Editors' Choice—Capacity Fading Mechanisms of NCM-811 Cathodes in Lithium-Ion Batteries Studied by X-ray Diffraction and Other Diagnostics

Ni-rich layered oxides, like NCM-811, are promising lithium-ion battery cathode materials for applications such as electric vehicles. However, pronounced capacity fading, especially at high voltages, still lead to a limited cycle life, whereby the underlying degradation mechanisms, e.g. whether they are detrimental reactions in the bulk or at the surface, are still controversially discussed. Here, we investigate the capacity fading of NCM-811/graphite full-cells over 1000 cycles by a combination of in situ synchrotron X-ray powder diffraction, impedance spectroscopy, and X-ray photoelectron spectroscopy. In order to focus on the NCM-811 material, we excluded Li loss at the anode by pre-lithiating the graphite. We were able to find a quantitative correlation between NCM-811 lattice parameters and capacity fading. Our results prove that there are no considerable changes in the bulk structure, which could be responsible for the observed ≈20% capacity loss over the 1000 cycles. However, we identified the formation of a resistive surface layer, which is responsible for (i) an irreversible loss of capacity due to the material lost for its formation, and (ii) for a considerable impedance growth. Further evidence is provided that the surface layer is gradually formed around the primary NCM-811 particles.