Operando single-particle imaging reveals that asymmetric ion flux contributes to capacity degradation in aged Ni-rich layered cathodes

Extensive worldwide efforts have been made to understand the degradation behavior of layered Ni-rich LiNixMnyCo(1−x−y)O2 (NMC) cathodes. The majority of studies carried out to date have focused on thermodynamic perspectives and are conducted ex situ; operando investigations on aged materials, especially those that can resolve dynamic information in a single-particle level remain sparse, preventing the development of long-term stable NMCs. Here, we directly visualize the real-time Li-ion transport kinetics of aged Ni-rich single-crystal NMC under operando conditions and at single-particle level using a recently developed optical microscopy technique. For both fresh and aged particles, we identify Li-ion concentration gradients developing during the early stages of delithiation – resulting in a Li-rich core and Li-poor surface – as observed previously and attributed to low Li-ion diffusivity at high Li-occupancies. Critically, in contrast to fresh particles, the Li-ion gradients in aged particles become markedly asymmetric, with the Li-rich core shifted away from the center of mass of the particle. Using ex situ transmission electron microscopy, we show that cell aging produces an uneven build-up of a surface rocksalt layer. Supported by finite-element modelling, we attribute the asymmetric delithiation behavior of the aged particles to this uneven rocksalt layer, which impedes the Li-ion flux heterogeneously at the particle surface. Our results demonstrate a new mechanism that contributes to the capacity and rate degradation of Ni-rich cathodes, highlighting the importance of controlling the build-up of detrimental interfacial layers in cathodes and providing a rational for improving the long-term stability and rate capabilities of Ni-rich NMC cathodes.