Non‐Entangled Chains Enable Rapid Na + Transport Through Ion‐Traps in Gel Polymer Electrolytes at Low Temperatures

ABSTRACT Polymer electrolytes are promising for all‐climate rechargeable batteries due to their safety and compatibility with high‐energy‐density battery systems. However, topological traps induced by chain entanglement become a major transport bottleneck limiting continuous ion motion and interfacial charge transfer as temperature and liquid‐phase content decrease. Here, we unveil that temperature‐dependent ion‐traps in the entangled gel polymer are a key factor for slow Na + transport at low temperatures. Specifically, we propose a low‐temperature‐tolerant gel polymer electrolyte, denoted as non‐entangled poly(1,3‐dioxolane) (NPDOL), which promotes sodium bis(trifluoromethylsulfonyl)imide (NaTFSI) dissociation and provides homogeneous coordination sites for continuous Na + transport. Meanwhile, the non‐entangled, high‐entropy polymer framework decreases chain relaxation time and expands free volume, thereby reducing the density of ion‐traps and enhancing Na + diffusion kinetics. Furthermore, reduced ion‐trap density improves the Na + transference number ( t Na+ = 0.85), resulting in a thin and uniform solid electrolyte interphase (SEI) with improved interfacial Na + charge‐transfer. The NPDOL electrolyte exhibits high ionic conductivity ( σ ) of 0.25 mS cm −1 at ‐50°C, enabling Na//NPDOL//Na 3 V 2 (PO 4 ) 3 full cells to deliver nearly 100% capacity retention at ‐40°C. This strategy of reducing chain entanglement to suppress Na + traps widens the low‐temperature operational window of batteries, paving the way for high‐performance energy storage systems.