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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Electrophoretically deposited copper manganese spinel protective coatings on metallic interconnects for prevention of Cr-poisoning in solid oxide fuel cells

Sun, Zhihao 23 October 2018 (has links)
Metallic interconnects in intermediate temperature solid oxide fuel cells (IT-SOFC) stacks form Cr2O3 scales on their surface. Such oxide scales can be further oxidized to Cr6+ containing gaseous species that migrate and deposit at the cathode triple phase boundaries, causing significant degradation in the performance of the SOFCs. This phenomenon is termed as ‘Cr-poisoning’. A solution to this problem is the application of coatings on the interconnects that act as a diffusion barrier to Cr migration. Two different Cu/Mn spinel compositions, Cu1.3Mn1.7O4 and CuMn1.8O4, were studied as coating materials. Dense coatings were deposited on both flat plates and meshes by electrophoretic deposition (EPD) followed by subsequent thermo-mechanical or thermal densification steps. At room temperature, Cu1.3Mn1.7O4 coatings were found to have a mixture of CuO and spinel phases, while CuMn1.8O4 coatings were found to have a mixture of Mn3O4 and spinel phases. However, CuMn1.8O4 is a pure spinel phase between 750 °C and 850 °C. After densification processing and high temperature oxidation, a Cr2O3 layer was formed at the coating/alloy interface, which partially reacted with the spinel coatings to form a dense cubic spinel layer of the general composition (Cu,Mn,Cr)3-xO4. In addition, Cr-rich precipitates, formed in the dense layer close to coating/alloy interface. It is believed that these are Cr2O3 precipitates, formed when the solubility of Cr in the spinel phase is reached. Solubility experiments using powders showed that 1 mole of CuMn1.8O4 can effectively getter 1.83 moles of Cr2O3 at 800°C. Electrical conductivity of (Cu,Mn,Cr)3-xO4 was found to be at least two orders of magnitude higher than that of Cr2O3. The coatings acted as an effective Cr getter whose lifetime depends on the oxidation temperature, coating thickness, and the overall porosity in the coating. In-cell electrochemical testing showed that the CuMn1.8O4 coatings on Crofer 22 APU meshes performed significantly better than commercial Cu/Mn spinel coatings. The CuMn1.8O4 coatings gettered Cr effectively for 12 days at 800 ºC, leading to no performance loss of the cell due to Cr-poisoning. Significantly longer lifetime can be achieved at 750 ºC or lower, which is the target operational temperature regime of IT-SOFCs.
2

Chromium poisoning of cathode in solid oxide fuel cells: mechanisms and mitigation strategies

Wang, Ruofan 02 November 2017 (has links)
Solid oxide fuel cells (SOFCs) have gained renewed interest due to their high energy-conversion efficiency, new discovery of fossil fuel sources, and low greenhouse gas emission. However, performance degradation during long-term operation is one of the greatest challenges to overcome for commercialization of SOFCs. At intermediate temperatures, chromium (Cr) vapor species that form over chromia-forming alloy interconnect, can transport and deposit in the cathode, and poison the cathode performance. Although extensive studies have been conducted on the Cr-poisoning phenomena, the mechanism of cathode performance degradation still needs to be clarified. Therefore, there is an urgent need to understand the degradation mechanisms and develop corresponding mitigation strategies. In this research, anode-supported cells with (La,Sr)MnO3-based cathode were fabricated. The cells were electrochemically tested with and without the presence of chromia-forming alloy interconnect, and operating conditions including cathode atmosphere, current condition, and interconnect contact were varied independently. It was found that both humidity and cathodic current promote chromium poisoning. Microstructural characterizations also confirmed that larger amounts of chromium-containing deposits are present at the cathode/electrolyte interfaces of the cell tested with cathodic current and/or humidity. With the help of free energy minimization calculations, the equilibrium cell potentials for Cr vapor species reductions are estimated and found to be very close to the open-circuit potential of the cell. Combining the experimental and computational results, the roles of humidity and cathodic current in Cr-poisoning are evaluated, and a mechanism associated to Cr vapor species dissociation at the triple-phase-boundaries is proposed. To evaluate the Cr-poisoning effects on cell performance, an analytical polarization model is used for quantitatively separating the contribution of various cell polarizations. By curve-fitting the current-voltage traces to this model, the changes of cathode polarizations due to Cr-poisoning are quantified. Under normal operating conditions, the cathodic activation polarization is determined to be most negatively impacted by Cr-poisoning. Mitigation of the Cr-poisoning effects using a dense lab-developed CuMn1.8O4 spinel interconnect coating was demonstrated. Employing the spinel coated interconnect mesh in on-cell tests, it was found that both the degradation in cell performance and Cr deposition in the cathode are significantly mitigated.

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