Li3-2xNbxCr2-x(PO4)3 Complex Phosphates with the Nasicon Structure: Synthesis and lon Conductivity

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Abstract

One of the main trends in the development of metal-ion batteries is the transition to lithium anodes, the safe use of which is impossible without replacing liquid membranes with solid membranes, primarily inorganic ones. Lithium-niobium-chromium phosphates with calculated compositions Li3–2xNbxCr2–x(PO4)3 (x = 0.95, 1.00, 1.05) were obtained by solid-state synthesis and characterized by XRD analysis and impedance spectroscopy. The obtained complex lithium-niobium-chromium phosphates with the NASICON structure crystallize in hexagonal modification. The lattice parameters of the synthesized materials decrease with increasing chromium content. The material of composition Li1.1Nb0.95Cr1.05(PO4)3 (3.10–5 S/cm at 25 °C) possesses the highest ionic conductivity and the lowest activation energy, which indicates a greater mobility of lithium ions by the interstitial mechanism even in the region of its own disorderliness.

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About the authors

S. A. Novikova

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

Author for correspondence.
Email: yaroslav@igic.ras.ru
Russian Federation, Moscow

A. B. Yaroslavtsev

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

Email: yaroslav@igic.ras.ru
Russian Federation, Moscow

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2. Fig. 1. Fragments of X-ray diffraction patterns of LiNbCr(PO4)3 obtained at 850-1150°C (a), Li3-2xNbxCr2-x(PO4)3 (x = 0.95, 1.00, 1.05) synthesised at 1100°C (b) and 1150°C (c). Fragments containing reflections of germanium, which was used as a standard, were cut out in the 2Ɵ~27° region. Symbols +, # and * denote impurity phases of monoclinic and tetragonal modifications of NbOPO4 and LiCrP2O7

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3. Fig. 2. Typical impedance hodographs using Li0.9Nb1.05Cr0.95(PO4)3 as an example at different temperatures (a, b). Temperatures are given in the figure

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4. Fig. 3. Temperature dependence of conductivity for Li3-2xNbxCr2-x(PO4)3

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