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In this work, Nb-substituted barium strontium cobaltites Ba0.5Sr0.5Co1-xNbxO3-δ (x = 0 – 0.4) have been fabricated and studied. The structural analysis showed that the Nb content influences the lattice constant as well as the distance between the (Co, Nb) and oxygen atoms. The study of morphology of samples showed that the Nb content does not change the porosity, grain size and morphology of the ceramics. The total electrical conductivity was studied as a function of temperature and pO2/pH2O. It was shown, that total conductivity is influenced by the cobalt to niobium ratio while the conduction mechanism was similar in all analyzed samples. Transport properties and the presence of protonic conductivity were studied in a dry and humidified atmosphere. A non-negligible difference between total conductivities in dry and wet atmospheres below 500 °C was observed what indicates the presence of protonic defects in these structures. Hydrogenation as a predominant protons formation mechanism was proposed.

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.

In this work, BaxSr1−xTi1−yFeyO3−δ perovskite-based mixed conducting ceramics (for x = 0, 0.2, 0.5 and y = 0.1, 0.8) were synthesized and studied. The structural analysis based on the X-ray diffraction results showed significant changes in the unit cell volume and Fe(Ti)–O distance as a function of Ba content. The morphology of the synthesized samples studied by means of scanning electron microscopy has shown different microstructures for different contents of barium and iron. Electrochemical impedance spectroscopy studies of transport properties in a wide temperature range in the dry- and wet air confirmed the influence of barium cations on charge transport in the studied samples. The total conductivity values were in the range of 10−3 to 100 S cm−1 at 600 °C. Depending on the barium and iron content, the observed change of conductivity either increases or decreases in humidified air. Thermogravimetric measurements have shown the existence of proton defects in some of the analysed materials. The highest observed molar proton concentration, equal to 5.0 × 10−2 mol mol−1 at 300 °C, was obtained for Ba0.2Sr0.8Ti0.9Fe0.1O2.95. The relations between the structure, morphology and electrical conductivity were discussed.

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.

The single phase lanthanum orthoniobate with tetragonal structure has been synthesized by the means of mechanosynthesis method. The studies have shown the crystal structure of La0.98Ca0.02NbO4 depends on the synthesis stage. The samples were predominantly in the tetragonal phase with a trace amount of the monoclinic phase. The SEM studies of morphology and microstructure have shown nanocrystallinity of the materials. The Raman studies showed the significant difference between the Raman spectra of nano- and microcrystalline La0.98Ca0.02NbO4. A decrease of Debye temperature, shown a change of thermal properties due to the presence of nano-sized particles in La0.98Ca0.02NbO4. Electrical characterization results suggest the protons are predominant charge carries in the material for the whole measured range of temperature and shows the total conductivity value of 4.0 × 10−5 S cm−1 at 600 °C in wet air. The calculated activation energies were equal to (0.81 ± 0.04) eV under dry and (0.73 ± 0.06) eV under humidified conditions. That indicates that nanostructuring was successfully stabilized the high-temperature tetragonal phase.

[EN] The cubic Ba0.5La0.5CoO3-delta was synthesized using solid state reaction. The structural properties were determined by the simultaneous refinement of Synchrotron Powder X-ray Diffraction and Neutron Powder Diffraction data. Iodometric titration was used to examine the oxygen stoichiometry and average cobalt oxidation state. Low-temperature magnetic studies show soft ferromagnetic character of fully oxidized material, with theta(P) = 198(3) K and mu(eff) = 2.11(2) mu(B). Electric measurements show the thermally activated nature of conductivity at low temperatures, whereas, due to the variable oxidation and spin state of cobalt, a single charge transport mechanism cannot be distinguished. Around room temperature, a wide transition from thermally activated conductivity to semi-metallic behavior is observed. Under the inert atmosphere, the oxygen content lowers and the cation ordering takes place, leading to coexistence of two, ordered and disordered, phases. As a result of this change, thermally activated conductivity is observed also at high temperatures in inert atmosphere., The authors acknowledge the skillful assistance from the staff of the Swiss-Norwegian Beamline (SNBL), at the European Synchrotron Radiation Facility (ESRF), Grenoble, France. The research has been supported by the National Science Centre Poland under m.ERA.net funding scheme (2016/22/Z/ST5/00691). Funding from the Spanish Government (PCIN-2017-125, RTI2018-102161) is kindly acknowledged. Financial and scientific contributions from the Research Council of Norway (Grant no 272797 "GoPHy MiCO") through the M-ERA.NET Joint Call 2016.

The results of ionic transport and structural measurements for the lanthanum orthoniobate doped by praseodymium are presented and discussed. The influence of calcium co-doping on these properties has also been analyzed. The results suggest the predominant protonic conductivity for the investigated system in the whole range of investigated temperatures. The influence of calcium co-doping on phase purity is analyzed.

In this work, Fe-doped strontium titanate SrTi1-xFexO3-x/2-&delta, for x = 0&ndash, 1 (STFx), has been fabricated and studied. The structure and microstructure analysis showed that the Fe amount in SrTi1-xFexO3-x/2-&delta, 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 &gt, 0.3) exhibit higher oxygen vacancies concentration of the order of magnitude 1022&ndash, 1023 cm&minus, 3. The proton uptake investigations have been done using thermogravimetry in wet conditions, and the results showed that the compositions with x &lt, 0.5 exhibit hydrogenation redox reactions. Proton concentration at 400 &deg, C depends on the Fe content and was estimated to be 1.0 &times, 10&minus, 2 mol/mol for SrTi0.9Fe0.1O2.95 and 1.8 &times, 5 mol/mol for SrTi0.5Fe0.5O2.75. Above 20 mol% of iron content, a significant drop of proton molar concentrations at 400 &deg, 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-&delta, 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.

The results of electrical conductivity studies, structural measurements and thermogravimetric analysis of La1&minus, xTbxNbO4+&delta, (x = 0.00, 0.05, 0.1, 0.15, 0.2, 0.3) are presented and discussed. The phase transition temperatures, measured by high-temperature x-ray diffraction, were 480 &deg, C, 500 &deg, C, and 530 &deg, C for La0.9Tb0.1NbO4+&delta, La0.8Tb0.2NbO4+&delta, and La0.7Tb0.3NbO4+&delta, respectively. The impedance spectroscopy results suggest mixed conductivity of oxygen ions and electron holes in dry conditions and protons in wet. The water uptake has been analyzed by the means of thermogravimetry revealing a small mass increase in the order of 0.002% upon hydration, which is similar to the one achieved for undoped lanthanum orthoniobate.