Self‐Assembled Alluaudite Na2Fe3−xMnx(PO4)3 Micro/Nanocompounds for Sodium‐Ion Battery Electrodes: A New Insight into Their Electronic and Geometric Structure

A series of alluaudite Na₂Fe_3?xMn_x(PO₄)₃ microcompounds, which self‐assembled from primary nanorods, were prepared successfully through a solvothermal method. As a promising candidate cathode for sodium‐ion batteries, it is necessary to obtain a deeper understanding of the relationship between the structure and physicochemical properties of these materials. The local electronic and geometric environments were systematically investigated, for the first time, by using a combination of soft/hard X‐ray absorption, IR, and Mössbauer spectroscopy. The results show that the electrochemical performance is not only associated with morphology, but also with the electronic and crystalline structure. With the introduction of manganese into the lattice, the long‐range order maintains the isostructural framework and the lattice parameters expand as expected. However, for short‐range order, PO₄ tetrahedra and MO₆ octahedra (M=Fe and Mn) become more severely distorted as a function of Mn concentration. Meanwhile, larger MnO₆ octahedra will compress the space of FeO₆ octahedra, which will result in stronger core/electron–electron interactions for Fe, as characterized by hard/soft X‐ray absorption spectra. These slight changes in the electronic and local structures lead to different electrochemical performances with changes to the manganese content. Moreover, other physicochemical properties, such as magnetic behavior, are also confirmed to be correlated with these different electron interactions and local geometric environments.