Tailoring Electrolyte Dehydrogenation with Trace Additives: Stabilizing the LiCoO₂ Cathode beyond 4.6 V

Extending the charge cutoff voltage of cathode (e.g., LiCoO2) is a promising way to increase the energy density of Li-ion batteries, but critical challenges lie in the threats triggered by structural distortion and an unstable electrode/electrolyte interface. The general approach to enhance the stability of the cathode/electrolyte interface (CEI) consists of replacing the decomposition or sacrificing sources of carbonate solvents (e.g., EC) with concentrated or fluorinated electrolyte strategies. Herein, without following typical replacement strategies, we introduce a trace electrolyte additive and refine the dehydrogenation process of the original carbonate solvents, resulting in an enhanced CEI and long-term cycling stability of LiCoO2 up to 4.65 V. We demonstrate that cathode structure distortion, LiPF6 hydrolysis, and Co dissolution and shuttling have been simultaneously restrained. With the achievement of a long-life 250 and 270 Wh/kg pouch cells (assembled with a commercial graphite and SiO anodes), the refinement of the “old-school” electrolyte additive strategy opens up avenues toward the design of practical high-voltage full-cell systems.