Formation of LiF‐rich Cathode‐Electrolyte Interphase by Electrolyte Reduction

The capacity of transition metal oxide cathode for Li‐ion batteries can be further enhanced by increasing the charging potential. However, these high voltage cathodes suffer from fast capacity decay because the large volume change of cathode breaks the active materials and cathode‐electrolyte interphase (CEI), resulting in electrolyte penetration into broken active materials and continuous side reactions between cathode and electrolytes. Herein, a robust LiF‐rich CEI was formed by potentiostatic reduction of fluorinated electrolyte at a low potential of 1.7 V. By taking LiCoO2 as a model cathode, we demonstrate that the LiF‐rich CEI maintains the structural integrity and suppresses electrolyte penetration at a high cut‐off potential of 4.6 V. The LiCoO2 with LiF‐rich CEI exhibited a capacity of 198 mAh g−1 at 0.5C and an enhanced capacity retention of 63.5 % over 400 cycles as compared to the LiF‐free LiCoO2 with only 17.4 % of capacity retention. A robust LiF‐rich cathode‐electrolyte interphase (CEI) is successfully constructed on LiCoO2 cathode by potentiostatic reduction of fluorinated electrolyte at 1.7 V. LiF‐rich CEI maintains the structural integrity and suppresses electrolyte penetration and Co dissolution during cycling at a high cut‐off voltage of 4.6 V, demonstrating an excellent cyclability with high capacity retention of 63.5 % over 400 cycles at 0.5C.