Liquid-Phase Synthesis of Halide Solid Electrolytes for All-Solid-State Batteries Using Organic Solvents

Abstract

Halide solid electrolytes (SEs) show high ionic conductivity and good compatibility with cathode active materials, providing long-life all-solid-state lithium-ion batteries (ASSLIBs). Liquid-phase synthesis technology is a feasible option for the large-scale manufacturing of halide SEs. However, no leading liquid-phase synthesis method for halide SEs has been developed because of a limited understanding of the solvent effect on the formation of halide SEs. Herein, a scalable and universal liquid-phase synthesis method for halide SEs using organic solvents is reported. The Li_3−xYCl_6−x SEs synthesized via pyridine transform trigonal structure to metastable orthorhombic structure as the Li concentration decreases, forming a highly pure orthorhombic phase with an ionic conductivity of 1.3 × 10⁻⁴ S cm⁻¹ at 25 °C in the composition of x = 1. Spectroscopic analysis indicates that pyridine acts as a reducing ligand, stabilizing the orthorhombic Li₂YCl₅ by modulating the valence state of yttrium ions. Additionally, the developed synthesis method is extended to the synthesis of bromide SEs with high ionic conductivity. ASSLIBs using LiNi_0.8Co_0.1Mn_0.1O₂-Li₂YCl₅ cathode composites demonstrate good cycling stability for 100 cycles. The liquid-phase synthesis technology reported here opens opportunities for the practical manufacturing of halide-based ASSLIBs.

Keywords

all-solid-state battery / halide solid electrolyte / liquid-phase synthesis

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2025 The Author(s). Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.