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Thermal stability and electrophysical properties of oxide tungsten bronzes produced by electrolysis of melts
- Authors: Semerikova O.L.1, Kosov A.V.1, Grishenkova O.V.1, Shchelkanova M.S.1
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Affiliations:
- Institute of High-Temperature Electrochemistry, Ural Branch of the RAS
- Issue: No 6 (2024)
- Pages: 596-608
- Section: Articles
- URL: https://journals.rcsi.science/0235-0106/article/view/273409
- DOI: https://doi.org/10.31857/S0235010624060028
- ID: 273409
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Abstract
Oxide tungsten bronzes (OTB) of cubic, tetragonal and hexagonal structure were electrodeposited under galvanostatic conditions. Electrolysis of polytungstate melts 0.8Na2WO4–0.2WO3, 0.25Na2WO4–0.25K2WO4–0.5WO3 and 0.1K2WO4–0.55Li2WO4–0.35WO3 was performed at a temperature of 973 K and a cathode current density of 25 mA cm–2 for 20 min. The synthesized OTB powders were studied by X-ray diffraction analysis, laser diffraction, and scanning electron microscopy coupled with energy dispersive spectroscopy. To determine the upper limit of the thermal stability range, the phase composition of OTB powders with an average particle size of 40–50 μm was studied after isothermal annealing at 373–1173 K for 2 h in an air or argon atmosphere. OTB powders with a tetragonal structure were additionally studied by synchronous thermal analysis. The electrical resistance of the samples sintered at 473 K was measured in air using direct and alternating current. It has been established that the most stable are the hexagonal OTBs isostructural to K0.3WO3, since their phase composition does not change up to 773 K during heat treatment in air and remains constant over the entire studied temperature range in an inert atmosphere. Tetragonal OTB powders isostructural to K0.475WO3 and Na0.28WO3 are stable up to 1073 K in argon and partially oxidize in air above 673 K to form OTBs with lower alkali metal content, WO3 and Na2W2O7. The phase composition of cubic OTB isostructural to Na0.74WO3, is stable up to 673 K in air and up to 873 K in argon. Conductivity studies of all samples indicate mixed ion-electron conductivity with a predominance of the electronic component. Аt 298–573 K, the specific electrical conductivity values vary within the range of 0.035–0.051, 0.012–0.030 and 0.005–0.019 (Ohm⋅cm)–1 for the OTB samples of tetragonal, cubic and hexagonal structures, respectively.
About the authors
O. L. Semerikova
Institute of High-Temperature Electrochemistry, Ural Branch of the RAS
Author for correspondence.
Email: o.semerikova@ihte.ru
Russian Federation, Yekaterinburg
A. V. Kosov
Institute of High-Temperature Electrochemistry, Ural Branch of the RAS
Email: o.semerikova@ihte.ru
Russian Federation, Yekaterinburg
O. V. Grishenkova
Institute of High-Temperature Electrochemistry, Ural Branch of the RAS
Email: o.semerikova@ihte.ru
Russian Federation, Yekaterinburg
M. S. Shchelkanova
Institute of High-Temperature Electrochemistry, Ural Branch of the RAS
Email: o.semerikova@ihte.ru
Russian Federation, Yekaterinburg
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