Multi‐Selective Dominant Coordination in Multi‐Salt High‐Entropy Electrolytes Toward High‐Performance Silicon Anodes

High‐entropy electrolytes (HEEs) are revolutionizing the design of electrolytes for lithium‐ion batteries. However, significant gaps and numerous uncertainties still persist in this field. To address these issues, we originally proposed the multi‐selective dominant coordination mechanism, which reveals the origin of the anion‐rich solvation environment in multi‐salt high‐entropy electrolytes (HEE salts ). Using commercially available lithium salts, we designed single‐salt (SS), triple‐salt (TS), parent/auxiliary salt (PAS), and mixed pentasalt (MixS) electrolytes to systematically investigate the regulating role of entropy on the electrochemical performance of alloying‐type anodes. Molecular dynamics (MD) simulations and spectroscopic characterization confirm that increased coordination selectivity of anions enables Li + to enter a highly delocalized and dynamically reconfigurable solvation environment, driving the system to spontaneously evolve toward a stable, anion‐rich state. Post‐cycle analysis reveals that HEE salts induce the formation of a thin, uniform, and robust solid electrolyte interphase (SEI), with an inorganic content up to 49.2%. As a result, the entropy‐driven solvation reconfiguration synergistically accelerates ion bulk transport and interfacial reaction kinetics. Accordingly, MixS endows significantly improved electrochemical performance compared to other electrolytes. Remarkably, a 250 mAh pouch cell exhibits a capacity retention rate of 97.18% after 200 cycles, demonstrating the excellent industrial practicability of HEE salts .