The main objective of the present work was the systematic study of BaSn1-xMxO3-d (M = Y, Gd, Sc, In, ...) as proton conductors. We first developed a synthesis route based on the acrylic acid polymerization. This allowed us obtaining pure nanopowders and dense ceramics after a classical sintering process. We then studied the influence of dopant nature and content on the structural and electrical properties. This study was coupled to theoretical calculations which helped us predicting the most probable defects within the structure. Results indicate that the substitution model is closely linked with dopant size. For small cations, the substitution on B-site occurs as foreseen by the original compound formula. For big cations (La, Nd and Sm), the modeling anticipates a possible partial substitution on A-site, confirmed by an anomaly observed on the evolution of cell parameters. Concerning electrical properties, we did not observe any significant trend as a function of dopant size. It seems nevertheless that best dopants in terms of anion or proton conduction are those presenting the smaller dopant-defect interaction energy as revealed by semi-empirical calculations. In the case of yttrium, the evolution of conduction with Y3+ content is linked both to the increase of charge carriers due to doping and to the increase of grain size with increasing dopant content. We also showed that the stability is strongly linked with the doping level. While highly doped compounds are unstable in humid atmosphere, slightly doped compounds present good stability in humid, hydrogen and CO2 containing atmosphere. Finally, we showed that ZnO as an additive could be used to lower the sintering temperature without changing the conduction properties. This study thus showed that BaSn1-xMxO3-d(M = Y, Gd, Sc, In, ...) may find applications as proton conductors if dopant level is limited for stability reasons, grain size important for better conduction properties and the elaboration process optimised to ensure high density.
| Identifer | oai:union.ndltd.org:CCSD/oai:tel.archives-ouvertes.fr:tel-00453315 |
| Date | 25 September 2009 |
| Creators | Wang, Yanzhong |
| Publisher | Ecole Centrale Paris |
| Source Sets | CCSD theses-EN-ligne, France |
| Language | English |
| Detected Language | English |
| Type | PhD thesis |
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