Engineering Na‐Rich P2‐Type Layered Oxides Through Li/Ti Dual Doping for Oxygen Redox Activation and Superior Structural Stability

ABSTRACT Sodium layered oxides Na _x MO ₂ ( x ≤ 1 and M = transition metal ions) have gained significant interest as sodium‐ion battery (NIB) cathodes owing to their high operating voltages and potential for higher energy density compared with polyanion and Prussian blue–type cathodes. However, their practical applications are often hindered by the irreversible structural transitions leading to capacity fading during cycling. The nature and substitution of transition metal ions define the material properties and electrochemical performance. In this study, through comprehensive electrochemical characterization combined with multi‐scale structural and spectroscopical analyses, we demonstrate the synergistic impacts of Lithium and Titanium doping, which not only increases overall capacity by boosting cation and anion cooperative redox contributions but also improves the rate capability and cycling stability. Specifically, Li ⁺ doping enhances the available sodium inventory for extraction, while Ti ^{4 +} disrupts Na ⁺ /vacancy ordering at lower voltages (< 4 V) and mitigates the detrimental P2→OP4/O2 phase transition during cycling. The combined effect of Lithium and Titanium doping promotes more charge localization on Oxygen, which activates reversible lattice oxygen redox reactions at elevated voltages, contributing additional capacity beyond conventional cationic redox. This work provides crucial insights into the design of high‐performance, high‐capacity P2‐type layered cathode materials for sodium‐ion batteries.