Proton conducting oxides such as BaCe0.9Y0.1O3-delta have considerable promise for intermediate temperature fuel cells. Unfortunately these tend to be unstable, e. g. to attack by carbonation. Previous work has highlighted the possibility of utilising barium zirconate to provide a chemically stable electrolyte; however such materials are difficult to sinter yielding very high overall resistances. Whilst this sintering problem is soluble, there are still very significant questions about the intrinsic grain conductivity, which varies by orders of magnitude for different reports. Here we demonstrate that there are two variants of BaZr0.9Y0.1O2.95, both with the cubic perovskite structure. The a-form exhibits a slightly smaller unit cell and much lower protonic conductivity than the beta-form. The alpha-form is observed in better equilibrated samples and neutron diffraction demonstrates that this difference originates in a small degree of cross substitution of the Y atom onto the A-sites for the beta-form, suggesting a novel approach to enhance ionic conductivity by reducing defect association through A-site substitution
BaZr0.9Y0.1O3‐δ has been synthesised by three different methods: the solid‐state reaction, the spray pyrolysis and the spray drying. Significantly different apparent lattice parameters (between 0.4192 nm for the sample prepared by the solid‐state reaction method and sintered at 1,500 °C and 0.4206 nm for the sample prepared by the solid‐state reaction method and sintered at 1,720 °C) are observed after calcination and sintering, depending on the synthesis method and the sintering temperature. The bulk conductivity values also vary over several orders of magnitude (–7.2< log σb <–3.6 at 300 °C) depending on the synthesis method and the sintering temperature. These variations of the bulk conductivity and also the activation energy are correlated with variations of the apparent lattice parameter. The influence of the preparation method on the electrical properties is discussed. The grain boundaries are more resistive than the bulk. The variation of the grain boundary conductivity could be correlated to the microstructure in terms of the grain size.
The thermally activated proton diffusion in BaZr 0.9 Y 0.1 O 3-d was studied with electrochemical impedance spectroscopy (IS) and quasi-elastic neutron scattering (QENS) in the temperature range 300-900 K. The diffusivities for the bulk material and the grain boundaries as obtained by IS obey an Arrhenius law with activation energies of 0.46 eV and 1.21 eV, respectively. The activation energies obtained by IS for the bulk are 0.26 eV above 700 K and 0.46 eV, below 700 K. The total diffusivity as obtained by IS is by one order of magnitude lower than the microscopic diffusivity as obtained by QENS. The activation energies obtained by QENS are 0.13 eV above 700 K and 0.04 eV, below 700 K. At about 700 K, the diffusion constants for IS and QENS have a remarkable crossover, suggesting two processes with different activation energies.
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