Evolution of Structure and Lithium Dynamics in LiNi0.8Mn0.1Co0.1O2 (NMC811) Cathodes during Electrochemical Cycling

The nickel-rich layered oxide LiNi0.8Mn0.1Co0.1O2 (NMC811) is a promising future cathode material for lithium-ion batteries in electric vehicles due to its high specific energy density. However, it exhibits fast voltage and capacity fading. In this article, we combine electrochemistry, operando synchrotron X-ray diffraction (XRD), and ex situ solid-state NMR spectroscopy to provide new insights into the structural changes and lithium dynamics of NMC811 during electrochemical charge and discharge, which are essential for a better understanding of its fast degradation. The evolution of the interlayer spacing is tracked by XRD, showing that it gradually increases upon delithiation before collapsing at high state-of-charge (SOC). Importantly, no two-phase O3 -> O1 transition is observed at high SOC, demonstrating that this cannot be a major cause of degradation. A strong increase of Li dynamics accompanies the increase of the interlayer spacing, which is shown by Li-7 NMR and electrochemical characterization. At high SOC, Li mobility drops considerably, and Li/vacancy ordering can be observed by NMR. A detailed analysis of Li-7 NMR spectra at different SOC is provided, demonstrating how Li NMR can be used to extract information on the dynamics of such challenging paramagnetic samples with several hundred different local Li environments. The insights on the evolution of structure and dynamics of NMC811 will further the understanding of its cycling behavior and contribute to the efforts of mitigating its performance fade.