A Dual‐Bond Crosslinking Strategy Enabling Resilient and Recyclable Electrolyte Elastomers for Solid‐State Lithium Metal Batteries

Abstract Elastomeric solid polymer electrolytes (SPEs) are highly promising to address the solid‐solid‐interface issues of solid‐state lithium metal batteries (LMBs), but compromises have to be made to balance the intrinsic trade‐offs among their conductive, resilient and recyclable properties. Here, we propose a dual‐bond crosslinking strategy for SPEs to realize simultaneously high ionic conductivity, elastic resilience and recyclability. An elastomeric SPE is therefore designed with hemiaminal dynamic covalent networks and Li + ‐dissociation co‐polymer chains, where the −C−N‐ bond maintains the load‐bearing covalent network under stress but is chemically reversible through a non‐spontaneous reaction, the weaker intramolecular hydrogen bond is mechanically reversible, and the soft chains endow the rapid ion conduction. With this delicate structure, the optimized SPE elastomer achieves high elastic resilience without loading‐unloading hysteresis, outstanding ionic conductivity of 0.2 mS cm −1 (25 °C) and chemical recyclability. Then, exceptional room‐temperature performances are obtained for repeated Li plating/stripping tests, and stable cycling of LMBs with either LiFePO 4 or 4.3 V‐class LiFe 0.2 Mn 0.8 PO 4 cathode. Furthermore, the recycled and reprocessed SPEs can be circularly reused in LMBs without significant performance degradation. Our findings provide an inspiring design principle for SPEs to address the solid‐solid‐interface and sustainability challenges of solid‐state LMBs.