Electrochromism of W-Ti Oxide Thin Films: Cycling Durability, Potentiostatic Rejuvenation, and Modelling of Electrochemical Degradation

Thin films of electrochromic W oxide and W-Ti oxide were prepared by reactive DC magnetron sputtering and were cycled voltammetrically in an electrolyte of lithium perchlorate in propylene carbonate. Film degradation was studied for up to 500 voltammetric cycles in voltage ranges between 1.5-4.0 and 2.0-4.0 V vs. Li/Li+. Optically and electrochemically degraded films were subjected to potentiostatic posttreatment at 6.0 V vs. Li/Li+ to achieve ion de-trapping and rejuvenation so that the films partly regained their original properties. Ti incorporation and potentiostatic posttreatment jointly yielded superior electrochromic properties provided the lower limit of the voltage range was above 1.6-1.7 V vs. Li/Li+. Degradation dynamics for as-deposited and rejuvenated thin films was modeled successfully by power-law kinetics; this analysis indicated coexistence of two degradation mechanisms, one based on dispersive chemical kinetics and operating universally and another, of unknown origin, rendered inactive by rejuvenation. The results of the present study are of large interest for the development of electrochromic devices with exceptional durability.