Structural Insights Into Phase Formation of Sodium Layered Cathodes Materials with Prominent Electrochemical Performances

The electrochemical performances of layered cathodes for sodium‐ion batteries (SIBs) are intimately dependent on their structural characteristics. However, realizing accurate regulation of structure by phase engineering is challenging, primarily due to constrained synthesis methods and the existing gaps in understanding of specialized phase structures. Herein, a series of P′2‐Na 0.67 Fe 0.05 Ti 0.1 Mn 0.85 O 2 cathode material with prominent electrochemical performances were successfully synthesized, based on an in‐depth understanding of structural insights into P′2 phase. By analyzing the structural evolution and Mn‐valence changes during synthesis, we found that oxygen vacancies play a significant role in determining the P′2–P2 phase transition. Moreover, these insights not only identified the oxygen release and uptake behaviors in phase formation but also expanded synthesis strategy with enhanced operational feasibility. Benefits from expanded Mn redox range and stable oxygen vacancies during cycling, the obtained P′2‐Na 0.67 Fe 0.05 Ti 0.1 Mn 0.85 O 2 demonstrated a capacity increase of over ∼40 mAh g −1 at 0.1 C, maintaining ∼93 mAh g −1 even after 1000 cycles at 10 C, with an impressive retention rate of 87.5%. This research significantly advances the comprehension of both synthesis mechanism and electrochemical properties optimization mechanisms of P′2 phase materials, offering a pragmatic strategy for elevating the performance of SIB materials.