Des oxydes appartenant au type structural Ruddlesden-Popper (RP) sont des matériaux de cathode prometteursdes piles à combustible à oxyde électrolyte solide (SOFC) fonctionnant à température intermédiaire (~ 500-700 °C). L’objectif de cette thèse est l’élaboration de conducteurs ioniques et électroniques, mixtes (MIEC) tels que la solution solide, La2-xPrxNiO4+δ, 0 ≤ x ≤ 2, des phases RP de formule Lan+1NinO3n+1 (n= 1, 2 and 3) et les composites associés à la cérine gadoliniée, Ce0.9Gd0.1O2-δ (CGO).Une microstructure et une architecture innovantes de ces électrodes ont été obtenues avec succès en utilisant l’atomisation électrostatique (ESD) et la sérigraphie (SP). La structure, la composition, la non-stoechiométrie en oxygène et la microstructure de ces matériaux ont été caractérisées par diffraction des rayons X, par spectroscopie de rayons X à dispersion d'énergie, par analyse thermogravimétrique et par microscopie électronique à balayage. Les propriétés électrochimiques et la stabilité chimique de ces électrodes à oxygène sont discutées en fonction de leur architecture et de la composition en utilisant la spectroscopie d'impédance électrochimique (SIE) et la diffraction des rayons X, respectivement. Enfin, une cellule complète SOFC intégrant la cathode LaPrNiO4+δ a été testée.Mots Clés: Pile à combustible à haute température (SOFC), Conducteur ionique et électronique mixte (MIEC), Cathode, Nickelates, Ce0.9Gd0.1O2-δ (CGO), Microstructure de type corail, Design architectural, Interfaces, Stabilité chimique, Atomisation électrostatique (ESD), Sérigraphie (SP), Spectroscopie d’impédance électrochimique (EIS). / Layered Ruddlesden-Popper type (RP) oxides are promising cathodes for solid oxide fuel cells operating at intermediate temperature (~500 - 700 °C).This thesis is focused on the synthesis of mixed ionic-electronic conducting materials such as pure La2-xPrxNiO4+δ, 0 ≤ x ≤ 2, higher order Lan+1NinO3n+1 (n= 1, 2 and 3) RP phases and composites adding Ce0.9Gd0.1O2-δ (CGO) component. An innovative microstructure and architecture of these electrodes were successfully prepared using electrostatic spray deposition (ESD) and screen-printing (SP) processes. These materials were evaluated through structural, compositional, oxygen non-stoichiometry and microstructural characterizations using X-ray diffraction, energy-dispersive X-ray spectroscopy, thermogravimetric analysis and scanning electron microscopy. The electrochemical properties and chemical stability of these oxygen electrodes are discussed according to the architectural design and composition using electrochemical impedance spectroscopy (EIS) and X-ray diffraction, respectively. Finally, a single SOFC based on LaPrNiO4+δ cathode has been tested.Keywords: Solid Oxide Fuel cell(SOFC), Mixed Ionic and Electronic Conductor (MIEC), Cathode, Nickelates, Ce0.9Gd0.1O2-δ (CGO), Coral-type microstructure, architectural design, interfaces, chemical stability, Electrostatic Spray Deposition (ESD), Screen-Printing (SP), Electrochemical Impedance Spectroscopy (EIS).

Le « Power-to-Gas » pourrait devenir une solution attractive pour le stockage des énergies renouvelables, pourvu que des électrolyseurs soient capables de fonctionner efficacement dans des conditions intermittentes à un coût abordable. Ce travail a pour objectif d'évaluer la faisabilité technique du fonctionnement intermittent de systèmes d'électrolyse à oxyde solide (SOEC) autour de 1073 K. Des conditions réalistes défavorables sont considérées, consistant en un système autonome sans source externe de chaleur et intégrant une compression d'hydrogène à 3 MPa. La problématique se compose de deux aspects : i) la gamme de fonctionnement du système, limitée à 60-100% en raison de gradients thermiques, est étendue via des stratégies de contrôle efficaces, ii) des procédures sont définies pour minimiser l'impact de l'intermittence sur la durée de vie. Premièrement, une stratégie de contrôle modulaire est proposée, consistant en l'utilisation de plusieurs unités indépendantes qui fonctionnent dans une gamme de puissance tolérable, ou sont arrêtées. La gamme de fonctionnement du système est ainsi étendue à 15-100% dans le cas de quatre unités. Une stratégie de contrôle complémentaire, consistant en un chauffage électrique interne, permet d'étendre la gamme de fonctionnement en réduisant les gradients thermiques, mais elle est susceptible de diminuer la durée de vie. Elle n'est donc appliquée qu'à une unité afin de suivre la courbe de charge et d'étendre la gamme de fonctionnement du système à 3-100%. Deuxièmement, 1800 cycles électriques on-off sont appliqués à une SOEC sans impact sur la dégradation, ce qui montre que des arrêts/démarrages répétés ne diminuent pas la durée de vie. De plus, des procédures de démarrage, standby et arrêt sont définies. Enfin, deux études de systèmes Eolien-SOEC et Solaire-SOEC fonctionnant pendant un an montrent que, avec les stratégies de contrôle implémentées, le système SOEC stocke la puissance appliquée avec un rendement de 91% sur PCS en moyenne, alors que les unités fonctionnent dans des conditions tolérables mis à part une unité qui suit la courbe de charge et est susceptible d'avoir une durée de vie diminuée. / Power-to-Gas could become an attractive solution for renewable electricity storage, provided that affordable electrolysers are able to operate efficiently under intermittent conditions. This work aims to assess the technical feasibility of operating intermittently a Solid Oxide Electrolysis Cell (SOEC) system around 1073 K. Realistic unfavourable conditions are considered, consisting in a standalone system operated with no external heat source and integrating hydrogen compression to 3 MPa. Two challenges are tackled in this work: i) the system power load range, limited to 60-100% due to thermal gradients, is extended via efficient control strategies, ii) procedures are defined to minimise the impact of the intermittency on the lifetime. First, a modular control strategy is proposed, consisting in the use of several SOEC units which are either operated in a tolerable power load range, or switched off. The system power load range is hence extended to 15-100% in the case of four units. A complementary control strategy, consisting in internal electrical heating, enables to extend the load range by reducing thermal gradients, but it may decrease the lifetime. Thus, it is applied to only one unit for it to follow the load curve and extend the system power load range to 3-100%. Secondly, 1800 on-off electric cycles are applied to an SOEC with no degradation increase, which shows that repeated start/stops do not decrease the lifetime. Start-up, standby and shut-down procedures are also defined. Finally, two case studies of Wind-SOEC and Solar-SOEC systems operated over one year show that, with the implemented control strategies, the SOEC system stores the applied power with an average efficiency of 91% vs. HHV, while units operate under tolerable conditions apart from one unit which follows the load curve and may have a decreased lifetime.

Les travaux présentés s'intéressent à la réalisation de piles SOFC de 3éme génération. La problématique essentielle de cette configuration concerne le processus de mise en forme de la cellule devant permettre l'obtention d'un électrolyte dense (haute température) associé à un métal poreux (basse température). Afin de répondre à cette problématique, nous proposons une approche innovante consistant à élaborer et mettre en forme, à haute température, un empilement de précurseurs oxydes réduits dans une deuxième étape à température modérée pour générer les parties métalliques. La voie sol-gel dérivée du procédé Pechini réputée pour permettre l'obtention à moindre coût d'échantillons homogènes de composition complexe et à microstructure contrôlée a permis d'obtenir les précurseurs oxydes des constituants de la cellule. Leur mise en forme a été réalisée par frittage flash, technique sélectionnée pour la rapidité de traitement permettant de contrôler la densification, préserver la microstructure et limiter les réactions interfaciales lors de l'assemblage de matériaux différents. Les paramètres de densification puis les conditions de réduction ont été optimisés pour chaque précurseur avant d'être transférés pour la réalisation d'une demi-cellule. Le départ de l'oxygène se traduit par une augmentation de la porosité sans coalescence des parties métallique ni décollement au niveau des interfaces entre constituants. Ainsi, les résultats présentés valident l'approche proposée montrant le bénéfice attendu de l'utilisation de précurseurs oxydes permettant la dissociation de l'étape mise en forme et densification de l'électrolyte de celle de l'obtention du métal poreux. Après réalisation des tests électrochimiques sur la demi-cellule, la réalisation d'une cellule complète pourra être proposée avant d'envisager un transfert d'échelle, rendu possible par l'utilisation de procédés facilement industrialisables. / The works presented concern in the realization of a third generation of SOFC cell. The main problem is the shaping process of the cell which must allows obtaining a dense (high temperature) electrolyte associated with a porous metal (low temperature). In order to solve this issue, we propose an innovative approach consisting in developing and shaping, at high temperature, a stack of oxide precursors which will be reduced in a second step at moderate temperature to generate the metal parts. The sol-gel route derived from the Pechini process, known to allow obtaining at low cost homogeneous samples of complex composition and controlled microstructure, was used to obtain the oxide precursors of the constituents of the cell. Their shaping was carried out by flash sintering, a technique selected for the speed of treatment allowing to control the densification, to preserve the microstructure and to limit the interfacial reactions during the assembly of different materials. The densification parameters and then the reduction conditions were optimized for each precursor before being transferred for the production of a half-cell. The departure of the oxygen results in an increase in the porosity without coalescence of the metal parts or detachment at the interfaces between constituents. Thus, the results presented validate the proposed approach showing the expected benefit of the use of oxide precursors allowing the dissociation of the shaping and densification step of the electrolyte from that of the obtaining of the porous metal. After carrying out the electrochemical tests on the half-cell, the full cell will be produced the upscaling, facilitated by the use of adequate chemical processes will be considered.

Ziel der Arbeit war die Nutzbarmachung von Bioethanol zur Wandlung in Strom und Wärme in einer Hochtemperaturbrennstoffzelle. Dazu waren neben der Entwicklung eines langzeitstabilen, effektiven Katalysators zur Synthesegaserzeugung und dessen Testung sowie der Übertragung gewonnener Erkenntnisse auf in einem Reformer einsetzbare Konzepte die Verifizierung kommerzieller Katalysatorsysteme für die partielle Oxidation von Ethanol notwendig. Außerdem ist für die Entwicklung eines ethanolbetriebenen SOFC-Systems eine pulsations- und ablagerungsfreie Verdampfung von unvergälltem und vergälltem Ethanol – welche nicht Stand der Technik ist – erforderlich, für die ein geeignetes Verdampferkonzept entwickelt und getestet wurde. Experimentell konnte die Betreibbarkeit eines SOFC-Systems mit Ethanol an einem für den Betrieb mit LPG ausgelegten System nachgewiesen werden.

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Hydrogen has the potential to become an important energy carrier in the future with many areas of applications, as a clean fuel for transportation, heating, power generation in places where electricity use is not fit, etc. Already today hydrogen plays a key role in numerous industries such as petroleum refineries and chemical industries. There are different production methods for hydrogen. Today, natural gas reforming is the most commonly used. With the growing importance of green production paths, hydrogen production by electrolysis is expected to grow. Two main electrolyzer technologies are used today; alkaline and polymer electrolyte membrane electrolyzer. High-temperature electrolyzers are also interesting techniques, where solid oxide is under development and molten carbonate electrolyzers is researched. In this thesis, a comparative life cycle analysis was performed on the alkaline and molten carbonate electrolyzer. Due to inaccurate inventory data for the molten carbonate electrolyzer, those results are excluded from the published thesis. The environmental performance of the alkaline electrolyzer technology was compared to that of the solid oxide and the polymer electrolyte membrane electrolyzers. The system boundaries were set as cradle to gate. Thereby, the life cycle steps included in the study are raw material extraction, electrolyzer manufacturing, hydrogen production, and transports in between these steps. The functional unit was chosen as 100 kg produced hydrogen gas. The results show that the polymer electrolyte membrane electrolyzer has the lowest environmental impact out of the compared technologies. It is also determined that the lifetime and the current density of the electrolyzers have significant impact on their environmental performance. Moreover, it is established that electricity for hydrogen production has the highest environmental impact out of the electrolyzers life cycle steps. Therefore, it is important to make sure that the electricity used for hydrogen production derives from renewable sources. / Vätgas har potential att spela en viktig roll som energibärare i framtiden med många användningsområden, såsom ett rent bränsle för transporter, uppvärmning, kraftförsörjning där elproduktion inte är lämpligt, med mera. Redan idag är vätgas ett viktigt inslag i flera industrier, där ibland raffinaderier och kemiska industrier. Det finns flera metoder för att producera vätgas, där reformering av naturgas är den största produktionsmetoden idag. I framtiden spås vätgasproduktion med elektrolys bli allt viktigare, då hållbara produktionsprocesser prioriteras allt mer. Idag används främst två elektrolysörtekniker, alkalisk och polymerelektrolyt. Utöver dessa är högtemperaturelektrolysörer också intressanta tekniker, där fastoxidelektrolysören är under utveckling och smältkarbonatelektrolysören är på forskningsstadium. I det här examensarbetet har en jämförande livscykelanalys utförts på alkalisk- och smältkarbonatelektrolysören. På grund av felaktiga indata för smältkarbonatelektrolysören har dessa resultat uteslutits från den publika rapporten. Miljöpåverkan från den alkaliska elektrolysören har sedan jämförts med miljöpåverkan från fastoxid- och polymerelektrolytelektrolysörerna. Systemgränserna sattes till vagga till grind. De livscykelsteg som inkluderats i studien är därmed råmaterialutvinning, elektrolysörtillverkning, vätgasproduktion och transporter mellan dessa steg. Den funktionella enheten valdes till 100 kg producerad vätgas.  Resultaten visar att polymerelektrolytteknologin har den lägsta miljöpåverkan utav de tekniker som jämförts. Resultaten påvisar också att livstiden och strömtätheten för de olika teknikerna har signifikant påverkan på teknikernas miljöpåverkan. Dessutom fastslås att elektriciteten för vätgasproduktion har högst miljöpåverkan utav de studerade livscykelstegen. Därför är det viktigt att elektriciteten som används för vätgasproduktionen kommer ifrån förnybara källor.

Mesoscale optical phenomena occur when light interacts with a number of different types of materials, such as biological and chemical systems and fabricated nanostructures. As a framework, mesoscale optics unifies the interpretations of the interaction of light with complex media when the outcome depends significantly upon the scale of the interaction. Most importantly, it guides the process of designing an optical sensing technique by focusing on the nature and amount of information that can be extracted from a measurement. Different aspects of mesoscale optics are addressed in this dissertation which led to the solution of a number of problems in complex media. Dynamical and structural information from complex fluids—such as colloidal suspensions and biological fluids—was obtained by controlling the size of the interaction volume with low coherence interferometry. With this information, material properties such as particle sizes, optical transport coefficients, and viscoelastic characteristics of polymer solutions and blood were determined in natural, realistic conditions that are inaccessible to conventional techniques. The same framework also enabled the development of new, scale-dependent models for several important physical and biological systems. These models were then used to explain the results of some unique measurements. For example, the transport of light in disordered photonic lattices was interpreted as a scale-dependent, diffusive process to explain the anomalous behavior of photon path length distributions through these complex structures. In addition, it was demonstrated how specialized optical measurements and models at the mesoscale enable solutions to fundamental problems in cell biology. Specifically, it was found for the first time that the nature of cell motility changes markedly with the curvature of the substrate that the cells iv move on. This particular work addresses increasingly important questions concerning the nature of cellular responses to external forces and the mechanical properties of their local environment. Besides sensing of properties and modeling behaviors of complex systems, mesoscale optics encompasses the control of material systems as a result of the light-matter interaction. Specific modifications to a material’s structure can occur due to not only an exchange of energy between radiation and a material, but also due to a transfer of momentum. Based on the mechanical action of multiply scattered light on colloidal particles, an optically-controlled active medium that did not require specially tailored particles was demonstrated for the first time. The coupling between the particles and the random electromagnetic field affords new possibilities for controlling mesoscale systems and observing nonequilibrium thermodynamic phenomena

Работа содержит 71 страницу, 52 рисунка, 8 таблиц, 73 наименования в списке литературы. Ключевые слова: ТВЕРДООКСИДНЫЙ ТОПЛИВНЫЙ ЭЛЕМЕНТ, КАТОДНЫЙ МАТЕРИАЛ, СТРУКТУРА РАДДЛЕСДЕНА-ПОППЕРА, ТЕРМИЧЕСКОЕ РАСШИРЕНИЕ, ЭЛЕКТРОПРОВОДНОСТЬ, ХИМИЧЕСКАЯ СОВМЕСТИМОСТЬ. Методом пиролиза глицерин-нитратных композиций проведен синтез сложных оксидов Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.4). Методом рентгеновской дифракции определен фазовый состав порошков Nd1.6Ca0.4Ni1 yCuyO4+δ (y = 0.0-0.4) (ДРОН-6). Методом Ритвелда при использовании программного пакета FullProf Suite уточнены кристаллоструктурные параметры Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.3) при 25 С. Проведены высокотемпературные рентгеновские исследования порошков Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0 - 0.3). Методами термогравиметрии (NETZSCH STA 449F3) и окислительно-восстановительного (потенциометрического) титрования (Аквилон АТП-02) проведено определение абсолютного содержания кислорода в образцах Nd1.6Ca0.4Ni1 yCuyO4+δ (y = 0.0-0.3) на воздухе. Методом дилатометрии (Netzsch DIL 402C) исследовано термическое расширение спеченных образцов Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.3). Из наклона экспериментальных зависимостей относительного удлинения образцов рассчитаны изобарические линейные коэффициенты термического расширения Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.3). Четырех-зондовым методом на постоянном токе на воздухе с использованием автоматической системы Zirconia-318 получены температурные зависимости проводимости спеченных образцов Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.3). Проведены исследования химической совместимости Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0; 0.2; 0.4) с оксидными материалами для традиционных электролитов ТОТЭ. На анализаторе дисперсности SALD-7101 Shimadzu методом лазерного светорассеяния выполнено определение распределения частиц по размерам в порошках Nd1.6Cа0.4Ni1-yCuyO4+δ (y = 0.0-0.4). Величины удельной поверхности Nd1.6Cа0.4Ni1-yCuyO4+δ (y = 0.0-0.4) оценивали методом тепловой десорбции азота на автоматическом анализаторе поверхности и пористости SoftSorbi-II ver.1.0. Определение коэффициента диффузии ионов кислорода проводили методом температурно-программируемого изотопного обмена. Электрохимическая активность катодных материалов Nd1.6Cа0.4Ni1-yCuyO4+δ (y = 0.0; 0.1; 0.3) исследована методом импедансной спектроскопии с помощью потенциостата SI 1260 и электрохимического интерфейса SI 1287 (Solartron Industries Inc.). На основе полученных данных сделан вывод о перспективности оксидных материалов Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0 0.4) в качестве катодных материалов для среднетемпературных ТОТЭ. / Present work contains 71 pages, 52 figures, 8 tables, 73 references in the literature list. Keywords: SOLID OXIDE FUEL CELLS, CATHODE, RUDDLESDEN-POPPER STRUCTURE, THERMAL EXPANSION, ELECTROCONDUCTIVITY, CHEMICAL COMPATIBILITY. Synthesis of the Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.4) complex oxides was carried out by the glycerol-nitrate compositions pyrolysis. Phase composition of the Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.4) powders was determined by the X-ray diffraction (DRON-6). The crystal structure parameters of the Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.4) oxides at 25 °C were refined by the Rietveld method using the FullProf Suite software package. High-temperature X-ray studies were performed on the Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.3) powders. The thermogravimetry (NETZSCH STA 449F3) and redox titration (potentiometric) methods (Aquilon ATP-02) were used for the determination of an absolute oxygen content in the Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.4) samples in air. Thermal expansion of the compact Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.4) samples were studied using the dilatometry (Netzsch DIL 402C) method. The isobaric linear coefficients of the Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.4) thermal expansion were calculated from linearization of the experimental dependencies of samples’ relative elongation. The temperature dependencies of the Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.4) compact samples’ conductivity were obtained using the four-probe method at direct current in air with automatic system Zirconia-318. Chemical compatibility of the Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0; 0.2; 0.4) with electrolytes oxide materials for solid oxide fuel cells (SOFC) has been studied. Particle size distribution in the Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.4) powders was determined by laser light scattering using a SALD-7101 Shimadzu dispersion analyzer. The values of the Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.4) specific surface were estimated by the method of nitrogen thermal desorption on an automatic surface and porosity analyzer SoftSorbi-II ver.1.0. The oxygen ion diffusion coefficients were determined by temperature programmed isotope exchange of oxygen. Electrochemical activity of the Nd1.6Ca0.4Ni1-yCuyO4+δ (y = 0.0-0.4) cathode materials was investigated by impedance spectroscopy using a SI 1260 potentiostat and SI 1287 electrochemical interface (Solartron Industries Inc.). Based on the obtained data, it could be concluded that the Nd1.6Ca0.4Ni1-yCuyO4+δ oxide materials are promising as cathode materials for intermediate-temperature SOFC’s.

Outlined herein is the Modular Vehicle [MODV] concept as a cost effective, utilitarian, and highly functional vehicle concept for the changing demands placed on a MAGTF [Marine Air-Ground Task Force] or SP-MAGTF [Special Purpose Marine Air-Ground Task Force] in the 21st century. A large focus is put on the importance of modularity and cost effectiveness of having a 24 hour configurable vehicle to a specific mission and area of operation. Off-road vehicle progression through history is presented and successful design features are noted in order to develop underlying goals for the modular vehicle. The thesis emphasizes recent technology advancements that can shift the foundations of vehicle design including wheel hub motors, high capacity batteries, solid oxide fuel cells, autonomy, structural health monitoring, energy harvesting shock absorbers, non-pneumatic tires, and drive-by-wire options. Predictions on the outlook for the technology progressions is discussed to give insight into the viability of basing a vehicle concept on these technologies. Finally, physical design bounds are presented to provide a foundation for the future design of such a vehicle. / Master of Science

Two computational fluid dynamics models are developed to predict the performance of a solid oxide fuel cell stack, a detailed and a simplified model. In the detailed model, the three dimensional momentum, heat, and species transport equations are coupled with electrochemistry. In the simplified model, the diffusion terms in the transport equations are selectively replaced by rate terms within the core region of the stack. This allows much coarser meshes to be employed at a fraction of the computational cost. Following the mathematical description of the problem, results for single-cell and multi-cell stacks are presented. Comparisons of local current density, temperature, and cell voltage indicate that good agreement is obtained between the detailed and simplified models, verifying the latter as a practical option in stack design. Then, the simplified model is used to determine the effects of utilization on the electrochemical performance and temperature distributions of a 10 cell stack. The results are presented in terms of fluid flow, pressure, species mass fraction, temperature, voltage and current density distributions. The effects of species and flow distributions on electrochemical performance and temperature are then analyzed for a 100 cell stack. The discussion highlights the importance of manifold design on performance and thermal management of large stacks. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2013-09-30 15:55:18.627