P2/O3 composite sodium layered oxide has emerged as a promising cathode for high-performance Na-ion batteries. However, it has been challenging to regulate accurately the phase ratio of P2/O3 composite due to their high compositional diversity, which brings about some difficulty in manipulating the electrochemical performance of P2/O3 composite. Here, we explore the effect of Ti substitution and the synthesis temperature on the crystal structure and Na storage performance of Na_0.8Ni_0.4Mn_0.6O₂. The investigation indicates Ti-substitution and altering synthesis temperature can rationally manipulate the phase ratio of P2/O3 composite, thereby purposefully regulating the cycling and rate performance of P2/O3 composite. Typically, O3-rich Na_0.8Ni_0.4Mn_0.4Ti_0.2O₂-950 shows excellent cycling stability with a capacity retention of 84% (3C, 700 cycles). By elevating the proportion of P2 phase, Na_0.8Ni_0.4Mn_0.4Ti_0.2O₂-850 displays concurrently improved rate capability (65% capacity retention at 5 C) and comparable cycling stability. These findings will help guide the rational design of high-performance P2/O3 composite cathodes for sodium-ion batteries.

P2-type layered oxides have been considered as promising cathode materials for Na-ion batteries, but the capacity decay resulting from the Na⁺/vacancy ordering and phase transformation limits their future large-scale applications. Herein, the impact of Li-doping in different layers on the structure and electrochemical performance of P2-type Na_0.7Ni_0.35Mn_0.65O₂ is investigated. It can be found that Li ions successfully enter both the Na and transition metal layers. The strategy of Li-doping can improve the cycling stability and rate capability of P2-type layered oxides, which promotes the development of high-performance Na-ion batteries.