Narendar Nasani

Exploring the mixed transport properties of sulfur(VI)-doped Ba2In2O5 for intermediate-temperature electrochemical applications

A stabilised orthorhombic perovskite Ba2In1.8S0.2O5+δ was synthesised by a solid state reaction at low-temperature. The mixed (electronic–protonic–oxide-ionic) conducting properties of this composition were investigated in detail for potential interest in a wide range of membrane applications including protonic ceramic fuel cells. The electrochemical analyses performed include impedance spectroscopy under wet/dry conditions of N2 and O2 and modified electromotive force measurements in wet/dry mixtures of N2/O2. Under dry oxidising conditions, the sample possesses mixed electronic–oxide-ionic contributions to the electrical transport in the whole range of temperatures, associated with the equilibrium between oxygen vacancies and holes. In wet atmospheres, protonic species arise from the hydration reaction. Protons represent the dominant charge carriers for temperatures lower than 550 °C, while oxide-ions and holes are the major mobile species for temperatures higher than 700 °C. Appreciable mixed contributions to the electrical transport from protons, oxide ions and holes are confirmed between 550 and 700 °C. The experimental data obtained from modified electromotive force measurements and impedance spectroscopy fit well with the expected results according to the proposed defect chemistry model.

Dehydrogenation Properties of Magnesium Hydride Loaded with Fe, Fe−C, and Fe−Mg Additives

This study highlights that Fe additives offer better catalytic properties than carbon, Fe-C (iron carbide/carbon composites), and Fe-Mg (Mg2 FeH6 ) additives for the low-temperature dehydrogenation of magnesium hydride. The in situ X-ray diffraction measurements prove the formation of a Mg2 FeH6 phase in iron additive loaded MgH2 . Nonetheless, differential scanning calorimetry data suggest that this Mg2 FeH6 phase does not have any influence on dehydrogenation properties of MgH2 . On the other hand, the composite system Mg2 FeH6 /MgH2 shows significantly improved dehydrogenation properties even in absence of further additives. It is suggested that the improved system performance of Fe loaded MgH2 is attributed to restrictions on crystal growth of MgH2 and the catalytic behavior of Fe nanoparticles, rather than any intrinsic catalytic properties offered by the formed mixed metal phase Mg2 FeH6 .

Exploring the Thermoelectric Performance of BaGd2NiO5 Haldane Gap Materials

One-dimensional Haldane gap materials, such as the rare earth barium chain nickelates, have received great interest due to their vibrant one-dimensional spin antiferromagnetic character and unique structure. Herein we report how these 1D structural features can also be highly beneficial for thermoelectric applications by analysis of the system CaxBaGd2-xNiO5 0 ≤ x ≤ 0.25. Attractive Seebeck coefficients of 140-280 μV K-1 at 350-1300 K are retained even at high acceptor-substitution levels, provided by the interplay of low dimensionality and electronic correlations. Furthermore, the highly anisotropic crystal structure of Haldane gap materials allows very low thermal conductivities, reaching only 1.5 W m-1 K-1 at temperatures above 1000 K, one of the lowest values currently documented for prospective oxide thermoelectrics. Although calcium substitution in BaGd2NiO5 increases the electrical conductivity up to 5-6 S cm-1 at 1150 K < T < 1300 K, this level remains insufficient for thermoelectric applications. Hence, the combination of highly promising Seebeck coefficients and low thermal conductivities offered by this 1D material type underscores a potential new structure type for thermoelectric materials, where the main challenge will be to engineer the electronic band structure and, probably, microstructural features to further enhance the mobility of the charge carriers.