Materials Letters 292 (2021) 129592

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Materials Letters
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All-solid-state electrochromic devices based on the LiAlSiO4 electrolyte

Yingming Zhao a, Xiang Zhang a,⇑, Xi Chen a, Wenjie Li b, Zitong Li a, Mingjun Chen b,
Wenhai Sun a, Jiupeng Zhao b, Yao Li a,⇑
a
Center for Composite Materials and Structure, Harbin Institute of Technology, Harbin 150001, PR China
b
School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Herein, LiAlSiO4 was used as electrolyte material for all-solid-state electrochromic devices for the first
Received 3 December 2020 time, and an electrochromic device (ECD) with the structure of glass/ITO/NiO/Ta2O5/LiAlSiO4/Ta2O5/
Received in revised form 5 February 2021 WO3/ITO was prepared by magnetron sputtering method. Since LiAlSiO4 electrolyte exhibits high trans-
Accepted 19 February 2021
parency and good ionic conductivity, the ECD shows good electrochromic performance including: large
Available online 25 February 2021
optical transmittance modulations (50.8% at 586 nm, 64.1% at 1000 nm), good stability (optical modula-
tion is still maintained at 81.4% (586 nm) and 89.0% (1000 nm) of initial state after 1000 cycles) and high
Keywords:
coloration efficiency (60.3 cm2 C
1 at 586 nm, 150.6 cm2 C
1 at 1000 nm). Considering the low cost and
Sputtering
Thin films
abundance of Al and Si, LiAlSiO4 may be acknowledged as a sustainable electrolyte for future high-
Electrochromic device performance ECDs.
Electrolyte Ó 2021 Elsevier B.V. All rights reserved.
LiAlSiO4
All-solid-state

1. Introduction modulation of 31.4% [6]. Although there have been increasing

Electrochromic (EC) materials have been greatly developed and
are applied in many fields due to their optical modulation ability
by the adjustment of operating voltage, such as smart windows,
electronic display, and anti-glare mirrors. Specifically, smart win-
dows based on electrochromic devices (ECDs) exhibit the ability
to regulate indoor light and heat flow into buildings via changing
the transparency or reflectance, resulting in a savings of >40% of
the energy consumption [1].
All-solid-state ECDs have received extensive interest due to
their favorable properties, e.g., excellent environmental stability
and large optical transmittance modulation [2,3]. In a typical all-
solid-state ECD, the electrolyte layer is of importance to provide
active ions such as H+ or Li+ as conducting ions. However, the per-
formances of electrolytes containing H+ are greatly affected by
environmental humidity, which limits their practical application
[4]. In contrast, lithium-based solid electrolytes have better elec-
trochemical stability and weatherability, so their applications in
all-solid-state ECDs have attracted enormous research interests
[5–7]. For example, Song et al prepared all-thin-film ECD employed
LiTaO3 as electrolyte, which showed an excellent transmittance
modulation of 67% [8]. Atak et al. prepared an all-solid-state ECD
using LiNbO3 as electrolyte, which exhibited a large transmittance
⇑ Corresponding authors.
E-mail addresses: zhangxhit@hit.edu.cn (X. Zhang), yaoli@hit.edu.cn (Y. Li).
reports on all-solid-state ECDs, LiTaO3 and LiNbO3 are used as elec-
trolyte layers in most all-solid-state ECDs. However, the limited
storage and high price of tantalum and niobium limit their practi-
cal application in large-scale production. LiAlSiO4 is one of the
most promising candidate electrolytes applied in all-solid-state
ECDs owing to its high ionic conductivity (10
7–10
9 S cm
1 at
room temperature) [9], high transmittance, abundant element
reserves (Al and Si) and relatively low cost. However, to the best
of our knowledge, there is no research on all-solid-state ECDs using
LiSiAlO4 as electrolyte up till now. In this research, LiAlSiO4 film
has been prepared by radio frequency (RF) magnetron sputtering
using LiAlSiO4 target and applied in all-solid-state ECD with the
structure of glass/ITO/NiO/Ta2O5/LiAlSiO4/Ta2O5/WO3/ITO. The
ECD exhibits large optical transmittance modulation, good stability
and high coloration efficiency. This work proves that LiAlSiO4 has a
significant potential as a Li+ electrolyte in all-solid-state ECDs with
high performances.
2. Experimental section
The all-solid-state ECDs were prepared via RF magnetron sput-
tering layer by layer on ITO-coated glass substrates (8 X/square),
where WO3, NiO, Ta2O5, LiAlSiO4 and ITO were employed as EC,
ion storage, interface protective, electrolyte and transparent con-
ductive layer, respectively (Fig. 1a). The corresponding sputtering
targets were metal W (99.99%), Ni (99.99%), Ta (99.99%), LiAlSiO4

https://doi.org/10.1016/j.matlet.2021.129592
0167-577X/Ó 2021 Elsevier B.V. All rights reserved.
Y. Zhao, X. Zhang, X. Chen et al.
Fig. 1. Structural schematic diagram (a) and cross-sectional SEM image (b) of the ECD.
ceramic plate (99.99%) and ITO ceramic plate (99.99%). Previously,
the cleaned ITO glass substrates were placed in a vacuum sputter-
ing chamber. The base pressure in chamber was kept below
3  10
3 Pa, and the distance between target and substrate was
6.5 cm. Before each layer was deposited, the targets were pre-
sputtered for 10 min under Ar to prevent cross-contaminants.
The substrate was rotated at 5 rpm in deposition process to ensure
the homogeneity of the films. The deposition parameters of WO3,
NiO, Ta2O5 and LiAlSiO4 films are shown in Table S1. The ECDs were
annealed at 350 °C in air after deposition to improve their cyclic
stability.
The structural profiles of the ECD with cross-sectional images
were obtained by scanning electron microscopy (SEM, Zeiss supra
55) at an acceleration voltage of 20 kV. The crystal structures of
films were characterized by a X’ pert Pro-diffractometer (with Cu
Ka radiation of k = 1.5405 Å) at a constant incidence angle of 0.2°.
The electrochromic and electrochemical properties of the ECDs
were recorded on a Vis-NIR optic spectrometer (MAYA 2000-Pro,
Ocean Optics) and an electrochemical station (CHI 660E). The
transmittance modulation and response time of the ECDs at differ-
ent voltages (
2.0 V and +2.0 V) were recorded by chronoamper-
ometry at the specific wavelength of 586 nm and 1000 nm.
3. Results and discussion
The transmittance spectra of the films prepared on ITO glass
substrates are shown in Fig. S1. The LiAlSiO4 film has high trans-
mittance in the wavelength range of 400–1100 nm, confirming
its suitability as electrolyte for ECDs. Besides, the ITO glass, WO3,
NiO and Ta2O5 layer also exhibit high transmittance in the range
of 400–1100 nm. Fig. 1b illustrates the cross-sectional images of
the ECD, which is the structure of ITO/NiO/Ta2O5/LiAlSiO4/Ta2O5/
WO3/ITO from bottom to top, and corresponding thicknesses are
200, 130, 30, 60, 30, 470 and 180 nm, respectively. In order to
investigate the microstructure of each layer in ECD, XRD analysis
was carried out and the XRD patterns of WO3, NiO, Ta2O5 and
LiAlSiO4 films are shown in Fig. S2. The WO3 and NiO films show
the characteristic crystalline phases of monoclinic WO3 (JCPDF-
#43-1035) and face-centered cubic NiO (JCPDF-#47-1049), which
indicate their crystalline structures. For the Ta2O5 and LiAlSiO4
film, no diffraction peaks can be observed, indicating that these
films are amorphous in nature. Before studying the electrochemi-
cal and electrochromic properties of the ECD, the ionic conductiv-
ity of the LiAlSiO4 film was tested by AC impedance and it was
determined to be about 2.7*10
8 S cm
1 (see Fig. S3). In addition,
the ionic conductivity of LiAlSiO4 is also affected by oxygen
vacancy concentration, lithium ions vacancy concentration and
2
Materials Letters 292 (2021) 129592
undesired doping effects [10–12]. And these will be reported in a
succeeding paper.
The electrochemical properties of the ECD were characterized
by cyclic voltammetry (CV) and Chronoamperometry (CA) tests.
The CV tests in the 1st cycle and 1000th cycle of the ECD were car-
ried out at a scan rate of 100 mV s
1 in a voltage range of
2.0 to
2.0 V (Fig. S4). The shape of CV curves of the ECD is similar to those
of single-layer WO3 films reported in previous literatures [13,14].
Besides, the area of voltammograms in the 1000th cycle was
slightly smaller than that in the 1st cycle, which indicates that
the active units in the ECD participate in EC reaction are slightly
reduced due to the ion-trapping effect existed in WO3 and NiO
layers.
The in-situ transmittance test was conducted by applying con-
stant voltages (
2.0 V for 30 s in the coloration process, 2.0 V for
60 s in the bleaching process) to investigate the EC behaviors of
ECD. As shown in Fig. 2, the blue and orange lines represent
bleached and colored state of the ECD, respectively. And the ECD
displays a relatively high bleached-state transmittance (Tb) in the
visible and NIR region, showing a transparent feature. When a volt-
age of
2.0 V is applied, the ECD changes to colored state with a
relatively low colored-state transmittance (Tc). The transmittance
modulation DT (DT = Tb
Tc) of the ECD at the wavelength of
586 nm and 1000 nm reaches 50.8% and 64.1%, respectively. The
digital photographs of the ECD at bleached and colored states are
shown in Fig. S5. After 1000 cycles, the DT values of the ECD at
586 nm and 1000 nm still remain at 41.4% and 57.1%, respectively,
indicating good optical modulation ability of the ECD.
Response time is defined as the time required for a 90% change
in transmittance modulation [15]. The transmittance-time curves
of the ECD at 586 nm and 1000 nm in 1st cycle and 1000th cycle
are shown in Fig. 3a and b. The coloration and bleaching time of
the ECD are listed in Table S2. There is no obvious difference
between coloration time of the ECD in the 1st and 1000th cycle.
While the response speed in bleaching process becomes faster after
1000 cycles. The mechanism of response change of the device is
studied by the electrochemical impedance spectroscopy of ECD
in 1st cycle and 1000th cycle. And the results are shown in
Fig. S6 and Table S3.
Coloration efficiency (CE) is another important parameter to
evaluate the performances of the ECD, which can be evaluated
according to the following equations [16–18]:
CEðkÞ ¼ DOD=Q ð1Þ
DODðkÞ ¼ logðT b =T c Þ ð2Þ
Z
Q¼ jdt ð3Þ
Y. Zhao, X. Zhang, X. Chen et al. Materials Letters 292 (2021) 129592

Fig. 2. Transmittance spectra of the ECD at bleached and colored state in the 1st cycle (a) and 1000th cycle (b).

Fig. 3. The coloration/bleaching response time (a, b) and coloration efficiency (c, d) of the ECD in the 1st cycle and 1000th cycle at the wavelength of 586 nm and 1000 nm.

where Q denotes inserted charge density during coloration process,
and j and t are current density and time derived from CA tests.
Fig. S7 exhibits CA curves of the ECD. Fig. 3c and d compare the cor-
responding relationship of optical density (OD) relative to charge
density for the ECD in the 1st and 1000th cycle at the wavelength
of 586 nm and 1000 nm. The calculated CE values of the ECD are
listed in Table S2. Obviously, the ECD exhibits a higher CE value
in NIR region (at 1000 nm) than that in visible region (at 586 nm),
which is attributed to larger transmittance modulation of the ECD
in NIR region than in visible region. The high CE values indicate that
3
the ECD could obtain large optical modulation with small changes
of inserted charges. In addition, the CE values decrease after cycling,
which are ascribed to the decreases of optical density changes and
the existence of leakage current [19].
4. Conclusion
In summary, LiAlSiO4 film prepared by RF magnetron sputtering
method, has been used as electrolyte in the all-solid-state ECD
with the structure of glass/ITO/NiO/Ta2O5/LiAlSiO4/Ta2O5/WO3/
Y. Zhao, X. Zhang, X. Chen et al.
ITO for the first time, owing to its high transparency and good ionic
conductivity. The ECD shows outstanding EC performance, includ-
ing large optical transmittance modulations, good stability and
high coloration efficiency. This work indicates that LiAlSiO4 devel-
oped in this study is a promising electrolyte for all-solid-state
ECDs.
CRediT authorship contribution statement
Yingming Zhao: Conceptualization, Methodology, Software,
Writing - original draft. Xiang Zhang: Conceptualization, Formal
analysis, Writing - original draft. Xi Chen: Validation, Formal anal-
ysis, Data curation. Wenjie Li: Resources, Data curation. Zitong Li:
Visualization, Software. Mingjun Chen: Writing - review & editing.
Wenhai Sun: Resources, Software. Jiupeng Zhao: Supervision, Pro-
ject administration, Writing - review & editing. Yao Li: Funding
acquisition, Project administration.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
We thank National Key Research & Development Program
(2016YFB0303903, 2016YFE0201600), National Natural Science
Foundation of China (52002097) and Foundation of Equipment
Development Department (6220914010901).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.matlet.2021.129592.
Materials Letters 292 (2021) 129592
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