PNNL

Abstract

Elemental surface segregation in cathode materials is critical for determining the phase and interfacial reaction between electrode and electrolyte, which consequently affects the electrochemical properties. Single-crystal cathode of Li1.2Ni0.2Mn0.6O2 and Li1.2Ni0.2Mn0.6O1.95F0.05 with an octahedral morphology of (102) and (003) dominated facets have been manifested to show enhanced electrochemical properties. However, the surface structural features of such single crystals have not been investigated. Herein, using scanning transmission electron microscopy, energy dispersive X-ray spectroscopy, and electron energy loss spectroscopy, we probe the elemental surface segregation characteristics in these single-crystal cathode. We reveal that Ni surface segregation shows dependence on the crystal facet such that it occurs on crystal facets with a mix of cations and anions, but not on the facets with only cations or anions. Furthermore, facet-dependent surface reconstructions are observed, featuring a spinel-like structure at the Ni-rich facet but rock-salt structure at the facet without Ni segregation. The commonly known Mn reduction appears at the single crystal surfaces, more pronounced at the facet without Ni segregation. We further reveal that fluorination leads to the stabilization of surface oxygens. This study provides detailed structural and chemical information about the facet-dependent Ni surface segregation and the resulted phase formation in the rather less explored micron-sized octahedral Li1.2Ni0.2Mn0.6O2 and Li1.2Ni0.2Mn0.6O1.95F0.05 single crystals, which is key to further exploration of electrochemical properties of cathode in the form of micro-sized single crystal.