Spatially Orchestrated Oxygen Motifs Decouple Ion Dissociation/Migration in Liquid Crystal Elastomer for High‐ Performance Solid‐State Li Metal Batteries

Abstract Solid polymer electrolytes (SPEs) emerge as prime candidates for next‐generation solid‐state lithium metal batteries, capitalizing on their intrinsic electrochemical robustness and enhanced safety profiles. However, overcoming the inherent trade‐off between efficient lithium‐salt dissociation and rapid ion migration remains a fundamental challenge for SPEs. We propose a programmable liquid crystal elastomer (LCE) framework with spatially patterned carbonyl (─C═O) and ether (─C─O─C─) oxygen motifs. In this hierarchical architecture, carbonyl groups act as stationary anchors to dissociate LiTFSI via strong coordination, while ether chains serve as dynamic relays enabling barrier‐reduced Li⁺ hopping along oriented mesophases. This decoupled “anchor‐relay” mechanism achieves outstanding room‐temperature performance: ionic conductivity of 4.05 × 10 −3 S cm −1 and Li⁺ transference number of 0.78. The synergistically induced LiF‐rich interphase further suppresses dendrite growth, the symmetric Li//Li cell exhibits a long‐term cycling lifespan over 1000 h with a low overpotential of 300 mV, delivering exceptional cycling stability in both LiFePO 4 //Li cell (90.1% capacity retention after 500 cycles) and high‐voltage LiNi 0.8 Co 0.1 Mn 0.1 O 2 //Li cell systems. The proposed LCEs as a transformative platform for next‐generation solid‐state batteries through rational molecular engineering.