Fluorinated Gel Polymer Electrolyte With Dynamically Reconfigurable Hydrogen‐Bond Networks for High‐Voltage and Wide‐Temperature Lithium Metal Batteries

ABSTRACT In situ formed gel polymer electrolytes (GPEs) improve safety and interfacial compatibility in high‐energy lithium metal batteries (LMBs), yet, simultaneously achieving long‐term cyclability, high energy density, superior rate capability, and all‐climate adaptability remains challenging. We report a viscoelastic and self‐healing GPE synthesized via a thermally triggered concurrent reaction: (i) radical copolymerization, (ii) in‐situ generation of primary amines via isocyanate hydrolysis and their subsequent nucleophilic addition to residual isocyanates to form urea, and (iii) nucleophilic ring‐opening of fluoroethylene carbonate. The dynamic hydrogen‐bond network enables autonomous healing of microcracks induced by electrode volume fluctuations, preserving intimate electrode–electrolyte contact. Polymer−solvent interactions facilitate Li + desolvation while suppressing solvent decomposition. The polymer‐DFOB − ‐derived interphase suppresses side reactions and accommodates cathode volume changes. In Li||LiNi 0.83 Co 0.11 Mn 0.06 O 2 (NCM83) cells, the GPE‐based cell delivers 151.7 mAh g −1 at 5 C with 81.1% retention after 800 cycles. Notably, the cells exhibit exceptional wide‐temperature durability, delivering 82.9 mAh g −1 after 600 cycles at −40°C and 165.9 mAh g −1 over 200 cycles at 70°C. Even at 10 mg cm −2 , the cell achieves 197.2 mAh g −1 at 0.5 C with 92.4% retention after 200 cycles. This work establishes a feasible molecular‐level paradigm for realizing high‐energy‐density, fast‐charging, and all‐climate‐adaptable LMBs.