Guanyu Zhong, Songtao Li, Wang Zhao, Guoying Zhou, Zhixian Dong, Jinbao Xu, Caihong Lei
ABSTRACT Lithium metal batteries (LMBs) are highly promising for addressing fossil fuel‐related environmental issues, but traditional liquid electrolytes suffer from inherent safety hazards and poor recyclability. Polymer‐ceramic composite solid electrolytes (CSEs) have emerged as ideal alternatives, and lithium aluminum titanium phosphate (Li 1 + X Al X Ti 2 − X (PO 4 ) 3 , 0 ≤ x ≤ 0.5, LATP)—a typical NASICON‐type ceramic exhibiting high room temperature ionic conductivity, air stability, and excellent mechanical strength, has attracted extensive attention in CSEs. This review systematically studies the application of LATP‐based CSEs for LMBs, involving the elaboration of LATP's microstructure (e.g., tetrahedral‐octahedral 3D network and element doping effects) on ionic conductivity, the exploration of key factors regulating CSEs' ionic conductivity (such as synthetic methods, particle size/morphology and LATP content), the clarification of Li + conduction mechanisms in CSEs, and the clarification of LATP/polymer interface modification strategies (unmodified mixing, inorganic/organic modification, in situ polymerization). It provides valuable insights for optimizing the design of LATP‐based polymer/ceramic CSEs and lays a foundation for the scalable fabrication of high performance solid‐state LMBs for next generation energy storage systems.