Construction of Gel Electrolyte with High‐Entropy Polymer Matrix for All‐Weather Stable‐Operatable Li‐Metal Batteries

ABSTRACT Recently developed high‐entropy gel‐polymer electrolytes (GPEs), which are mainly constructed by diversifying the components of liquid electrolytes (LEs), are attractive to achieve safe and stable lithium‐metal batteries while posing persistent challenges in low‐temperature operation. Herein, we develop a high‐entropy GPE via the incorporation of a high‐entropy single‐ion conducting polymer (HESIP) matrix that has a synergistic effect with low‐temperature operable LE (LOLE) for efficient ionic transport and a stable interface. The multi‐functional HESIP matrix can modulate the Li + solvation structure by competitive coordination, achieving high ionic conductivity (5.33 mS cm −1 @ 25 °C) and cation transport number (0.77) of high‐entropy GPE. It further demonstrates reduced degradation of the NCM811 cathode with suppressed HF release and mitigated side reactions at the electrode‐electrolyte interphase. The high‐entropy GPE enables stable cycling performance of NCM811 (1.2 mAh cm −2 , active materials >97 %)//Li cell at both ambient temperature (25 °C, capacity retention 79.5 % over 400 cycles) and low temperature (−25 °C, capacity retention 99.9 % over 500 cycles). Such high‐entropy GPE provides new insights into the future application prospects for safe and high‐performance all‐weather operable batteries.