First Cycle Cracking Behaviour Within Ni-Rich Cathodes During High-Voltage Charging

Increasing the operating voltage of lithium-ion batteries unlocks access to a higher charge capacity and therefore increases the driving range in electric vehicles, but doing so results in accelerated degradation via various mechanisms. A mechanism of particular interest is particle cracking in the positive electrode, resulting in losses in capacity, disconnection of active material, electrolyte side reactions, and gas formation. In this study, NMC811 (LiNi_0.8Mn_0.1Co_0.1O₂) half-cells are charged to increasing cut-off voltages, and ex situ X-ray diffraction and X-ray computed tomography are used to conduct post-mortem analysis of electrodes after their first charge in the delithiated state. In doing so, the lattice changes and extent of cracking that occur in early operation are uncovered. The reversibility of these effects is assessed through comparison to discharged cathodes undergoing a full cycle and have been relithiated. Comparisons to pristine lithiated electrodes show an increase in cracking for all electrodes as the voltage increases during delithiation, with the majority of cracks then closing upon lithiation.