Abstract: | Over the last decade, Na‐ion batteries have been extensively studied as low‐cost alternatives to Li‐ion batteries for large‐scale grid storage applications; however, the development of high‐energy positive electrodes remains a major challenge. Materials with a polyanionic framework, such as Na superionic conductor (NASICON)‐structured cathodes with formula NaxM2(PO4)3, have attracted considerable attention because of their stable 3D crystal structure and high operating potential. Herein, a novel NASICON‐type compound, Na4MnCr(PO4)3, is reported as a promising cathode material for Na‐ion batteries that deliver a high specific capacity of 130 mAh g?1 during discharge utilizing high‐voltage Mn2+/3+ (3.5 V), Mn3+/4+ (4.0 V), and Cr3+/4+ (4.35 V) transition metal redox. In addition, Na4MnCr(PO4)3 exhibits a high rate capability (97 mAh g?1 at 5 C) and excellent all‐temperature performance. In situ X‐ray diffraction and synchrotron X‐ray diffraction analyses reveal reversible structural evolution for both charge and discharge. |