Peculiarities of Phase Formation in Mn-Based Na SuperIonic Conductor (NaSICon) Systems: The Case of Na 1+2 x Mn x Ti 2- x (PO 4 ) 3 (0.0 ≤ x ≤ 1.5).

NAtrium SuperIonic CONductor (NASICON) structured phosphate framework compounds are attracting a great deal of interest as suitable electrode materials for "rocking chair" type batteries. Manganese-based electrode materials are among the most favored due to their superior stability, resource non-criticality, and high electrode potentials. Although a large share of research was devoted to Mn-based oxides for Li- and Na-ion batteries, the understanding of thermodynamics and phase formation in Mn-rich polyanions is still generally lacking. In this study, we investigate a bifunctional Na-ion battery electrode system based on NASICON-structured Na 1+2 x Mn x Ti 2- x (PO 4 ) 3 (0.0 ≤ x ≤ 1.5). In order to analyze the thermodynamic and phase formation properties, we construct a composition-temperature phase diagram using a computational sampling by density functional theory, cluster expansion, and semi-grand canonical Monte Carlo methods. The results indicate finite thermodynamic limits of possible Mn concentrations in this system, which are primarily determined by the phase separation into stoichiometric Na 3 MnTi(PO 4 ) 3 ( x = 1.0) and NaTi 2 (PO 4 ) 3 for x < 1.0 or NaMnPO 4 for x > 1.0. The theoretical predictions are corroborated by experiments obtained using X-ray diffraction and Raman spectroscopy on solid-state and sol-gel prepared samples. The results confirm that this system does not show a solid solution type behavior but phase-separates into thermodynamically more stable sodium ordered monoclinic α-Na 3 MnTi(PO 4 ) 3 (space group C 2) and other phases. In addition to sodium ordering, the anti-bonding character of the Mn-O bond as compared to Ti-O is suggested as another important factor governing the stability of Mn-based NASICONs. We believe that these results will not only clarify some important questions regarding the thermodynamic properties of NASICON frameworks but will also be helpful for a more general understanding of polyanionic systems.