Coupled Cation-Anion Dynamics Enhances Cation Mobility in Room-Temperature Superionic Solid-State Electrolytes.

Abstract

Single-ion conducting solid electrolytes are gaining tremendous attention as essential materials for solid-state batteries, but a comprehensive understanding of the factors that dictate high ion mobility remains elusive. Here, for the first time, we use a combination of the Maximum Entropy Method analysis of room-temperature neutron powder diffraction data, ab initio molecular dynamics, and joint-time correlation analysis to demonstrate that the dynamic response of the anion framework plays a significant role in the new class of fast ion conductors, Na11Sn2PnX12 (Pn = P, Sb; X = S, Se). Facile [PX4]3- anion rotation exists in superionic Na11Sn2PS12 and Na11Sn2PSe12, but greatly hindered [SbS4]3- rotational dynamics are observed in their less conductive analogue, Na11Sn2SbS12. Along with introducing dynamic frustration in the energy landscape, the fluctuation caused by [PX4]3- anion rotation is firmly proved to couple to and facilitate long-range cation mobility, by transiently widening the bottlenecks for Na+-ion diffusion. The combined analysis described here resolves the role of the long-debated paddle-wheel mechanism, and is the first direct evidence that anion rotation significantly enhances cation migration in rotor phases. The joint-time correlation analysis developed in our work can be broadly applied to analyze coupled cation-anion interplay where traditional transition state theory does not apply. These findings deliver important insights into the fundamentals of ion transport in solid electrolytes. Invoking anion rotational dynamics provides a vital strategy to enhance cation conductivity and serves as an additional and universal design principle for fast ion conductors.