Electrolyte-Regulated Ion Accommodation and Microstructural Stability in WO₃ Electrochromic Thin Films

Electrochromic tungsten oxide (WO₃) films suffer from gradual performance degradation during repeated ion insertion/extraction processes, while the relationship between electrolyte-dependent ion accommodation and structural stability remains insufficiently understood. Herein, magnetron-sputtered WO₃ thin films were systematically investigated in H₂SO₄, LiClO₄, ZnSO₄, and Al₂(SO₄)₃ electrolytes to clarify the coupling relationship among ion accommodation, electronic structure evolution, microstructural retention, and electrochromic durability. Combined electrochemical measurements with UV-visible spectroscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and reflected electron energy loss spectroscopy (REELS) reveal that electrolyte chemistry regulates the balance between electrochemical activation and structural tolerance. Highly mobile H⁺ and strongly interacting Al³⁺ ions promote rapid ion transport and enhanced W⁶⁺ reduction but may induce excessive structural perturbation, defect accumulation, and accelerated degradation during cycling. Zn²⁺ exhibits intermediate behavior, whereas Li⁺ enables balanced ion accommodation through reversible W⁶⁺/W⁵⁺ conversion while preserving the WO₃ framework. Consequently, the LiClO₄ electrolyte achieves superior electrochromic performance with an optical modulation of 80.97% and improved cycling stability. These results demonstrate that durable electrochromic behavior is governed not by maximizing ion transport or reduction degree, but by achieving a reversible ion accommodation regime compatible with the structural tolerance of the host framework. This work provides a microstructure-oriented strategy for designing stable WO₃-based electrochromic devices through electrolyte regulation.