Anomalous ionic transport in glassy electrolytes

Abstract

We discuss the dynamic structure model recently introduced by Bunde, Maass and Ingram to account for the anomalies of ionic transport in glassy ionic conductors. The model is based on the experimental evidence that ions in glass maintain their distinct local environments. Key features include a site memory effect that introduces vacancies appropriate to each kind of mobile ion, and a mismatch energy that emerges whenever an ion attempts to enter a different kind of site, the combination of both leads to the formation of fluctuating percolation pathways. The connectivity of these pathways determines the ion mobility in the glassy network. The exploration of this model by numerical methods leads i) to a power law relationship between ionic conductivity and cation content (now confirmed in the literature) and ii) to the elucidation of many facets of the mixed alkali effect. It is suggested that the model could form the basis for a comprehensive theory of vitreous electrolytes.