Highly Tough Slide‐Crosslinked Gel Polymer Electrolyte for Stable Lithium Metal Batteries

Abstract Gel polymer electrolytes (GPEs) hold great promise for the practical application of lithium metal batteries. However, conventional GPEs hardly resists lithium dendrites growth and maintains long‐term cycling stability of the battery due to its poor mechanical performance. Inspired by the slide‐ring structure of polyrotaxanes (PRs), herein we developed a dynamic slide‐crosslinked gel polymer electrolyte (SCGPE) with extraordinary stretchability of 970.93 % and mechanical strength of 1.15 MPa, which is helpful to buffer the volume change of electrodes and maintain mechanical integrity of the battery structure during cycling. Notably, the PRs structures can provide fast ion transport channels to obtain high ionic conductivity of 1.73×10 −3 S cm −1 at 30 °C. Additionally, the strong polar groups in SCGPE restrict the free movement of anions to achieve high lithium‐ion transference number of 0.71, which is favorable to enhance Li + transport dynamics and induce uniform Li + deposition. Benefiting from these features, the constructed Li|SCGPE‐3|LFP cells exhibit ultra‐long and stable cycle life over 1000 cycles and high‐capacity retention (89.6 % after 1000 cycles). Even at a high rate of 16 C, the cells deliver a high capacity of 79.2 mAh g −1 . The slide‐crosslinking strategy in this work provides a new perspective on the design of advanced GPEs for LMBs.