Abstract
Irreversible structural transformation in intercalation-type cathode materials, which has been frequently observed, has been perceived as a principal cause of capacity fading and voltage decay in (uni) multivalent batteries. Herein, we explored the electron beam-induced spinel to defective rocksalt phase transitions in MgCrMnO4, a potential multivalent cation intercalation cathode, using atomic-resolution imaging and spectroscopy in an aberration-corrected scanning transmission electron microscope. This dynamic electron beam irradiation study of specific structural transformations provides an atomistic understanding of the structural evolution observed in transition-metal oxide spinels during electrochemical cycling using multivalent cations, such as Mg2+. By combining an imaging study with first-principles modeling, we demonstrate that the mechanism of the spinel to defective rocksalt transformation in MgCrMnO4 nanostructures is enabled by the presence of oxygen vacancies and is, therefore, very similar to that observed in transition-metal oxide spinels upon Li intercalation.