LAUSR

The development of large‐scale energy storage systems (EESs) is pivotal for applying intermittent renewable energy sources such as solar energy and wind energy. Lithium‐ion batteries with LiFePO4 cathode have been explored in the integrated wind and solar power EESs, due to their long cycle life, safety, and low cost of Fe. Considering the penurious reserve and regional distribution of lithium resources, the Fe‐based sodium‐ion battery cathodes with earth‐abundant elements, environmental friendliness, and safety appear to be the better substitutes in impending grid‐scale energy storage. Compared to the transition metal oxide and Prussian blue analogs, the Fe‐based polyanionic oxide cathodes possess high thermal stability, ultra‐long cycle life, and adjustable voltage, which is more commercially viable in the future. This review summarizes the research progress of single Fe‐based polyanionic and mixed polyanionic oxide cathodes for the potential sodium‐ion batteries EESs candidates. In detail, the synthesized method, crystal structure, electrochemical properties, bottlenecks, and optimization method of Fe‐based polyanionic oxide cathodes are discussed systematically. The insights presented in this review may serve as a guideline for designing and optimizing Fe‐based polyanionic oxide cathodes for coming commercial sodium‐ion batteries EESs.