Superior stable high‐voltage LiCoO₂ enabled by modification with a layer of lithiated polyvinylidene fluoride‐derived LiF

Abstract High‐voltage LiCoO₂ (LCO) can deliver a high capacity and therefore significantly boost the energy density of Li‐ion batteries (LIBs). However, its cyclability is still a major problem in terms of commercial applications. Herein, we propose a simple but effective method to greatly improve the high‐voltage cyclability of an LCO cathode by constructing a surface LiF modification layer via pyrolysis of the lithiated polyvinylidene fluoride (Li‐PVDF) coating under air atmosphere. Benefitting from the good film‐forming and strong adhesion ability of Li‐PVDF, the thus‐obtained LiF layer is uniform, dense, and conformal; therefore, it is capable of acting as a barrier layer to effectively protect the LCO surface from direct exposure to the electrolyte, thus suppressing the interfacial side reactions and surface structure deterioration. Consequently, the high‐voltage stability of the LCO electrode is significantly enhanced. Under a high charge cutoff voltage of 4.6 V, the LiF‐modified LCO (LiF@LCO) cathode demonstrates a high capacity of 201 mA h g⁻¹ at 0.1 C and a stable cycling performance at 0.5 C with 80.5% capacity retention after 700 cycles, outperforming the vast majority of high‐voltage LCO cathodes reported so far.