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Unraveling Anionic Redox for Sodium Layered Oxide Cathodes: Breakthroughs and Perspectives

Sodium‐ion batteries (SIBs) as the next generation of sustainable energy technologies have received widespread investigations for large‐scale energy storage systems (EESs) and smart grids due to the huge natural abundance and low cost of sodium. Although the great efforts are made in exploring layered transition metal oxide cathode for SIBs, their performances have reached the bottleneck for further practical application. Nowadays, anionic redox in layered transition metal oxides has emerged as a new paradigm to increase the energy density of rechargeable batteries. Based on this point, in this review, the development history of anionic redox reaction is attempted to systematically summarize and provide an in‐depth discussion on the anionic redox mechanism. Particularly, the major challenges of anionic redox and the corresponding available strategies toward triggering and stabilizing anionic redox are proposed. Subsequently, several types of sodium layered oxide cathodes are classified and comparatively discussed according to Na‐rich or Na‐deficient materials. A large amount of progressive characterization techniques of anionic oxygen redox is also summarized. Finally, an overview of the existing prospective and the future development directions of sodium layered transition oxide with anionic redox reaction are analyzed and suggested.