Taming Interfacial Kinetics and Interphase Stability for Fast‐Charging Red Phosphorus/Carbon Anodes

Abstract Fast‐charging strategies become imperative for lithium‐ion batteries (LIBs) due to the increasing range anxiety. Existing technology is constrained by the low specific capacity and lithiation potential of graphite, as well as the sluggish interface dynamics. Synchronous strategies targeted at improving electrode materials and interfacial kinetics are critical for achieving fast‐charging LIBs. Herein, a highly fluorinated weakly‐solvating electrolyte (HFW) is introduced to enable the fast‐charging capability of red phosphorus/carbon (P/C) anode. The inherent high capacity and reliable working voltage of the P/C couple with the facile charge transfer capability of HFW facilitate expeditious high‐rate electrochemical behaviors. The anion‐enrichment solvation structure and highly fluorinated solvents promote the generation of LiF‐rich solid electrolyte interface (SEI), whose high interfacial energy and electronic insulation suppress the cracking and persistent parasitic reaction of the P/C. The developed HFW electrolyte enables Li||P/C half‐cells to achieve stable cycling and high specific capacity at elevated current densities (1061 mAh g −1 at 7.5 A g −1 ). Practical P/C||LiNi 0.6 Co 0.2 Mn 0.2 O 2 cells with this HFW also reveal stable cycling performance and good rate capability above 500 cycles with a high coulombic efficiency of 99.9%.