The Effect of Solid-Phase and Melt Synthesis Methods on Dipole Ordering and Ion Conductivity of the Polar α-Phase of Na3Fe2(PO4)3 Polycrystals

The article investigates the dielectric and conductive properties of the polar α-phase of Na3Fe2(PO4)3 polycrystals synthesized by solid-phase (sample type 1), melt (type 2), and melt-quenching (type 3) methods. To enable a rapid assessment of the dielectric properties of the polar α-phase of Na3Fe2(PO4)3, the thermo-polarization mobility parameter μTp(T, E(ω)) was introduced. By studying the dielectric properties, it was concluded that the polar α-phase of type 1 samples consists of large and small dipoles and ordered sodium cations, which possess low values of μTp(T, E(ω)), indicating the presence of strong interaction forces between the crystal lattice and the cationic part of the polycrystal. Additional studies of the samples’ conductivity confirm this conclusion. Studies of the polar α-phase of Na3Fe2(PO4)3 in type 2 samples have established that their structure contains dipoles and sodium cations with higher values of μTr(T, E(ω)), and also exhibits higher conductivity than Type 1 samples. These data indicate a weakening of the interaction forces between the cationic and anionic components in type 2 polycrystals due to a partial increase in crystal symmetry. The results of studies of the polar α-phase of type 3 samples show that their structure contains dipoles and sodium cations with higher values of μTr(T, E(ω)), and also exhibits higher conductivity than type 2 samples. It is concluded that the structure of type 3 samples is characterized by weak interaction forces between the cationic and anionic parts as a result of an increase in the symmetry of the polar α-phase of Na3Fe2(PO4)3, caused by sharply graded temperature conditions during the synthesis of polycrystals. By studying the dielectric properties of cathode materials, it is possible to obtain information on the extent of interactions between the cationic and anionic components in polycrystals. It is, therefore, appropriate to use this approach when investigating a wide range of new dielectric and ion-conducting materials.