基于高电导率的疏水气相SiO2复合凝胶电解质的高性能电致变色器件

doi:10.15541/jim20200376

无机材料学报 ›› 2021, Vol. 36 ›› Issue (2): 161-167.DOI: 10.15541/jim20200376

所属专题：电致变色材料与器件；功能材料论文精选(2021)；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

基于高电导率的疏水气相SiO₂复合凝胶电解质的高性能电致变色器件

赵起¹(), 乔科¹, 姚勇吉¹, 陈长¹, 陈东初²(), 高彦峰¹()

1.上海大学材料科学与工程学院, 上海 200444
2.佛山大学材料科学与能源工程学院, 佛山 528000

收稿日期:2020-07-06 修回日期:2020-10-29 出版日期:2021-02-20 网络出版日期:2020-11-05
通讯作者: 高彦峰, 教授. E-mail: yfgao@shu.edu.cn;
作者简介:赵起(1995–), 男, 博士研究生. E-mail: zq0911@shu.edu.cn

High-conductivity Hydrophobic Fumed-SiO₂ Composite Gel Electrolyte for High Performance Electrochromic Devices

ZHAO Qi¹(), QIAO Ke¹, YAO Yongji¹, CHEN Zhang¹, CHEN Dongchu²(), GAO Yanfeng¹()

1. School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
2. School of Materials Science and Energy Engineering, Foshan University, Foshan 528000, China

Received:2020-07-06 Revised:2020-10-29 Published:2021-02-20 Online:2020-11-05
Contact: GAO Yanfeng, professor. E-mail: yfgao@shu.edu.cn;
About author:ZHAO Qi(1995–), male, PhD candidate. E-mail: zq0911@shu.edu.cn
Supported by:
Foundation item: Ministry of Science and Technology of China(2016YFB0303901-05);Innovation Program of Shanghai Municipal Education Commission(2019-01-07-00-09-E00020);Science and Technology Commission of Shanghai Municipality(18JC1412800);Cheung Kong Scholars Programme of China(T2015136)

摘要/Abstract

摘要：

凝胶电解质具有化学稳定、难燃和易于封装等特点, 其低离子电导率(10^-4~10^-5S?cm^-1)阻碍了电致变色器件(ECDs)凝胶电解质的进一步发展。本研究制备了一种高电导率的疏水SiO₂/PMMA/PC/LiClO₄凝胶聚合物电解质(H-SiO₂ GPEs), 并用电化学阻抗谱(EIS)、循环伏安法(CV)和计时电流法(CA)分析了ECDs的电化学行为。实验结果表明, 仅引入0.5wt%的疏水性气相SiO₂, 即可使H-SiO₂ GPEs的离子电导率达到5.14 mS?cm^-1(25 ℃时)。离子电导率的增加归因于SiO₂添加物和有机电解质之间良好的相容性和疏水-疏水吸引力促进了高氯酸锂的离解。同时, 不同气相二氧化硅含量的GPEs的粘度与剪切速率的关系表现出剪切稀化行为, 这表明研究体系形成了三维网状结构。该结构为离子提供了传输通道, 进而提高了基于H-SiO₂ GPEs电致变色器件的响应速度(t_bleaching= 4 vs 8 s和t_coloring = 14 vs 16 s)。同样, 通过探究添加疏水性气相SiO₂对液态电解液的影响表明：复合疏水性气相SiO₂使得LiClO₄/PC液态电解液的离子电导率由原来的6.94 mS?cm^-1增大到7.58 mS?cm^-1。疏水性气相SiO₂作为填料对电解质的离子电导率具有一定的积极作用, H-SiO₂ GPEs的研究为解决ECDs高离子电导率和易泄漏之间的矛盾提供了新思路。

关键词: 凝胶电解质, 电致变色, 疏水性, SiO₂

Abstract:

Gel electrolytes are chemically stable, nonflammable and easy to encapsulate, however, their moderate ionic conductivity (10^-4-10^-5S?cm^-1) hinders their further development for the usage in electrochromic devices (ECDs). Here, we developed a highly conductive hydrophobic SiO₂/PMMA/PC/LiClO₄ gel polymer electrolyte (H-SiO₂ GPE). Electrochemical behaviors of ECDs were characterized by electrochemical impedance spectroscope (EIS), cyclic voltammetry (CV) and chronoamperometry (CA). Systematic analyses show that the ionic conductivity of the H-SiO₂ GPE can reach 5.14 mS?cm^-1 (at 25 ℃) by introducing only 0.5wt% hydrophobic fumed SiO₂. This increase is due to the good compatibility and hydrophobic-hydrophobic attractions between SiO₂ additive and organic electrolyte, which promotes the dissociation of lithium perchlorate. Additionally, the viscosity as a function of shear rate for GPE with various fumed silica contents shows the behavior of shear thinning, which indicates the formation of a three-dimensional network structure. This structure provides ion transport channels, leading to a clearly improved switching speed for ECDs assembled with hydrophobic SiO₂ GPEs (t_bleaching=4 vs 8 s and t_coloring=14 vs 16 s). Similarly, the investigation of hydrophobic fumed SiO₂ in liquid electrolyte is demonstrated that the ionic conductivity of LiClO₄/PC liquid electrolyte without and with hydrophobic fumed SiO₂ increases from 6.94 to 7.58 mS?cm^-1, respectively. Therefore, hydrophobic fumed SiO₂ as a filler has a positive effect on electrolytes, and the proposal of the H-SiO₂ GPE provides a new idea for offsetting the trade-off between a high ionic conductivity and easy leakage when applied in ECDs.

Key words: gel electrolyte, electrochromic, hydrophobic, SiO₂

中图分类号:

TQ174

赵起, 乔科, 姚勇吉, 陈长, 陈东初, 高彦峰. 基于高电导率的疏水气相SiO₂复合凝胶电解质的高性能电致变色器件[J]. 无机材料学报, 2021, 36(2): 161-167.

ZHAO Qi, QIAO Ke, YAO Yongji, CHEN Zhang, CHEN Dongchu, GAO Yanfeng. High-conductivity Hydrophobic Fumed-SiO₂ Composite Gel Electrolyte for High Performance Electrochromic Devices[J]. Journal of Inorganic Materials, 2021, 36(2): 161-167.

图/表 9

Fig. S1 Static water contact angle (CA) of hydrophobic fumed SiO2

Fig. S2 Particle size of hydrophobic fumed silica (a) and hydrophilic fumed silica (b) in PC

Fig. 1 FT-IR spectrum of hydrophobic fumed SiO2

Table 1 Ion conductivity of gel electrolytes from the literature

Electrolyte	Ionic conductivity/(mS·cm^-1)
PMMA/LiClO₄/hydrophobic SiO₂(This work)	5.14
PMMA/LiClO₄/hydrophilic SiO₂^[1]	3.8
P(BMA-St)/hydrophilic SiO₂^[2]	2.15
PEO/LiCF₃SO₃/TiO₂^[3]	0.16
PVDF/LiClO₄/palygorskite^[4]	0.12
PMMA/LiClO₄/[Emim]BF₄^[5]	2.9
PVB/LiClO₄^[6]	0.04
PVDF-HFP/LiCF₃SO₃/ZrO₂^[7]	1.78
PAN/LiClO₄/Li_0.33La_0.557TiO₃^[8]	0.0605

Fig. S3 SEM images of pure GPEs (a) and 0.5wt% H-SiO2 GPEs (b)

Fig. S4 XRD patterns of the as-prepared WO3(a), SEM image of WO3 films coated on ITO substrates(b), TEM images of WO3 dispersion (c) and typical nanorod (d) with high magnification

Fig. 2 Nyquist plots (a), ionic conductivity (b) and viscosity (c) of PMMA-based GPEs with 0, 0.2wt%, 0.5wt%, 0.8wt% and 1.0wt% fumed SiO2. Electrochromic switching behaviors at 633 nm (e), colored state EIS (d) and CV curves (f) of ECDs contained PMMA-based GPEs with 0, 0.5wt% fumed SiO2. Scan rate: 100 mV/s

Fig. 3 Schematic diagram of the transportation of Li+ ion through H-SiO2GPEs with three-dimensional structure

Fig. 4 Ionic conductivity of liquid electrolyte with 0, 0.2wt%, 0.5wt%, 0.8wt%, and 1.0wt% fumed SiO2 (a), and colored state Nyquist plots (b) and CV curves (c) of WO3 films in liquid electrolyte with 0, 0.2wt%, 0.5wt%, 0.8wt% and 1.0wt% fumed SiO2. Scan rate: 100 mV/s

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基于高电导率的疏水气相SiO₂复合凝胶电解质的高性能电致变色器件

High-conductivity Hydrophobic Fumed-SiO₂ Composite Gel Electrolyte for High Performance Electrochromic Devices

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