Les recherches scientifiques sur la pile à combustible échangeuse de protons (PEMFC) ont, jusqu’il y a peu, concerné presque exclusivement les aspects fondamentaux liés à l’électrochimie, particulièrement la conception, le dimensionnement, les performances et le diagnostic. Récemment, les objectifs de durée de vie ont ouvert un nouvel axe de recherche sur le comportement mécanique de la PEMFC devant conduire à son optimisation statique et dynamique. Parallèlement les installations vibroclimatiques de la plateforme d’essais « Systèmes Pile à Combustible » de Belfort ont été développées. La thèse de Vicky ROUSS soutenue en 2008 montre l’intérêt et le potentiel de la modélisation type « boîte noire » pour simuler le comportement mécanique de la PEMFC, et de la technique des signatures mécaniques expérimentales pour mettre en évidence la présence des phénomènes physiques à l’intérieur de la PEMFC. Dans ce contexte les travaux de la présente thèse ont concerné le pilotage des essais de durabilité par simulation boîte noire temps réel et l’exploitation de cette dernière en vue de la découverte des phénomènes physiques à l’intérieur de la PEMFC. La modélisation par réseaux de neurones des systèmes simples de type oscillateur harmonique a représenté le premier pas pour la définition d’un modèle neuronal de pilotage des essais de durabilité en temps réel. Le cas du système mécanique excité par la base qui correspond à une pile à combustible fixée sur la plateforme vibratoire, a été considéré. L’architecture neuronale optimale a été définie en plusieurs étapes en utilisant différents algorithmes. Elle utilise en entrée le signal de commande du système et la réponse mesurée sur la pile à combustible au moment t et en sortie on obtient la réponse prédite du comportement de la pile à combustible au moment t+1. Cette architecture a été mise au point et validée par des essais sur la plateforme. D’autres essais ont permis de mettre en évidence différents comportements de la pile à combustible en fonction de l’amplitude de sollicitation, de la pression et de la température de la pile à combustible. Les signatures mécaniques obtenues réalisées à partir des essais de durabilité complètent la bibliothèque de signatures déjà existante et mettent en évidence de nouveaux comportements de la pile à combustible. / Scientific research on cell proton exchange fuel cells (PEMFC) have, until recently, almost exclusively concerned fundamental aspects of electrochemistry, particularly the design, sizing, the electrochemical performance and diagnostics. Recently, the objectives of life cycle have opened a new direction of research on the mechanical behavior of the PEMFC leading to its static and dynamic optimization. At the same time new environmental facilities of the test platform "Fuel Cell Systems" at Belfort are developed. Vicky ROUSS thesis sustained in 2008 shows the importance and the potential of the black box modeling to simulate the mechanical behavior of the PEMFC and experimental mechanical signatures to highlight the presence of physical phenomena inside PEMFC. In this context the work of this thesis concerned the monitoring of durability tests by simulation and real-time black-box operation to explore the physical phenomena inside the PEMFC. Modeling neural networks simple systems such as harmonic oscillator represented the first step towards the definition of a neural control model of real time environmental tests. Then, it was considered the case of the harmonic oscillator excited by the base, which corresponds to the fuel cell mounted on the vibration platform. The optimal neural architecture has been defined in several stages using different algorithms. This architecture uses as input the control signal of the system and the measured signal on the fuel cell at the time t and as output the predicted response behavior of the fuel cell at time t+1. This architecture has been developed and validated by tests on the platform. Other tests have allowed demonstrating the different behavior of the fuel cell in accordance with the amplitude of solicitation, the pressure and temperature of the fuel cell. Mechanical signatures made from tests complete the existing library of signatures and demonstrate new behaviors of the fuel cell.

Ces dernières années, la pile à combustible à membrane échangeuse de proton (PEMFC) a fait l’objet d’un intérêt particulier pour des applications liées au transport. De par le fait qu’elle fonctionne à une température de fonctionnement relativement basse (50-100°C) combiné à une membrane polymère solide empêchant tout risque de fuite. Dans ce travail, des expérimentations ont été effectuées pour démontrer que la distribution de température à une influence significative sur les performances de la PEMFC. Par ailleurs, ce travail comporte une analyse ayant pour but de d’indiquer une amélioration de la résistivité ionique de la membrane, de la vitesse de réaction et de la diffusion des gaz en fonction de la température. Des expérimentations sur une cellule puis sur un stack complet ont permis d’évaluer l’impact de la température à l’aide d’un modèle 3D développé simulant les performances de la pile en relation avec la distribution de température. Dans cette thèse, deux piles à combustible ont permis de valider le comportement et d’en déduire une relation entre la tension de sortie et la distribution de température dans différentes conditions de fonctionnement. Une étude expérimentale prenant en compte la tension et la température a été effectuée sur une cellule en mesurant la température et le voltage en douze points à l’aide de thermocouples et de sonde de tension. Le modèle 3D proposé permet ainsi d’améliorer la durée de vie d’une pile ainsi que sa fiabilité, il permet aussi d’effectuer un diagnostic et de détecter en ligne un défaut. Ceci est effectué en calculant la densité de courant localement à différentes conditions de fonctionnement en utilisant la méthode de Newton Raphson. De par le développement de ce modèle sensible à un défaut, un algorithme de détection de défaut ainsi que la stratégie de diagnostic ont été développé en utilisant des réseaux de neurones artificiels (RNN). Ces derniers ont été utilisés pour la classification supervisée de défaut permettant ainsi le diagnostic. / In recent years, according to the upcoming challenge of pollution, fuel saving, to use on FCEV is increasing. It can be that fuel cell power train divided in the PEMFC, Batteries, DC/DC converters, DC/AC inverters and electrical motors. The Proton Exchange Membrane Fuel cells (PEMFC) have consistently been considered for transportation application. Characteristic features of PEMFC include lower temperature (50 to 100 °C) and solid polymer electrolyte membrane. In this work, experiments have shown that the temperature distributions can significant influence on the performance of the PEMFC. Also analytical studies have indicated improvement of ionic resistivity of the electrolyte membrane, kinetics of electrochemical reaction and gas diffusion electrodes have directly related to temperature. This work evaluated the effectiveness of temperature on a single and stack fuel cell. In addition, a 3D model is developed by effective of temperature on performance on the fuel cell. In this thesis, two PEM fuel cells have been considered to find out the relationship and analyze the behaviors of the cell voltage and temperature distributions under various operating conditions. An experimental study for voltage and temperature has been executed, using one cell, 12 thermocouples and 12 voltage sensors have been installed at different points of the cell. In this work a new model was proposed to improve the lifetime and reliability of the power train and to detect online faults. Besides, current distributions in different points of the cell based on varying operating conditions are calculated by the Newton Raphson method. On the basis of the developed fault sensitive models above, an ANN based fault detection; diagnosis strategy and the related algorithm have been developed. The identified patterns ANN have been used in the supervision and the diagnosis of the PEMFC drivetrain. The ANN advantages of the ability to include a lot of data made possible to classify the faults in terms of their type.

La pile à combustible est un générateur électrique qui s'appuie sur un effet électrochimique découvert au 19èmesiècle par Christian Schönbein. Cette technologie a connu des périodes de développement et de désintéressementsuccessives jusqu'à nos jours. Suite à une flambé du prix du baril de pétrole et à la sensibilisation des populationsaux problèmes environnementaux engendrés par les rejets de gaz à effet de serre, la quantité annuelle depublications sur la pile à combustible a augmenté d'une manière continue. Son rendement, souvent supérieur àcelui des technologies de production d'énergie par combustion, et la possibilité d'utiliser des carburants non fossileset non polluants en font un candidat de substitution attractif. Cependant, son cout, sa durée de vie, sa puissancemassique et d'autres problèmes liés au stockage de son carburant ne lui permet pas de détrôner les technologiesactuelles qui sont bien rodées et qui profitent d'une économie d'échelle. Il faut donc continuer à améliorer la pile àcombustible pour qu'elle devienne un jour économiquement viable.L'une des voies pour atteindre cet objectif, est la modélisation qui permet une réflexion, une meilleurecompréhension de la pile à combustible, ainsi que la possibilité de tester des idées à moindre cout.Malheureusement, la pile à combustible est un système complexe combinant des phénomènes fluidique, thermiqueet électrochimique. Des modèles en 1 dimension et en temps réels ont déjà été développés. Mais pour étudiercorrectement ce qui se passe à l'intérieur, il faut au moins disposer d'un modèle en 2 dimensions. Cependant lesmodèles en 2 dimensions demandent des méthodes de calcul par éléments finis qui nécessitent des ressources decalcul importantes, ainsi, jusqu'ici, ils ne permettaient pas de réaliser des calculs en temps réel. C'est pourtant ledéfi relevé par cette thèse : développer un modèle en deux dimensions ou plus et être capable de le faire tourner entemps réel sur un ordinateur comme sur un processeur embarqué.Pour arriver à cette performance, les concepts physiques, mathématiques et informatiques ont été combinés etintégrés grâce à des astuces organisationnelles en un programme en langage C, peu gourmand en mémoire et enpuissance de calculs. Toutes les hypothèses simplificatrices et les méthodes mathématiques modifiées etimplantées selon des schémas informatiques peu communément utilisés dans ce domaine ont fait apparaitre denouveaux problèmes. Des nouvelles méthodes de calculs ont dû alors être développées pour gérer ces nouveauxproblèmes.Finalement, un modèle de pile à combustible multidimensionnel et temps réel a été conçu et ses paramètresphysiques ont été ajustés par un programme pour faire correspondre les résultats à ceux d'une pile à combustibleréelle sur laquelle des essais ont été réalisés. Les résultats obtenus ont été analysés à l'aide d'un procédéd'observation structuré. Le résultat de ces observations a permis d'arriver à des conclusions dans le domaine de lamodélisation multidimensionnelle et multiphysique de la pile à combustible pour des applications en temps réel. / The fuel cell is an electric generator which uses an electrochemical effect discovered in 18 century by ChristianSchönbein. This technology has gotten successively periods of development and periods of void in the pastdecades. After the petrol barrel price rising and the people¿s awareness of environmental problem such asgreenhouse effect, the research in fuel cell field has been increasing constantly. Its higher efficiency compared tothermal technology to produce electricity, the possibility to use no fossil fuel and no pollution final products make thefuel cell an attractive substitution candidate for energy production. However, its cost, life time, power density andother problems related to the fuel storage do not allow it to replace immediately the actual technology which is elderand benefit about scale economy effect. Thus, the fuel cell technology must be improved to become economicallyviable.One of the ways to do it, is to model the fuel cell in order to reflect, analyze and better understand its behavior with aminimal cost. Unfortunately, the fuel cell is a complex system which combines fluidic, thermic and electrochemicaleffects. In literature, many one dimensional real time models have been developed. But to analyze and predict localphenomena, a 2 dimensional model is needed. However, the general two dimensional models use finite elementcalculation methods that cannot be done in real time due to their complex mathematical calculation. In spirit toovercome this calculation complexity problem, the challenge of this thesis is defined: develop a 2 dimensional modelwho are able to be executed in real time on an ordinary computer or an embedded system.In order to achieve the desired real time performance, the physical, mathematical and computer concepts of realtime 2D fuel cell model are developed, combined and integrated with specific organization methods in a C languageprogram which does not requires an important calculation power or memory to run. All the modeling assumptionsand the modified mathematic methods are implanted following an innovative modeling approach.Finally, a 2D, multiphysique, multidimensional real time fuel cell model is developed and its parameters are adjustedwith a real fuel cell stack from different experiments. The results are then analyzed with a structured observationmethod with conclusions given at last.

Ce travail a été réalisé dans le cadre du projet Systèmes Mécaniques Adaptatifs (SMA)du laboratoire mécatronique M3M de l’UTBM impliqué dans l’institut FCLAB de recherche sur les systèmes pile à combustible et du projet de l’équipe de recherche «Modélisation Multiphysique », en cours de constitution, du département Sciences et Technologies de l’USEK. Les PEMFC font l’objet de nombreuses recherches pour augmenter leurs performances et diminuer leur coût mais la plupart des études se concentrent sur leurs aspects physicochimiques.Cette thèse par contre se propose de mettre en évidence l’influence, sur la production d’énergie, des sollicitations mécaniques statiques, dynamiques voire thermiques (serrages, vibrations, frottements, …) comme phénomènes couplés relevant du domaine multiphysique (interactions fluide-structure, électrique …). En premier, une analyse des différents paramètres de modèles dépendant des aspects mécaniques a été effectuée et les principaux paramètres à étudier dans le cadre de cette thèse ont été sélectionnés : porosité, perméabilité et coefficients de diffusion de la GDL, conductivité électrique du contact GDL/PB et volume des canaux après compression de la cellule. Ensuite, un modèle partiel de représentation mécanique de la GDL d’une PEMFC du côté cathode a été mis en oeuvre afin de déterminer la déformation de la GDL comprimée par une force répartie sur la PB. Sur la base des contraintes mécaniques calculées dans la GDL, les champs locaux de porosité, de perméabilité et de résistance électrique de contact GDL/PB sont obtenus. D’autre part, une modélisation 3D de type volumes finis pour l’étude de la pression du fluide à l’interface GDL/PB a été élaborée. L’analyse a permis de déterminer le champ local de pression d’oxygène sur l’interface GDL/PB du côté cathode. Les champs locaux de porosité et de perméabilité de la GDL, de résistance électrique de contact GDL/PB et de pression d’interface GDL/PB sont alors introduits dans le modèle multiphysique 2D d’une cellule de pile PEMFC. Une étude détaillée du comportement de la pile et de la modification de sa performance a pu être réalisée. Les résultats ont été présentés sous forme de courbes de polarisation et de densité de puissance. Finalement tous les résultats ont été rassemblés pour une analyse d’influence et de sensibilité afin d’identifier les paramètres qui auront le plus d'influence sur les variables simulées. Cette étude peut s'avérer un outil fort utile à la prise de décision concernant la géométrie de la dent des PB, la nature des PB, … / Most of the studies related to PEMFC emphasize on their physico-chemical aspects. The present study is concerned by the modeling for which a multiphysical coupling is primary for the balance of the energetic performance of the fuel cell. An analysis for the different parameters that depend on mechanical aspects is done and the major parameters for study are selected : prosity, permeability, diffusion coefficients of the GDL, electrical conductivity of the contact GDL / BP and volume of the channels after compression of the cell. The rectangular sections of graphite BP and trapezoid sections with or without a radius of curvature for steel BP are chosen. A partial model for the mechanical representation of the GDL of a PEMFC from the cathode side is first implemented in order to determine the deformation of the GDL induced by a uniformly distribued force. On the base of the mechanical constraints that are calculated in the GDL, the local fields of porosity abd contact resistance GDL / BP are obtained.The local field of the oxygen pressure on the GDL from the cathode side is determined by a 3D modeling. The local fields of GDL porosity, electrical contact resistance GDL / BP and pressure at the interface GDL / BP are then introduced in the 2D multiphysical model of the fuel cell. The results are presented as polarization and power density curves.Finally, all the results are gathered for an analysis of influence and sensibility in order to identify the parameters that wil have the bigger influence on the simulated variables.

Solid Oxide Fuel Cells (SOFCs) are devices that directly convert chemical energy into electrical energy, without proceeding through a Carnot combustion cycle. These devices are based on the usage of solid oxide electrolytes operating at relatively elevated temperatures. Two major hurdles must be overcome in order to decrease the operating temperatures of practical SOFCs. The first relates to reducing ohmic losses within solid electrolytes. The second relates to the need for developing high performance electrodes since electrolyte reaction rates at both anode and cathode are affected detrimentally as operating temperatures fall. This PhD project has focussed on addressing the first hurdle in two innovative ways: 1. the implementation of solid electrolytes with higher ionic conductivity than zirconia, 2. the development of very thin film electrolytes as thick as 5ƒÝm. Several thin films with novel electrode-electrolyte structures were fabricated and evaluated in order to demonstrate the viability of low temperature SOFC operations. Development of such thin films was innovative and challenging to achieve. The approach taken in this work involved fabricating a dense and thin gadolinia doped ceria (10GDC - Gd 10wt%, Ce 90wt%) oxide electrolyte. 10GDC is an electrolyte exhibiting higher conductivities than conventional materials during low temperature operations. A research contribution of this PhD was the demonstration of the deposition of 10GDC thin films using RF magnetron sputtering for the first time. 10GDC thin film electrolytes with thickness in a range between 0.1 to 5ƒÝm were fabricated on 10 yttrium stabilised zirconium (10YSZ) substrates by using a RF magnetron sputterer. The primary parameters controlling 10GDC thin film deposition using this method were explored in order to identify optimal conditions. The fabricated films were subsequently analysed for their morphology, composition and stoichiometry using a variety of methods, including Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Spectrometry (EDS), optical microscopy, X-ray Photoelectron Spectroscopy (XPS), and X-ray Diffraction (XRD). A preliminary test was conducted in order to examine the function of 10GDC thin film electrolytes together with the cathode and anode substrates at intermediate temperatures (700oC). A complete planar single cell was designed and assembled for this purpose. However, when fully assembled and tested, the cell failed to generate any voltage or current. Consequently, the remainder of the PhD work was focused on systematically exploring the factors contributing to the assembled fuel cell failure. As fabrication failure analysis is seldom reported in the scientific literature, this analysis represents a significant scientific contribution. This analysis proceeded in a series of steps that involved several different methods, including SEM, red dye analysis, surface morphology and cross section analysis of the cell. It was found that pinholes and cracks were present during the fuel cell operating test. Cathode delamination was also found to have occurred during the test operation. This was determined to be due to thermal expansion mismatch between the cathode substrate and the 10GDC electrolyte thin film. A series of suggestions for future research are presented in the conclusion of this work.

<p>Computational methods are combined with synchrotron-based techniques to analyze the structure and bonding of water and water plus hydroxyl at metal surfaces under UHV and at near-ambient conditions. Water-metal interaction plays a crucial role in a multitude of cosmic, atmospheric and biological phenomena as well as heterogeneous catalysis, electrochemistry and corrosion. A spotlight of renewed interest has recently been cast on water-metal systems due to their relevance for surface chemical reactions related to the production and utilization of hydrogen as a clean energy carrier. In particular, H2O and OH are essential reaction intermediates in the renewable production of hydrogen from sunlight and water and in fuel cell electrocatalysis.</p><p>Fuel cells are considered one of the most promising power generation technologies for a sustainable energy future. A mechanistic understanding of the oxygen reduction reaction (ORR) pathway, including the role of electronic and geometric structure of the catalyst, is essential to the design of more efficient fuel cell catalysts. This is intimately connected to fundamental factors that affect the ability to form water-metal bonds as well as the site occupation and orientation of the adsorbed H2O and OH at active metal surfaces.</p><p>Key relationships related to critical issues in the fuel cell reaction are illuminated by the synergy of theory and experiment in this thesis. We emerge with a detailed understanding of the structure of the water-metal interface and the factors that rule the wettability of a metal surface, including geometric and electronic structure effects and the influence of coadsorbed species. We show that the preferred microscopic orientation of the water monolayer has consequences for macroscopic properties, and reveal the origin of the hydrophobic water layer. Finally, we identify a cooperativity effect that drives the stability of the mixed water/hydroxyl layer at metal surfaces, an important ORR intermediate.</p>

Microbial electrochemical systems (MESs) have attracted much research attention in recent years due to their promising applications in renewable energy generation, bioremediation, and wastewater treatment. In a MES, microorganisms interact with electrodes via electrons, catalyzing oxidation and reduction reactions at the anode and the cathode. The bacterial community of a high power mixed consortium MESs (maximum power density is 6.5W/m��) was analyzed by using denature gradient gel electrophoresis (DGGE) and 16S DNA clone library methods. The bacterial DGGE profiles were relatively complex (more than 10 bands) but only three brightly dominant bands in DGGE results. These results indicated there are three dominant bacterial species in mixed consortium MFCs. The 16S DNA clone library method results revealed that the predominant bacterial species in mixed culture is Geobacter sp (66%), Arcobacter sp and Citrobacter sp. These three bacterial species reached to 88% of total bacterial species. This result is consistent with the DGGE result which showed that three bright bands represented three dominant bacterial species. Exoelectrogenic bacterial strain SX-1 was isolated from a mediator-less microbial fuel cell by conventional plating techniques with ferric citrate as electron acceptor under anaerobic conditions. Phylogenetic analysis of the 16S rDNA sequence revealed that it was related to the members of Citrobacter genus with Citrobacter sp. sdy-48 being the most closely related species. The bacterial strain SX-1 produced electricity from citrate, acetate, glucose, sucrose, glycerol, and lactose in MFCs with the highest current density of 205 mA/m�� generated from citrate. Cyclic voltammetry analysis indicated that membrane associated proteins may play an important role in facilitating electron transfer from the bacteria to the electrode. This is the first study that demonstrates that Citrobacter species can transfer electrons to extracellular electron acceptors. Citrobacter strain SX-1 is capable of generating electricity from a wide range of substrates in MFCs. This finding increases the known diversity of power generating exoelectrogens and provids a new strain to explore the mechanisms of extracellular electron transfer from bacteria to electrode. The wide range of substrate utilization by SX-1 increases the application potential of MFCs in renewable energy generation and waste treatment. Anode properties are critical for the performance of microbial electrolysis cells (MECs). Inexpensive Fe nanoparticle modified graphite disks were used as anodes to preliminarily investigate the effects of nanoparticles on the performance of Shewanella oneidensis MR-1 in MECs. Results demonstrated that average current densities produced with Fe nanoparticle decorated anodes were up to 5.9-fold higher than plain graphite anodes. Whole genome microarray analysis of the gene expression showed that genes encoding biofilm formation were significantly up-regulated as a response to nanoparticle decorated anodes. Increased expression of genes related to nanowires, flavins and c-type cytochromes indicate that enhanced mechanisms of electron transfer to the anode may also have contributed to the observed increases in current density. The majority of the remaining differentially expressed genes were associated with electron transport and anaerobic metabolism demonstrating a systemic response to increased power loads. The carbon nanotube (CNT) is another form of nano materials. Carbon nanotube (CNT) modified graphite disks were used as anodes to investigate the effects of nanostructures on the performance S. oneidensis MR-1 in microbial electrolysis cells (MECs). The current densities produced with CNT decorated anodes were up to 5.6-fold higher than plain graphite anodes. Global transcriptome analysis showed that cytochrome c genes associated with extracellular electron transfer are up-expressed by CNT decorated anodes, which is the leading factor to contribute current increase in CNT decorated anode MECs. The up regulated genes encoded to flavin also contribute to current enhancement in CNT decorated anode MECs. / Graduation date: 2013

This work is focused on a state-of-the-art tubular micro-solid oxide fuel cell (TSOFC), ~3 millimeters in diameter and ~300 microns thick, with Ni/YSZ and LSM/YSZ composite electrodes and a YSZ electrolyte. A 2D axi-symmetric, multi-scale CFD model is developed which includes the fluid flow, mass transfer, and heat transfer within the gas channels and the porous electrodes. The electrochemical reactions are modeled within the volume of the electrodes, enabling the model to account for the extent of the reaction zone. Thermodynamic expressions are developed to estimate the single-electrode reversible heat generation and the single-electrode electromotive force of a non-isothermal electrochemical cell. The isothermal, non-isothermal, and transient models are each validated against the experimental results, and consistent with the physical reality of the TSOFC. A novel approach is used to estimate the kinetic parameters, enabling the simulations to be used as a diagnostic tool. The model is used to gain a thorough insight about the TSOFC. The cathode electrochemical activity and the anode support ohmic loss are identified as the two major performance bottlenecks for this cell. Including radiation is found to be essential for a physically meaningful heat transfer model. The thermoelectric effects on the cell overall electromotive force is found to be negligible. It is found that the anode reaction is always endothermic, while the cathode reaction is always exothermic, and that the temperature gradients across the cell layers are less than 0.05C The cell transient response is found to be fast, and dominated by the thermal transients. Several physical properties used in the model are measured experimentally, indicating that that the correlations used in the literature are not always suitable, especially when new fabrication techniques are used. The conductivity of the anode support was measured to be several orders of magnitude lower than expected and very sensitive to temperature, which explains the lower than expected and occasionally degrading cell performance. A hypothesis is proposed to explain this phenomenon based on the thermal expansion effects which result in the formation and disruption of particle to particle contacts within the composite electrode. / Chemical Engineering

As the demand for green energy and fuel cells grows, more attention is drawn towards Solid Oxide Fuel Cells (SOFCs). Random and complex structure of composite electrodes and underlying electrochemical process has not been completely unveiled yet and further study is required to acquire more understanding. Modeling in this regard plays an important role as it pinpoints key parameters in optimum design of the cell without resorting to costly and uncertain experiments which might even lead to misinterpretations due to random nature of experimental data. The aim of this work is to develop a new rigorous model to study the structure performance relationship of (SOFC) composite electrodes. The work has been conducted in two phases, a two-dimensional continuous approach and three-dimensional discrete model. A new two-dimensional, geometrical model which captures the inhomogeneous nature of the location of electrochemical reactions based on random packing of electronic and ionic conducting particles has been developed. The results show that the concentration of oxygen inside the cathode in the two-dimensional model is not only a function of the electrode depth but also changes along the width of the electrode. Furthermore the effect of composition of the electrode on the length of three phase boundary (TPB) and total polarization resistance has been demonstrated. A parametric study of the effect of the conductivity of ionic conductor and diffusion coefficient on the performance of the electrode has been given. To make a more realistic analysis, a three-dimensional reconstruction of (SOFC) composite electrodes was developed to evaluate the performance and further investigate the effect of microstructure on the performance of electrodes. To enhance connectivity between particles and increase the length of TPB, sintering process is mimicked by enlarging particles to certain degree. Geometrical characteristics such as length of TBP and active contact area as well as porosity can easily be calculated using the current model. Electrochemical process is simulated using resistor-network model and complete Butler-Volmer equation is used to deal with charge-transfer process on TBP. The model shows that TPBs are not uniformly distributed across the electrode and location of TPBs as well as amount of electrochemical reaction is not homogeneous. Effects of particle size, electrode thickness, particle size ratio, electron and ion conductor conductivities and rate of electrochemical reaction on overall electrochemical performance of electrode are investigated. / Chemical Engineering

This thesis describes a systematical study, including multidisciplinary modeling, simulation, control, and optimization, of a fuel cell - gas turbine hybrid power system that aims to increase the system efficiency and decrease the energy costs by combining two power sources. The fuel cell-gas turbine hybrid power systems can utilize exhaust fuel and waste heat from fuel cells in the gas turbines to increase system efficiency. This research considers a hybrid power system consisting of an internally reforming solid oxide fuel cell and a gas turbine. In the hybrid power system, the anode exhaust, which contains the remainder of the fuel, is mixed with the cathode exhaust as well as an additional supply of fuel and compressed air and then burned in a catalytic oxidizer. The hot oxidizer exhaust is expanded through the turbine section, driving an electric generator. After leaving the gas turbine, the oxidizer exhaust passes through a heat recovery unit in which it preheats the compressed air that is to be supplied to the fuel cell and the oxidizer. This research concentrates on multidisciplinary modeling and simulation of the fuel cell-gas turbine hybrid power system. Different control strategies for the power sharing between the subsystems are investigated. Also, the power electronics interfaces and controls for the hybrid power system are discussed. Two different power sharing strategies are studied and compared. Simulation results are presented and analyzed. Transient response of the hybrid energy system is studied through time-domain simulation. In addition, in this effort, Particle Swarm Optimization (PSO) is used to optimize the power sharing for the hybrid power system to increase the efficiency and decrease the fuel consumption.