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

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.