Harnessing Disorder for High-Performance Solid-State Electrolytes

Solid-state electrolytes (SSEs) have emerged as transformative alternatives to traditional liquid electrolytes, addressing critical challenges while enabling safer, wider operational voltage windows and higher density batteries. High ionic conductivity inorganic solid-state electrolytes (HC-ISEs), such as LGPS (Li 10 GeP 2 S 12 ), exhibit exceptional ionic conductivity but suffer from interfacial instability, grain boundaries resistance, poor compatibility with lithium metal anodes, and environmental sensitivity. Recent studies have revealed that engineered disorder, through cationic site disordering, amorphous phase integration, and glass–ceramic structural irregularities, can optimize ion diffusion pathways, mitigate interfacial resistance, and enhance electrochemical stability. This review systematically analyzes how controlled disorder elevates HC-ISEs’ performance, explores strategies to tailor disordered architectures, and underscores their pivotal role in realizing next-generation solid-state batteries with high reliability and energy density.