Multiple Dynamic Bonds‐Driven Integrated Cathode/Polymer Electrolyte for Stable All‐Solid‐State Lithium Metal Batteries

All‐solid‐state lithium metal batteries (LMBs) are considered as the promising higher‐energy and improved‐safety energy‐storage systems. Nevertheless, the electrolyte‐electrodes interfacial issues due to the limited solid physical contact lead to discontinuous interfacial charge transport and large interfacial resistance, thereby suffering from unsatisfactory electrochemical performance. Herein, we construct an integrated cathode/polymer electrolyte for all‐solid‐state LMBs under the action of polymer chains exchange and recombination originating from multiple dynamic bonds in our well‐designed dynamic supramolecular ionic conductive elastomers (DSICE) molecular structure. The DSICE acts as polymer electrolytes with excellent electrochemical performance and mechanical properties, achieving the ultrathin pure polymer electrolyte thickness (12 μm). Notably, the DSICE also functions as lithium iron phosphate (LiFePO4, LFP) cathode binders with enhanced adhesive capability. Such well‐constructed Li|DSICE|LFP‐DSICE cells generate delicate electrolyte‐electrodes interfacial contact at the molecular level, providing continuous Li+ transport pathways and promoting uniform Li+ deposition, further delivering superior long‐term charge/discharge stability (>600 cycles, Coulombic efficiency, >99.8 %) and high capacity retention (80 % after 400 cycles). More practically, the Li|DSICE|LFP‐DSICE pouch cells show stable electrochemical performance, excellent flexibility and safety under abusive tests. An integrated cathode/ultrathin polymer electrolyte for all‐solid‐state lithium‐metal batteries was constructed driven by multiple dynamic bonds in a dynamic supramolecular ionic conductive elastomer (DSICE), thus achieving minimum thickness of pure polymer electrolyte and maximum compatibility of the solid electrolyte‐electrodes interface at the molecular level. The well‐constructed cells present superior cycling stability, excellent flexibility and safety.