Investigating potential proton conductors: Doping BaTiO3 and SrTiO3 with Fe and Al

University essay from Uppsala universitet/Strukturkemi

Abstract: There are many interesting applications of proton conducting oxides, such as electrolytes in fuel cells, hydrogen sensors and catalytic membranes for hydrogenation or dehydrogenation of organic compounds. Previous work explored doping BaTiO3 with the Rare Earth Element (REE) Sc to introduce oxygen vacancies in the structure, making it a Proton Conductor (PC). PC oxides are often perovskite materials, ABX3, wherethe A- or B-site are doped in such a way that less oxygen can be contained, creating oxygen vacancies. When these materials are then hydrated so that water molecules occupy the vacancies, hydrogen is essentially added to the system in the form of protons. This study expanded on those results, exploring possible dopants that are non-REEs, theoretically improving availability and cost. Fe and Al were chosen as B-site dopants and Sr was included as an alternative to Ba as the A-site cation, compensating for the smaller size of the Fe- and Al atoms compared to Ti. Solid state synthesis was used to manufacture the different compounds and then X-Ray Diffraction (XRD), ThermoGravimetric Analysis (TGA) and Differential Thermal Analysis (DTA) were used inorder to investigate their properties. The main focus was to explore ift he materials could be synthesised using this method, their structures and how they reacted to hydration. All Al doped samples could not be made phase pure with the synthesis parameters used. BaTi0.5Fe0.5Oy was stabilised by the inclusion of Ti, as it did not decompose during hydration, unlike pure BaFeOx. Significant hydration was achieved in a wet nitrogen atmosphere at 185°C, but its structure type was hexagonal, which is known to be unfavourable for proton conduction. SrTi0.5Fe0.5Oy had a cubic structure which is a beneficial structural trait for proton conduction, but negligible hydration was observed by TGA. A small increase in cell volume indicates that it might still have taken up some water, but the methods used for hydration were not optimal for this material. The oxygen content of the materials was not determined in this project and methods such as Mössbauer spectroscopy and iodometric titration should be included in any related future studies.

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