This study investigated the overpotential performance enhancement of cathodes in low temperature solid oxide fuel cells (LT-SOFCs) due to the addition of carbonates to traditional Ce0.9Gd0.1O2 solid oxide fuel cell (SOFC) electrolytes. It was postulated in this study that this enhancement was due to the protonic conductivity of the carbonates. This provided an electrolyte with a dual conduction mechanism which improves the catalytic performance of the cathode. The cathode systems investigated were characterised for overpotential loss, conductivity and thermal expansion matching with the electrolyte. This produced results which predicted power outputs for a standard SOFC configuration as high as 970, 524 and 357 mW/cm2 at operational temperatures of 650oC, 600oC and 550oC. The benefits of these high power outputs and their potential to further reduce SOFC operational temperature was discussed. This study developed a cost-effective, reliable and commercially scalable manufacturing process for carbonate/Ce0.9Gd0.1O2 electrolytes. This pressureless sintering method is the first reported in literature, and is a promising replacement for the current hot-pressing technique currently used for these electrolytes. The electrolyte composition examined was 70 wt% Ce0.9Gd0.1O2 with 30 wt% carbonates (67 mol% Li2CO3 / 33 mol% Na2CO3). The cathode examined in this study was a composite cathode consisting of 50-90 wt% functional cathode material (Gd1-xSrxCoO3 with 10 to 30 mol% Sr doping on the Gd site) with a balance of electrolyte. It was determined that the composite cathode system with 10 wt% electrolyte and 20-30 mol% Sr doping was the optimal composition when operating at 600oC and above, with predicted power densities of 524 and 510 mW/cm2 at 600oC. At operational temperatures between 550oC and 600oC (and potentially lower), it was determined that a composite cathode system with 30 wt% electrolyte and 10-30 mol% Sr doping was the optimal composition. It was found that the presence of carbonates in the electrolyte decreased the overpotential losses of the cathode by 50-70% at 600oC for system studied; indicating that an improvement in cathodic performance coupled with the high conductivities of the electrolyte is most likely responsible for the high power outputs seen in literature. / Thesis (Ph.D, Mechanical and Materials Engineering) -- Queen's University, 2009-04-25 15:53:37.928

A steady-state simulation of a diesel-fuelled SOFC system was developed using a process simulation software package (VMGSim). The system was studied by conducting a sensitivity analysis of six independent variables (steam to carbon ratio, oxygen to carbon ratio, fuel utilization, air utilization, reformer pre-heater approach temperature and cathode temperature to the SOFC) and their effect on three response variables (net system efficiency, stack efficiency, system exhaust temperature). The steam to carbon ratio, fuel utilization and air utilization were the most influential independent variables and thus affected the greatest change in the performance metrics. Secondly, a multi-variable study was carried out on the most influential variables and constrained optima for the efficiencies (45% net system, 47% stack) and system exhaust temperature (78 degrees Celsius) were obtained. For the second part of this work, a steam reforming heat-exchange reactor was modeled using COMSOL. The reactor performance was assessed on the basis of selectivity and residence time for a given conversion. Both the kinetic models of Parmar et al. (2010) and Shi et al. (2009) for catalytic diesel steam reforming were applied and compared. Differences in performance were attributed to differences in the catalyst support and the reaction mechanisms used for deriving the reforming rate expressions. Finally, a proof of concept multi-scale modeling and design tool was developed by integrating the CFD model with the process simulation. Two-way communication between four different software components; COMSOL, VMGSim, Matlab and Microsoft Excel was achieved. / Thesis (Master, Chemical Engineering) -- Queen's University, 2012-04-18 01:12:27.072

abstract: The behavior of a solid oxide fuel cell (SOFC) cermet (ceramic-metal composite) anode under reaction conditions depends significantly on the structure, morphology and atomic scale interactions between the metal and the ceramic components. In situ environmental transmission electron microscope (ETEM) is an important tool which not only allows us to perform the basic nanoscale characterization of the anode materials, but also to observe in real-time, the dynamic changes in the anode material under near-reaction conditions. The earlier part of this dissertation is focused on the synthesis and characterization of Pr- and Gd-doped cerium oxide anode materials. A novel spray drying set-up was designed and constructed for preparing nanoparticles of these mixed-oxides and nickel oxide for anode fabrication. X-ray powder diffraction was used to investigate the crystal structure and lattice parameters of the synthesized materials. Particle size distribution, morphology and chemical composition were investigated using transmission electron microscope (TEM). The nanoparticles were found to possess pit-like defects of average size 2 nm after subjecting the spray-dried material to heat treatment at 700 °C for 2 h in air. A novel electron energy-loss spectroscopy (EELS) quantification technique for determining the Pr and Gd concentrations in the mixed oxides was developed. Nano-scale compositional heterogeneity was observed in these materials. The later part of the dissertation focuses mainly on in situ investigations of the anode materials under a H2 environment in the ETEM. Nano-scale changes in the stand-alone ceramic components of the cermet anode were first investigated. Particle size and composition of the individual nanoparticles of Pr-doped ceria (PDC) were found to affect their reducibility in H2 gas. Upon reduction, amorphization of the nanoparticles was observed and was linked to the presence of pit-like defects in the spray-dried material. Investigation of metal-ceramic interactions in the Ni-loaded PDC nanoparticles indicated a localized reduction of Ce in the vicinity of the Ni/PDC interface at 420 °C. Formation of a reduction zone around the interface was attributed to H spillover which was observed directly in the ETEM. Preliminary results on the fabrication of model SOFCs and in situ behavior of Ni/Gd-doped ceria anodes have been presented. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2011

Solid oxide fuel cells with graded electrodes consisting of multiple composite layers yield generally lower polarization resistances than single layer composite electrodes. Optimization of the performance of solid oxide fuel cells with graded electrode composition and/or microstructure requires an evaluation of both the three phase boundary length per unit volume and the effective diffusion coefficient in order to provide insight into how these properties vary over the design space. A numerical methodology for studying the three phase boundary length and effective diffusivity in composite electrode layers with controlled properties is developed. A three dimensional solid model of a sintered composite electrode is generated for which the mean particle diameter, composition, and total porosity may be specified as independent variables. The total three phase boundary length for the modeled electrode is calculated and tomographic methods are used to estimate the fraction of this length over which the electrochemical reactions can theoretically occur. Furthermore, the open porosity of the modeled electrode is identified and the effective diffusion coefficient is extracted from the solution of the concentration of the diffusing species within the open porosity. Selected example electrode models are used to illustrate the application of the methods developed, and the resulting connected three phase boundary length and diffusion coefficients are compared. A significant result is the need for thickness-specific effective diffusivity to be determined, rather than the general volume averaged property, for electrodes with porosity between the upper and lower percolation thresholds. As the demand for current increases, more of the connected three phase boundaries become active, and therefore a greater fraction of the electrode layer is utilized for a given geometry, resulting in a higher apparent effective diffusivity compared to the same electrode geometry operating at a lower current. The methods developed in this work may be used within a macroscopic electrode performance model to investigate optimal designs for solid oxide fuel cell electrodes with stepwise graded composition and/or microstructure. / Applied Science, Faculty of / Mechanical Engineering, Department of / Graduate

A numerical model of the steady state and alternating current behaviour of a solid-oxide fuel cell is presented to explore the possibilities to diagnose and identify degradation mechanisms in a minimally invasive way using impedance spectroscopy. This is the first report of an SOFC impedance model to incorporate degradation, as well as the first one to include the ribbed interconnect geometry, using a 2-D approximation. Simulated degradation modes include: electrode/electrolyte delamination, interconnect oxidation, interconnect/electrode interface detachment, and anode sulfur poisoning. Detailed electrode-level simulation replaces the traditional equivalent circuit approach, allowing the simulation of degradation mechanisms that alter the shape of the current path. The SOFC impedance results from calculating the cell response to a small oscillatory perturbation in potential. Starting from the general equations for mass and charge transport, and assuming isothermal and isobaric conditions, the system variables are decomposed into a steady-state component and a small perturbation around the operating point. On account of the small size of the imposed perturbation, the time dependence is eliminated, and the original equations are converted to a new linear, time independent, complex-valued system, which is very convenient from a numerical viewpoint. Geometrical and physical modifications of the model simulate the aforementioned degradation modes, causing variations in the impedance. The possibility to detect unique impedance signatures is discussed, along with a study of the impact of input parameter inaccuracies and parameter interaction on the presented results. Finally, a study of pairs of concurrent degradation modes reveals the method’s strengths and limitations in terms of its diagnosis capabilities. / Applied Science, Faculty of / Mechanical Engineering, Department of / Graduate

Ce travail de thèse se situe dans la thématique des oxydes dérivés de la pérovskite ayant des propriétés de conduction mixte tels que les structures de type K2NiF4, les pérovskites doubles et la brownmillérite. Cette aptitude à conduire à la fois l'oxygène et les électrons présente un intérêt pour des dispositifs électrochimiques fonctionnant à haute température et notamment en tant qu'électrode pour les piles à combustible à oxyde solide. Plus précisément, cette thèse concerne la synthèse et l'étude cristallochimique avancée de la réactivité de ces matériaux essentiellement par les grands instruments par le biais de la diffraction de neutrons (NPD) et des rayons X synchrotron. Le travail préliminaire à ces études implique de la synthèse inorganique par voie solide ou par voie sol-gel, l'analyse thermogravimétrique et la titration iodométrique. Des cellules de réactivité originales ont été développées spécialement à l'ISCR pour l'étude in situ du comportement redox sous différents flux gazeux et en fonction de la température à la fois dans le cadre de la diffraction des neutrons et rayons X synchrotron. L'étude in situ par NPD des composés La2-xSrxMnO4±δ où x = 2,0 et x = 0,8 qui dérivent du composé de cathode de référence La1-xSrxMnO3 a permis de suivre l'évolution structurale en fonction du δ en conditions réductrices pour x = 2,0 et en conditions oxydantes pour x = 0,8. L'étude DRX synchrotron de Pr2NiO4,22 a permis de mettre en évidence la symétrie monoclinique à température ambiante alors que les études précédentes annonçaient une symétrie orthorhombique. Les variations structurales notamment la transition vers la phase HTT sont accompagnées d'une modulation incommensurable qui persiste jusqu'à au moins 900 °C. L'étude des pérovskites doubles NdBaCo2−xMnxO5+δ où 0 ≤ x ≤ 2 a permis de montrer que ces matériaux présentent des conductivités électriques totales très prometteuses pour des applications en tant que cathode de SOFC. De plus, la confrontation de la dynamique moléculaire et de la NPD combinée à la MEM pour le composé x = 0 a permis d'élucider le mécanisme de diffusion de l'oxygène dans cette famille de composés. L'étude par NPD de la réduction de LaSrFeCoO6 vers LaSrFeCoO5 de structure brownmillérite a permis de mettre en évidence que la structure réduite persiste à haute température et l'évolution de la mise en ordre des moments magnétiques lors du refroidissement de LaSrFeCoO5. / This thesis is focused on oxides related to perovskite such as K2NiF4 structure-type, double perovskite and brownmillerite with mixed conduction properties. This ability to conduct both oxygen ions and electrons is relevant for electrochemical devices operating at high temperature, particularly as an electrode for solid oxide fuel cell. Specifically, this thesis deals with the synthesis and advanced crystal structure characterization of the reactivity of these materials mainly through large scale facilities by means of neutron powder diffraction (NPD) and X-ray synchrotron. Preliminary work in these studies involves inorganic synthesis by solid-state or by sol-gel route, thermogravimetric analysis and the iodometric titration. Original reactivity cells have been developed at the ISCR to study redox behavior under different gas flow and as a function of temperature for both neutron diffraction and X-ray synchrotron experiment. In situ study by NPD of La2-xSrxMnO4 ± δ compounds where x = 2.0 and x = 0.8 which derived from the compound cathode reference La1-xSrxMnO3 allowed to follow the structural evolution as a function of δ in reducing conditions for x = 2.0 and oxidizing conditions for x = 0.8. The synchrotron study of Pr2NiO4.22 helped to highlight the monoclinic symmetry at room temperature while previous studies announced an orthorhombic symmetry. Besides, structural changes including the transition to the HTT phase are accompanied by an incommensurable modulation that persists at least up to 900 °C. The study of double perovskites NdBaCo2-xMnxO5+δ where 0 ≤ x ≤ 2 showed that these materials exhibit a promising electrical conductivities for SOFC applications as cathode. In addition, the comparison of the molecular dynamics and NDP combined with MEM for x = 0 compound has elucidated the oxygen diffusion mechanism in these compounds. The study by NPD in reducing condition of LaSrFeCoO6 to the brownmillerite LaSrFeCoO5 has showed that the reduced structure persists at high temperatures and allowed to follow the evolution in the ordering of the magnetic moments while cooling LaSrFeCoO5.

京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第22859号 / 人博第967号 / 新制||人||229(附属図書館) / 2020||人博||967(吉田南総合図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 内本 喜晴, 教授 吉田 寿雄, 准教授 戸﨑 充男 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

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京都大学 / 新制・課程博士 / 博士(工学) / 甲第23192号 / 工博第4836号 / 新制||工||1755(附属図書館) / 京都大学大学院工学研究科航空宇宙工学専攻 / (主査)教授 吉田 英生, 教授 江口 浩一, 教授 岩井 裕 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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