Dynamic Self‐Adaption Supramolecular Binder for Silicon Anodes: Anhydride Activation Enabling Practical Lithium‐Ion Battery

Abstract Designing intelligent binders with dynamic adaptability remains crucial yet challenging for mitigating the structural degradation of silicon‐based anodes in lithium‐ion batteries. Here, an innovative aqueous supramolecular binder is presented featuring robust covalent‐anhydride bridges and dynamic hydrogen‐bond networks, synergistically constructed through molecular engineering of poly(methyl vinylether maleic acid) (PEA) and polyvinyl alcohol (PVA). The activated anhydride moieties enable stable covalent bond reconfiguration while maintaining robust interfacial adhesion, complemented by energy‐dissipating hydrogen bonds that collectively accommodate severe volume fluctuation of silicone anodes. This dual dynamic network demonstrates remarkable self‐healing capability and stress redistribution characteristics, endowing the silicone anodes with exceptional mechanical integrity (peeling force of 10.87 N) and cycling stability (78.40% capacity retention after 150 cycles). Simultaneously, the optimized binder architecture facilitates efficient lithium‐ion transport, achieving high‐rate capability (1414 mAh g −1 at 2C). Practical validation using 2.5‐Ah pouch cells demonstrates over 93% capacity retention after 350 cycles at 1C, significantly outperforming conventional binder systems. This supramolecular engineering strategy establishes a universal platform for developing next‐generation sustainable electrodes, showcasing the potential of dynamically adaptive interfacial chemistry in advanced energy storage systems.