Theoretical Prediction of Surface Stability and Morphology of LiNiO₂ Cathode for Li Ion Batteries

Ni-rich layered oxides are considered to be a promising cathode material with high capacity, and their surface structure should be extensively explored to understand the complex associated phenomena. We investigated the surface stability and morphology of LiNiO 2 as a representative of these materials by using density functional theory calculations. The results reveal that the Li-exposed surfaces have lower energies than the oxygen surfaces, irrespective of the facets, and the Ni-exposed ones are the least stable. The equilibrium morphology can vary from truncated trigonal bipyramid to truncated egg shape, according to the chemical potential, whose range is confined by the phase diagram. Moreover, the electrochemical window of stable facets is found to strongly depend on the surface elements rather than the facet directions. Contrary to the stable Li surfaces, oxygen exposure on the surface considerably lowers the Fermi level to the level of electrolyte, thereby accelerating oxidative decomposition of the electrolyte on the cathode surface.