High oxide ion and proton conductivity in a disordered hexagonal perovskite.

Oxide ion and proton conductors, which exhibit high conductivity at intermediate temperature, are necessary to improve the performance of ceramic fuel cells. The crystal structure plays a pivotal role in defining the ionic conduction properties, and the discovery of new materials is a challenging research focus. Here, we show that the undoped hexagonal perovskite Ba7Nb4MoO20 supports pure ionic conduction with high proton and oxide ion conductivity at 510 °C (the bulk conductivity is 4.0 mS cm-1), and hence is an exceptional candidate for application as a dual-ion solid electrolyte in a ceramic fuel cell that will combine the advantages of both oxide ion and proton-conducting electrolytes. Ba7Nb4MoO20 also showcases excellent chemical and electrical stability. Hexagonal perovskites form an important new family of materials for obtaining novel ionic conductors with potential applications in a range of energy-related technologies.

Dielectric Barrier Plasma Discharge Exsolution of Nanoparticles at Room Temperature and Atmospheric Pressure.

Exsolution of metal nanoparticles (NPs) on perovskite oxides has been demonstrated as a reliable strategy for producing catalyst-support systems. Conventional exsolution requires high temperatures for long periods of time, limiting the selection of support materials. Plasma direct exsolution is reported at room temperature and atmospheric pressure of Ni NPs from a model A-site deficient perovskite oxide (La0.43Ca0.37Ni0.06Ti0.94O2.955). Plasma exsolution is carried out within minutes (up to 15 min) using a dielectric barrier discharge configuration both with He-only gas as well as with He/H2 gas mixtures, yielding small NPs (<30 nm diameter). To prove the practical utility of exsolved NPs, various experiments aimed at assessing their catalytic performance for methanation from synthesis gas, CO, and CH4 oxidation are carried out. Low-temperature and atmospheric pressure plasma exsolution are successfully demonstrated and suggest that this approach could contribute to the practical deployment of exsolution-based stable catalyst systems.

Disruption of extended defects in solid oxide fuel cell anodes for methane oxidation.

Point defects largely govern the electrochemical properties of oxides: at low defect concentrations, conductivity increases with concentration; however, at higher concentrations, defect-defect interactions start to dominate. Thus, in searching for electrochemically active materials for fuel cell anodes, high defect concentration is generally avoided. Here we describe an oxide anode formed from lanthanum-substituted strontium titanate (La-SrTiO3) in which we control the oxygen stoichiometry in order to break down the extended defect intergrowth regions and create phases with considerable disordered oxygen defects. We substitute Ti in these phases with Ga and Mn to induce redox activity and allow more flexible coordination. The material demonstrates impressive fuel cell performance using wet hydrogen at 950 degrees C. It is also important for fuel cell technology to achieve efficient electrode operation with different hydrocarbon fuels, although such fuels are more demanding than pure hydrogen. The best anode materials to date--Ni-YSZ (yttria-stabilized zirconia) cermets--suffer some disadvantages related to low tolerance to sulphur, carbon build-up when using hydrocarbon fuels (though device modifications and lower temperature operation can avoid this) and volume instability on redox cycling. Our anode material is very active for methane oxidation at high temperatures, with open circuit voltages in excess of 1.2 V. The materials design concept that we use here could lead to devices that enable more-efficient energy extraction from fossil fuels and carbon-neutral fuels.

A new anode for solid oxide fuel cells with enhanced OCV under methane operation.

A new SOFC anode material based upon oxygen excess perovskite related phases has been synthesised. The material shows better electrochemical performance than other alternative new anodes and comparable performance to the state-of-art of the electrodes, Ni-YSZ cermets, under pure hydrogen. Furthermore, this material shows an enhanced performance under methane operation with high open circuit voltages, i.e. 1.2-1.4 V at 950 degrees C, without using steam excess. The effect of the anode configuration was tested in one and four layer configurations. The optimised electrode polarisation resistances were just 0.12 ohm cm(2) and 0.36 ohm cm(2), at 950 degrees C, in humidified H(2) and humidified CH(4), respectively. Power densities of 0.5 W cm(-2) and 0.35 W cm(-2) were obtained in the same conditions. A very low anodic overpotential of 100 mV at 1 A cm(-2) was obtained under humidified H(2) at 950 degrees C. Samples were tested for two days in reducing and oxidising conditions, alternating heating and cooling processes from 850 degrees C to 950 degrees C, showing stable electrode performance and open circuit voltages. The results show that the substituted strontium titanates are very promising anode materials for SOFC.