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Phase transition is common during (de)-intercalating layered sodium oxides, which directly affects the structural stability and electrochemical performance. However, the artificial control of phase transition to achieve advanced sodium-ion batteries is lacking, since the remarkably little is known about the influencing factor relative to the sliding process of transition-metal slabs upon sodium release and uptake of layered oxides. Herein, we for the first time demonstrate the manipulation of oxygen vacancy concentrations in multinary metallic oxides has a significant impact on the reversibility of phase transition, thereby determining the sodium storage performance of cathode materials. Results show that abundant oxygen vacancies intrigue the return of the already slide transition-metal slabs between O3 and P3 phase transition, in contrast to the few oxygen vacancies and resulted irreversibility. Additionally, the abundant oxygen vacancies enhance the electronic and ionic conductivity of the Na0.9Ni0.3Co0.15Mn0.05Ti0.5O2 electrode, delivering the high initial Coulombic efficiency of 97.1%, large reversible capacity of 112.7 mAh∙g−1, superior rate capability upon 100 C and splendid cycling performance over 1, 000 cycles. Our findings open up new horizons for artificially manipulating the structural evolution and electrochemical process of layered cathodes, and pave a way in designing advanced sodium-ion batteries.
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