Materials Letters 166 (2016) 179–182

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Hydrothermal synthesis of vanadium oxide nanorods and their

electrochromic performance
Jia Chu a,n, Zhenzhen Kong a, Dengyu Lu a, Wenlong Zhang a, Xianshan Wang a, Yifan Yu a,
Sai Li a, Xiaoqin Wang a, Shanxin Xiong a,n, Jing Ma b,n
a
College of Chemistry and Chemical Engineering, Xi'an University of Science and Technology, Xi'an 710054, China
b
School of Metallurgical Engineering, Xi'an University of Architecture and Technology, Xi'an 710055, China

art ic l e i nf o a b s t r a c t

Article history: Nanorod-like V2O5 was fabricated using a simple one-step hydrothermal method using NH4VO3 and
Received 17 October 2015 oxalic acid as precursors. The morphology and structure of the as-prepared V2O5 nanocrystals were
Received in revised form characterized by different techniques. Furthermore, based on the analyses of cyclic voltammetric curves
1 December 2015
and electrochromism test, the thin V2O5 nanorod film have been found to exhibit promising electro-
Accepted 16 December 2015
Available online 18 December 2015
chromic performance, which can be attributed to their nanorod architecture. The as-prepared V2O5
nanocrystals are promising electrochromic candidate for potential application in smart window.
Keywords: & 2015 Published by Elsevier B.V.
Vanadium oxide
Nanorods
Hydrothermal
Electrochromism
Electronic materials
Semiconductor

1. Introduction friendly approach to prepare materials in different nanoarchi-

Vanadium oxide (V2O5) is an important transition metal oxide
in different areas, such as lithium ion battery, supercapacitor, gas
sensors, photocatalyst, electrochromic devices and so on [1–6].
Due to its layered structure, which facilitates ion intercalation, the
electrochromic behavior of V5 þ and V4 þ oxides is well known [7].
V2O5 can reversibly change from one colored state to another upon
supplying a suitable charge, which made it a promising candidate
for smart window [8].
There has been always a strong correlation between the
structure and its electrochemical properties. It is well known that
the nanosized materials have better electrochemical performance
than the large size particles, which will provide more effective
electrical transport continuity and facilitates Li þ ion intercalation
[9]. Specially, thin film is one of the most favorite structures for
smart window applications [10]. Obviously, fabricating high qual-
ity electrochromic thin films in low cost is very important for
applications. Therefore, many attempts have been adopted to en-
hance the electrochromic performance of V2O5 such as controlled
morphology, composite materials and different synthesis methods
[11–13]. Hydrothermal technique is a low-cost, environmental
n
Corresponding authors.
E-mail address: chujia@xust.edu.cn (J. Chu).
tectures such as nanorods, nanowires and nanoparticles and so
forth [14,15].
Here in this paper, the electrochromic V2O5 film with organized
nanostructures are prepared by hydrothermal treatment so as to
get the best electrochemical properties.
2. Experimental
V2O5 nanorod array was grown on a fluorine-doped tin oxide
(FTO) glass substrate using a hydrothermal method. The substrates
were cleaned with acetone, ethanol, finally rinsed with deionized
water and dried in air. Hydrothermal synthesis was carried out for
V2O5:0.5850 g NH4VO3 dissolved in 50 mL deionized water and
then 1.1206 g oxalic acid was added to the system to form an or-
ange solution. The resulting solution was stirred at for 15 min
before the addition of 50 mL deionized water. Then 10 drop of HCl
was added. The resultant solution was transferred to a Teflon-lined
stainless steel autoclave and the FTO substrate was placed at an
angle against the wall of the Teflon lined with the conductive side
facing down. The hydrothermal was conducted at 180 °C for 3.5 h
and then cooled overnight. After rinsed extensively with deionized
water and dried in ambient air, a V2O5 nanorod array film was
uniformly coated on the FTO glass substrate. The samples were

http://dx.doi.org/10.1016/j.matlet.2015.12.067
0167-577X/& 2015 Published by Elsevier B.V.
180 J. Chu et al. / Materials Letters 166 (2016) 179–182

Fig. 1. SEM images of the as-synthesized V2O5 at (a) low and (b) high magnification.

annealed at 300 °C for 1 h then 500 °C for 2 h to create a V2O5
layer.
The synthesized sample was investigated by a FEI Quanta
200FEG SEM. FT-IR spectrum was collected on a Perkin-Elmer
spectrometer. Raman spectra were collected on a Renishaw inVia
Raman microscope with an Ar þ laser (532 nm) excitation source.
The cyclic voltammetry test was carried out in a three-electrode
environment with the V2O5 on FTO/glass as the working electrode,
neat FTO glass as the counter electrode. 1 M lithium perchlorate in
propylene carbonate was used as the electrolyte. The electro-
chromic behavior of V2O5 films was examined using an Autolab
PGSTAT30 potentiostat with the UV–vis spectrometer (SHIMADZU
UV2550).
3. Results and discussion
After calcination of the hydrothermal sample, a nanorod-like
V2O5 structure can be seen lying on the FTO glass as shown in the
SEM image of Fig. 1. It is clearly shown that the product is made up
of nanorods with widths about 80–100 nm and lengths of 1–
10 μm The SEM image demostrate that V2O5 tends to form 1-D
nanostructure under the hydrothermal conditions as reported in
previous literature [16].
The FT-IR spectrum of V2O5 is presented in Fig. 2a. The peak at
1000 cm  1 and 818 cm  1 correspond to V ¼ O terminal oxygen
and V–O–V asymmetric stretching modes [17,18]. The peak at
474 cm  1 is related to the stretching mode of the oxygen atom
shared between three vanadium atoms. Raman spectroscopy is a
useful technique to give the in-situ vibrational spectra of V2O5. A
number of well-defined bands assigned to V2O5 crystal phase were
found in the region of 200–1400 cm  1, as shown in Fig. 2b. The
Raman spectrum of V2O5 film shows features that are consistent
with the positions and assignments of the bands for nano-crys-
talline nature of the previously reported V2O5 [19,20]. The peaks at
285 cm  1, 403 cm  1 are assigned to the bending vibration of the
V ¼O bonds. The peak at 529 cm  1 and 489 cm  1 are assigned to
the terminal oxygen (V3–O) stretching mode and the V–O–V
stretching mode. The peak present at 997 cm  1 corresponds to the
stretching mode of the V–O bonds.
Cyclic voltammetry measurements were carried out at various
sweep rates between  1.0 and 1.0 V to determine the oxidation–
reduction peak potentials of the V2O5, as presented in Fig. 3a. The
measurements were carried out at various sweeping rates from 10
to 50 mV/s. During the test, the film exhibits well reversible color
change from yellow–green to pale blue reversibly. This process is
in accordance with insertion (extraction) of the Li þ into (out from)
the V2O5 films:
V2O5 + xLi+ + xe−=LixV2O5

Fig. 2. (a) FTIR spectra and (b) Raman spectra of the as-synthesized V2O5 film.
 J. Chu et al. / Materials Letters 166 (2016) 179–182
Fig. 3. (a) Cyclic voltammograms of V2O5 thin film at various sweeping rates: 10 mV/s, 20 mV/s, 30 mV/s, 40 mV/s and 50 mV/s. (b) UV–vis spectra and digital photographs of
the as-prepared V2O5 nanorods film measured at  0.5 V and 0.5 V, respectively. Inset is the switching time characteristic between the colored and bleached states of V2O5
nanorods film, measured at 70.5 V with an absorbance wavelength of 400 nm. (For interpretation of the references to color in this figure legend, the reader is referred to the
web version of this article.)
In the present study, the change in color is governed by the
progressive pentavalent/tetravalent V ions reduction/oxidation by
the double injection/extraction of electrons and Li þ ions into/from
the V2O5 matrix. Increasing the scan rate has a direct impact on
the diffusion of Li þ ions into the V2O5 matrix. The faster scan rate
will lead to the reduction peaks shift to more cathodic potentials
while the oxidation peaks move to more anodic values when the
scan rate is increased from 10 to 50 mV s  1. Hence, it is clear that
when the scan rate is higher the rate of double injection/extraction
of electrons and Li þ ions into/from the V2O5 matrix is limited,
leading to a slower electrochromism process [21–23].
The Electrochromic properties of the V2O5 nanorods were in-
vestigated. Fig. 3b shows the UV–vis spectra along with photo-
graphs of the V2O5 in the bleached and colored states. Upon the
application of  0.5 V, V2O5 becomes pale blue and returns to
yellow–green when driven by 0.5 V. The films show reversible
chromism during Li þ ion insertion/extraction process. The
switching characteristics of the V2O5 film are investigated by
chronoamperometry between potential 70.5 V at an optical wa-
velength of 400 nm as shown in inset Fig. 3b. The V2O5 film pre-
sents a durable and reversible performance which indicates the
high stability of the as-prepared V2O5 nanorods.
4. Conclusion
In summary, we describe a simple protocol for the construction
of an electrochromic film based on V2O5 nanorods. The structural,
electrochromical and electrochromism studies of V2O5 thin films
are presented. With the application of a potential of approximately
0.5 V, the color change from yellow–green to pale blue in case of
V2O5 is observed by visual inspection. Results of this work suggest
that the synthesized V2O5 is favorable in the development of smart
window application and secondary lithium batteries. In addition,
the V2O5 nanowire arrays will also have applications in lithium ion
battery, supercapacitor and gas sensors.
Acknowledgments
This study was financially supported by the National Natural
Science Foundation of China (NSFC, No. 51503169, 51402231, and
21406176), the Research program from Education Department of
Shaanxi Province (2013JK0650, 2013JK0677) and the Natural
181
Science Foundation of Shaanxi Province (2014JQ2072,
2014JQ2076).
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