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

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 Li 2 Sc 2/3 Cl 4 , a rare superionic conductor among cubic spinel halide materials. Li ions in Li 2 Sc 2/3 Cl 4 prefer to occupy some of the tetrahedral 8a, octahedral 16c, and octahedral 16d sites, leading to disordered Li distribution. Li ions in Li 2 Sc 2/3 Cl 4 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 Li 2 MgCl 4 , the same cubic spinel as Li 2 Sc 2/3 Cl 4 , 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 Li 2 Sc 2/3 Cl 4 than in Li 2 MgCl 4 is because the concentration of Sc 3+ /Mg 2+ cations blocking the movement of Li ions at the 16d site is lower in Li 2 Sc 2/3 Cl 4 than in Li 2 MgCl 4 . 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.