Influence of Solid-Phase and Melt-Quenching Na3Fe2(PO4)3 Polycrystal Production Technology on Their Structure and Ionic Conductivity

Abstract

This article studies the influence of solid-phase (type 1 samples) and melt-quenching (type 2 samples) technological modes of obtaining Na3Fe2 (PO4 )3 polycrystals on their structures and ion-conducting properties. α-Na3Fe2 (PO4 )3 polycrystals of the 1st type are formed predominantly under an isothermal firing regime, and the synthesis of the 2nd type is carried out under sharp temperature gradient conditions, contributing to the formation of glassy precursors possessing a reactive and deformed structure, in which the crystallization of crystallites occurs faster than in precursors obtained under isothermal firing. The elemental composition of α-Na3Fe2 (PO4 )3 type 2 polycrystals is maintained within the normal range despite the sharp non-equilibrium thermodynamic conditions of synthesis. The microstructure of the type 1 Na3Fe2 (PO4 )3 polycrystals is dominated by chaotically arranged crystallites of medium (7–10 µm) and large (15–35 µm) sizes, while the polycrystals of type 2 are characterized by the preferential formation of small (3–4 µm) and medium (7–10 µm) crystallites, causing uniaxial deformations in their structure, which contribute to a partial increase in their symmetry. The advantage of type 2 polycrystals is that they have higher density and conductivity and are synthesized faster than type 1 samples by a factor of 4. The article also considers the issues of crystallization in a solid-phase precursor from the classical point of view, i.e., the process of the formation of small solid-phase nuclei in the metastable phase and their growth to large particles due to association with small crystallites using phase transitions. Possible variants and models of crystallite growth in Na3Fe2 (PO4 )3 polycrystals, as well as distinctive features of crystallization between two types of samples, are discussed.