Verlag des Forschungszentrums Jülich

JUEL-3442
Bausch, Stefan
Impedanzanalyse und mechanische Relaxation von keramischen Protonenleitern
107 S., 1997



High temperature proton conductors are candidate materials for solid electrolytes in different applications like sensors or fuel cells. Non-stoichiometric compounds like BaCa0.393NbO.607O3-[gamma] or BaCe0.9 YO.1O3-[gamma] show considerable water uptake and subsequent proton conductivity after exposure to wet atmospheres. In order to study the microscopic details of the diffusion process of the protons )impedance measurements and anelastic relaxation spectroscopy have been combined. The conductivity of the complex perovskite BaCa0.393NbO.607O3-[gamma] has been determined for different samples prepared with the conventional rnixed oxide or a wet chemical route after various sintering temperatures. The main results are:

Using impedance spectroscopy the contributions from the bulk and the grain boundary regions to the conductivity have been separated. In the wet state the main charge carriers in the bulk are protons and the conductivity decreases with increasing sintering temperature. In the dry state hole conduction dominates both in the bulk and at grain boundaries which form effective barriers for charge transport. For samples prepared after the wet chemical route the conductivity at grain boundaries in the wet state is considerably higher than in the dry state. In contrast, the grain boundary conductivity in conventionally prepared samples remains unaffected after charging with protons.

Maxima in the loss tangent have been observed as a function of temperature or frequency which can be explained by conductivity contributions to the dielectric loss. No further loss contributions -e. g. due to local defect reorientations -could have been identified. This has been shown for the system BaCa0.393NbO.607O3-[gamma], also.

By means of anelastic relaxation measurements the internal friction of the samples has been found to be related to the proton content of the samples. The stoichiometric compound BaCa0.33NbO.66O3 did not show any water uptake and no relaxation maxima at all. For dry, nonstoichiometric samples contributions to the damping with Ea~1.0eV and Ea~ 1.2 eV have been found. After proton incorporation, contributions to the damping with Ea~O.6 eV and Ea~O.7 eV have been identified. An atomistic model is presented with attributes these contributions to local reorientations of Vo-CaNb-pairs and (OH)o-CaNb-pairs, respectively.

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Letzte Änderung: 07.06.2022