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Alluaudite-type materials are systematically attracting more attention as prospective cathode materials for sodium ion batteries. In this paper, we strove to optimize various synthesis parameters of three alluaudite compositions (Na2Fe3(PO4)3-FFF, Na2VFe2(PO4)3-VFF, and Na2VFeMn(PO4)3-VFM) to obtain nanostructured alluaudite-type glass-ceramics with high phase purity. We systematically investigated the role of the chemical reactions, temperature and time of melting, cooling rate, and reducing factors on the quality of