Formation and effect of orientation domains in layered oxide cathodes of lithium-ion batteries

Abstract We show that in layered oxides that are employed as cathodes in lithium-ion batteries, the cation layers can order on different {111}NaCl planes within a single particle, which makes the lithium layer discontinuous across a particle. The findings challenge previous assertions that lithium undergoes 2-D diffusion in layered oxides and the data provide new insights into the decrease in rate capabilities for some layered oxides. Therefore, it is critically important to understand how these discontinuities form and how the loss of 2-D diffusion impacts the overall performance of the layered oxide cathode materials. Employing X-ray diffraction (XRD) and aberration-corrected scanning transmission electron microscopy (STEM), we find that as the material transitions from a disordered to an ordered state, it forms four orientation variants corresponding to the four {111}NaCl planes. This transition is not intrinsic to all layered oxides and appears to be more strongly affected by nickel. Furthermore, with energy dispersive spectroscopy (EDS), we show that there is an increase in the nickel concentration at the interface between each orientation variant. This reduces the rate of lithium diffusion, negatively affects the rate capability, and could be contributing to the overall capacity fade.