei University of Technology,

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No.193 Tunxi Road, Hefei, Anhui 230009, China.

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Email:*Yong Zhang : zhangyong.mse@hfut.edu.cn *Yucheng Wu:ycwu@hfut.edu.cn
This preprint research paper has not been peer reviewed. Electronic copy available at: https://ssrn.com/abstract=4500318
Abstract
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Electrochromic capacitor energy storage device is an important part of
the renewable energy infrastructure. While light transmittance can be
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regulated by changing the brightness of the device, the clear color change
of the device makes the remaining power visible. Herein, hierarchical
porous NiO@Ni(OH)2 heterostructure nanoarrays are fabricated by a
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simple hydrothermal process with following electrodeposited treatment.
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Ni(OH)2 nanosheets with very narrow widths are uniformly grown on the
surface of underlying NiO nanosheets which are synthesized on FTO

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substrates. The nanostructure exhibits enhanced electrochromic
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performance with high optical modulation (87.4% at 550 nm), fast
switching time (5.8/7.2 s) and exceedingly good cycle stability (80.0%
contrast retention after 500 cycles). The morphology of the nanostructure

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results in increased areal capacitance (104.0 mF/cm2), good rate property

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and cycle property of the film. The obtained improved electrochemical
performances are mainly contributed to the structure design and the

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synergism between NiO and Ni(OH)2 which increase structural robustness
whilst more exposing more surface area to facilitate ion and electron
diffusion. This work provides a practical pathway to design multi-

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component electrochromic energy storage devices with outstanding
performance.
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Keywords: NiO@Ni(OH)2; Electrochromic; Hierarchical porous
nanoarrays; Energy storage
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1. Introduction
Electrochromic materials are materials whose optical transmittance
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undergoes a stable and reversible color change under different applied
biases.[1-5] This phenomenon has been widely used in energy saving
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applications and for visual modulation.[6-10] For most inorganic materials,
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the principle of color change is based on reversible electrochemical redox
reactions with extraction and insertion of charges and ions.[11-16] Because

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of their similar operational principle with capacitors, electrochromic
materials also exhibit the characteristics of a capacitor during operation.

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The charging/discharging process of capacitors corresponds to the
coloring/bleaching process of electrochromic materials.[17-22] Therefore,
bifunctional materials with capacitive characteristics which can efficiently

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store energy, and electrochromic characteristics which can effectively

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control optical transmittance and color are expected to become a new
generation of energy materials.[23-29]

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With increasing research on bifunctional materials, much progress has
been made in recent years. The electrochromic property of NiO-based

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materials is mainly caused by the redox reaction between Ni2+ (transparent)
and Ni3+ (dark brown). Accordingly, NiO also shows good capacitive
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performance. However, its intrinsic poor conductivity and low reaction
activity limit its use in practical applications.[30-35]
Ni(OH)2 is receiving increasing focus on its utilization in many fields,
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such as water splitting, photocatalysts, and supercapacitors due to its highly
capacitance. However, its electrochromic property has not been
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investigated in detail. It is known from electrochromism of NiO, that
Ni(OH)2 will directly convert to colored NiOOH by applying a positive
voltage, thereby exhibiting potential electrochromic ability.[36-40]
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To date, rational design of hierarchical structures and heterostructures
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can efficiently improve the electrochemical properties of materials. Firstly,
the hierarchical structures (especially porous hierarchical structures) can

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improve the electrochemical exposed area to promote the penetration of
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electrolyte and accelerate charge transfer and surface/interface reactions.
Secondly, heterostructures can make the most of the synergistic effect of
multiple components to adjust the electronic structure, regulate the

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intermediate adsorption and expose more active sites. However, designing
NiO-based heterointerfaces with high electrochromic properties remains a

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challenge.[39, 41-47]
In this paper, films consisting of hierarchical porous NiO@Ni(OH)2

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nanosheet heterostructure array were designed and prepared. The excellent
electrochemical performances are derived from the synergism between

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NiO and Ni(OH)2, resulting in structural stability and large surface area.
The porous nanosheet array films exhibit excellent bifunctional

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electrochromic and capacitive performance, with a wide optical
modulation, rapid color transformation, excellent cyclic stability and high
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surface capacitance. Our findings pave the way for designing and
manufacturing more advanced future-oriented electrochromic capacitor
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materials and new intelligent windows.
2. Experiment
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2.1 Materials
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Nickel nitrate (Ni(NO3)2·6H2O, 99.9%, Alfa Aesar),
hexamethylenetetramine (HMTA, C6H12N4, 99.5%, Alfa Aesar), ethanol

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(C2H6O, 99%, Alfa Aesar), and potassium hydroxide (KOH, 99.9%, Alfa
Aesar) were used directly without any further purification.

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2.2 Preparation of NiO nanosheet arrays
FTO coated glass substrates (3×5 cm2 in size) were cleaned by an
ultrasonic method in acetone, ethanol and de-ionized water sequentially for

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30 min each. Firstly, 1 mmol Ni(NO3)2·6H2O and 4 mmol HMTA were

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dissolved in 50 mL deionized (DI) water and stirred until the solution
became clear. The solution was then transferred into a Teflon-lined

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stainless-steel autoclave (100 mL), and then the post-treated FTO glass
substrates were immersed in the solution to initiate growth of the film. NiO
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precursor layer was obtained by solution phase reaction at 120 °C for 6 h.
After the autoclave had cooled down to room temperature naturally, the
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prepared samples were washed several times with DI water. This precursor
layer was then transformed into NiO by annealing at 350 °C for 2 h in air
at a heating rate of 2 °C/min. The synthesis method of comparison samples
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was similar, except the hydrothermal temperature and time were changed
to 90,120 and 150 °C and 1, 3, 6 and 9 h.
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2.3 Preparation of Ni(OH)2 nanosheet arrays
The hierarchical Ni(OH)2 arrays were prepared by a simple
electrodeposition method in a three-electrode electrodeposition system,
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where FTO glass (as the working electrode, WE) was immersed into the
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electrolytic cell, which contained 0.02 M Ni(NO3)2 6H2O and 0.06 M
HMTA aqueous electrolyte. The temperature was set to 60 °C and kept for
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60 s under a constant current density of -1 mA cm2. A Pt electrode served
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as the counter electrode (CE) during the whole process. Finally, the
obtained samples were washed with deionized water and ethanol several
times. A schematic illustrating the synthesis process is shown in Fig. 1.

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2.4 Material Characterization
The surface morphologies of the samples were investigated by

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scanning electron microscopy (SEM, Hitachi Regulus 8020) and
transmission electron microscopy (TEM, JEM-2100F). X-ray diffraction

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(XRD) patterns of the samples from 10 to 90 degrees were obtained at room
temperature on a XˊPert Pro MPD (PANalytical B.V.) using a Cu target

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(λ= 0.154 nm). X-ray photoelectron spectroscopy (XPS) data was obtained
with a Thermo ESCALAB250Xi system using Al K radiation.

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2.5 Electrochemical measurements
Electrochemical and electrochromic measurements were carried out
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in a three-electrode system consisting of 1 M KOH aqueous solution as the
electrolyte. The sample, an Ag/AgCl electrode and a Pt wire were used as
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the working electrode, reference electrode and counter electrode,
respectively. Cyclic voltammetry (CV), chronoamperometry (CA) and
galvanostatic charge–discharge (GCD) tests were performed with in situ
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spectroscopic measurement at 550 nm via the combination of an
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electrochemical workstation (CHI760E) and a Shimadzu UV-3600 UV-
VIS-NIR spectrophotometer. The CV measurements were carried out in

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the potential range of -1.0 to +1.0 V with a scanning rate of 50 mV/s. The
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optical transmittance of the film was measured from 300 to 1300nm.
Measurement voltage was between -1.0 V and +1.0 V with a time step of
20 s, and the dynamic optical modulation of the sample was recorded at

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550 nm. Electrochemical impedance spectroscopy (EIS) was performed
under open circuit voltage conditions with an AC amplitude of 5 mV over

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a frequency range of 0.1~100kHz.

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3. Result and discussion

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Fig. 1. Fabrication scheme illustration of the hierarchical NiO@Ni(OH)2 nanostructures.
The synthesis process of the NiO@Ni(OH)2 nanostructures is shown in

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Fig. 1. The porous NiO nanosheets array film was prepared by
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solvothermal method and heat treatment process in advance, and then the
Ni(OH)2 nanosheet array was uniformly grown on the surface by
electrodeposition method, forming the overall three-dimensional

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hierarchical structure.
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Fig. 2. FESEM image of synthesized (a) NiO and (b) Ni(OH)2. Low (c) and high (d)
resolution FESEM image of NiO@Ni(OH)2. TEM image of synthesized (a) NiO
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nanosheet and (b) NiO@Ni(OH)2 hierarchical nanostructure.
Firstly, a series of NiO nanosheets with different morphological
characteristics were synthesized by using different hydrothermal

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parameters. Fig. S1-S3 exhibit the influence of solvothermal temperature
and time on the morphology of the NiO nanostructures. Generally, a dense

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array of NiO nanosheets array is uniformly grown over the FTO surface.
At lower temperatures and reaction times, the nanosheets were relatively

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thicker and denser, with small gaps between the sheets. With increasing
reaction temperature and time, the thickness of the nanosheets decreases
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and the number of voids increases, forming a porous structure with cross-
linking between the nanosheets. In addition, when the temperature is too
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high and the reaction time is too long, the nanosheets themselves will
gradually generate pores, causing their fragmentation and eventually the
collapse of the overall structure. As shown in Fig. S2, the NiO sample
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prepared for 6 h at 120°C exhibits a uniform porous nanosheet array
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structure, forming a stable network-like structure. The lateral length of
each NiO nanosheet is in the micrometer range, and their thickness is

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determined to be ~7 nm, as indexed in FESEM images.
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The high resolution SEM images of thin Ni(OH)2 film surfaces with
FTO glass as substrate are shown in Fig. 2b and Fig. S4. The deposited
Ni(OH)2 sample exhibits a porous array consisting of many interconnected

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nanosheets, forming a mesh-like structure. However, the relatively fast
electrochemical deposition process prompts a stacked growth of Ni(OH)2

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nanosheets, where the individual nanosheets grow on top of each other to
form a three-dimensional structure, resulting in an overall smaller internal

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space that can hamper the penetration of the electrolyte and inhibiting ion
exchange. Therefore, this type of nanostructure is not conducive to

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electrochemical reactions.
As for hierarchical NiO@Ni(OH)2 nanostructure arrays, the SEM

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images (Fig. 2c,d) exhibit that the numerous Ni(OH)2 nanoarrays form a
network-like structure, vertically aligned and uniformly over the entire
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NiO nanosheets. This particular geomertry provides a larger specific
surface area for interaction with electrolyte. Fig. 2e, f show the TEM
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images of NiO and NiO@Ni(OH)2, respectively. The NiO film exhibits a
prominent nanosheet structure. After electrodeposition, various tiny
Ni(OH)2 nanosheets are formed on the surficial layer of the NiO nanosheets
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with a length of less than 100 nm.
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As shown in Fig. 3, The clear lattice fringe with a spacing of about
0.24 nm matches along with the (111) crystal plane of NiO. Simultaneously,
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the lattice fringes with a interplanar spacing of 0.20 and 0.23 nm match
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respectively with the (200) plane of NiO and the (015) plane of Ni(OH)2,
respectively. At the same time, many lattice fringes overlap each other,
which is also due to the small Ni(OH)2 nanosheet overlapping on the

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surficial layer of NiO nanosheet, corroborating with the above SEM
images. Furthermore, the diffraction patterns shown in Fig. 3b can be

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accurately indexed the cubic phase of NiO of the (111), (200), and (220)
lattice planes. The energy dispersive spectroscopic maps of NiO and

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NiO@Ni(OH)2 definitely exhibit an even distribution of Ni and O
elements.[21, 48, 49]

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To further investigate the crystal structure of samples, NiO nanosheet
film was removed from the FTO glass to obtain the corresponding XRD
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patterns as shown in Fig. S5a. The X-ray diffraction peaks at 36.9°, 43.1°
and 62.3° match well with (110), (200) and (220) crystal planes of cubic
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phase NiO (PDF card: No.47-1049), respectively.[50-52] The crystallite
size can also be estimated from following Scherrer's formula which was
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applied to the diffraction peak at ~37°:
D = kλ/(βcosθ)
where k is the Scherrer constant taken as 0.89, λ is the wavelength of
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used X-ray (1.54Å), β is the FWHM of the chosen low angle peak and θ is
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the Bragg angle. The calculated β and crystallite size are 1.305° and 6.02
nm for NiO synthesized at 120℃ for 6 h. According to previous reports,

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the activation energy of charge transfer and ion diffusion of nanomaterials
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with smaller grain size are much lower than those with bigger grain size.
Simultaneously, the smaller grain size has more surface area to facilitate
redox reaction, which can lead to enhanced electrochemical

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performance.[53, 54]
The Raman scattering spectra of these samples at room temperature

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are exhibited in Fig. S5b. The prominent broad peaks centered at 459, 498
and 1092 cm-1 can be indexed to the first-order TO phonon mode, LO

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phonon mode, and two phonon 2LO of cubic NiO, respectively. The above
analysis additionally demonstrated the crystal morphology of the NiO film.

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Fig. 3. FETEM images and corresponding EDS maps of (a) NiO and (b) NiO@Ni(OH)2.
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Fig. 4. The (a) Ni 2p and (b) O 1s XPS spectra of various films investigated.
Due to the strong signal from the FTO substrate, it is difficult to

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distinguish the composition information of Ni(OH)2 and NiO@Ni(OH)2
films. So as to check the surficial component and elemental valence states

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of the samples, XPS test was further conducted. As displayed in Fig. 4a,
the Ni 2p3/2 can be deconvoluted to Ni-O at 853.7 eV and Ni-OH at 855.5

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eV. For the Ni 2p of Ni(OH)2 and NiO@Ni(OH)2, two peaks centered at
855.8 and 873.4 eV can match well with the Ni 2p3/2 and Ni 2p1/2,
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respectively. The peaks centered at 861.4 and 879.3 eV refer to the
corresponding satellite peaks. Obviously, the binding energy difference of
the Ni 2p3/2 and Ni 2p1/2 peaks is 17.6 eV, which confirms the existence of
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Ni(OH)2. For O 1s XPS shown in Fig. 4b, the peaks at ~529.2 and ~530.8
eV can refer to lattice oxygen (i.e., Ni–O) and OH groups (i.e., Ni–OH),
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respectively. Reversely, the peak at 529.2 eV for Ni–O is absent in the rest,
indicating the different components of the surface among these films. For
NiO@Ni(OH)2, the peak center exhibits the slight shift to higher binding
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energy position, suggesting strong electron interactions. It is worth noting
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that the XPS peak pattern of the NiO@Ni(OH)2 resembles that of Ni(OH)2.
This suggests that NiO is not detected in the hierarchical NiO@Ni(OH)2

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film. Considering that the detection depth of XPS is around 10 nm, we
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speculate that the Ni(OH)2 prepared by electrodeposition not only grows
vertically on the surficial layer of NiO nanoarrays, but also covers the
surface of NiO. To confirm this, we further analyze the hierarchical

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NiO@Ni(OH)2 film by in situ Ar+ etching during XPS measurements (Fig.
5). With prolonged etching time, the Ni 2p peak of Ni-O at 853.7 eV begins
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to appear. Similarly, the O 1s peak of Ni-O at 529.2 eV can also be seen,
thereby confirming our speculation that Ni(OH)2 has grown not only as
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nanosheets on the NiO nanosheets, but also forming a layer to cover the
nanosheets. Simultaneously, elemental analysis at different etching times

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were also experimented and the corresponding data are exhibited in Fig.
S6. With increasing etching time, the proportion of Ni signal gradually

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increases from 32% to 51%, as expected since the proportion of Ni in NiO
is higher than in Ni(OH)2, further validating the formation of a Ni(OH)2
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layer over the NiO nanosheets.[25, 29, 55]
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Fig. 5. The (a) Ni 2p and (b) O 1s XPS spectra measured after etching of the
NiO@Ni(OH)2 layer for various durations. (c) Raman and FTIR spectra of the films.
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In order to confirm the surface of films, corresponding Raman spectra
were obtained in Fig. 5c. As for NiO film, the Raman bands centered at
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463 and 492 cm-1 match well with the A1g stretching modes of Ni-O band.
There are no obvious peak of Ni(OH)2 ,which can be affected by the low
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mass loading of Ni(OH)2 on FTO glass. Furthermore, the analogous Raman
spectra were obtained for the NiO@Ni(OH)2 film. Notably, the slight shift
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towards a lower wavenumber can be observed owning to the small size of
the Ni(OH)2 nanosheets in NiO@Ni(OH)2 nanoarrays.[25, 56] Fig. 5d

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exhibits the FTIR spectrum of the synthesized nanoarrays film samples.
The two broad peaks at 1622 and 1385 cm-1 can match well with the
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interlayered H2O molecules and NO3-. An Ni-O-H mode is centered at 656
cm-1 with a Ni-O mode centering at 565 cm-1 (Fig. 2a).[57, 58] According
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to the above analysis, it can be determined that the hierarchical structure
contains the inner NiO core and outer tiny Ni(OH)2 shell.
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Fig. 6. The transmittance spectra of (a) NiO, (b) Ni(OH)2, and (c) NiO@Ni(OH)2 under
different bias. (d) Temporal optical transmittance response at 550 nm of the films
between +1.0 and −1.0 V and a pulse width of 20 s. (e) CV curves at a scan rate of
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0.005 V/s of the samples. (f) EIS of the samples at an applied AC voltage of 5 mV.
In order to test the electrochromic properties of the films, we
investigated the transmittance of different colored and bleached states in
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the wavelength region of 300-1300 nm by adjusting the applied voltage
(Fig. 6a-c). As expected, high transmittance occurs when the prepared film
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is in the bleached state (−1.0 V vs. Ag/AgCl). Inversely, for the colored
films, the corresponding transmittance decreases considerably and the
sample turns dark brown. Optical modulation (ΔT), which is used to
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characterize the electrochromic performance, which is recognized as the
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difference of transmittance at bleaching and coloring states. According to
the result, the NiO@Ni(OH)2 film exhibits wideband optical modulation,

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reaching a modulation of 87.4% at 550 nm. Notably, the Ni(OH)2 film
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exhibit the highest optical modulation of 94.9%, while that of the NiO film
is only 85.1%. For the sake of quantitatively assessing the switching
properties of the films, in situ dynamic transmittance data were recorded

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between +1.0 and −1.0 V (vs. Ag/AgCl) with a duration of 20 s (Fig. 6d)
at 550 nm. Changing time is a vital parameter to assess electrochromic

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properties, which can be explained as the time approach 90% of the max
color change. The coloring and bleaching time of NiO, Ni(OH)2 and
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NiO@Ni(OH)2 films obtained from in situ transmission spectrum are
shown in Table S1. According to the table, the switching speed of

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NiO@Ni(OH)2 film (tc = 5.8 s, tb = 7.2 s) is superior to that of Ni(OH)2
film, with NiO film having the fastest response. Hence our NiO@Ni(OH)2
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film is able to utilize the synergistic effects of Ni(OH)2 (high optical
modulation) and NiO (fast response).[57, 59, 60] The optical photographs
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of the samples at pristine, colored and bleached states are shown in Fig. S7
and Fig. S8.
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To further understand the fundamental electrochemical processes
occurring in these samples, CV measurements were performed. It can be
seen that for all films, there is a significant oxidation peak during the
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positive sweep cycle and a reduction peak during the negative cycle, which
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is mainly caused by the redox reaction related to Ni2+/Ni3+. The reactions
involved in the whole EC process can be explained as follows:

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NiO + OH- → NiOOH + e-
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Ni(OH)2 + OH- ↔ NiOOH + H2O + e-
As shown in Fig. S9 and Fig. 6e, the closed area and peak current
density of NiO@Ni(OH)2 is dramatically larger than that of the other two

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films, suggesting that more OH- is involved in being extracted out and
inserted into the heterostructure, which has more reactive area and is able
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to perform redox reactions more quickly.[37, 57, 61-63]
CV curves of all samples at diverse scan rates from 10 to 50 mV/s are

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displayed in Fig. S10. Along with increasing scan rate, the cathodic and
anodic peaks exhibit prominent shift to negative and positive potentials,

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respectively. Simultaneously, the anode and cathode peak current densities
of all films show an almost linear relationship to the square root of the scan
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rate, implying the whole electrochemical reaction process is dominated by
diffusion process. A higher slope implies a higher diffusion rate. Moreover,
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the diffusion coefficients of OH- in NiO, Ni(OH)2, and NiO@Ni(OH)2 can
be derived on the base of the following Randles-Sevcik equation:
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I = 2.69 × 105An3/2C0D1/2ⱱ1/2
where I is peak current (A), A the reaction area (cm2), n the transferred
electron number, C0 the ions concentration in the electrolyte (mol/L) and ⱱ
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the scan rate (V/s). By carefully calculating the value of DOH-, the value of
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DOH- of NiO@Ni(OH)2 (9.33×10-9 cm2s-1) is determined to be larger than
that of NiO (7.76×10-9 cm2s-1) and Ni(OH)2 (6.28×10-9 cm2s-1). The

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improved diffusion coefficient implies the superior reaction kinetics,
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which contribute to the enhanced electrochemical activity.[64-66]
Electrochemical impedance spectroscopy is often utilized to assess
the interfacial properties of electrochemical materials and determine the

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resistance for charge transfer of the electrode using Nyquist diagram. Fig.
6f shows the electrochemical impedance spectrum and the illustration

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describes the equivalent circuit model, where Re and Rct represent the
resistance for electrolyte and charge transfer, respectively. In addition, Cdl

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represents the capacitance of the double electric layer. For the linear
portion of the graph, the steeper the line, the faster the ion diffusion. As
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shown in Table S5, the charge transfer impedance of the NiO@Ni(OH)2
film sample is obtained to be 35.8 Ω, which is less than 37.1 Ω of the NiO
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film and 44.5 Ω of the Ni(OH)2 film, indicating the fastest charge transfer
rate and the highest conductivity, which can greatly increase the rate of
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electrochemical reaction. Additionally, the Cdl value of the NiO@Ni(OH)2
film is 0.047 μF, which is higher than 0.029 μF of the NiO film and 0.032
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μF of the Ni(OH)2 film, manifesting the sample has the highest
electrochemical active surface area, consistent with the above analysis
from previous scan morphology and cyclic voltammetry. The
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electrochromic properties of NiO films synthesized at different
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experimental parameters are also evaluated as shown in Fig. S11 and Table
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In terms of electrochromic properties, the NiO film has a relatively
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faster color change, which may be due to the tight binding between NiO
and the substrate, and the interconnection between the nanosheets, forming
a porous three-dimensional structure, which can contribute to fast charge

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transfer. On the other hand, Ni(OH)2 film displays a slower electrochromic
speed. In the kinetic curve, the voltage application time of 20 s cannot

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complete the electrochromic transformation process due to the dense
arrangement which slows down ion transport. However, Ni(OH)2 can carry
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out electrochromic reaction more directly and efficiently. Therefore, within
20 s of an applied bias, a fuller electrochemical reaction and a wider range

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of optical modulation can be achieved.
However, the electrochromic properties of Ni(OH)2 are not equal to

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those of NiO. Therefore NiO@Ni(OH)2 film, to take advantage of the
high charge transfer speed of NiO and the high optical modulation
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performance Ni(OH)2, the hierarchical NiO@Ni(OH)2 film is elaborately
designed and produced. By using with NiO as the base and Ni(OH)2 as the
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surficial layer and on the surface, the problem of active material congestion
and space compaction caused by direct deposition is alleviated, and a three-
dimensional electrochromic system is formed which can carry out charge
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transfer rapidly and thus allow reactive material to participate more fully
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in the reaction.
Fig. 7a displays the absorption spectra of all the synthesized films.

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Obviously, the absorption edge of the NiO@Ni(OH)2 film manifests a
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significantly redshift compared to that of the NiO film, indicating that there
is an electronic interaction between surficial Ni(OH)2 and inner NiO in the
hierarchical nanostructure. Fig. 7b shows the Tauc curve of the samples.

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Here, the optical gap value can be determined by the Tauc equation:
(αhν)n = A(hν-Eg)
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where α is the absorption coefficient, ν is the light frequency, Eg is the
bandgap, A is the constant of absorption, and n depends on the

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characteristics of the semiconductor material, that is, for indirect bandgap
material is 1/2, and the direct bandgap material is 2. For NiO, n=2.
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According to Fig. 7b, the bandgap (3.25 eV) of the NiO@Ni(OH)2 film is
less than that of the NiO film (3.42 eV). This phenomenon indicates that
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the interaction between the two components of the hierarchical structure
creates a synergistic effect, leading to stronger absorption of visible light
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and improving the overall conductivity.[67, 68]
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Fig. 7. (a) The UV-vis absorption spectra and (b) corresponding Tauc plot
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of synthesized NiO and NiO@Ni(OH)2 film.
Fig. 8a exhibits that the galvanostatic charge-discharge curves are

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symmetric, demonstrating the great reversibility, which is consistent with
previous CV results. Fig. 8b displays the GCD curves of the films at the
constant current density of 0.14 mA/cm2, due to which NiO@Ni(OH)2

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exhibits a longer discharging time compared to other samples due to the

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improved electric conductivity and more electrochemical active surface.
So as to further gain an even deeper understanding of the charge

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storage mechanism, the battery (diffusion control) and capacitor
(capacitance control) behaviors can be distinguished according to the

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relationship between the obtained current (I) and the scanning rate (mV/s)
in the CV curve as shown in Fig. S12:

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I = aⱱb
where a and b are constants. b is calculated by the slope of log (I)
versus log (ⱱ). It is common knowledge that the b value approaches 1.0 for
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surface capacitance-dominated processes and 0.5 for diffusion-controlled
processes. According to the obtained results, the value of b is close to 0.5,
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which is typical of diffuse-limited pseudo-capacitor cells. Moreover, the
NiO@Ni(OH)2 sample shows the highest b value (0.62 at the anode
peak), indicating favorable capacitive dynamics.[24, 26, 69]
v
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ot
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Fig. 8. (a) Galvanostatic charge/discharge curves of the NiO@Ni(OH)2 film at different

current densities. (b) GCD curves and (c) corresponding obtained areal capacitance at
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different current densities of the various films. (d) Capacitance retention of the films
over 3000 cycles at the constant current density of 0.42 mA/cm2.
According to previous tests, the tangible electrocapacitive

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performance data of the samples are displayed in Fig. 8c. The highest areal
capacitance is achieved in NiO@Ni(OH)2, reaching 104 mF/cm2 at 0.14

Pr
mA/cm2 and remains at 61% while the discharge current density rises to
1.12 mA/cm2. In comparison, the NiO film can only reach 55.8 mF/cm2
while Ni(OH)2 sample achieves only 41.5 mF/cm2,. The capacitance of the
ed
Ni(OH)2 film dropped by about 74.7% as the discharge current density is
increased 8-fold. In addition, repetitive charge/discharge tests were
iew
experimented at 0.42 mA/cm2 to assess the cycling stability. It is obvious
from Fig. 8d the NiO@Ni(OH)2 film retains 56.0% of its initial capacitance
after 3000 cycles. In contrast, the synthesized NiO and Ni(OH)2 samples
v
display a rapid capacitance drop after 1000 cycles and 2000 cycles,
re
respectively. The better stability is attributed to the robustness of
hierarchical nanostructures. The bifunctional electrochromic capacitance

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properties are prior to those of previously reported NiO-based materials
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(Table S6), revealing that the NiO@Ni(OH)2 film exhibits much
comparable optical modulation and energy storage ability. [63, 70]

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tn
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ep
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Fig. 9. (a) Current density of NiO@Ni(OH)2 before and after 500 cycles at 550 nm
between +1 and -1 V. (b) Transmittance spectra of NiO@Ni(OH)2 after 500 cycles. (c,
d) Low and high resolution FESEM images of NiO@Ni(OH)2 after 500 cycles.
ed
For commercial applications, ideal electrochromic materials should
maintain high performance despite long-term variations in voltage. In Fig.
iew
9a, the NiO@Ni(OH)2 sample is cycled 500 times between -1.0 V and +1.0
V by the chronoamperometry method. During the cycle, the corresponding
current in injecting and extracting of the film remains essentially constant.
v
At the same time, the optical modulation of the thin film is 80.0% after 500
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cycles, exhibiting good cycle stability. The SEM images in Fig. 9c and Fig.
9d display the well-defined morphology of the sample after cycling, where

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the hierarchical nanosheet structure is still retained, indicating robustness
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of the NiO@Ni(OH)2 film.[71-73]
4. Conclusions
To summarize, the unique NiO@Ni(OH)2 films prepared by

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solvothermal method combined with subsequent electrochemical

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deposition process show a hierarchical structure containing an array of
nanosheets forming a three-dimensional porous network. The film has

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excellent electrochromic properties and optical modulation range, rapid
color transformation and with long-term cyclic performance. In addition,

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it also has high capacitive energy storage properties and superb rate
capacity. The improved performance is essentially ascribed to the porous

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hierarchical structure formed combining the bottom NiO nanosheets with
finer Ni(OH)2 nanosheets on the top, resulting in more exposed active area
to promote charge transfer and material diffusion and more micropores to
ed
buffer the volume expansion caused by phase transition during
electrochromic process. The synergistic effect of each material also can
iew
regulate the intermediate adsorption and fully utilize the high charge
transfer speed of NiO and the high optical modulation performance
Ni(OH)2. The results from this work will help researchers design and
v
fabricate high-performance electrochromic capacitor materials that can
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lead to prospective applications in energy saving and storage devices.
Appendix A. Supplementary data

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The following is the Supplementary data to this article:
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CRediT authorship contribution statement
Shangzhi Yao: Writing – original draft, Formal analysis, Data curation.

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Yong Zhang: Writing – review & editing, Conceptualization. Jingyi Cai:
Investigation. Yong Hong: Investigation. Yan Wang: Methodology. Jiewu

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Cui: Formal analysis. Xia Shu: Formal analysis. Jiaqin Liu: Investigation.
Hark Hoe Tan: Formal analysis. Yucheng Wu: Writing – review & editing,
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Formal analysis.
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Declaration of competing interest
The authors declare that they have no known competing financial interests
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or personal relationships that could have appeared to influence the work
reported in this paper.
Acknowledgments
ed
This project is supported by the National Natural Science Foundation of China
(Nos. 52072106, U1810204), Science and Technology Major Project of Anhui
iew
Province (202003a05020007), the Key R&D Projects of Anhui Province
(202104b11020016), Natural Science Foundation of Anhui Province (2108085MB45),
We also would like to thank the financial support from the Higher Education Discipline
v
Innovation Project "New Materials and Technology for Clean Energy" (B18018).
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H. H. T. acknowledges the award of the Overseas Distinguished Professorship (Haiwai
Mingshi) by the Chinese Ministry of Education.

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Contruction of electrochromic porous NiO@Ni(OH)2

a. School of Materials Science and Engineering, Hefei University of Technology, Hefei,

Hefei, 230009, China. er

e. Department of Electronic Materials Engineering, Research School of Physics and

Engineering, The Australian National University, Canberra, ACT 2601, Australia.

d. Institute of Industry & Equipment Technology, Hefei University of Technology,

No.193 Tunxi Road, Hefei, Anhui 230009, China.

Email:*Yong Zhang : zhangyong.mse@hfut.edu.cn *Yucheng Wu:ycwu@hfut.edu.cn

the renewable energy infrastructure. While light transmittance can be

of the device makes the remaining power visible. Herein, hierarchical

porous NiO@Ni(OH)2 heterostructure nanoarrays are fabricated by a

surface of underlying NiO nanosheets which are synthesized on FTO

switching time (5.8/7.2 s) and exceedingly good cycle stability (80.0%

contrast retention after 500 cycles). The morphology of the nanostructure

results in increased areal capacitance (104.0 mF/cm2), good rate property

and cycle property of the film. The obtained improved electrochemical

performances are mainly contributed to the structure design and the

synergism between NiO and Ni(OH)2 which increase structural robustness

diffusion. This work provides a practical pathway to design multi-

component electrochromic energy storage devices with outstanding

Keywords: NiO@Ni(OH)2; Electrochromic; Hierarchical porous

Electrochromic materials are materials whose optical transmittance

biases.[1-5] This phenomenon has been widely used in energy saving

reactions with extraction and insertion of charges and ions.[11-16] Because

materials also exhibit the characteristics of a capacitor during operation.

coloring/bleaching process of electrochromic materials.[17-22] Therefore,

bifunctional materials with capacitive characteristics which can efficiently

store energy, and electrochromic characteristics which can effectively

control optical transmittance and color are expected to become a new

generation of energy materials.[23-29]

With increasing research on bifunctional materials, much progress has

been made in recent years. The electrochromic property of NiO-based

materials is mainly caused by the redox reaction between Ni2+ (transparent)

performance. However, its intrinsic poor conductivity and low reaction

activity limit its use in practical applications.[30-35]

capacitance. However, its electrochromic property has not been

Ni(OH)2 will directly convert to colored NiOOH by applying a positive

voltage, thereby exhibiting potential electrochromic ability.[36-40]

the hierarchical structures (especially porous hierarchical structures) can

Secondly, heterostructures can make the most of the synergistic effect of

multiple components to adjust the electronic structure, regulate the

intermediate adsorption and expose more active sites. However, designing

NiO-based heterointerfaces with high electrochromic properties remains a

In this paper, films consisting of hierarchical porous NiO@Ni(OH)2

nanosheet heterostructure array were designed and prepared. The excellent

electrochemical performances are derived from the synergism between

The porous nanosheet array films exhibit excellent bifunctional

electrochromic and capacitive performance, with a wide optical

manufacturing more advanced future-oriented electrochromic capacitor

hexamethylenetetramine (HMTA, C6H12N4, 99.5%, Alfa Aesar), ethanol

Aesar) were used directly without any further purification.

FTO coated glass substrates (3×5 cm2 in size) were cleaned by an

ultrasonic method in acetone, ethanol and de-ionized water sequentially for

30 min each. Firstly, 1 mmol Ni(NO3)2·6H2O and 4 mmol HMTA were

dissolved in 50 mL deionized (DI) water and stirred until the solution

became clear. The solution was then transferred into a Teflon-lined

precursor layer was obtained by solution phase reaction at 120 °C for 6 h.

to 90,120 and 150 °C and 1, 3, 6 and 9 h.

Email:Yong Zhang : zhangyong.mse@hfut.edu.cn Yucheng Wu:ycwu@hfut.edu.cn