Multifunctional Design of Solid Polymer Electrolytes: Paving the Way for High‐Performance All‐Solid‐State Batteries

ABSTRACT All‐solid‐state batteries (ASSBs) have emerged as a pivotal direction in next‐generation energy storage, driven by their compelling potential for enhanced safety and superior energy density. Among the key enabling materials, solid polymer electrolytes (SPEs) stand out due to their structural tunability, manufacturing scalability, and robust interfacial contact, offering a viable pathway toward practical ASSBs. This review systematically bridges the gap between molecular‐level design and macroscopic performance of SPEs. It begins by establishing the structure–property relationships underpinning different SPE categories, and then critically assesses conventional and emerging processing techniques in relation to their electrochemical and mechanical performance. Furthermore, the article synthesizes current challenges and strategic solutions for optimizing SPEs, with an emphasis on integrated approaches that balance ionic conductivity, interfacial stability, and processability. By presenting a coherent technological landscape, this work aims to guide the rational design of SPE materials to accelerate the development of reliable, high‐performance ASSBs.