Structure and Physical Properties of Ceramic Materials Based on ZrO2-Sc2O3 for SOFC Electrolytic Membranes Obtained from Powders of Melted Solid Solutions with a Similar Composition.

This paper presents the results of studying the phase composition, luminescent characteristics, and ionic conductivity of ceramic scandium-stabilized solid solutions of zirconium dioxide containing 9 and 10 mol% Sc2O3. Ceramic samples were prepared by sintering powders obtained by grinding melted solid solutions of the same composition. A comparative analysis of the obtained data with similar characteristics of single crystals has been carried out. Differences in the phase composition of ceramics and initial single crystals were found. The effect of the structure and properties of grain boundaries on the ionic conductivity of ceramic samples is discussed. It is shown that the differences in the ionic conductivity of ceramic samples and crystals are mainly due to changes in the structure and phase composition.

Long-Term Conductivity Stability of Electrolytic Membranes of Scandia Stabilized Zirconia Co-Doped with Ytterbia.

The effect of high-temperature aging for 4800 h at a temperature of 1123 K on the crystal structure and the conductivity of (ZrO2)0.90(Sc2O3)0.09(Yb2O3)0.01 and (ZrO2)0.90(Sc2O3)0.08(Yb2O3)0.02 single-crystal membranes were studied. Such membrane lifetime testing is critical to the operation of solid oxide fuel cells (SOFCs). The crystals were obtained by the method of directional crystallization of the melt in a cold crucible. The phase composition and structure of the membranes before and after aging were studied using X-ray diffraction and Raman spectroscopy. The conductivities of the samples were measured using the impedance spectroscopy technique. The (ZrO2)0.90(Sc2O3)0.09(Yb2O3)0.01 composition showed long-term conductivity stability (conductivity degradation not more than 4%). Long-term high-temperature aging of the (ZrO2)0.90(Sc2O3)0.08(Yb2O3)0.02 composition initiates the t″ → t' phase transformation. In this case, a sharp decrease in conductivity of up to 55% was observed. The data obtained demonstrate a clear correlation between the specific conductivity and the change in the phase composition. The (ZrO2)0.90(Sc2O3)0.09(Yb2O3)0.01 composition can be considered a promising material for practical use as a solid electrolyte in SOFCs.

Stability of the Structural and Transport Characteristics of (ZrO2)0.99-x(Sc2O3)x(R2O3)0.01 (R-Yb, Y, Tb, Gd) Electrolytic Membranes to High-Temperature Exposure.

The effect of long-term high-temperature annealing on the phase composition, local crystal structure, and oxygen-ion conductivity of SOFC membranes based on zirconium dioxide solid solutions was studied. Crystals with the composition of (ZrO2)0.99-x(Sc2O3)x(R2O3)0.01 (where x = 0.08-0.1; R-Yb, Y, Tb, Gd) were obtained by the method of directed melt crystallization in a cold crucible. The crystals were annealed in air at a temperature of 1000 °C for 400 h. The phase analysis of the crystals before and after annealing was studied by X-ray diffractometry and Raman spectroscopy. The study of the ionic conductivity of the crystals was carried out by the method of impedance spectroscopy in the temperature range 400-900 °C. It has been shown that when various rare earth cations (Yb, Y, Tb, and Gd) are used, the maximum conductivity is observed for the compositions (ZrO2)0.91(Sc2O3)0.08(Yb2O3)0.01, (ZrO2)0.89(Sc2O3)0.1(Y2O3)0.01, (ZrO2)0.90(Sc2O3)0.09(Tb2O3)0.01, and (ZrO2)0.89(Sc2O3)0.1(Gd2O3)0.01. At the same time, these crystals have a highly symmetrical pseudocubic structure, which is retained even after crystal annealing. At comparable concentrations of Sc2O3, the conductivity of crystals decreases with an increase in the ionic radius of the rare earth cation. The high-temperature degradation of the conductivity is also discussed depending on the type of rare earth oxide and the concentration of scandium oxide.