Monofluorinated Phosphate with Unique P−F Bond for Nonflammable and Long‐Life Lithium‐Ion Batteries

Lithium-ion batteries (LIBs) with conventional carbonate-based electrolytes suffer from safety concerns in large-scale applications. Phosphates feature high flame retardancy but are incompatible with graphite anode due to their inability to form a passivated solid electrolyte interphase (SEI). Herein, we report a monofluorinated co-solvent, diethyl fluoridophosphate (DEFP), featuring a unique P-F bond that allows a trade-off between safety and electrochemical performance in LIBs. The P-F bond in DEFP weakens ion-dipole interactions with Li⁺ ions, lowering the desolvation barrier, and simultaneously reduces the lowest unoccupied molecular orbital (LUMO) of DEFP, promoting the formation of a robust and inorganic-rich SEI. Additionally, DEFP exhibits improved thermal stability due to both robust SEI and the inherent flame-retardant properties of the P-F bond. Consequently, the optimized DEFP-based electrolyte exhibits improved cyclability and rate capacity in LiNi_0.8Co_0.1Mn_0.1O₂||graphite full cells compared with triethyl phosphate-based electrolytes and commercial carbonate electrolytes. Even at a low E/C ratio of 3.45 g Ah^-1, the 1.16 Ah NCM811||Gr pouch cells achieve a high capacity retention of 94.2 % after 200 cycles. This work provides a promising approach to decouple phosphate safety and graphite compatibility, paving the way for safer and high-performance lithium-ion batteries.