From Lab to Application: Challenges and Opportunities in Achieving Fast Charging with Polyanionic Cathodes for Sodium‐Ion Batteries

Abstract Sodium‐ion batteries (SIBs), recognized for balanced energy density and cost‐effectiveness, are positioned as a promising complement to lithium‐ion batteries (LIBs) and a substitute for lead–acid batteries, particularly in low‐speed electric vehicles and large‐scale energy storage. Despite their extensive potential, concerns about range anxiety due to lower energy density underscore the importance of fast‐charging technologies, which drives the exploration of high‐rate electrode materials. Polyanionic cathode materials are emerging as promising candidates in this regard. However, their intrinsic limitation in electronic conductivity poses challenges for synchronized electron and ion transport, hindering their suitability for fast‐charging applications. This review provides a comprehensive analysis of sodium ion migration during charging/discharging, highlighting it as a critical rate‐limiting step for fast charging. By delving into intrinsic dynamics, key factors that constrain fast‐charging characteristics are identified and summarized. Innovative modification routes are then introduced, with a focus on shortening migration paths and increasing diffusion coefficients, providing detailed insights into feasible strategies. Moreover, the discussion extends beyond half cells to full cells, addressing challenges and opportunities in transitioning polyanionic materials from the laboratory to practical applications. This review aims to offer valuable insights into the development of high‐rate polyanionic cathodes, acknowledging their pivotal role in advancing fast‐charging SIBs.