In Situ Atomic‐Scale Investigation of Structural Evolution During Sodiation/Desodiation Processes in Na(3)V(2)(PO(4))(3)‐Based All‐Solid‐State Sodium Batteries

Recently, all‐solid‐state sodium batteries (Na‐ASSBs) have received increased interest owing to their high safety and potential of high energy density. The potential of Na‐ASSBs based on sodium superionic conductor (NASICON)‐structured Na(3)V(2)(PO(4))(3)(Na(3)VP) cathodes have been proven by their high capacity and a long cycling stability closely related to the microstructural evolution. However, the detailed kinetics of the electrochemical processes in the cathodes is still unclear. In this work, the sodiation/desodiation process of Na(3)VP is first investigated using in situ high‐resolution transmission electron microscopy (HRTEM). The intermediate Na(2)V(2)(PO(4))(3) (Na(2)VP) phase with the P2(1)/c space group, which would be inhibited by constant electron beam irradiation, is observed at the atomic scale. With the calculated volume change and the electrode–electrolyte interface after cycling, it can be concluded that the Na(2)VP phase reduces the lattice mismatch between Na(3)VP and NaV(2)(PO(4))(3) (NaVP), preventing structural collapse. Based on the density functional theory calculation (DFT), the Na(+) ion migrates more rapidly in the Na(2)VP structure, which facilitates the desodiation and sodiation processes. The formation of Na(2)VP phase lowers the formation energy of NaVP. This study demonstrates the dynamic evolution of the Na(3)VP structure, paving the way for an in‐depth understanding of electrode materials for energy‐storage applications.