Rational Design of High-Performance PEO/Ceramic Composite Solid Electrolytes for Lithium Metal Batteries

Composite solid electrolytes (CSEs) with poly(ethylene oxide) (PEO) have become fairly prevalent for fabricating high-performance solid-state lithium metal batteries due to their high Li⁺ solvating capability, flexible processability and low cost. However, unsatisfactory room-temperature ionic conductivity, weak interfacial compatibility and uncontrollable Li dendrite growth seriously hinder their progress. Enormous efforts have been devoted to combining PEO with ceramics either as fillers or major matrix with the rational design of two-phase architecture, spatial distribution and content, which is anticipated to hold the key to increasing ionic conductivity and resolving interfacial compatibility within CSEs and between CSEs/electrodes. Unfortunately, a comprehensive review exclusively discussing the design, preparation and application of PEO/ceramic-based CSEs is largely lacking, in spite of tremendous reviews dealing with a broad spectrum of polymers and ceramics. Consequently, this review targets recent advances in PEO/ceramic-based CSEs, starting with a brief introduction, followed by their ionic conduction mechanism, preparation methods, and then an emphasis on resolving ionic conductivity and interfacial compatibility. Afterward, their applications in solid-state lithium metal batteries with transition metal oxides and sulfur cathodes are summarized. Finally, a summary and outlook on existing challenges and future research directions are proposed.