Enhancing Lithium Conductivity Using High-Valence Cations in Cubic Spinel Halide Solid Electrolytes.

ABSTRACT

Halide solid electrolytes for all-solid-state batteries have recently emerged as competitors to oxide and sulfide solid electrolytes due to their excellent electrochemical properties. This ab initio study unveils the dynamic nature of Li2Sc2/3Cl4, a rare superionic conductor among cubic spinel halide materials. Li ions in Li2Sc2/3Cl4 prefer to occupy some of the tetrahedral 8a, octahedral 16c, and octahedral 16d sites, leading to disordered Li distribution. Li ions in Li2Sc2/3Cl4 diffuse through the single-ion diffusion mechanism rather than the concerted diffusion mechanism, providing a high conductivity of 1.36 mS cm-1. Li ions at the 16d site diffuse as actively as those at the 8a/16c site, an unexpected result that runs counter to the conventional view. In Li2MgCl4, the same cubic spinel as Li2Sc2/3Cl4, Li ions at the 8a/16c site diffuse actively, but those at the 16d site are almost immobile, resulting in a very low conductivity of 5.3 × 10-4 mS cm-1. The extremely higher conductivity in Li2Sc2/3Cl4 than in Li2MgCl4 is because the concentration of Sc3+/Mg2+ cations blocking the movement of Li ions at the 16d site is lower in Li2Sc2/3Cl4 than in Li2MgCl4. Designing cubic spinel materials containing high-valence cations is proposed as a way to increase conductivity by reducing the concentration of multivalent cations that impede Li diffusion. This study sheds new light on how to control conductivity using site-dependent Li mobility in solid electrolytes.