Ion Trapping and Detrapping in Amorphous Tungsten Oxide Thin Films Observed by Real-Time Electro-Optical Monitoring

Several technologies for energy saving and storage rely on ion exchange between electrodes and electrolytes. In amorphous electrode materials, a detailed knowledge of Li-ion intercalation is hampered by limited information about the structure and transport properties of the materials. Amorphous tungsten oxide is the most studied electrochromic material and suffers from ion trapping-induced degradation of charge capacity and optical modulation span upon extensive electrochemical cycling. In this paper, we investigate trapping and detrapping processes in connection with performance degradation and specifically use real-time electro-optical monitoring to identify different trap energy ranges pertinent to the ion-intercalated system. Evidence of three kinds of traps that degrade electrochromic tungsten oxide during ion intercalation is presented: (i) shallow traps that erode the colored state, (ii) deep traps that lower the bleached-state transmittance, and (iii) irreversible traps. Importantly, Li-ion detrapping from shallow and deep traps takes place by different processes: continuous Li-ion extraction is possible from shallow traps, whereas a certain release time must be exceeded for detrapping from deep traps. Our notions for ion trapping and detrapping, presented here, may serve as a starting point for discussing ion intercalation in various amorphous materials of interest for energy-related applications.