Unexpected Li displacement and suppressed phase transition enabling highly stabilized oxygen redox in P3-type Na layered oxide cathode

Abstract

Oxygen redox is considered a new paradigm for increasing the practical capacity and energy density of the layered oxide cathodes for Na-ion batteries. However, severe local structural changes and phase transitions during anionic redox reactions lead to poor electrochemical performance with sluggish kinetics. Here, we propose a synergy of Li-Cu cations in harnessing the full potential of oxygen redox, through Li displacement and suppressed phase transition in P3-type layered oxide cathode. P3-type Na0.7[Li0.1Cu0.2Mn0.7]O2 cathode delivers a large specific capacity of ∼212 mA h g−1 at 15 mA g−1. The discharge capacity is maintained up to ∼90% of the initial capacity after 100 cycles, with stable occurrence of the oxygen redox in the high-voltage region. Through advanced experimental analyses and first-principles calculations, it is confirmed that a stepwise redox reaction based on Cu and O ions occurs for the charge-compensation mechanism upon charging. Based on a concrete understanding of the reaction mechanism, the Li displacement by the synergy of Li-Cu cations plays a crucial role in suppressing the structural change of the P3-type layered material under the oxygen redox reaction, and it is expected to be an effective strategy for stabilizing the oxygen redox in the layered oxides of Na-ion batteries.