溶胶-凝胶旋涂法制备电致变色智能窗用钛酸锂薄膜

doi:10.15541/jim20200584

无机材料学报 ›› 2021, Vol. 36 ›› Issue (5): 471-478.DOI: 10.15541/jim20200584

所属专题：电致变色材料与器件；【虚拟专辑】电致变色与热致变色材料；电致变色专栏2021

• 专栏:电致变色材料与器件(特邀编辑:王金敏,刁训刚) • 上一篇下一篇

溶胶-凝胶旋涂法制备电致变色智能窗用钛酸锂薄膜

王天悦¹^,²(), 王梦颖¹(), 黄庆姣³, 杨佳明³, 王顺花², 刁训刚¹()

1.北京航空航天大学能源与动力工程学院, 北京 100191
2.兰州交通大学材料科学与工程学院, 兰州 730070
3.北京航空航天大学物理学院, 北京 100191

收稿日期:2020-10-14 修回日期:2020-11-25 出版日期:2021-05-20 网络出版日期:2021-04-19
通讯作者: 王梦颖, 博士. E-mail:mercy@buaa.edu.cn; 刁训刚, 教授. E-mail: diaoxg@buaa.edu.cn
作者简介:王天悦(1994-), 男, 硕士. E-mail:Oceanwty@163.com
基金资助:
国家自然科学基金(51862022);国家自然科学基金(61875005)

Preparation of Lithium Titanate Thin Film for Electrochromic Smart Window by Sol-Gel Spin Coating Method

WANG Tianyue¹^,²(), WANG Mengying¹(), HUANG Qingjiao³, YANG Jiaming³, WANG Shunhua², DIAO Xungang¹()

1. School of Energy and Power Engineering, Beihang University, Beijing 100191, China
2. School of Materials Science and Engineering, Lanzhou Jiaotong University, Lanzhou 730070, China
3. School of Physics, Beihang University, Beijing 100191, China

Received:2020-10-14 Revised:2020-11-25 Published:2021-05-20 Online:2021-04-19
Contact: WANG Mengying, PhD. E-mail: mercy@buaa.edu.cn; DIAO Xungang, professor. E-mail: diaoxg@buaa.edu.cn
About author:WANG Tianyue(1994-), male, master. E-mail:Oceanwty@163.com
Supported by:
National Natural Science Foundation of China(51862022);National Natural Science Foundation of China(61875005)

摘要/Abstract

摘要：

从可见光到近红外波段透过率可调制的电致变色材料, 对于智能窗及其热管理方面的应用来说极具吸引力。钛酸锂是一种有潜力的电致变色阴极材料, 但对其在智能窗领域的应用前景还缺乏相关的数据支持。本工作采用溶胶-凝胶旋涂法制备透过率高、结晶性好的钛酸锂(Li₄Ti₅O₁₂)薄膜, 通过联用电化学工作站和紫外-可见分光光度计原位表征了其电致变色性能。实验发现所有Li₄Ti₅O₁₂薄膜对扫描速率等测试条件十分敏感, 且有优异的双波段调制性能。此外, Li₄Ti₅O₁₂薄膜厚度对材料的初始态透过率、调制幅度、响应时间、电压窗口和循环耐久性均有显著影响。其中450 nm厚的Li₄Ti₅O₁₂着色/褪色响应时间分别为19.1和8.9 s, 透过率调制在可见光区(550 nm处)为45%, 经过20000 s连续循环, 性能未发生明显衰退。Li₄Ti₅O₁₂薄膜在近红外波段(1000 nm处)的透过率调制高达80%, 表现出优秀的节能潜力。本研究成功组装了由灰色至蓝色、循环性能良好的全固态无机电致变色器件: Glass/FTO/Li₄Ti₅O₁₂/LiNbO₃/NiO_x/ITO, 证明钛酸锂作为电致变色智能窗材料有潜力走向普及应用。

关键词: 电致变色, Li₄Ti₅O₁₂, 全固态无机器件, 循环耐久

Abstract:

Electrochromic materials are attractive for applications like smart windows and thermal management which can modulate transmittance from visible to near-infrared wavelengths. Lithium titanate has been proven to be a potential electrochromic cathode material, but its application prospects in the field of smart windows still lack data support. In this work, Li₄Ti₅O₁₂ thin films with high transmittance and good crystallinity were prepared by Sol-Gel spin coating. The electrochromic properties of the films were characterized by different methods. It is found that all Li₄Ti₅O₁₂ thin films are very sensitive to the test conditions, such as scanning rate, displaying excellent dual band modulation property. Also, the thickness has a significant effect on the initial state transmittance, modulation amplitude, response time, voltage window and cycle durability of the Li₄Ti₅O₁₂ thin films. The colored and bleached response time of the 450 nm Li₄Ti₅O₁₂ is 19.1 and 8.9 s, respectively, while the transmittance modulation is 45% in the visible light region (550 nm). The performance of the films have not been significantly degraded after 20000 s continuous cycle. It is worth mentioning that the transmittance modulation in the near infrared band (1000 nm) is as high as 80%, showing excellent energy saving potential. Finally, Glass/FTO/Li₄Ti₅O₁₂/LiNbO₃/NiO_x/ITO, an all-solid-state inorganic electrochromic device with good cycle performance from gray to blue was successfully assembled. Above data demonstrate that lithium titanate is a strong competitive material for the popularization of electrochromic smart window.

Key words: electrochromic, Li₄Ti₅O₁₂, all-solid-state inorganic device, cycle durability

中图分类号:

TB381

王天悦, 王梦颖, 黄庆姣, 杨佳明, 王顺花, 刁训刚. 溶胶-凝胶旋涂法制备电致变色智能窗用钛酸锂薄膜[J]. 无机材料学报, 2021, 36(5): 471-478.

WANG Tianyue, WANG Mengying, HUANG Qingjiao, YANG Jiaming, WANG Shunhua, DIAO Xungang. Preparation of Lithium Titanate Thin Film for Electrochromic Smart Window by Sol-Gel Spin Coating Method[J]. Journal of Inorganic Materials, 2021, 36(5): 471-478.

图/表 11

表1 全固态无机器件Glass/FTO/Li4Ti5O12/LiNbO3/NiOx/ITO的制备参数

Table 1 Preparation parameters of all-solid-state inorganic devices Glass/FTO/Li4Ti5O12/LiNbO3/NiOx/ITO

Target	Power source	Pressure/ Pa	Atmosphere (Ar : O₂)	Power/ W	Time/ min
LiNbO₃	RF	0.8	95 : 5	300	120
Ni	DC	1.5	94 : 6	200	25
ITO	DC	0.3	78.4 : 21.6	200	20

图1 不同厚度Li4Ti5O12薄膜的XRD图谱

Fig. 1 XRD patterns of Li4Ti5O12 thin films with different thicknesses

表2 不同厚度Li4Ti5O12薄膜的晶格常数、晶面间距和晶粒尺寸

Table 2 Lattice constant, interplanar spacing and grain size of Li4Ti5O12 thin films with different thicknesses

Sample	Lattice constant/nm	Interplanar spacing/nm	Average crystallite size/nm
LTO-1	0.834463	0.48055	14.9
LTO-2	0.834586	0.48055	16.2
LTO-3	0.834554	0.48068	15.8
LTO-4	0.834637	0.48055	18.5
LTO-5	0.834687	0.48055	19.4

图2 不同厚度Li4Ti5O12薄膜的SEM表/截面(a~e)和TEM照片(f)

Fig. 2 SEM surface images (a-e) with insets showing cross-sectional structures and TEM image (f) of Li4Ti5O12 thin films with different thicknesses

图3 不同厚度Li4Ti5O12薄膜的CA曲线(a)及其原位透过率光谱(b)

Fig. 3 CA curves (a) and in-situ transmittance spectra (b) of Li4Ti5O12 thin films with different thicknesses

表3 不同厚度Li4Ti5O12薄膜的透过率和着褪色时间

Table 3 Transmittance and response time of Li4Ti5O12 thin films with different thicknesses

Sample	T_b/%	T_c/%	ΔT/%	t_c/s	t_b/s
LTO-1	91.84	72.7	19.14	26.3	3.6
LTO-2	90.07	64.35	25.72	20.5	4.5
LTO-3	88.04	37.28	50.76	19.1	8.9
LTO-4	87.4	34.35	53.05	21.8	7.6
LTO-5	75.12	26.19	48.93	28.6	12.0

图4 LTO-3在不同扫描速率下的CV曲线(a)和原位透过率光谱图(b), 适压范围的变扫速CV曲线(c)和原位透过率光谱图(d)

Fig. 4 CV curves under limited voltage condition (a), in-situ transmittance spectra (b) and CV curves under reasonable voltage condition (c), and in-situ transmittance spectra (d) of LTO-3 at various scan rates

图5 不同厚度Li4Ti5O12薄膜100圈内的CV曲线(a~e)和20000 s内的原位透过率光谱(f~j)

Fig. 5 CV curves (a-e) within 100 cycles and in-situ transmittance spectra (f-j) within 20000 s of Li4Ti5O12 thin films with different thicknesses

图6 不同厚度的Li4Ti5O12薄膜在400~1100 nm波段的着/褪色透过率光谱

Fig. 6 Colored and bleached transmittance spectra of Li4Ti5O12 films with different thicknesses in the wavelength 400-1100 nm

图7 全固态无机器件Glass/FTO/Li4Ti5O12/LiNbO3/NiOx/ITO的结构示意图

Fig. 7 Schematic diagram of the structure of the all-solid- state inorganic device Glass/FTO/Li4Ti5O12/LiNbO3/NiOx/ITO

图8 Glass/FTO/Li4Ti5O12/LiNbO3/NiOx/ITO全固态无机器件的电致变色性能

Fig. 8 Electrochromic performance of all-solid-state inorganic Glass/FTO/Li4Ti5O12/LiNbO3/NiOx/ITO devices (a) In-situ transmittance spectrum; (b) STEP curves; (c) Transmittance spectrum in the wavelength of 400-1100 nm; (d) Li4Ti5O12 colored and bleached photographs

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溶胶-凝胶旋涂法制备电致变色智能窗用钛酸锂薄膜

Preparation of Lithium Titanate Thin Film for Electrochromic Smart Window by Sol-Gel Spin Coating Method

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