Vibrational Properties of LaNb0.8 M0.2 O4-δ (M=As, Sb, V, and Ta).

LaNb0.8 M0.2 O4-δ (where M=As, Sb, V, and Ta) oxides with pentavalent elements of different ionic sizes were synthesized by a solid-state reaction method. The vibrational properties of these oxides have been investigated. These studies revealed that the substituent element influences both Debye temperature value as well as the Raman active vibrational modes. Additionally, the low-temperature vibrational properties of LaNb0.8 Sb0.2 O4-δ have been determined to show the phase transition occurrence at 260 K which is lower than previously reported.

Praseodymium Orthoniobate and Praseodymium Substituted Lanthanum Orthoniobate: Electrical and Structural Properties.

In this paper, the structural properties and the electrical conductivity of La1-xPrxNbO4+δ (x = 0.00, 0.05, 0.1, 0.15, 0.2, 0.3) and PrNbO4+δ are presented and discussed. All synthesized samples crystallized in a monoclinic structure with similar thermal expansion coefficients. The phase transition temperature between the monoclinic and tetragonal structure increases with increasing praseodymium content from 500 °C for undoped LaNbO4+δ to 700 °C for PrNbO4+δ. Thermogravimetry, along with X-ray photoelectron spectroscopy, confirmed a mixed 3+/4+ oxidation state of praseodymium. All studied materials, in humid air, exhibited mixed protonic, oxygen ionic and hole conductivity. The highest total conductivity was measured in dry air at 700 °C for PrNbO4+δ, and its value was 1.4 × 10-3 S/cm.

High-Temperature Proton Conduction in LaSbO4.

Lanthanum orthoantimonate was synthesized using a solid-state synthesis method. To enhance the possible protonic conductivity, samples with the addition of 1 mol % Ca in La-site were also prepared. The structure was studied by the means of X-ray diffraction, which showed that both specimens were single phase. The materials crystallized in the space group P21 /n. Dilatometry revealed that the material expanded non-linearly with the temperature. The nature of this deviation is unknown; however, the calculated linear fraction thermal expansion coefficient was 9.56×10-6 K-1 . Electrical properties studies showed that the material is a proton conductor in oxidizing conditions, which was confirmed both by temperature studies in wet in dry air, but also by the H/D isotope exchange experiment. The conductivity was rather modest, peaking at the order of 10-6  S cm-1 at 800 °C, but this could be further improved by microstructure and doping optimization. This is the first time protonic conductivity in lanthanum orthoantimonates is reported.

Signature of Oxide-Ion Conduction in Alkaline-Earth-Metal-Doped Y3GaO6.

We have studied alkaline-earth-metal-doped Y3GaO6 as a new family of oxide-ion conductor. Solid solutions of Y3GaO6 and 2% -Ca2+-, -Sr2+-, and -Ba2+-doped Y3GaO6, i.e., Y(3-0.06)M0.06GaO6-δ (M = Ca2+, Sr2+, and Ba2+), were prepared via a conventional solid-state reaction route. X-ray Rietveld refined diffractograms of all the compositions showed the formation of an orthorhombic structure having the Cmc21 space group. Scanning electron microscopy (SEM) images revealed that the substitution of alkaline-earth metal ions promotes grain growth. Aliovalent doping of Ca2+, Sr2+, and Ba2+ enhanced the conductivity by increasing the oxygen vacancy concentration. However, among all of the studied dopants, 2% Ca2+-doped Y3GaO6 was found to be more effective in increasing the ionic conductivity as ionic radii mismatch is minimum for Y3+/Ca2+. The total conductivity of 2% Ca-doped Y3GaO6 composition calculated using the complex impedance plot was found to be ∼0.14 × 10-3 S cm-1 at 700 °C, which is comparable to many other reported solid electrolytes at the same temperature, making it a potential candidate for future electrolyte material for solid oxide fuel cells (SOFCs). Total electrical conductivity measurement as a function of oxygen partial pressure suggests dominating oxide-ion conduction in a wide range of oxygen partial pressure (ca. 10-20-10-4 atm). The oxygen-ion transport is attributed to the presence of oxygen vacancies that arise from doping and conducting oxide-ion layers of one, two-, or three-dimensional channels within the crystal structure. The oxide-ion migration pathways were analyzed by the bond valence site energy (BVSE)-based approach. Photoluminescence analysis, dilatometry, Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscopy studies were also performed to verify the experimental findings.

Structural Properties and Water Uptake of SrTi1-xFexO3-x/2-δ.

In this work, Fe-doped strontium titanate SrTi1-xFexO3-x/2-δ, for x = 0-1 (STFx), has been fabricated and studied. The structure and microstructure analysis showed that the Fe amount in SrTi1-xFexO3-x/2-δ has a great influence on the lattice parameter and microstructure, including the porosity and grain size. Oxygen nonstoichiometry studies performed by thermogravimetry at different atmospheres showed that the Fe-rich compositions (x > 0.3) exhibit higher oxygen vacancies concentration of the order of magnitude 1022-1023 cm-3. The proton uptake investigations have been done using thermogravimetry in wet conditions, and the results showed that the compositions with x < 0.5 exhibit hydrogenation redox reactions. Proton concentration at 400 °C depends on the Fe content and was estimated to be 1.0 × 10-2 mol/mol for SrTi0.9Fe0.1O2.95 and 1.8 × 10-5 mol/mol for SrTi0.5Fe0.5O2.75. Above 20 mol% of iron content, a significant drop of proton molar concentrations at 400 °C was observed. This is related to the stronger overlapping of Fe and O orbitals after reaching the percolation level of approximately 30 mol% of the iron in SrTi1-xFexO3-x/2-δ. The relation between the proton concentration and Fe dopant content has been discussed in relation to the B-site average electronegativity, oxygen nonstoichiometry, and electronic structure.