基于Cu3(HHTP)2薄膜的离子液体电致变色电极

doi:10.15541/jim20220097

无机材料学报 ›› 2022, Vol. 37 ›› Issue (8): 883-890.DOI: 10.15541/jim20220097 CSTR: 32189.14.10.15541/jim20220097

所属专题：【信息功能】敏感陶瓷（202409）；【能源环境】金属有机框架材料(202309)；【信息功能】电致变色与热致变色材料(202312)

基于Cu₃(HHTP)₂薄膜的离子液体电致变色电极

张笑宇(), 刘永盛, 李然, 李耀刚, 张青红, 侯成义, 李克睿(), 王宏志()

东华大学材料科学与工程学院, 纤维材料改性国家重点实验室, 上海 201620

收稿日期:2022-02-28 修回日期:2022-05-31 出版日期:2022-08-20 网络出版日期:2022-06-03
通讯作者: 王宏志, 教授. E-mail: wanghz@dhu.edu.cn;
李克睿, 教授. E-mail: likr@dhu.edu.cn
作者简介:张笑宇(1998-), 男, 硕士研究生. E-mail: dhuzxyu@163.com
基金资助:
国家自然科学基金(51972054)

Cu₃(HHTP)₂ Film-based Ionic-liquid Electrochromic Electrode

ZHANG Xiaoyu(), LIU Yongsheng, LI Ran, LI Yaogang, ZHANG Qinghong, HOU Chengyi, LI Kerui(), WANG Hongzhi()

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China

Received:2022-02-28 Revised:2022-05-31 Published:2022-08-20 Online:2022-06-03
Contact: WANG Hongzhi, professor. E-mail: wanghz@dhu.edu.cn;
LI Kerui, professor. E-mail: likr@dhu.edu.cn
About author:ZHANG Xiaoyu(1998-), male, Master candidate. E-mail: dhuzxyu@163.com
Supported by:
National Natural Science Foundation of China(51972054)

摘要/Abstract

摘要：

室温离子液体具有宽电化学窗口和良好的环境稳定性, 是电致变色器件的理想电解质。然而传统电致变色材料的晶格间隙较窄, 限制了离子液体中大尺寸离子的扩散, 且大离子反复脱/嵌会破坏传统电致变色材料的结构, 导致性能衰减。金属有机框架材料(MOFs)是一种具有拓扑结构的多孔晶态材料, 有望为离子液体中大尺寸离子的传输提供通道。本工作在导电玻璃表面制备了三亚苯类Cu₃(HHTP)₂(HHTP=2,3,6,7,10,11-六羟基三苯并菲) MOF薄膜, 并研究了Cu₃(HHTP)₂薄膜在离子液体电解质中电化学和电致变色行为和性能。结果表明, 相对于传统的LiClO₄/PC和NaClO₄/PC电解质, Cu₃(HHTP)₂薄膜在离子液体[EMIm]BF₄中表现出更低的接触电阻和更高的离子扩散效率, 电极的着色/褪色速度得到了显著提高(着色时间由10.3 s缩短至8.0 s, 褪色时间由23.6 s缩短至5.2 s)。同时, Cu₃(HHTP)₂薄膜在[EMIm]BF₄中也具有更高的光调制范围和着色效率。这项工作展现出MOFs/离子液体电化学体系在电致变色领域中的潜在应用价值。

关键词: 金属有机框架材料, 薄膜, 离子液体, 电致变色

Abstract:

Room temperature ionic liquid shows wide electrochemical windows and good environmental stability, which is expected as an ideal electrolyte for electrochromic devices. However, the small crystal spacing of traditional electrochromic materials limits the diffusion of large ions in ionic liquid. Repeated deintercalation/ intercalation of large ions could also destroy the structure of traditional electrochromic materials, resulting in performance degradation. Metal-organic frameworks (MOFs) are topologically porous materials with a large intrinsic nano to microporous structure in crystalline, which are expected to provide channels for transporting large-sized ions in ionic liquids. In present work, triphenylene-based MOFs Cu₃(HHTP)₂ films were prepared on the surface of the conductive glass. Electrochemical and electrochromic behavior of Cu₃(HHTP)₂ films were studied in traditional propylene carbonate (PC)-based electrolyte and ionic liquid-based electrolytes. The results show that, compared with the traditional LiClO₄/PC or NaClO₄/PC electrolyte, Cu₃(HHTP)₂ film displays low contact resistance and high ion diffusion efficiency in the ionic liquid [EMIm]BF₄electrolyte. Switch speed of the electrochromic electrode is significantly improved with coloring time being reduced from 10.3 s to 8.0 s, and bleaching time being reduced from 23.6 s to 5.2 s. Meanwhile, Cu₃(HHTP)₂/[EMIm]BF₄ electrochromic system also shows a larger light modulation range and coloring efficiency. This work demonstrates the potential of MOFs/ionic liquid electrochemical system in the field of electrochromic device.

Key words: MOFs, film, ionic liquid, electrochromism

中图分类号:

TN303
TB389

张笑宇, 刘永盛, 李然, 李耀刚, 张青红, 侯成义, 李克睿, 王宏志. 基于Cu₃(HHTP)₂薄膜的离子液体电致变色电极[J]. 无机材料学报, 2022, 37(8): 883-890.

ZHANG Xiaoyu, LIU Yongsheng, LI Ran, LI Yaogang, ZHANG Qinghong, HOU Chengyi, LI Kerui, WANG Hongzhi. Cu₃(HHTP)₂ Film-based Ionic-liquid Electrochromic Electrode[J]. Journal of Inorganic Materials, 2022, 37(8): 883-890.

图/表 6

图1 (a) Cu3(HHTP)2薄膜的表征结果

Fig. 1 Characterization of Cu3(HHTP)2 films (a) Change of absorbance at 800 nm wavelength with film thickness, inset showing the pictures of Cu3(HHTP)2 films obtained in different growth-cycles; (b) Surface SEM image of the Cu3(HHTP)2 film obtained from 20 cycles; (c) XRD patterns of Cu3(HHTP)2; (d) Raman spectra of Cu3(HHTP)2 and HHTP ligand

图2 Cu3(HHTP)2的XPS谱图和孔径分布图

Fig. 2 XPS spectrum and poresize distribution of Cu3(HHTP)2 (a) XPS full spectrum; (b) High resolution XPS spectrum of Cu2p3/2; (c) Pore size distribution diagram with inset showing N2 adsorption isotherm curves for Cu3(HHTP)2 powders measured at 77 K

图3 (a)不同厚度的Cu3(HHTP)2薄膜在[EMIm]BF4中-0.9和0.4 V的恒定电压下, 在800 nm波长处的透过率变化图谱(插图为20C薄膜在-0.9 和0.4 V下的照片); (b) 20C薄膜在不同电解质中, -0.9和0.4 V下的紫外-可见透过光图谱(300~800 nm); (c) 20C薄膜在不同电解质中, 在波长800 nm处的透过光谱时间响应图; (d) 20C薄膜分别在LiClO4/PC、NaClO4/PC、[EMIm]BF4和[BMIm]BF4溶液中800 nm波长处的着色效率

Fig. 3 (a) Transmittance at 800 nm wavelength for Cu3(HHTP)2 films with different thicknesses at constant voltages of -0.9 and 0.4 V in [EMIm]BF4 with inset photos showing 20C film at -0.9 V and 0.4 V ; (b) UV-Vis transmission spectra of 20C films measured in various electrolytes at wavelength from 300 to 800 nm; (c) Temporal response of the transmittance of 20C films measured in various electrolytes; (d) Coloring efficiencies of 20C films in various electrolytes, respectively

图4 20C薄膜在LiClO4/PC(a)、NaClO4/PC(b)、[EMIm]BF4(c)和[BMIm]BF4(d)中10~70 mV∙s-1扫描速率下的循环伏安曲线(插图为不同扫速下峰值电流(ip)与扫描速率平方根(V1/2)的函数; (e) 20C薄膜分别在不同电解质中的Nyquist阻抗数据(点)和相应拟合结果(线)(插图为对应的等效电路); (f)从电化学阻抗谱和循环伏安测试中计算得出20C薄膜在不同电解质中的扩散系数

Fig. 4 Cyclic voltammetry curves of 20C films at scan rates from 10 to 70 mV∙s-1 in (a) LiClO4/PC, (b) NaClO4/PC solution, (c) [EMIm]BF4, and (d) [BMIm]BF4 with inset showing peak current at different scan rates (ip) as a function of square root of the scan rate (V1/2)); (e) Nyquist impedance data (dots) and corresponding fitting results (lines) of 20C films in various electrolytes, respectively with inset showing corresponding equivalent circuit; (f) Calculated diffusion coefficients of 20C films in various electrolytes from electrochemical impedance spectroscopy and cyclic voltammetry, respectively

图5 Cu3(HHTP)2基电致变色器件在(a)初始态和(b)透明态的照片; (c)器件在+3和-3 V电压下的紫外-可见光透射图谱

Fig. 5 Photos of (a) bleaching state and (b) coloring state of Cu3(HHTP)2 EC device, and (c) UV-Vis transmission spectra of Cu3(HHTP)2 EC devices at voltages of +3 and -3 V

图6 (a)基于Cu3(HHTP)2和PEDOT电致变色全器件结构示意图和(b)电致变色全器件在+3和-3 V电压下的紫外-可见光透射图谱

Fig. 6 (a) Structure diagram of Cu3(HHTP)2 and poly (3,4-ethylene dioxythiophene) (PEDOT) electrochromic multiple device, and (b) UV-Vis transmission spectra of multiple devices at voltages of +3 and -3 V

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基于Cu₃(HHTP)₂薄膜的离子液体电致变色电极

Cu₃(HHTP)₂ Film-based Ionic-liquid Electrochromic Electrode

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