Tailored Inorganic Fillers in Composite Solid‐State Electrolytes: Enabling Synergistic Enhancement of Ionic Conduction and Interfacial Stability for High‐Performance ASSLBs

Abstract All‐solid‐state lithium‐ion batteries (ASSLBs) have emerged as a key development direction for next‐generation energy storage technologies due to their high energy density and intrinsic safety features. As the core component determining battery performance, the innovative research and development of solid‐state electrolytes (SSEs) systems is particularly crucial. Among various SSEs materials, organic–inorganic composite solid‐state electrolytes (CSEs) have become a research hotspot in the field of SSEs by achieving synergistic optimization of ionic conductivity, mechanical properties, and interfacial stability through the cooperative effects of organic polymer matrices and inorganic fillers. This review systematically examines the limitations of traditional polymer solid‐state electrolytes (PSEs) and recent advancements in CSEs. It elaborates on the contributions of inert and active fillers to the ionic conductivity, mechanical performance, and electrochemical stability of CSEs, while discussing potential mechanisms for conductivity enhancement through inorganic fillers. Finally, the paper addresses current challenges requiring resolution, outlines future research directions, and provides perspectives for developing high‐performance CSEs for ASSLBs.