Prediction of Ground State Configurations and Electrochemical Properties of Li3InCl6 Doped with F, Br, and Ga

Compared with conventional solid-state electrolytes, halide solid-state electrolytes have several advantages such as a wider electrochemical window, better compatibility with oxide cathode materials, improved air stability, and easier preparation conditions making them conductive to industrial production. We concentrate on a typical halide solid-state electrolyte, Li 3 InCl 6 , predict the most stable structure after doping with Br, F, and Ga by using the Alloy Theoretic Automated Toolkit based on first-principles calculations, and verify the accuracy of the prediction model. To investigate the potential of three equivalently doped ground state configurations of Li 3 InCl 6 as solid-state electrolytes for all-solid-state lithium-ion batteries, their specific properties such as crystal structure, band gap, convex packing energy, electrochemical stability window, and lithium-ion conductivity are computationally analyzed using first-principles calculations. After a comprehensive evaluation, it is determined that the F-doped ground state configuration Li 3 InCl 2.5 F 3.5 exhibits better thermal stability, wider electrochemical stability window, and better lithium ion conductivity (1.80 mS⋅cm −1 at room temperature). Therefore, Li 3 InCl 2.5 F 3.5 has the potential to be used in the field of all-solid-state lithium-ion batteries as a new type of halide electrolyte.