Annealing in Argon Universally Upgrades the Na‐Storage Performance of Mn‐Based Layered Oxide Cathodes by Creating Bulk Oxygen Vacancies

Manganese-rich layered oxide cathodes of sodium-ion batteries (SIBs) are extremely promising for large-scale energy storage owing to their high capacities and cost effectiveness, while the Jahn-Teller (J-T) distortion and low operating potential of Mn redox largely hinder their practical applications. Herein, we reveal that annealing in argon rather than conventional air is a universal strategy to comprehensively upgrade the Na-storage performance of Mn-based oxide cathodes. Bulk oxygen vacancies are introduced via this method, leading to reduced Mn valence, lowered Mn 3d-orbital energy level, and formation of the new-concept Mn domains. As a result, the energy density of the model P2-Na_0.75 Mg_0.25 Mn_0.75 O₂ cathode increases by ≈50 % benefiting from the improved specific capacity and operating potential of Mn redox. The Mn domains can disrupt the cooperative J-T distortion, greatly promoting the cycling stability. This exciting finding opens a new avenue towards high-performance Mn-based oxide cathodes for SIBs.