Master Thesis, Department of Mechanical Engineering / A comprehensive analytical model of an indirect internal reforming type tubular Solid Oxide Fuel Cell (IIR-T-SOFC) has been developed. Two-dimensional axisymmetric multicomponent gas flow fields and quasi-three-dimensional electric potential/current fields in the tubular cell are simultaneously treated in the model with consideration of the involved phenomena such as internal reforming, electrochemical reactions and radiative heat transfer. By using this model, the characteristics of the operating state of an IIR-T-SOFC were numerically examined. As a result, it was shown how the thermal field and power generation characteristics of the cell were affected by the gas inlet temperature, air flow rate, steam-methane ratio, reforming catalyst distribution and thickness of the electrodes. In particular, the optimized catalyst distribution greatly reduced both the maximum temperature and temperature gradients of the cell with little negative impact on the power generation performance of the cell. / 京都大学 / 0048 / 修士 / 修士(工学) / Kyoto University / TFtmp

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23577号 / 工博第4932号 / 新制||工||1770(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 江口 浩一, 教授 阿部 竜, 教授 岩井 裕 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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No / Traditionally materials with the fluorite and perovskite structures have dominated the research in the area of oxide ion/proton conducting solid electrolytes. In such cases, the key defects are oxide ion vacancies, and conduction proceeds via a simple vacancy hopping mechanism. In recent years, there has been growing interest in alternative structure types, many of which contain tetrahedral moieties. For these new systems, an understanding of the accommodation of defects and the nature of the conduction mechanism is important for the optimisation of their conductivities, as well as to help target related structures that may display high oxide ion/proton conduction. Computer modelling studies on a range of systems containing tetrahedral moieties are presented, including apatite-type La9.33+xGe6O26+3x/2, cuspidine-type La4Ga2-xTixO9+x/2 and La1-xBa1+xGaO4-x/2. The type of anion defect (vacancy or interstitial), their location and the factors affecting their incorporation are discussed. In addition, modelling data to help to understand their conduction mechanisms are presented, showing novel aspects including the important role of the tetrahedral moieties in the conduction processes.

No / Traditionally materials with the fluorite and perovskite structures have dominated the research in the area of oxide ion/proton conducting solid electrolytes. In such cases, the key defects are oxide ion vacancies, and conduction proceeds via a simple vacancy hopping mechanism. In recent years, there has been growing interest in alternative structure types, many of which contain tetrahedral moieties. For these new systems, an understanding of the accommodation of defects and the nature of the conduction mechanism is important for the optimisation of their conductivities, as well as to help target related structures that may display high oxide ion/proton conduction. Computer modelling studies on a range of systems containing tetrahedral moieties are presented, including apatite-type La9.33+xGe6O26+3x/2, cuspidine-type La4Ga2¿xTixO9+x/2 and La1¿xBa1+xGaO4¿x/2. The type of anion defect (vacancy or interstitial), their location and the factors affecting their incorporation are discussed. In addition, modelling data to help to understand their conduction mechanisms are presented, showing novel aspects including the important role of the tetrahedral moieties in the conduction processes

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.

This study presents a detailed gas-phase and surface kinetic model for n-tetradecane autothermal reforming to deconvolute the complex reaction network that provides the mechanistic understanding of reforming chemistry in a packed-bed reactor. A thermodynamic analysis study for diesel reforming was performed to map the carbon formation boundary for various reforming processes. Through a Langmuir-Hinshelwood-Hougen-Watson (LHHW) type of kinetic model, which was derived using a simple mechanistic study, the need for a detailed kinetic study including both gas-phase reactions and surface reactions was identified. Pt-CGO (Pt on Gd doped CeO2) and Rh-pyrochlore catalysts were synthesized and characterized. In an accelerated test for reforming of commercial-diesel, Rh-pyrochlore catalyst showed stable performance for 24 hrs, whereas Pt-CGO catalyst deteriorated in 4 hrs. Minimum structural change in Rh-pyrochlore catalyst compared to Pt-CGO catalyst was observed using redox experiments. An experimental kinetic study with an inert silica bed provided clear evidence that the gas-phase reactions are important to the kinetics of hydrocarbon reforming. “Reaction Mechanism Generator” (RMG) software was employed to generate a detailed gas-phase kinetic model containing nine thousand three hundred and forty-seven elementary reactions and four hundred and fifty-nine species. The model was validated against n-tetradecane ignition delay data, and inert bed autothermal reforming data. The RMG model was also extended to capture the high pressure and low temperature pyrolysis chemistry to predict pyrolysis experimental data. The reactor simulation using the RMG model identified the detailed chemistry of the reactions in the pre-catalytic zone. Gas-phase oxidation/pyrolysis converts the heavier hydrocarbons and oxygen in the pre-catalytic zone to lower molecular weight products prior to reaching the catalyst surface. The steam reforming reactions that are dominant on the surface of the catalyst primarily involve lower molecular weight oxidation/pyrolysis products. A multi-component micro-kinetic model containing two hundred and seventy surface reactions and fifty-two adspecies was developed using a semi-empirical Unity Bond Index-Quadratic Exponential Potential (UBI-QEP) method. Transition State Theory estimates were used for elementary reactions up to C3 species, and simple fragmentation reactions were assumed for higher hydrocarbon species. Model simulations indicated on the catalyst surface that hydrogen is initially produced by the water-gas-shift reaction and subsequently by steam reforming reactions. A major reaction path for ethylene formation from 1,3 butadiene in the post-catalytic zone of the reactor was also identified. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2013-04-24 13:23:31.163

Solid oxide fuel cells represent a potentially important application for ceramic materials. There are, however, some significant issues which can affect the reliability and durability of the cell. Mechanical failure owing to stress is one of the critical factors which can affect the stability and working life of the fuel cell stacks. These stresses generate in Solid Oxide Fuel Cells (SOFCs) owing to mechanical forces and change in temperature during fabrication, assembly and operating conditions. There can be chances of cell delamination and micro-cracks in cell electrodes if these stresses are too high. The elastic properties and thermal expansion coefficient play a vital role to improve cell stability and performance. These properties depend on the types of materials and geometries of the composites. In this research, a numerical framework to predict the effective elastic properties and the effective thermal expansion coefficient for porous Yttria-Stabilized Zirconia (YSZ) electrode microstructures in a Solid Oxide Fuel Cell is presented. The electrodes of Solid Oxide Fuel Cells are discretized as porous microstructures that are formed by randomly distributed and overlapping spheres with particle size distributions that match those of actual ceramic powder. Three-dimensional (3D) microstructures of YSZ-pore are formed with a porosity ranging from 25% to 40%. The technique involves the construction of the YSZ-pores microstructures based on measurable starting parameters and subsequent numerical prediction of effective elastic properties and effective thermal expansion coefficient. Three domain sizes are considered for the generation of YSZ-pore microstructures. The method of prediction of effective Young’s modulus (Eeff), effective Poisson’s ratio , effective bulk modulus effective shear modulus , and effective thermal expansion coefficients for various porosities (P) of Yttria-Stabilized Zirconia (YSZ) electrode material in Solid Oxide Fuel Cells is based on the Finite Volume analysis which in turn is based on the solution of the linear elastic stress analysis problem. The predicted results are compared with some theoretical correlations of two-phase composites for effective elastic properties and effective thermal expansion coefficient. It has been found that predicted results are falling inside of the upper and lower bounds. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2013-10-01 17:01:05.068

In this study, Lithium iron oxide (LiFeO₂ – LFO) was investigated as a new anode material for the high temperature SOFCs. From the DC conductivity measurement in argon containing 5% H₂, LFO exhibits good electronic conductivity of 5.08 Scm⁻¹ at 650 °C. LFO poses a high TEC value of 19.5 x 10⁻⁶ K⁻¹ in air. However, the TEC values of the commonly used 8YSZ and CGO electrolytes are much lower, 10.5 x 10⁻⁶ K⁻¹ and 12.5 x 10⁻⁶ K⁻¹ respectively. In order to resolve the mismatch in the TEC values between the electrode and the electrolyte, button fuel cells were fabricated via tape casting. LFO was infiltrated onto the porous and stable scaffold. Presently, the predominant electrolyte material used for the high temperature SOFC is 8YSZ. Due to this reason, the initial performance of LFO as an anode material was tested on tape-cast 8YSZ electrolyte-supported cell. The 8YSZ electrolyte-supported infiltrated with 30 wt% LFO for the anode and 40 wt% LSF for the cathode achieved a maximum power density of 50 mWcm⁻² at 700 °C in humidified H₂. Increasing the weight loading of LFO to 40 wt% worsen the performance. XRD pattern of the sintered powder containing 50 wt% LFO and 50 wt% 8YSZ confirmed that LFO and 8YSZ react with each other. CGO was considered as an alternative electrolyte material to 8YSZ. XRD pattern of the sintered powder containing 50 wt% LFO and 50 wt% CGO confirmed that they are compatible with each other. The CGO electrolyte supported cell infiltrated with 40 wt% LFO for the anode and 40 wt% LSC for the cathode achieved a maximum power density of 180 mWcm⁻² at 650 °C in humidified H₂. The addition of 10 wt% ceria to the LFO anode enhances the electrochemical activities of the cell. However, the overall performance of the cell decreased due to a larger increase in the series resistance. Since CGO electrolyte is easily reduced when testing at temperature higher than 550 °C, LSGM was used to increase the testing temperature. The 245 µm thick LSGM electrolyte-supported cell infiltrated with 40 wt% LSC and 30 wt% LFO obtained a maximum power density of 227 mWcm⁻² at 700 °C in humidified H₂. Decreasing the electrolyte thickness from 245 µm to 130 µm increased the performance of the cell. The 130 µm LSGM electrolyte-supported cell infiltrated with 40 wt% LSC and 30 wt% LFO was tested with the carbon/carbonate fuel as a HDCFC. Performance measurements of the cell was conducted at 650 °C and 700 °C with N₂ flowing at 20 ml/min. The cell performed better when testing at higher temperature. Recently, there has been great interest in developing a SOFC system for the cogeneration of electricity and valuable C₂ chemicals. The catalytic testing for oxidative methane coupling of methane revealed a high C₂ selectivity for the LFO powder. Cell testing of a sample infiltrated with 40 wt% LSC and 30 wt% LFO also achieved a methane conversion of ~3% and a C₂ selectivity of ~80% in methane at 700 °C.