Composite solid electrolytes MWO4–SiO2 (M = Ca, Sr) and Ln2W3O12–SiO2 (Ln = La, Nd): synthesis and study of electrical transport properties

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Abstract

Composite solid electrolytes based on alkaline earth tungstates MWO4–SiO2 (M = Ca, Sr) and rare earth metals Ln2W3O12–SiO2 (Ln = La, Nd) with the addition of nanodispersed silicon oxide were synthesized and their morphology, thermal, structural and electrical transport properties were studied. The absence of thermal effects on DSC of tungstates and silica mixtures as well as the absence of reflections of any foreign phases in the diffraction patterns of the composites, confirms their thermodynamic stability. The ionic nature of the composite conductivity is confirmed by the high values of ionic transfer numbers about 0.8–0.9 (EMF method) and the horizontal plot of conductivity versus oxygen pressure in the gas phase. The concentration dependence of the conductivity of the composites (1–x)MeWO4–xSiO2 (M = Ca, Sr), (1–x)Ln2W3O12–xSiO2 (Ln = La, Nd) passes through a maximum at x = 0.03–0.30 (x – mole fraction). The 0.70Nd2W3O12–0.30SiO2 composite has the best conductivity of 3.2 × 10−2 S/cm at 900°C.

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About the authors

A. F. Guseva

Ural Federal University

Author for correspondence.
Email: Natalie.Pestereva@urfu.ru
Russian Federation, Yekaterinburg, 620002

N. N. Pestereva

Ural Federal University

Email: Natalie.Pestereva@urfu.ru
Russian Federation, Yekaterinburg, 620002

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Supplementary files

Supplementary Files
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2. Fig. 1. Concentration dependence of the effective density of the (1–x)Nd2W3O12–xSiO2 composites.

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3. Fig. 2. XRD data for the (1–x)MWO4–xSiO2 (M = Ca (a), Sr (b)) and (1–x)Ln2W3O12–xSiO2 (Ln = La (c), Nd (d)) composites.

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4. Fig. 3. TG-DSC results for the 0.5CaWO4–0.5SiO2 (a), 0.5SrWO4–0.5SiO2 (b), 0.5Ln2W3O12–0.5SiO2 (c) and 0.5Nd2W3O12–0.5SiO2 (d) mixtures, the mass of the 0.5CaWO4–0.5SiO2 composite (d).

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5. Fig. 4. SEM images and elemental composition of composites according to EDS data: 0.7CaWO4–0.3SiO2 (a), 0.75SrWO4–0.25SiO2 (b), 0.7La2W3O12–0.3SiO2 (c), 0.7Nd2W3O12–0.3SiO2 (d).

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6. Fig. 5. Dependence of electrical conductivity of pure tungstates (a) and composites 0.7MWO4–0.3SiO2 (M = Ca, Sr), 0.7Ln2W3O12–0.3SiO2 (Ln = La, Nd) (b) on the reciprocal temperature.

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7. Fig. 6. Dependence of electrical conductivity of composites (1–x)MWO4–xSiO2 and (1–x)Ln2W3O12–xSiO2 on partial pressure of oxygen in the gas phase.

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8. Fig. 7. Temperature dependence of the sum of ionic transport numbers of composites 0.75SrWO4–0.25SiO2, 0.70La2W3O12–0.30SiO2 and 0.75Nd2W3O12–0.25SiO2.

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9. Fig. 8. Dependence of the relative electrical conductivity of composites (1–x)CaWO4–xSiO2 (a), (1–x)SrWO4–xSiO2 (b), (1–x)La2W3O12–xSiO2 (c) and (1–x)Nd2W3O12–xSiO2 (d) on the molar and volume fraction of SiO2 at 900°C.

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