Suppressing the P2‐O2 phase transition and Na+/vacancy ordering in Na0.67Ni0.33Mn0.67O2 by a delicate multicomponent modulation strategy

Abstract P2‐type Na 0.67 Ni 0.33 Mn 0.67 O 2 is a promising cathode for sodium‐ion batteries with features of high specific capacity and air resistance, whereas its cycling stability and rate performance are dissatisfactory suffering from the disastrous P2‐O2 phase transition and Na + /vacancy ordering during sodium‐ion de/intercalation, which makes it an obstruction for future practical applications. Herein, a delicate multicomponent modulation strategy is proposed to tackle these two issues simultaneously, in which Li + and Ti 4+ are introduced to replace the Ni 2+ and Mn 4+ , respectively, whereas the Na + content is also designed according to the principle of charge balance. Consequently, the designed cathode (Na 0.72 Ni 0.28 Li 0.05 Mn 0.57 Ti 0.10 O 2 ) can deliver an enchanting cycling stability of 80% at 1 C after 200 cycles along with a considerable rate performance of 82.7 mAh g −1 at 5 C. In situ X‐ray diffraction measurement demonstrates the destructive P2‐O2 phase transition is suppressed and converted into a P2‐Z phase transition with superior reversibility as well as smooth charge/discharge curves with better Na + /vacancy disordering. In addition, the full cell matched with hard carbon anode delivers an excellent energy density of 263.4 Wh kg −1 at 37.3 W kg −1 , exhibiting great practicality. Our work presents a mean to rationally design the component of layered oxide cathode and achieve fabulous performance for sodium ion batteries.