Unravelling the Nature of the Intrinsic Complex Structure of Binary‐Phase Na‐Layered Oxides

The layered sodium transition metal oxide, NaTMO2 (TM = transition metal), with a binary or ternary phases has displayed outstanding electrochemical performance as a new class of strategy cathode materials for sodium-ion batteries (SIBs). Herein, an in-depth phase analysis of developed Na1-x TMO2 cathode materials, Na0.76 Ni0.20 Fe0.40 Mn0.40 O2 with P2- and O3-type phases (NFMO-P2/O3) is offered. Structural visualization on an atomic scale is also provided and the following findings are unveiled: i) the existence of a mixed-phase intergrowth layer distribution and unequal distribution of P2 and O3 phases along two different crystal plane indices and ii) a complete reversible charge/discharge process for the initial two cycles that displays a simple phase transformation, which is unprecedented. Moreover, first-principles calculations support the evidence of the formation of a binary NFMO-P2/O3 compound, over the proposed hypothetical monophasic structures (O3, P3, O'3, and P2 phases). As a result, the synergetic effect of the simultaneous existence of P- and O-type phases with their unique structures allows an extraordinary level of capacity retention in a wide range of voltage (1.5-4.5 V). It is believed that the insightful understanding of the proposed materials can introduce new perspectives for the development of high-voltage cathode materials for SIBs.