Controlling Interlayer Disorder Toward Reversible Phase Transition in a Layered Sodium Manganese Oxide Cathode

Sodium manganese oxides are promising Na-ion battery cathodes but they suffer from irreversible phase transitions during electrochemical reactions. Most strategies to date have aimed to suppress the phase transitions by stabilizing their layered structures through limiting the content of extractable Na⁺. Here, we conversely increase atomic disorder in the Na-birnessite, a layered sodium manganese oxide, and thereby modulate its phase transition behavior toward improved electrochemical reversibility. Our study reveals that Mn vacancies and Mn migrated into the interlayer affect interlayer local environment of Na⁺ and water molecules consequently enhancing Na⁺ mobility. We observe better capacity retention for disordered "D-Na-birnessite", which undergoes a reversible phase transition from the birnessite-type structure to an O'3-type α-Na_xMnO₂-like structure through another intermediate metastable birnessite-type phase. This research highlights the positive effects of atomic disorder to regulate phase transition routes for achieving superior electrochemical reversibility, finally paving the way to overcoming the limits of layered oxide cathodes.