无机材料学报 ›› 2022, Vol. 37 ›› Issue (8): 883-890.DOI: 10.15541/jim20220097
所属专题: 【能源环境】金属有机框架材料
张笑宇(), 刘永盛, 李然, 李耀刚, 张青红, 侯成义, 李克睿(), 王宏志()
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;作者简介:
张笑宇(1998-), 男, 硕士研究生. E-mail: dhuzxyu@163.com
基金资助:
ZHANG Xiaoyu(), LIU Yongsheng, LI Ran, LI Yaogang, ZHANG Qinghong, HOU Chengyi, LI Kerui(), WANG Hongzhi()
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;About author:
ZHANG Xiaoyu(1998-), male, Master candidate. E-mail: dhuzxyu@163.com
Supported by:
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。
中图分类号:
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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