Unfolding the structural features of NASICON materials for sodium‐ion full cells

Abstract Sodium‐ion batteries (SIBs) are potential candidates for the replacement of lithium‐ion batteries to meet the increasing demands of electrical storage systems due to the low cost and high abundance of sodium. Sodium superionic conductor (NASICON) structured materials have attracted enormous interest in recent years as electrode materials for safer and long‐term performance of SIBs for electric energy storage smart grids. These materials have a three‐dimensional robust framework, high redox potential, thermal stability, and a fast Na + ‐ion diffusion mechanism. However, NASICON has low intrinsic electronic conductivity, which limits the electrochemical performance. This review describes the structural features of NASICONs to illustrate the ion storage mechanism and electrochemical performance of SIBs. Details of the NASICON crystal structure, the affiliated Na + ‐ion diffusion mechanism, morphology, and electrochemical performance of these materials in sodium‐ion half‐cells as well as full cells are described. In addition to the application as electrode materials, the use of NASICONs as solid electrolytes is also elaborated in solid‐state SIBs. Based on these aspects, we have provided more perspectives in terms of the commercialization of SIBs and strategies to overcome the limitations of NASICONs. Hence, this review is expected to provide the researchers of energy storage with an in‐depth understanding of NASICON materials with the knowledge of structural features, which will provide a new avenue on the practicality of SIBs.