Insight into the Contribution of Nitriles as Electrolyte Additives to the Improved Performances of the LiCoO₂ Cathode

Nitriles have been successfully used as electrolyte additives for performance improvement of commercialized lithium-ion batteries based on the LiCoO₂ cathode, but the underlying mechanism is unclear. In this work, we present an insight into the contribution of nitriles via experimental and theoretical investigations, taking for example succinonitrile. It is found that succinonitrile can be oxidized together with PF₆^- preferentially on LiCoO₂ compared to the solvents in the electrolyte, making it possible to avoid the formation of hydrogen fluoride from the electrolyte oxidation decomposition, which is detrimental to the LiCoO₂ cathode. Additionally, inorganic LiF and -NH group-containing polymers are formed from the preferential oxidation of succinonitrile, constructing a protective interphase on LiCoO₂, which suppresses electrolyte oxidation decomposition and prevents LiCoO₂ from structural deterioration. Consequently, the LiCoO₂ cathode presents excellent stability under cycling and storing at high voltages.