Phase transformation mechanism in lithium manganese nickel oxide revealed by single-crystal hard X-ray microscopy

Abstract Understanding the reaction pathway and kinetics of solid-state phase transformation is critical in designing advanced electrode materials with better performance and stability. Despite the first-order phase transition with a large lattice mismatch between the involved phases, spinel LiMn 1.5 Ni 0.5 O 4 is capable of fast rate even at large particle size, presenting an enigma yet to be understood. The present study uses advanced two-dimensional and three-dimensional nano-tomography on a series of well-formed Li x Mn 1.5 Ni 0.5 O 4 (0≤ x ≤1) crystals to visualize the mesoscale phase distribution, as a function of Li content at the sub-particle level. Inhomogeneity along with the coexistence of Li-rich and Li-poor phases are broadly observed on partially delithiated crystals, providing direct evidence for a concurrent nucleation and growth process instead of a shrinking-core or a particle-by-particle process. Superior kinetics of (100) facets at the vertices of truncated octahedral particles promote preferential delithiation, whereas the observation of strain-induced cracking suggests mechanical degradation in the material.