Layered sodium manganese-based oxides are appealing cathode candidates due to their high capacity and cost-effectiveness, yet performance degradation related with unwanted structural evolution still remains a disturbing disadvantage. Herein, atomic resolution STEM (scanning transmission electron microscopy) images of Na-extracted Na2/3NixCo1/3-xMn2/3O2 (x = 0, 1/6, 1/3) are collected and analyzed, to decipher the effect of cobalt and nickel substitution on the structural integrity of layered manganese-based oxides. Cobalt substitution is demonstrated to alleviate the lattice stress and retain the layered structure after sodium removal, and only a local P2-to-O2 phase transition could be identified. By contrast, various types of defects and phase transformation, including rarely reported P2-to-O3, are discovered in the Ni-substituted oxides. The generation of spinel and rock-salt phases is the critical evidence of cation mixing that leads to unrecoverable capacity loss. The interplay of different transition metals is complex, and compositional optimization is encouraged to minimize the effect of the concomitant phase transition.
Keywords: P2-type layered oxides; phase transformation; sodium-ion batteries; structural evolution.