Anodic Electrochromism for Energy‐Efficient Windows: Cation/Anion‐Based Surface Processes and Effects of Crystal Facets in Nickel Oxide Thin Films

Anodic electrochromic (EC) oxides are of major interest as counter electrodes for smart window applications owing to their unique optical properties upon charge insertion and extraction. However, performance optimization of such oxides has been hampered by limited understanding of their EC mechanism, particularly in Li⁺‐conducting electrolytes. This paper reports on NiO_x films with 1.16 ≤ x ≤ 1.32, prepared by sputter deposition. These films are immersed in an electrolyte of lithium perchlorate in propylene carbonate, and EC properties are studied by cyclic voltammetry and in situ optical transmittance measurements. The electrochromism is significantly enhanced at large values of x. It has been found that charge exchange in Ni oxide is mainly due to surface processes and involves both cations and anions from the electrolyte, which is different from the case of cathodic EC materials such as WO₃. Whereas previous studies of Ni oxide have focused on cation intercalation, the cation/anion‐based mechanism presented here offers a new paradigm for designing and developing EC devices such as smart windows for energy efficient buildings.