Abundant Hydrogen Bonds Formed in a Urea‐Based Gel Polymer Electrolyte Improve Interfacial Stability in Lithium Metal Batteries

Abstract As an emerging and potential replacement system for liquid electrolytes, polymer electrolytes (PEs) exhibit unique capacity in suppressing metal dendrite formation and leakage risks. However, the most used polymer matrix, including polyether, polyester, and polysiloxane, still cannot meet the practical demands for metal electrode compatibility and long lifespan. In this study, gel polymer electrolytes consisting of a polyurea network with abundant hydrogen bonds and deep eutectic electrolyte (DEE) are designed and prepared in‐situ . The hydrogen bonding between polyurea chains and polyurea‐DEE provides good interfacial stability between PEs and lithium metal. As a result, the assembled Li/LiFePO 4 cells based on this electrolyte deliver a long cycle life with 90 % retention after 500 cycles and 76.5 % retention after 1000 cycles at 1 C. In addition, the flexible design characteristics of polyurea structure permit easy operation for performance optimization by modulating the composition of hard and soft segments, and enhanced ionic conductivity and self‐healing efficiency are obtained. This study provides a novel method for preparing advanced polymer electrolytes for lithium metal batteries.