柔性电致变色器件研究进展

doi:10.15541/jim20200073

无机材料学报 ›› 2021, Vol. 36 ›› Issue (2): 140-151.DOI: 10.15541/jim20200073 CSTR: 32189.14.10.15541/jim20200073

所属专题：电致变色材料与器件；功能材料论文精选(2021)；【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:刁训刚, 王金敏) • 上一篇下一篇

柔性电致变色器件研究进展

方华靖¹(), 赵泽天¹, 武文婷¹, 汪宏²()

1.西安交通大学材料科学与工程学院, 西安 710049
2.南方科技大学材料科学与工程系, 深圳 518055

收稿日期:2020-02-16 修回日期:2020-05-05 出版日期:2021-02-20 网络出版日期:2020-08-01
通讯作者: 汪宏, 教授. E-mail: wangh6@sustech.edu.cn
作者简介:方华靖(1989-), 男, 副教授. E-mail: fanghj@xjtu.edu.cn
基金资助:
国家自然科学基金(61631166004);国家自然科学基金(51902250)

Progress in Flexible Electrochromic Devices

FANG Huajing¹(), ZHAO Zetian¹, WU Wenting¹, WANG Hong²()

1. School of Material Science and Engineering, Xi’an Jiaotong University, Xi’an 710049, China
2. Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen 518055, China

Received:2020-02-16 Revised:2020-05-05 Published:2021-02-20 Online:2020-08-01
About author:FANG Huajing(1989-), male, associate professor. E-mail: fanghj@xjtu.edu.cn
Supported by:
National Natural Science Foundation of China(61631166004);National Natural Science Foundation of China(51902250)

摘要/Abstract

摘要：

电致变色材料是一类重要的光电功能材料, 可以随周期性调整的电压改变颜色。这种可控的光学吸收率和透过率的调制在智能窗户、电致变色显示和防眩光后视镜等应用场合大显身手。近年来电致变色技术发展迅速, 但当前的研究大多集中在传统刚性电致变色器件, 通常以氧化铟锡(ITO)等导电玻璃为基底。这些刚性变色器件存在厚度大、共型性差、机械强度低、成本高等不可忽视的问题, 阻碍了电致变色技术及其商业化的发展。伴随着开发可穿戴设备和电子皮肤等其他未来技术的热潮, 柔性电致变色器件因其可折叠性、可穿戴性甚至可嵌入性而备受关注, 已跻身成为电致变色领域的研究热点。本综述从制备柔性电致变色器件的材料出发, 系统地概述了无机、有机、无机/有机复合及其他新型柔性电致变色器件最新进展和趋势, 着重介绍了可拉伸电致变色器件的国内外研究进展。同时讨论了现阶段柔性电致变色器件在性能提升和实际应用等方面遇到的挑战, 以及国内外研究者采取的应对措施。最后明确了柔性电致变色器件制备与提升性能的关键, 并对未来的发展趋势做出展望。

关键词: 电致变色器件, 柔性器件, 可拉伸, 智能窗户, 制备, 综述

Abstract:

Electrochromic materials with ability of changing color in response to periodically adjusted bias are an important class of optoelectric functional materials. The controllable modulation of light absorption and transmission can make a great contribution in applications such as smart windows, electrochromic displays and antiglare rear-view mirrors. In recent years, electrochromic technology has developed rapidly. However, the research so far mainly focuses on the traditional rigid electrochromic devices (ECD), mostly based on transparent conductive glass such as indium tin oxide (ITO) glass. The rigid electrochromic devices have some noticeable problems such as large thickness, poor conformability, low mechanical strength, high cost, etc., which hinder their further development of electrochromic technology and their forward commercialization. With the upsurge of developing flexible devices that can be used in wearable devices and e-skin, flexible electrochromic devices (FECD) have attracted extensive attention due to their possibility of foldability, wearability and even embeddability, and have become a research hotspot in the electrochromic field. Starting from the materials for preparing FECD, this review systematically summarizes the recent progress and trend of flexible electrochromic devices based on inorganic, organic, inorganic/organic composite and other new materials. The review also focuses on the research progress of up to date stretchable electrochromic devices. At the same time, challenges in performance improvement and practical application of flexible electrochromic devices at the present stage as well as the corresponding measures taken in the literatures are discussed. Finally, the key to the preparation and performance improvement of flexible electrochromic devices is defined, and the future development trend is prospected.

Key words: electrochromic devices, flexible devices, stretchable, smart window, preparation, review

中图分类号:

TQ174

方华靖, 赵泽天, 武文婷, 汪宏. 柔性电致变色器件研究进展[J]. 无机材料学报, 2021, 36(2): 140-151.

FANG Huajing, ZHAO Zetian, WU Wenting, WANG Hong. Progress in Flexible Electrochromic Devices[J]. Journal of Inorganic Materials, 2021, 36(2): 140-151.

图/表 11

图1 溶剂热法制备的W18O49纳米线与Ag NWs在PET基底上共组装得到柔性变色薄膜[4]

Fig. 1 W18O49 nanowires and Ag NWs by solvothermal preparation co-assembled on PET substrate to obtain flexible color-changing film[4] (a) Schematic illustration of the curved Ag and W18O49 NW film with electrochromic property; (b,c) The film attached on the curved surface of the beaker before (bleached state) and after (colored state) applying voltage; (d) In situ electrical resistance change of flexible electrochromic film after 0, 100, 200, 300, 500, and 1000 bending cycles; (e) Switching behaviors of the ECD after 0, 100, 200, 300, 400, 500, and 1000 bending cycles

图2 基于普鲁士蓝的柔性传感器[29]

Fig. 2 Flexible sensor based on prussian blue[29]

表1 无机电致变色器件性能比较

Table 1 Performance comparison of inorganic FECD

Materials	Switching time/s	Coloration efficiency/(cm²·C^-1)	Transmittance modulation/%	Stability/cycles	Bending radius/mm	Ref.
W₁₈O₄₉	10.3/7.4	35.7	60	1000	12	[4]
WO₃/Ag/WO₃	11/10.5	136	53	3000	15	[10]
WO₃	3.5/8.4	60.1	73.3	200	5	[11]
WO₃-NiVO_x	6/5	-	42	8000	75	[15]
WO₃	30	139	49	1000	-	[16]
WO₃	9/19	58.95	89.7	300	2	[17]
MoO₃	6.2/10.9	34.7	27.7	150	11	[19]
NiO_x-WO₃	-	20-35	60	125	36	[22]
WO₃-ZnO	6.2/2.8	80.6	68.2	-	-	[23]
Prussian blue -WO₃	<10	-	52.4	2250	-	[28]

图3 基于PEDOT:PSS_PD电极的电致变色器件[39]

Fig. 3 Flexible ECD based on PEDOT:PSS_PD electrodes[39] (a) Colored state; (b) Bleached state

图4 基于紫精的多色柔性电致变色器件[44]

Fig. 4 Flexible multicolor ECD based on viologen[44]

表2 有机电致变色器件性能比较

Table 2 Performance comparison of organic FECD

Materials	Switching time/s	Coloration efficiency /(cm²·C^-1)	Transmittance modulation/%	Stability	Bending radius/mm	Ref.
PANI	40/20	22.9	34	200 cycles	6	[34]
PANI	3.9/2.61	80.9	49	500 cycles	10	[35]
PEDOT	4.1/3.4	-	21	10000 cycles	20	[38]
PEDOT: PSS	4.6/2	429	45	4000 cycles	-	[39]
ethyl viologen	41/395	117.7	92.1	60000 s	12.5	[43]
monoheptyl-viologen/diheptylviologen/diphenyl-viologen	20/34	87.3	25	3600 s	10	[44]
FeL	3.6/7.3	299.8	41	250 cycles	-	[47]
MEPE	2/26	445	40.1	-	10	[48]
Poly[Ni(salen)]-type polymer	157/145	130.4	88.7	3000 cycles	-	[49]

图5 银栅格/PEDOT:PSS/WO3复合膜弯曲循环后的变色性能[52]

Fig. 5 Electrochromic performance of the Ag grid/PEDOT: PSS/WO3 film after bending[52]

表3 无机/有机复合电致变色器件性能比较

Table 3 Performance comparison of inorganic/organic composite FECD

Materials	Switching time/s	Coloration efficiency /(cm²·C^-1)	Transmittance modulation/%	Stability/cycles	Bending radius/mm	Ref.
W₁₈O₄₉ NWs-PEDOT:PSS	18.2/6.6	118.1	34.3	-	2.5	[50]
PEDOT:PSS-WO₃	1.9/2.8	124.5	81.9	2000	20	[52]
WO₃·2H₂O-PEDOT	4.4/2.6	180.2	63.1	-	-	[53]
Viologen-TiO₂	8/6	226	53	1000	-	[54]
Ag NW/Ni(OH)₂-PEIE/PEDOT:PSS	0.3/0.6	517	30	100	1	[55]

图6 基于聚乙烯保鲜膜PE的ECD[61]

Fig. 6 ECD on household PE cling wrap[61] (a) Schematic illustration of the structure of the PE cling wrap-based hybrid EC film; (b) The color-changing e-skin (top) and PE cling wrap (bottom)

图7 可拉伸变色超级电容器[65]

Fig. 7 Stretchable electrochromic supercapacitor[65] T-S: Transparent stretchable; TSES: Transparent stretchable electrochromic supercapacitor

表4 拉伸电致变色器件性能比较

Table 4 Performance comparison of stretchable electrochromic devices

Materials	Switching time/s	Coloration efficiency /(cm²·C^-1)	Transmittance modulation/%	Stability	Bending radius/mm	Ref.
WO₃/Ag/PEDOT:PSS/WO₃	1.82/0.75	-	23	30000 s	5	[61]
Heptyl Viologen	32/43	31.82	74.5	100 cycles	4.8	[63]
WO₃nanotube / PEDOT: PSS	<10	83.9	37.7	20000 cycles	40	[65]
WO₃-PANI	4.1/2.1	75.5	40	500 cycles	5	[66]
poly(3-methylthiophene)/Prussian blue	1.3/1.2	201.6	17.8	180 cycles	2.5	[67]
copolymer DFTPA-PI-MA	5.3/12.2	82.2	60	100 cycles	-	[69]

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柔性电致变色器件研究进展

Progress in Flexible Electrochromic Devices

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