Breaking Anionic Solvation Barrier for Safe and Durable Potassium‐ion Batteries Under Ultrahigh‐Voltage Operation

F cathode can sustain 1600 cycles with 84.4 % of capacity retention at a high cutoff voltage of 4.95 V. Meanwhile, K plating/stripping process in our designed electrolyte also demonstrates optimized electrochemical reversibility and stability with effectively inhibited potassium dendrites. These findings underscore the critical impact of anion-dominated solvation configuration on synergistic interfacial modulation and electrochemical properties. This work provides new insights into rational design of ultrahigh-voltage and safe electrolyte for advanced PIBs.