Advances and Challenges of Porous Structure on Solid–Liquid Interfaces in Polyanionic Sodium‐Ion Batteries

Abstract The sodium‐ion batteries (SIBs) are expected to be the substitute for lithium‐ion batteries (LIBs) because of their low cost, high abundance, and similar working mechanism. Among them, polyanion‐type electrodes show great application prospects due to their superior ion diffusion channels and structural stability. However, there are still many scientific issues that need to be thoroughly investigated, especially the formation mechanism, structural stability, and interface impedance of solid–liquid interfaces. Therefore, it is of great significance to systematically study the mechanism of interface reaction and the electrochemical behavior, to promote the further practical application of SIBs. Fortunately, the polyanionic electrodes can effectively improve the transport dynamics and the interfacial stability of the solid–liquid interfaces through constructing the porous structure, surface modification, and electrolyte strategies, thus improving the cycle and rate performance. This review discusses the characteristics and formation mechanisms of electrode/electrolyte interface (EEI), as well as their electrochemical behavior in porous structures with different dimensions. Furthermore, this review covers the application of porous materials in improving transport kinetics and EEI. In particular, it highlights the various strategies employed to comprehend the interplay among structure, chemistry, preparation methods, and the mechanisms of porous electrodes that ultimately affect the electrochemical properties of SIBs.