Lithium metal anodes are hindered by dendrite growth, unstable solid electrolyte interphase (SEI), and irreversible dead lithium accumulation. Here we report a synergistic electrolyte design using cesium iodide and lithium difluoro(oxalato)borate (LiDFOB) that simultaneously regulates solvation structure, stabilizes the interface, and recovers inactive lithium. The cesium cation adsorbs on lithium protrusions to suppress dendrite nucleation through electrostatic shielding. The iodide anion performs dual functions: it generates an I3⁻/I⁻ redox shuttle that reacts with trapped metallic lithium and Li₂O into soluble Li⁺ species, enabling lithium inventory recovery; more importantly, it selectively coordinates to the electrophilic oxygen in LiDFOB, redirecting its decomposition from thermodynamically favored B–F bond cleavage to kinetically accessible B–O scission (activation energy: 2.056 eV vs. 2.282 eV). This iodide-mediated regulation mechanism yields a dense SEI rich in boron fluoride and lithium fluoride, exhibiting high Li+ conductivity and mechanical strength with a Young’s modulus of 7.9 GPa. Comprehensive spectroscopic and computational analyses confirm weakened Li+–solvent interactions, evidenced by elongation of the Li+-ODME bond from 2.02 Å to 2.63 Å, directly weakening Li⁺ solvation and facilitating desolvation. The resulting synergistic modulation of lithium-ion kinetics leads to significantly enhanced performance of Li||LFP full cells, which retain 85.5 % of their capacity after 330 cycles at 1C. Moreover, a 1.1 Ah pouch cell with a 50 μm lithium foil and a high-loading LiFePO₄ cathode (24 mg cm⁻²) retains 95 % of its capacity after 150 cycles at 1 C. This work establishes a paradigm of functionally integrated electrolytes, which bridges solvation chemistry, interfacial engineering, and active material regeneration, addressing long-standing trade-offs in lithium-metal batteries.
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