LAUSR

Increasing the upper cut‐off voltage of LiCoO2 (LCO) is one of the most efficient strategies to gain high‐energy density for current lithium‐ion batteries. However, surface instability is expected to be exaggerated with increasing voltage arising from the high reactivity between the delithiated LCO and electrolytes, leading to serious safety concerns. This work is aimed to construct a physically and chemically stable phosphate‐rich cathode–electrolyte interface (CEI) on the LCO particles to mitigate this issue. This phosphate‐rich CEI is generated during the electrochemical activation by using fluoroethylene carbonate and 1,1,2,2‐tetrafluoroethyl‐2,2,3,3‐tetrafluoropropyletherare as the solvents. Both solvents also demonstrate high thermal stability, reducing the intrinsic flammability of the commercial organic electrolyte, thereby eliminating the safety concern in the LCO‐based systems upon high‐voltage operation. This stable CEI layer on the particle surface can also enhance the surface structure by blocking direct contact between LCO and electrolyte, improving the cycling stability. Therefore, by using the proposed electrolyte, the LCO cathode exhibits a high‐capacity retention of 76.1% after 200 cycles at a high cut‐off voltage of 4.6 V. This work provides a novel insight into the rational design of high‐voltage and safe battery systems by adopting the flame‐retardant electrolyte.