Stabilized O3-Type Layered Sodium Oxides with Enhanced Rate Performance and Cycling Stability by Dual-Site Ti⁴⁺/K⁺ Substitution

High-capacity O-3-type layered sodium oxides are considered one of the most promising cathode materials for the next generation of Na-ion batteries (NIBs). However, these cathodes usually suffer from low high-rate capacity and poor cycling stability due to structure deformation, native air sensitivity, and interfacial side reactions. Herein, a multi-site substituted strategy is employed to enhance the stability of O-3-type NaNi0.5Mn0.5O2. Simulations indicate that the Ti substitution decreases the charge density of Ni ions and improves the antioxidative capability of the material. In addition, the synergistic effect of K+ and Ti4+ significantly reduces the formation energy of Na+ vacancy and delivers an ultra-low lattice strain during the repeated Na+ extraction/insertion. In situ characterizations verify that the complicated phase transformation is mitigated during the charge/discharge process, resulting in greatly improved structure stability. The co-substituted cathode delivers a high-rate capacity of 97 mAh g(-1) at 5 C and excellent capacity retention of 81% after 400 cycles at 0.5 C. The full cell paired with commercial hard carbon anode also exhibits high capacity and long cycling life. This dual-ion substitution strategy will provide a universal approach for the new rational design of high-capacity cathode materials for NIBs.