两步电沉积法制备Zn-Fe PBA薄膜及其在电致变色器件中的性能研究

doi:10.15541/jim20210724

无机材料学报 ›› 2022, Vol. 37 ›› Issue (9): 961-968.DOI: 10.15541/jim20210724

两步电沉积法制备Zn-Fe PBA薄膜及其在电致变色器件中的性能研究

张家强¹^,²(), 邹馨蕾¹, 王能泽³, 贾春阳¹()

1.电子科技大学电子科学与工程学院电子薄膜与集成器件国家重点实验室, 成都 610054
2.北京卫星制造厂有限公司, 北京 100094
3.电子科技大学(深圳) 高等研究院, 深圳 518110

收稿日期:2021-11-24 修回日期:2022-01-19 出版日期:2022-09-20 网络出版日期:2022-06-16
通讯作者: 贾春阳, 教授. E-mail: cyjia@uestc.edu.cn
作者简介:张家强(1985-), 男, 博士研究生. E-mail: jqzhangl@163.com
基金资助:
国家自然科学基金(51773027);中央高校基础研究经费(ZYGX2019Z007)

Zn-Fe PBA Films by Two-step Electrodeposition Method: Preparation and Performance in Electrochromic Devices

ZHANG Jiaqiang¹^,²(), ZOU Xinlei¹, WANG Nengze³, JIA Chunyang¹()

1. State Key Laboratory of Electronic Thin Films and Integrated Devices, School of Electronic Science and Technology, University of Electronic Science and Technology of China, Chengdu 610054, China
2. Beijing Satellite Manufacturing Plant Co., Ltd., Beijing 100094, China
3. Shenzhen Institute for Advanced Study, University of Electronic Science and Technology of China, Shenzhen 518110, China

Received:2021-11-24 Revised:2022-01-19 Published:2022-09-20 Online:2022-06-16
Contact: JIA Chunyang, professor. E-mail: cyjia@uestc.edu.cn
About author:ZHANG Jiaqiang (1985-), male, PhD candidate. E-mail: jqzhangl@163.com
Supported by:
National Natural Science Foundation of China(51773027);Fundamental Research Funds for the Central Universities of China(ZYGX2019Z007)

摘要/Abstract

摘要：

电致变色材料因其颜色随外加电压变化的特性, 可用于新型显示器件。目前, 彩色电致变色器件(Multicolor electrochromic devices, MCECDs)大多使用几种不同颜色的有机材料制备的, 流程较为复杂。为了简化制备流程, 本课题组提出了一种具有红、蓝、绿、黄四种典型颜色的普鲁士蓝类似物的复合电致变色(MC-PBA)薄膜, 以实现性能优异的变色器件。本工作通过两步电沉积法制备了锌铁普鲁士蓝类似物(Zn-Fe PBA)薄膜, 其循环伏安曲线仅有一对氧化还原峰, 对应于Fe^Ⅲ/Fe^Ⅱ间的氧化还原反应, 在10000圈循环后性能几乎不发生衰减。该薄膜为白色且在电化学循环过程中几乎不发生颜色变化, 在与MC-PBA薄膜组装相应的电致变色器件(Z-MCECD)时不会对颜色产生影响, 并且其作为离子存储层可以显著减低过电势(从4.0 V降低至1.5 V)。得益于此, 所组装的Z-MCECD在保有红、蓝、绿、黄四种典型颜色状态的同时, 工作电压更低, 循环稳定性也得到显著提高(2400 s内透过率调控范围几乎没有发生衰减, 在3600 s后仍保持有初始的74.4%; 而对照组在1200 s后发生不可逆的性能衰减)。基于Z-MCECD的电致变色器件在彩色电致变色显示领域表现出相当大的应用潜力。

关键词: 电致变色, 普鲁士蓝类似物, 离子存储层, 彩色

Abstract:

Electrochromic materials can be used in new display devices because of their color-changing properties with applied voltage. The current multicolor electrochromic devices (MCECDs) are mostly prepared using several organic materials of different colors, and their process is relatively complicated, leaving preparation of simple MCECDs is still a challenge. In order to simplify the preparation process, we proposed a Prussian blue analogue composite electrochromic (MC PBA) film with four typical color states of red, blue, green, and yellow for excellent performance ECD. In this work, the preparation of a Zn-Fe Prussian blue analogue composite (Zn-Fe PBA) film was proposed by a two-step electrodeposition method. It has only one pair of redox peaks in the cyclic voltammetry curve, which corresponds to the redox reaction between Fe^Ⅲ/Fe^Ⅱ. The electrochemical performance of the Zn-Fe PBA film is excellent, which hardly degrades after 10000 cycles. It is white with almost no color change during electrochemical redox, and does not affect the color when assembling multicolor electrochromic device (Z-MCECD) with MC-PBA film. In addition, the Zn-Fe PBA film is used as ion storage layer which can significantly reduce the overpotential from 4.0 V to 1.5 V in the corresponding ECD. Benefiting from the advantages of Zn-Fe PBA film, Z-MCECD maintains four typical color states of red, blue, green, and yellow, while the operating voltage is lower and the cycle stability is also significantly improved. The transmittance control range within 2400 s was almost no attenuated, and after 3600 s, transmittance still maintained 74.4% of the initial, while the multicolor group experienced completely irreversible performance loss after 1200 s. Z-MCECD has great application potential in color electrochromic display field.

Key words: electrochromism, Prussian blue analogues, ion storage layer, multicolor

中图分类号:

TQ174

张家强, 邹馨蕾, 王能泽, 贾春阳. 两步电沉积法制备Zn-Fe PBA薄膜及其在电致变色器件中的性能研究[J]. 无机材料学报, 2022, 37(9): 961-968.

ZHANG Jiaqiang, ZOU Xinlei, WANG Nengze, JIA Chunyang. Zn-Fe PBA Films by Two-step Electrodeposition Method: Preparation and Performance in Electrochromic Devices[J]. Journal of Inorganic Materials, 2022, 37(9): 961-968.

图/表 7

图1 锌薄膜和Zn-Fe PBA薄膜的形貌分析

Fig. 1 Topography analyses of Zn film and Zn-Fe PBA film (a) Digital photo and SEM images of Zn film; (b) Digital photo and SEM images of Zn-Fe PBA film

图2 Zn-Fe PBA薄膜的XRD图谱和生长原理示意图

Fig. 2 XRD patterns and growth principle of Zn-Fe PBA film

图3 Zn-Fe PBA薄膜XPS能谱

Fig. 3 XPS spectra of Zn-Fe PBA film (a) Full spectrum; (b-f) C1s, N1s, Fe2p, O1s, and Zn2p binding energy spectra. Colorful figures are available on website

图4 Zn-Fe PBA薄膜的电化学性能

Fig. 4 Electrochemical performance of Zn-Fe PBA film (a) Cyclic voltammetry curve; (b) Step cycle stability; (c) Response speed

图5 锌薄膜和Zn-Fe PBA薄膜的透过率光谱

Fig. 5 Transmittance spectra of Zn film and Zn-Fe PBA film Colorful figure is available on website

图6 彩色电致变色器件性能

Fig. 6 Performance of multicolor electrochromic devices (a) Schematic diagram of MCECD preparation process; (b) Cyclic voltammetry curves of MCECDs; (c) Transmittance spectra of MCECDs at the initial state; (d) Transmittance spectra under different applied voltages of Z-MCECD; (e) Step cycle stability of MCECDs; (f) Digital photos of Z-MCECD under different applied voltages. Colorful figures are available on website

图7 Z-MCECD响应速率

Fig. 7 Response speed of Z-MCECD (a-f) Transmittance time curves between (a) red and blue, (b) red and green, (c) red and yellow, (d) blue and green, (e) blue and yellow, and (f) green and yellow, respectively. Colorful figures are available on website

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两步电沉积法制备Zn-Fe PBA薄膜及其在电致变色器件中的性能研究

Zn-Fe PBA Films by Two-step Electrodeposition Method: Preparation and Performance in Electrochromic Devices

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