Boosting lithium ion conductivity of antiperovskite solid electrolyte by potassium ions substitution for cation clusters

Abstract Solid-state electrolytes with high ionic conductivities are crucial for the development of all-solid-state lithium batteries, and there is a strong correlation between the ionic conductivities and underlying lattice structures of solid-state electrolytes. Here, we report a lattice manipulation method of replacing [Li2OH]+ clusters with potassium ions in antiperovskite solid-state electrolyte (Li2OH)0.99K0.01Cl, which leads to a remarkable increase in ionic conductivity (4.5 × 10‒3 mS cm‒1, 25 °C). Mechanistic analysis indicates that the lattice manipulation method leads to the stabilization of the cubic phase and lattice contraction for the antiperovskite, and causes significant changes in Li-ion transport trajectories and migration barriers. Also, the Li||LiFePO4 all-solid-state battery (excess Li and loading of 1.78 mg cm‒2 for LiFePO4) employing (Li2OH)0.99K0.01Cl electrolyte delivers a specific capacity of 116.4 mAh g‒1 at the 150th cycle with a capacity retention of 96.1% at 80 mA g‒1 and 120 °C, which indicates potential application prospects of antiperovskite electrolyte in all-solid-state lithium batteries.