Severe volume changes and poor electrochemical performance are key barriers to the practical use of silicon anodes. In this study, a self-healing, multifunctional supramolecular binder system was introduced, which combines polymers, ionic liquids, and halometals to achieve dynamic cross linking during volume changes. The addition of specific halometals can adjust the Li⁺ solvation structure and energy, promoting the formation of a stable solid electrolyte interface (SEI) rich in LiF and facilitating Li⁺ desolvation. After 200 cycles, the Si@BF binder (with both ionic liquid and halometal) showed no cracks, indicating excellent structural stability. Additionally, Si||LiFePO₄ (LFP) full-cell tests at 5 C rate reveal drastic differences: The unmodified binder (the pristine Si) exhibits nearly 0% capacity retention after 400 cycles, the ionic liquid-modified system (Si@B) maintains 11.58%, while Si@BF achieves a remarkable 90.92% retention. Notably, Si@BF retains 78.72% capacity even after 800 cycles. This study offers new insights into dynamic cross-linking systems and solvation-structure regulation, providing references for developing advanced lithium-ion batteries with better performance.