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

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 LiFePO₄//Li cell (90.1% capacity retention after 500 cycles) and high-voltage LiNi_0.8Co_0.1Mn_0.1O₂//Li cell systems. The proposed LCEs as a transformative platform for next-generation solid-state batteries through rational molecular engineering.