Electron Acceptor-Driven Solid Electrolyte Interphases with Elevated LiF Content for 4.7 V Lithium Metal Batteries

• Incorporation of tris(pentafluorophenyl)borane as an electron acceptor into the electrolyte enables the formation of durable dual interfaces on both the Li metal anode and NCM811 cathode, effectively mitigating dendrite growth and enhancing cathode stability. • The additive-driven strategy allows lithium metal batteries to operate at ultra-high voltages up to 4.7 V, achieving high coulombic efficiency (98.96% in Li||Cu cells) and extended cycle life (4000 h in Li||Li symmetric cells). • Full cells with NCM811 cathode maintain 87.8% capacity retention after 100 cycles at 4.7 V, while Li||LNMO cells deliver 132.2 mAh g−1 at 10 C and retain 95.0% capacity after 250 cycles at 5 V. • NCM811||graphite pouch cells demonstrate exceptional long-term stability with 93.4% capacity retention after 1100 cycles at 1 C, highlighting the practical viability of this additive engineering approach.