Dynamic Li + Releasing‐Pulling Design of Weakly Coordinated Gel Polymer Electrolytes Realizing Practical Wide‐Temperature Lithium Metal Batteries

ABSTRACT Polymer lithium metal batteries are promising for next‐generation high‐safety and high‐energy‐density applications, but their wide‐temperature operation is still limited by poor ion transport and interfacial side reactions. Herein, we develop a dynamic “releasing‐pulling” design for wide‐temperature propylene carbonate (PC)‐based gel polymer electrolytes (NSP‐GPE) featuring with weak Li + ‐polymer and Li + ‐PC coordination, simultaneously. Weak Li + ‐polymer coordination enabled by synergistic delocalized π‐electron transfer from the amide (─NH─CO─) and sulfuryl (O═S═O) groups, endows the NSP‐GPE with dynamic Li + pulling sites and reduced Li + decoupling energy barrier, ultimately delivering fast ion transport; Weak Li + ‐PC coordination established by the ─NH─CO─ group as stationary PC anchors via hydrogen bonding, sequesters PC from the Li + solvation sheath to facilitate Li + release, thereby reducing the Li + desolvation energy barrier and alleviating interfacial side reactions. Ultimately, the assembled Li||NCM811 cells show superior wide‐temperature (‐20∼60°C) electrochemical performances. A stable Ah‐level pouch cell with a high specific energy of 403.26 Wh kg −1 and a high power density of 2866.8 W kg −1 is also demonstrated, concurrently showing excellent safety under thermal and mechanical abuse. This work demonstrates that rational polymer structure engineering enables precise regulation of the coordination environment in GPEs, overcoming the inherent contradiction between ionic conductivity and interfacial stability.