Development of direct hydrocarbon solid oxide fuel cells

The focus of this dissertation is the development of a Solid Oxide Fuel Cell (SOFC) that can operate with hydrocarbon fuels without the need for pre-reforming. The design of an active SOFC anode requires the consideration of a number of factors including the catalytic activity of the electrode towards fuel oxidation and electronic conductivity. This work focuses on a novel system for anode fabrication that allows the catalytically active and electronically conducting components of the anode to be easily varied. The catalytic properties of the SOFC anode were examined and a strong link between SOFC performance and oxidation activity demonstrated. Of the rare-earth catalysts investigated ceria was found to have the highest activity leading to the highest fuel cell power density. This activity was further improved, especially for methane fuel, by doping with a precious metal. Furthermore, it was shown that the catalyst not only increased the rate of reaction but increased the cell Open-Circuit Voltage (OCV) suggesting a change in mechanism that increased the cell efficiency. The necessity for high electronic conductivity and connectivity in the electrode was elucidated by studying the impact of anode copper content on cell performance. Low copper loading led to reduced cell performance due to a lack of conductive pathways from the active electrode region to the external circuit. It was observed that additional conductivity was provided by a thermally deposited carbonaceous phase formed upon exposure to hydrocarbon fuels. The electrochemical characterization of SOFC electrodes is a non-trivial problem. Literature reports on the properties of similar electrodes are inconsistent and often contradictory. Using a combined experimental and theoretical approach, significant problems were found with common experimental procedures used to separate the losses associated the cell cathode from those of the anode. By calculating the effect of test geometry on this separation, it was possible to design an experimental system to independently measure the properties of the two electrodes in a SOFC. In addition, it was demonstrated how the measured resistance of SOFC cathodes may vary by as much as an order of magnitude depending on the polarization history of the sample