Oxygen–Ion Conductivity, Dielectric Properties and Spectroscopic Characterization of “Stuffed” Tm₂(Ti_2−<i>x</i>Tm<i>_x</i>)O_{7−<i>x</i>/2} (<i>x</i> = 0, 0.1, 0.18, 0.28, 0.74) Pyrochlores

Abstract

Tm2(Ti2−xTmx)O7−x/2 (x = 0, 0.1, 0.18, 0.28, 0.74) solid electrolytes have been investigated as potential electrolyte materials for solid oxygen fuel cells (SOFCs), operating in the medium temperature range (600–700 °C). The design of new oxygen-conducting materials is of importance for their possible utilization in the solid oxide fuel cells. The oxygen–ion conductivity of the Tm2(Ti2−xTmx)O7−x/2 (x = 0, 0.1, 0.18, 0.28, 0.74) “stuffed” pyrochlores ceramics was investigated by electrochemical impedance spectroscopy (two-probe AC) in dry and wet air. The synthesis of precursors via co-precipitation and the precipitate decomposition temperature have been shown to be of key importance for obtaining dense and highly conductive ceramics. At ~770 °C, the highest total conductivity, ~3.16 × 10−3 S/cm, is offered by Tm2Ti2O7. The conductivity of the fluorite-like solid solution Tm2(Ti2−xTmx)O7−x/2 (x = 0.74) is an order of magnitude lower. However, for the first time a proton contribution of ~5 × 10−5 S/cm at 600 °C has been found in Tm2(Ti2−xTmx)O7−x/2 (x = 0.74) fluorite. Until now, compositions with proton conductivity were not known for the intermediate and heavy rare earth titanates Ln2(Ti2−xLnx)O7−x/2 (Ln = Ho − Lu) systems. The use of X-ray diffraction (structural analysis with Rietveld refinement), optical spectroscopy and dielectric permittivity data allowed us to follow structural disordering in the solid solution series with increasing thulium oxide content. High and low cooling rates have been shown to have different effects on the properties of the ceramics. Slow cooling initiates’ growth of fluorite nanodomains in a pyrochlore matrix. The fabrication of such nanostructured dense composites is a promising direction in the synthesis of highly conductive solid electrolytes for SOFCs. We assume that high-temperature firing of nanophase precursors helps to obtain lightly doped “stuffed” pyrochlores, which also provide the high oxygen–ion conductivity.

Keywords

• Tm₂Ti₂O₇
• “stuffed” pyrochlores
• co-precipitation method
• oxygen–ion conductivity