Surface Deposition of Ni(OH)2 and Lattice Distortion Induce the Electrochromic Performance Decay of NiO Films in Alkaline Electrolyte

NiO, an anodic electrochromic material, has applications in energy‐saving windows, intelligent displays, and military camouflage. However, its electrochromic mechanism and reasons for its performance degradation in alkaline aqueous electrolytes are complex and poorly understood, making it challenging to improve NiO thin films. We studied the phases and electrochemical characteristics of NiO films in different states (initial, colored, bleached and after 8000 cycles) and identified three main reasons for performance degradation. First, Ni(OH) 2 is generated during electrochromic cycling and deposited on the NiO film surface, gradually yielding a NiO@Ni(OH) 2 core–shell structure, isolating the internal NiO film from the electrolyte, and preventing ion transfer. Second, the core–shell structure causes the mode of electrical conduction to change from first‐ to second‐order conduction, reducing the efficiency of ion transfer to the surface Ni(OH) 2 layer. Third, Ni(OH) 2 and NiOOH, which have similar crystal structures but different b ‐axis lattice parameters, are formed during electrochromic cycling, and large volume changes in the unit cell reduce the structural stability of the thin film. Finally, we clarified the mechanism of electrochromic performance degradation of NiO films in alkaline aqueous electrolytes and provide a route to activation of NiO films, which will promote the development of electrochromic technology.