Cation‐/Anion‐Based Electrochemical Degradation and Rejuvenation of Electrochromic Nickel Oxide Thin Films,ChemElectroChem

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Cation‐/Anion‐Based Electrochemical Degradation and Rejuvenation of Electrochromic Nickel Oxide Thin Films
ChemElectroChem ( IF 3.5 ) Pub Date : 2018-09-05 , DOI: 10.1002/celc.201800791
Hui-Ying Qu _{1,

2} , Daniel Primetzhofer ₃ , Zhen Qiu ₁ , Lars Österlund ₁ , Claes G. Granqvist ₁ , Gunnar A. Niklasson ₁

Affiliation

Ni oxide thin films are widely used in electrochromic (EC) devices with variable throughput of visible light and solar energy. However, the mechanisms underlying the optical modulation – and its degradation under extended operation and subsequent rejuvenation – are poorly understood especially for Li⁺‐conducting electrolytes. Here, we report a comprehensive study of the EC properties of sputter‐deposited Ni oxide films immersed in an electrolyte of LiClO₄ in propylene carbonate. Cyclic voltammetry and optical transmittance measurements were used to document degradation and subsequent potentiostatic rejuvenation. X‐ray diffraction did not show evidence for accompanying changes in crystallinity, whereas vibrational spectroscopy indicated that degraded films had carbonaceous surface layers. Time‐of‐flight elastic recoil detection analysis demonstrated that both Li⁺ and Cl‐based ions participate in the electrochromism and its degradation and rejuvenation. A major result was that degradation is associated with a reduced difference in the concentrations of Li⁺ and Cl‐based ions in the nickel oxide during extended electrochemical cycling, and rejuvenation of degraded films is achieved by removal of Li⁺ ions and accumulation of Cl‐based anions to regain their initial concentration difference. Our work provides new insights into the use of ion‐exchange‐based devices incorporating nickel oxide.

中文翻译：

基于阳离子/阴离子的电致变色氧化镍薄膜的电化学降解和活化

氧化镍薄膜广泛用于电致变色（EC）器件中，具有可变的可见光和太阳能通过量。但是，对于光调制的基本机理及其在长时间运行和随后的再生中的降解，人们了解得很少，尤其是对于含Li ⁺的电解质而言。在这里，我们报告了对浸入LiClO ₄电解质中的溅射沉积Ni氧化膜的EC特性的全面研究。在碳酸亚丙酯中。循环伏安法和光透射率测量用于记录降解和随后的恒电位回春。X射线衍射没有显示伴随结晶度变化的证据，而振动光谱表明降解膜具有碳质表面层。飞行时间弹性反冲检测分析表明，Li ⁺和Cl基离子均参与电致变色及其降解和恢复活力。一个主要的结果是在延长的电化学循环过程中，降解与减少的氧化镍中Li ⁺和Cl-离子浓度差异的减少有关，并且通过去除Li ⁺可以实现降解膜的再生离子和基于Cl的阴离子的积累，以恢复其初始浓度差。我们的工作为结合使用氧化镍的基于离子交换的设备的使用提供了新的见解。

更新日期：2018-09-05

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