The Structural Stability Limit of Layered Lithium Transition Metal Oxides Due to Oxygen Release at High State of Charge and Its Dependence on the Nickel Content

The composition of layered transition metal oxides (LiMO2, M = Ni, Co, Mn) as cathode active materials (CAMs) is currently trending towards higher nickel contents, which can provide more capacity and energy. The origin of this performance improvement is often ascribed to the lower potential of nickel-rich CAMs, suppressing detrimental electrochemical electrolyte oxidation. In this study, it is shown that the stability limit of LiMO2-based CAMs is not determined by the stability window of typical electrolytes in terms of potential but by the CAM composition, governing the structural stability at high degrees of delithiation. The latter is investigated for five CAMs with distinct composition (LCO, NCM111, NCM622, NCM851005, and LNO) as a function of upper cutoff potential and thus state of charge (SOC). Short-term cycling experiments with an increasing upper cutoff potential as well as extended cycling to selected SOCs reveal stability limits between 66 and 86 %SOC depending on the CAM composition. On-line electrochemical mass spectrometry (OEMS) does not only allow to exclude any impact of electrochemical electrolyte oxidation on the determined stability window of the CAMs but also illuminates the concurrence of capacity fade and lattice oxygen release, with the latter being the origin of the CAM degradation.