Phase Behavior during Electrochemical Cycling of Ni-Rich Cathode Materials for Li-Ion Batteries

Although layered lithium nickel-rich oxides have become the state-of-the-art cathode materials for lithium-ion batteries in EV applications, they can suffer from rapid performance failure – particularly when operated under conditions of stress (temperature, high voltage), the underlying mechanisms of which are not fully understood. In this essay, we aim to connect the electrochemical performance with changes in structure during cycling. First, we compare the structural properties of LiNiO2, to the substituted Ni-rich compounds NMCs (LiNixMnyCo1-x-yO2) and NCAs (LiNixCoyAl1-x-yO2). Particular emphasis is placed on decoupling intrinsic behaviour and extrinsic “two-phases” reactions observed during initial cycles, as well as after extensive cycling for NMC and NCA cathodes. We highlight the need to revisit the various high-voltage structural change processes that occur in LiNiO2 with modern characterization tools to aid the understanding of the accelerated degradation for Ni- rich cathodes at high voltages