Evidence for Complex Dynamics in Glassy Fast Ion Conductors: The Case of Sodium Thiosilicates

Classical molecular dynamics is used to study the dynamics of alkali ions in a promising fast ion conductor glass system, i.e., Na2S-SiS2. Diffusion in such thiosilicates is found to display various salient features of alkali silicates, i.e., channel-like diffusion with typical length scales emerging as the temperature is decreased to the glassy state, and Arrhenius behavior for both Na ion diffusivity and calculated conductivity. The dynamics appears, however, to be largely heterogeneous as manifested by fast and slow Na ion motion at intermediate times, both in the high-temperature liquid and in the glassy state. In the former, a diffusion-limited regime is found due to the increased motion of the network-forming species that limits the Na ion dynamics, whereas at low temperatures, the typical dynamical heterogeneities are recovered as observed close to the glass transition.

Automated summary

Classical molecular dynamics is employed to investigate the dynamics of alkali ions in Na2S-SiS2 glass, a potential fast ion conductor. The research finds that the diffusion in such thiosilicates exhibits similar features to alkali silicates, including channel-like diffusion and Arrhenius behavior. However, the dynamics show significant heterogeneity, with fast and slow Na ion motion observed both in the high-temperature liquid and in the glassy state.