Optimization of Electrical Properties of Nanocrystallized Na3M2(PO4)2F3 NASICON-like Glasses (M = V, Ti, Fe)

Abstract

Recently, an interest in NASICON-type materials revived, as they are considered potential cathode materials in sodium–ion batteries used in large-scale energy storage. We applied a facile technique of thermal nanocrystallization of glassy analogs of these compounds to enhance their electrical parameters. Six nanomaterials of the Na3M2(PO4)2F3 (M = V, Ti, Fe) system were studied. Samples with nominal compositions of Na3V2(PO4)2F3, Na3Ti2(PO4)2F3, Na3Fe2(PO4)2F3, Na3TiV(PO4)2F3, Na3FeV(PO4)2F3 and Na3FeTi(PO4)2F3 have been synthesized as glasses using the melt-quenching method. X-ray diffraction measurements were conducted for as-synthesized samples and after heating at elevated temperatures to investigate the structure. Extensive impedance measurements allowed us to optimize the nanocrystallization process to enhance the electrical conductivity of cathode nanomaterials. Such a procedure resulted in samples with the conductivity at room temperature ranging from 1×10−9 up to 8×10−5 S/cm. We carried out in situ impedance spectroscopy measurements (in an ultra-high-frequency range up to 10 GHz) and compared them with thermal events observed in differential thermal analysis studies.