Olivine NaMn0.66Fe0.34PO4 as a Cathode Material for Advanced Sodium Ion Batteries

Abstract Sodium‐ion batteries continue to rise in the energy storage landscape, their increasing adoption being driven by factors such as cost‐effectiveness and sustainability. As a consequence, there is a growing emphasis on the development of new electrode materials. Among these, olivine phosphates emerge as a promising family of cathode materials. However, viable synthesis routes are still lacking. In this study, cathode materials of olivine NaMn 1‐x Fe x PO 4 (x=0.34 and 1) were prepared by directly sodiating Mn 1‐x Fe x PO 4 through a solid‐state process at 300 °C. X‐ray diffraction, Mössbauer spectroscopy and electrochemical measurements were employed to study their structural and electrochemical features. NaMn 0.66 Fe 0.34 PO 4 exhibits two pseudo‐plateaus profile with an average potential of ~3.2 V vs. Na + /Na 0 with a reversible capacity reaching 75 mAh/g at C/20 via a monophasic (de)intercalation mechanism. In parallel, the intermediate composition Na 0.5 Mn 0.66 Fe 0.34 PO 4 could be prepared via the solid‐state reaction of NaMn 0.66 Fe 0.34 PO 4 and Mn 0.66 Fe 0.34 PO 4 . Such a solvent‐free sodiation process not only provides a simplified preparation of NMFP, but also offers easy scalability compared to the more laborious electrochemical sodiation route, making it an interesting prospect for future industrialization. Finally, this research confirms that the olivine NMFP is indeed an attractive candidate as a cathode material for SIBs.