Structure and conductivity of lithium-doped fluorite-like Nd5Mo3O16 molybdates

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Abstract

Rare-earth molybdenum-containing oxides of nominal composition LixNd5 – xMo3O16 ± δ (x = 0, 0.05, 0.15, 0.25) with a fluorite-derived structure were first obtained as single crystals from a melt solution and by solid-phase synthesis in air as polycrystalline samples. The new phases were characterized by X-ray phase analysis, synchronous thermal analysis, and impedance spectroscopy. X-ray structural analysis showed that lithium atoms are localized near the positions of rare-earth cations. The chemical formula of the investigated single crystal was determined as Li0.216Nd4.784Mo3O14.1+δ. A small amount of lithium did not significantly affect the ability of the studied phases to undergo dissociative water absorption but led to a decrease in the total conductivity of lithium-doped LixNd5 – xMo3O16 ± δ ceramics.

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About the authors

E. I. Orlova

Lomonosov Moscow State University; Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Author for correspondence.
Email: agapova@polly.phys.msu.ru
Russian Federation, Moscow; Moscow

M. P. Trukhacheva

Lomonosov Moscow State University; Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: agapova@polly.phys.msu.ru
Russian Federation, Moscow; Moscow

T. A. Sorokin

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: agapova@polly.phys.msu.ru
Russian Federation, Moscow

V. B. Kvartalov

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: agapova@polly.phys.msu.ru
Russian Federation, Moscow

A. M. Antipin

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: agapova@polly.phys.msu.ru
Russian Federation, Moscow

N. V. Lyskov

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry of the RAS; HSE University

Email: agapova@polly.phys.msu.ru
Russian Federation, Chernogolovka, Moscow region; Moscow

E. P. Kharitonova

Lomonosov Moscow State University; Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: agapova@polly.phys.msu.ru
Russian Federation, Moscow; Moscow

N. E. Novikova

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: natnov@crys.ras.ru
Russian Federation, Moscow

N. I. Sorokina

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: agapova@polly.phys.msu.ru
Russian Federation, Moscow

O. A. Alekseeva

Shubnikov Institute of Crystallography of Kurchatov Complex of Crystallography and Photonics of NRC “Kurchatov Institute”

Email: agapova@polly.phys.msu.ru
Russian Federation, Moscow

V. I. Voronkova

Lomonosov Moscow State University

Email: agapova@polly.phys.msu.ru
Russian Federation, Moscow

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Supplementary files

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2. Fig. 1. Photograph of LiyNd5 - yMo3O16 ± δ single crystal illuminated by LED lamp (5600 K)

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3. Fig. 2. Diffractograms of single crystal samples of nominal composition LiyNd5 - yMo3O16 ± δ (1) and LixNd5 - xMo3O16 ± δ ceramics, x: 0 (2), 0.05 (3), 0.15 (4), 0.25 (5)

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4. Fig. 3. DSC data for single-crystal samples (1 - heating, 2 - cooling) and LixNd5 - xMo3O16 ± δ, x = 0.05 ceramics (3 - heating, 4 - cooling)

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5. Fig. 4. Thermogravimetry (TG) data for single-crystal samples, initial Nd5Mo3O16 + δ (1) and lithiated (2), and LixNd5 - xMo3O16 ± δ ceramics, x: 0 (3), 0.05 (4), 0.15 (5)

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6. Fig. 5. Projection of the crystal structure Li0.216Nd4.784Mo3O14.1 + δ on the bc plane

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7. Fig. 6. Temperature dependences of the conductivity of Li0.216Nd4.784Mo3O14.1 + δ ceramics at x = 0, 0.15 (dark and light symbols, respectively) measured in dry (shaded symbols) and humid (empty symbols) air

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