THERMOCHEMICAL AND STRUCTURAL PROPERTIES OF K2–2x Na2x Fe1.5Nb0.5(PO4)3 (0 ≤ x ≤ 1) SOLID SOLUTIONS WITH NASICON AND LANGBEINITE STRUCTURES

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Abstract

Solid solutions K2–2x Na2x Fe1.5Nb0.5(PO4)3 (0 ≤ x ≤ 1) are studied to determine the stability ranges of the NASICON and langbeinite structural types and to evaluate the mixing energetics. The materials under investigation may be used as cathodes for Na-ion batteries. Powder samples were obtained by a solid-state method and characterized by X-ray microanalysis, X-ray diffraction, and differential scanning calorimetry. Structural refinement was carried out by the Rietveld method using powder X-ray diffraction data at room temperature. It was established that phases isostructural to the mineral langbeinite (K2Mg2(SO4)3, space group P213) crystallize in the range 0 ≤ x ≤ 0.4, while phases isostructural to NASICON NaZr2(PO4)3 (space group R3-c) crystallize in the range 0.9 ≤ x ≤ 1. Standard enthalpies of formation were determined by high-temperature molten-salt calorimetry in a sodium molybdate melt (3Na2O·4MoO3) at 800°C using a Tian–Calvet-type isoperibolic differential calorimeter. The trends in the obtained energetic characteristics are discussed in relation to the structural evolutions across the indicated composition range of the solid solutions. This study expands current knowledge on the isomorphism of alkali cations in framework structures demonstrating possible pathways for changing properties within the investigated series.

About the authors

A. K Koryttseva

Lobachevsky State University of Nizhny Novgorod

Author for correspondence.
Email: koak@chem.unn.ru
Nizhny Novgorod, Russia

A. V Knyazev

Lobachevsky State University of Nizhny Novgorod

Email: koak@chem.unn.ru
Nizhny Novgorod, Russia

E. V Syrov

Lobachevsky State University of Nizhny Novgorod

Email: koak@chem.unn.ru
Nizhny Novgorod, Russia

D. G Fukina

Lobachevsky State University of Nizhny Novgorod

Email: koak@chem.unn.ru
Nizhny Novgorod, Russia

I. A Bazhenova

Lomonosov Moscow State University

Email: koak@chem.unn.ru
Moscow, Russia

V. V Cheverikin

Lomonosov Moscow State University

Email: koak@chem.unn.ru
Moscow, Russia

S. V Kuzovchikov

Lomonosov Moscow State University

Email: koak@chem.unn.ru
Moscow, Russia

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