Minimized Li + Coordinating Effect Enables 4.7 V‐Class Li 1.2 Mn 0.53 Ni 0.20 Co 0.07 O 2 ‐Li Batteries

ABSTRACT Achieving durable 4.7 V‐class Li 1.2 Mn 0.53 Ni 0.20 Co 0.07 O 2 ||Li batteries remains difficult because interfacial parasitic reactions are coupled with irreversible lattice oxygen loss in the Li‐ and Mn‐Rich oxide (LRMO) cathodes. Here, we report an all‐fluorinated ester electrolyte that delivers a minimized Li + coordinating effect and thereby regulates both solvation chemistry and electrode interphases. Weakened Li + ‐solvent interactions shift the primary solvation sheath toward anion‐rich coordination, enabling the formation of a LiF‐rich bilayer SEI on Li metal and a thin inorganic‐rich dual‐layer CEI on LRMO. More importantly, the stabilized cathode interphase preserves oxidized lattice oxygen as peroxo‐like species (O 2 ) n− , suppresses oxygen release and mitigates Mn reduction/dissolution and surface reconstruction, thus improving the reversibility of oxygen anionic redox. As a result, the optimized carbonate‐based electrolyte enables a high Coulombic efficiency of 98.5% in Li||Cu cells and markedly improves battery performance, delivering 84.9% capacity retention after 450 cycles at 1 C and 4.7 V, 81.7% retention after 100 cycles at 60°C, and 75.0% retention after 130 cycles in 4.7 V Li‐metal pouch cells. This work shows that minimizing Li + coordination is an effective route to simultaneously stabilize Li metal and anion‐redox LRMO cathodes for practical high‐energy lithium metal batteries.