Reversible Flat to Rippling Phase Transition in Fe Containing Layered Battery Electrode Materials

Abstract

Layered sodium transition metal oxides of NaTMO₂ (TM = 3d transition metal) show unique capability to mix different compositions of Fe to the TM layer, a phenomenon that does not exist in LiTMO₂. Here, a novel spontaneous TM layer rippling in the sodium ion battery cathode materials is reported, revealed by in situ X-ray diffraction, Cs-corrected scanning transmission electron microscopy, and density functional theory simulation, where the softening and distortion of FeO₆ octahedra collectively drives the flat TM planes into rippled ones with inhomogeneous interlayer distance at high voltage. In such a rippling phase, charge and discharge of Na ions take different evolution pathways, resulting in an unusual hysteresis voltage loop. Importantly, upon discharge beyond a certain Na composition, the rippling TM layer will go back to flat, giving the reversibility of such structural evolution in the following cycles.