Reinforcement of Positive Electrode‐Electrolyte Interface without Using Electrolyte Additives Through Thermoelectrochemical Oxidation of LiPF₆ for Lithium Secondary Batteries

Abstract Owing to the limited electrochemical stability window of carbonate electrolytes, the initial formation of a solid electrolyte interphase and surface film on the negative and positive electrode surfaces by the decomposition of the electrolyte component is inevitable for the operation of lithium secondary batteries. The deposited film on the surface of the active material is vital for reducing further electrochemical side reactions at the surface; hence, the manipulation of this formation process is necessary for the appropriate operation of the assembled battery system. In this study, the thermal decomposition of LiPF₆ salt is used as a surface passivation agent, which is autocatalytically formed during high‐temperature storage. The thermally formed difluorophosphoric acid is subsequently oxidized on the partially charged high‐Ni positive electrode surface, which improves the cycleability of lithium metal cells via phosphorus‐ and fluorine‐based surface film formation. Moreover, the improvement in the high‐temperature cycleability is demonstrated by controlling the formation process in the lithium‐ion pouch cell with a short period of high‐temperature storage before battery usage.