A Dilute Fluorinated Phosphate Electrolyte Enables 4.9 V‐Class Potassium Ion Full Batteries

Abstract Potassium ion batteries using graphite anode and high‐voltage cathodes are considered to be optimizing candidates for large‐scale energy storage. However, the lack of suitable electrolytes significantly hinders the development of high‐voltage potassium ion batteries. Herein, a dilute (0.8 m ) fluorinated phosphate electrolyte is proposed, which exhibits extraordinary compatibility with both graphite anode and high‐voltage cathodes. The phosphate solvent, tris(2,2,2‐trifluoroethyl) phosphate (TFP), has weak solvating ability, which not only allows the formation of robust anion‐derived solid electrolyte interphase on graphite anode but also effectively suppresses the corrosion of Al current collector at high voltage. Meanwhile, the high oxidative stability of fluorinated TFP solvent enables stable ultrahigh‐voltage (4.95 V) cycling of a potassium vanadium fluorophosphate (KVPO 4 F) cathode. Using TFP‐based electrolyte, the 4.9 V‐class potassium ion full cell based on graphite anode and KVPO 4 F cathode shows rather remarkable cycling performance with a high capacity retention of 87.2% after 200 cycles. This study provides a route to develop dilute electrolytes for high‐voltage potassium ion batteries, by utilizing solvents with both weak solvating ability and high oxidative stability.