Cerâmicas de silicato de lantânio tipo apatita têm sido estudadas devido ao grande interesse tecnológico para aplicação como eletrólito em células a combustível de óxido sólido de temperatura intermediária (IT-SOFC: Intermediate Temperature Solid Oxide Fuel Cell). A condutividade iônica dessas cerâmicas em temperaturas intermediárias (600-800°C) é maior do que a da YSZ (Ytria Stabilized Zirconia) utilizada como eletrólito em SOFCs de alta temperatura (800-1000°C). Neste trabalho, silicato de lantânio tipo apatita foi sintetizado pelo método sol-gel seguido de precipitação, a partir de Na2SiO3 como fonte de sílica. No método proposto, estudou-se rotas de síntese em meio ácido e básico para a formação do gel de sílica, seguida de precipitação. A fase cristalina de silicato de lantânio tipo apatita foi obtida pela calcinação de pós sintetizados a 900°C. Esta temperatura é muito inferior às praticadas em outros métodos convencionais de síntese. As análises por difração de raios X (DRX) mostraram silicato de lantânio tipo apatita como fase principal do material sintetizado na rota de síntese em pH ácido. No entanto, uma fase secundária indesejável, La2Si2O7, foi identificada quando o pó cerâmico foi calcinado a 1200°C. Por outro lado, pela rota básica, fase única de silicato de lantânio tipo apatita foi obtida após tratamento térmico dos precursores a 900 e 1200°C. Pastilha cerâmica obtida a partir dos pós obtidos e sinterizados a 1400°C por 4h, apresentaram fase cristalina pura de silicato de lantânio tipo apatita. Microscopia eletrônica de varredura (MEV) foi utilizada para observar a morfologia dos pós e microestrutura das pastilhas sinterizadas. Pós cerâmicos finos com tamanho de partículas submicrométricas e microestrutura típica de apatita foram alcançadas pelo método proposto. / Lanthanum silicate apatite-type ceramics have been studied because of the great technological interest for IT-SOFC applications as electrolyte (Intermediate Temperature Solid Oxide Fuel Cell). Ionic conductivity of those ceramics at intermediate temperatures (600-800°C) is higher than that of YSZ (Ytria Stabilized Zirconia) electrolyte used at high-temperatures (800-1000 °C) SOFCs. In this work, lanthanum silicate apatite-type was synthesized by sol-gel method followed by precipitation from Na2SiO3 as a source of silica. In the proposed method, synthesis routes in acid and basic medium to the formation of silica gel, followed by precipitation were studied. Apatite crystalline phase of lanthanum silicate ceramic was obtained by calcining the powders at 900°C. This temperature is much lower than those other conventional methods of synthesis. Analysis by x-ray diffraction (XRD) showed the lanthanum silicate apatite-type phase as the main phase of the synthesized material at the pH acid synthesis route. However, undesirable secondary phase, La2Si2O7, was recognized when the powder was calcined at 1200°C. On the other hand, by the basic route, single apatite-type phase powder was obtained after thermal treatment of the precursors at 900 and 1200°C. Ceramic pellet obtained from those powders sintered at 1400°C for 4h, presented pure apatite crystalline phase of lanthanum silicate. Scanning electron microscopy (SEM) was used to observe morphology of powders and microstructure of sintered pellets. Sub micrometric size powders and apatite typical microstructure ceramic were reached by the suggested method.

A demanda mundial por energia elétrica é uma tendência crescente, desta maneira há necessidade de diversificar e buscar por novas matrizes energéticas. Insere-se neste contexto, as células a combustível de Óxido Sólido de Temperatura Intermediária (Intermediate Temperature Solid Oxide Fuel Cells - IT-SOFC), que converte diretamente a energia de reações químicas em água e em energia elétrica e também em energia térmica (calor). As células a combustível do tipo IT-SOFC por utilizarem materiais cerâmicos em sua concepção, são capazes de suportarem temperaturas até 800°C e sem perderem suas propriedades físicas, químicas, elétricas e microestruturais. O presente trabalho tem como objetivo a síntese e a caracterização do material particulado de BaxSr1-xCoyFe1-yO3±δ BSCF e de amostras cerâmicas (variando os valores de x iguais a 0,4; e 0,6), visando sua utilização para fabricação de componente catódico de IT-SOFC. O particulado de BSCF foi obtido por meio do método de complexação por EDTA Citratos, que consiste nas reações de estado sólido e reações em fase líquida. A caracterização do material particulado BSCF e amostras cerâmicas foram realizada por difração de raios X (DRX), Espectroscopia de raios X por energia dispersiva (EDS), Análise Química por Fluorescência de raios X (identificação dos elementos constituintes na composição), Análise de Microscopia Eletrônica de Varredura - MEV (observação de morfologia e do tipo de aglomeração das partículas), e Picnometria por Gás Hélio (medidas de densidade real) e BET. Os resultados da caracterização dos particulados para a confecção do material catódico do BSCF apresentaram adequados para fabricação de componente catódico de IT-SOFC. A rota de síntese se mostrou bastante viável e adequada para formar a estrutura cristalina perovskita cubica desejada, além da estequiometria final muito próxima da calculada. Em relação a densidade aparente do corpo cerâmico x = 0,4 foi o que apresentou menor valor, importante para um material catódico, já que menor densidade aparente, maior a quantidade de poros, no qual x=0,4 obteve 21,74% de porosidade, valor ideal para a passagem do fluxo de gás considerado pela literatura. Em relação a condutividade elétrica dos corpos cerâmicos BSCF 64 apresentou valor de 11,212 S.cm-1 na temperatura de 392°C, maior que BSCF 46 que foi de 9,041 S.cm-1. Embora não seja apenas esses valores responsáveis pelas propriedades de um bom condutor elétrico que, já que as três amostras mostraram um ótimo comportamento ôhmico, adequado para a utilização em Cac do tipo IT- SOFC. Por fim, a partir de todos os estudos e ensaios realizados neste trabalho, fica evidente que o óxido misto BaxSr1-xCoyFe1-yO3±δ, x= 0,4, obtém as propriedades adequadas para serem utilizados como material catódico de célula a combustível de óxido sólido de temperatura intermediaria. / The global demand for energy is a growing and irreversible tendency. Therefore, there is a need to diversify and search for new energetic matrixes. Intermediate Temperature Solid Oxide Fuel Cells - IT-SOFC are part of this context, which converts chemical energy directly in to water, electric energy and thermal energy (heat). IT-SOFC uses ceramic materials in their design, and as a result they are able to operate in temperatures up to 1073K (800°C) without losing their physical, chemical, electrical and microstructural properties. This present work aims the synthesis and characterization of BaxSr1-xCoyFe1-yO3±δ BSCF particulate matter and ceramic sample (x= 0.4 and 0.6), aiming their use for manufacturing IT-SOFC cathode components. The BSCF particulate wasobtained through the complexation method with EDTA - citrates. The characterization of the BSFC particulate and ceramic samples have been given by X-ray diffraction (XRD), X-ray fluorescence chemical analysis (identification of the components in the composition), Secondary Electron Microscopy - SEM (observation of morphology and type of agglomeration of the particles) and helium gas pycnometry (real density measurements). The results of the characterization of particulates used in the production of BSCF cathodes are appropriate for manufacturing IT-SOFC components. . In relation to the apparent density of the ceramic BSCF 46 was the one that presented the smallest value, important for a cathodic material since lower bulk density (where x = 0.4) obtained 21.74% porosity, an ideal value for the flow of gas considered in the literature. Regarding the electrical conductivity of the ceramic bodies, the value of BSCF 64 was the most adequate, overcoming 11,212 S.cm-1 at a temperature of 570°C. Although it is not only these values responsible for the properties of a good electric conductor since the three samples presented an optimum ohmic behavior, suitable for use in Cac of type IT-SOFC. Finally, from all the studies and tests carried out in this work, it is evident that the mixed oxide BaxSr1-xCoyFe1-yO3±δ, x = 0.4 obtain the necessary properties to be used as intermediate temperature solid oxide fuel cell cathode material.

A demanda mundial por energia elétrica é uma tendência crescente, desta maneira há necessidade de diversificar e buscar por novas matrizes energéticas. Insere-se neste contexto, as células a combustível de Óxido Sólido de Temperatura Intermediária (Intermediate Temperature Solid Oxide Fuel Cells - IT-SOFC), que converte diretamente a energia de reações químicas em água e em energia elétrica e também em energia térmica (calor). As células a combustível do tipo IT-SOFC por utilizarem materiais cerâmicos em sua concepção, são capazes de suportarem temperaturas até 800°C e sem perderem suas propriedades físicas, químicas, elétricas e microestruturais. O presente trabalho tem como objetivo a síntese e a caracterização do material particulado de BaxSr1-xCoyFe1-yO3±δ BSCF e de amostras cerâmicas (variando os valores de x iguais a 0,4; e 0,6), visando sua utilização para fabricação de componente catódico de IT-SOFC. O particulado de BSCF foi obtido por meio do método de complexação por EDTA Citratos, que consiste nas reações de estado sólido e reações em fase líquida. A caracterização do material particulado BSCF e amostras cerâmicas foram realizada por difração de raios X (DRX), Espectroscopia de raios X por energia dispersiva (EDS), Análise Química por Fluorescência de raios X (identificação dos elementos constituintes na composição), Análise de Microscopia Eletrônica de Varredura - MEV (observação de morfologia e do tipo de aglomeração das partículas), e Picnometria por Gás Hélio (medidas de densidade real) e BET. Os resultados da caracterização dos particulados para a confecção do material catódico do BSCF apresentaram adequados para fabricação de componente catódico de IT-SOFC. A rota de síntese se mostrou bastante viável e adequada para formar a estrutura cristalina perovskita cubica desejada, além da estequiometria final muito próxima da calculada. Em relação a densidade aparente do corpo cerâmico x = 0,4 foi o que apresentou menor valor, importante para um material catódico, já que menor densidade aparente, maior a quantidade de poros, no qual x=0,4 obteve 21,74% de porosidade, valor ideal para a passagem do fluxo de gás considerado pela literatura. Em relação a condutividade elétrica dos corpos cerâmicos BSCF 64 apresentou valor de 11,212 S.cm-1 na temperatura de 392°C, maior que BSCF 46 que foi de 9,041 S.cm-1. Embora não seja apenas esses valores responsáveis pelas propriedades de um bom condutor elétrico que, já que as três amostras mostraram um ótimo comportamento ôhmico, adequado para a utilização em Cac do tipo IT- SOFC. Por fim, a partir de todos os estudos e ensaios realizados neste trabalho, fica evidente que o óxido misto BaxSr1-xCoyFe1-yO3±δ, x= 0,4, obtém as propriedades adequadas para serem utilizados como material catódico de célula a combustível de óxido sólido de temperatura intermediaria. / The global demand for energy is a growing and irreversible tendency. Therefore, there is a need to diversify and search for new energetic matrixes. Intermediate Temperature Solid Oxide Fuel Cells - IT-SOFC are part of this context, which converts chemical energy directly in to water, electric energy and thermal energy (heat). IT-SOFC uses ceramic materials in their design, and as a result they are able to operate in temperatures up to 1073K (800°C) without losing their physical, chemical, electrical and microstructural properties. This present work aims the synthesis and characterization of BaxSr1-xCoyFe1-yO3±δ BSCF particulate matter and ceramic sample (x= 0.4 and 0.6), aiming their use for manufacturing IT-SOFC cathode components. The BSCF particulate wasobtained through the complexation method with EDTA - citrates. The characterization of the BSFC particulate and ceramic samples have been given by X-ray diffraction (XRD), X-ray fluorescence chemical analysis (identification of the components in the composition), Secondary Electron Microscopy - SEM (observation of morphology and type of agglomeration of the particles) and helium gas pycnometry (real density measurements). The results of the characterization of particulates used in the production of BSCF cathodes are appropriate for manufacturing IT-SOFC components. . In relation to the apparent density of the ceramic BSCF 46 was the one that presented the smallest value, important for a cathodic material since lower bulk density (where x = 0.4) obtained 21.74% porosity, an ideal value for the flow of gas considered in the literature. Regarding the electrical conductivity of the ceramic bodies, the value of BSCF 64 was the most adequate, overcoming 11,212 S.cm-1 at a temperature of 570°C. Although it is not only these values responsible for the properties of a good electric conductor since the three samples presented an optimum ohmic behavior, suitable for use in Cac of type IT-SOFC. Finally, from all the studies and tests carried out in this work, it is evident that the mixed oxide BaxSr1-xCoyFe1-yO3±δ, x = 0.4 obtain the necessary properties to be used as intermediate temperature solid oxide fuel cell cathode material.

Cerâmicas de silicato de lantânio tipo apatita têm sido estudadas devido ao grande interesse tecnológico para aplicação como eletrólito em células a combustível de óxido sólido de temperatura intermediária (IT-SOFC: Intermediate Temperature Solid Oxide Fuel Cell). A condutividade iônica dessas cerâmicas em temperaturas intermediárias (600-800°C) é maior do que a da YSZ (Ytria Stabilized Zirconia) utilizada como eletrólito em SOFCs de alta temperatura (800-1000°C). Neste trabalho, silicato de lantânio tipo apatita foi sintetizado pelo método sol-gel seguido de precipitação, a partir de Na2SiO3 como fonte de sílica. No método proposto, estudou-se rotas de síntese em meio ácido e básico para a formação do gel de sílica, seguida de precipitação. A fase cristalina de silicato de lantânio tipo apatita foi obtida pela calcinação de pós sintetizados a 900°C. Esta temperatura é muito inferior às praticadas em outros métodos convencionais de síntese. As análises por difração de raios X (DRX) mostraram silicato de lantânio tipo apatita como fase principal do material sintetizado na rota de síntese em pH ácido. No entanto, uma fase secundária indesejável, La2Si2O7, foi identificada quando o pó cerâmico foi calcinado a 1200°C. Por outro lado, pela rota básica, fase única de silicato de lantânio tipo apatita foi obtida após tratamento térmico dos precursores a 900 e 1200°C. Pastilha cerâmica obtida a partir dos pós obtidos e sinterizados a 1400°C por 4h, apresentaram fase cristalina pura de silicato de lantânio tipo apatita. Microscopia eletrônica de varredura (MEV) foi utilizada para observar a morfologia dos pós e microestrutura das pastilhas sinterizadas. Pós cerâmicos finos com tamanho de partículas submicrométricas e microestrutura típica de apatita foram alcançadas pelo método proposto. / Lanthanum silicate apatite-type ceramics have been studied because of the great technological interest for IT-SOFC applications as electrolyte (Intermediate Temperature Solid Oxide Fuel Cell). Ionic conductivity of those ceramics at intermediate temperatures (600-800°C) is higher than that of YSZ (Ytria Stabilized Zirconia) electrolyte used at high-temperatures (800-1000 °C) SOFCs. In this work, lanthanum silicate apatite-type was synthesized by sol-gel method followed by precipitation from Na2SiO3 as a source of silica. In the proposed method, synthesis routes in acid and basic medium to the formation of silica gel, followed by precipitation were studied. Apatite crystalline phase of lanthanum silicate ceramic was obtained by calcining the powders at 900°C. This temperature is much lower than those other conventional methods of synthesis. Analysis by x-ray diffraction (XRD) showed the lanthanum silicate apatite-type phase as the main phase of the synthesized material at the pH acid synthesis route. However, undesirable secondary phase, La2Si2O7, was recognized when the powder was calcined at 1200°C. On the other hand, by the basic route, single apatite-type phase powder was obtained after thermal treatment of the precursors at 900 and 1200°C. Ceramic pellet obtained from those powders sintered at 1400°C for 4h, presented pure apatite crystalline phase of lanthanum silicate. Scanning electron microscopy (SEM) was used to observe morphology of powders and microstructure of sintered pellets. Sub micrometric size powders and apatite typical microstructure ceramic were reached by the suggested method.

La fabrication de cellules de piles à combustible IT-SOFC de large dimension par un nouveau procédé simple et peu coûteux est présentée dans ce manuscrit. L’optimisation de ce nouveau procédé en regard de l’utilisation d’agents de porosité, d’épaisseur de couches et de température de frittage a été réalisée. Les résultats des tests électrochimiques sur des cellules de surface active 10 cm2 réalisés dans le dispositif Fiaxell semi-ouvert ont été détaillés pour différentes cellules. Des tests de performance de longue durée ont également été menés sur le dispositif Fiaxell, présentés et discutés. La préparation et la réalisation d’un nouveau banc de test de stack a également été mené et présenté dans ces travaux. / The fabrications of large area IT-SOFC planar cell by new simple and cost effective process were explained. The optimization of the new process with respect to pore formers, thickness of layers, sintering temperature were performed. The electrochemical results of 10cm2 performed in Fiaxell open flange set up were detailed with respect to different configuration. Long term ageing performance tests of single cells were conducted in Fiaxell device and results are discussed. Preparation of new test bench and stacking process performed till now were briefed.

L’un des enjeux relatif au déploiement des piles à combustible à oxyde solide comme système de production d’une énergie propre relève de la température de fonctionnement qui est actuellement autour de 1000°C. Abaisser cette température tout en préservant les performances afin de réduire les coûts de fabrication et d’augmenter la durée de vie des systèmes a été l’objectif dece travail de doctorat.Un coeur de pile à combustible (anode-électrolyte-cathode) élaboré avec des procédés physiques de dépôts (projection par plasma atmosphérique et pulvérisation cathodique magnétron) a été développé et optimisé sur un support métallique poreux. Les matériaux étudiés ont été un cermet en Nickel-Zircone stabilisée à l’Ytttrium (Ni-YSZ) pour l’anode, un électrolyte en YSZ avec ou sans couche de cérine gadoliniée (GDC) et les nickelates de terres rares comme cathode. La maitrise des procédés de revêtements a permis de réduire les épaisseurs de chaque couche et d’assurer la cohésion de l’ensemble des 3 couches avec des caractéristiques cristallographiques, microstructurales et de porosité adaptées. . Les performances électrochimiques ont été étudiées pour chaque élément du coeur de pile puis pour l’ensemble du système élaboré sur métal poreux. Même si les performances atteintes ne sont pas encore suffisantes, les procédés de revêtements optimisés pour recouvrir un support métallique poreux ont confirmé leur potentiel. / Energy production by a clean and environmental processes is a real challenge. Fuel cell technology is good candidate to answer this objective. The major problem of the Solid Oxide Fuel Cell is their high operating temperature (around 1000°C) for a massive industrialisation. Decreasing these temperature at 700°C allows a reduction of cost manufacturing and increase the lifetime, in this case the new challenge is to avoid the performances losses.During this phD work, dry surface treatment processes are employed for produce the fuel cell core. The thickness reduction of each part limit the performances decreasing generate by the modification of the temperature. The materials used is a Ni-Yttria stabilised zirconia cermet (Ni-YSZ) for the anode, YSZ with or without gadolinnia doped ceria (GDC) for electrolyte and rare earth nickelate for the cathode component. All material are a usual employed in the SOFC technology. All coating are synthesized and characterised separately. After a third generation of fuel cell is realized on ITM porous metal support produced by PLANSEE. The anode has been deposit by atmospheric plasma spray, the electrolyte and cathode have been synthesised by reactive magnetron sputtering.

Proton conducting intermediate temperature (600oC-400oC) solid oxide fuel cells (IT-SOFC) have many potential advantages for clean and efficient power generation from readily available hydrocarbon fuels. However, it still has many unsolved problems, especially on the anode where the fuel got oxidized and the cathode where oxygen got reduced. In this study, for the anode, the effects of hydrogen sulfite (H2S) and carbon dioxide (CO2) as fuel contaminants were studied on the nickel (Ni) based cermet anode of proton conducting IT-SOFC using proton conducting electrolyte of BaZr0.1Ce0.7Y0.1Yb0.1O3 (BZCYYb). Both low-ppm level H2S and low-percentage level CO2 caused similar poisoning effects on the anode reaction. The H2S poisoning effect was also found to be much less than on oxide-ion conducting SOFC, which is attributed to the absence of water evolution for the anode reaction in proton conducting SOFC. In addition, the H2S/CO2 poisoning mechanisms were investigated using X-ray diffraction, energy dispersive spectroscopy (EDS), Raman spectroscopy, and secondary ion mass spectroscopy (SIMS). For H2S, other than possible sulfur dissolution into BZCYYb, no bulk reaction was found, suggesting sulfur adsorption contributes to the reduced performance. For CO2, reaction with BZCYYb to form BaCO3 and CeO2 is identified and is believed to be the reason for the sudden worsening in CO2 poisoning as temperature drops below ~550oC. For the cathode, several representative SOFC cathodes including silver (Ag), La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF), LSCF-BZCYYb composite, and Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) were evaluated based on BZCYYb electrolyte. LSCF give similar high interfacial resistance as Ag, while LSCF-BZCYYb composite cathode shows lower interfacial resistance, suggesting LSCF behaves like pure electronic conductor cathode in this case. For BSCF, it shows smallest interfacial resistance and the charge transfer process appears to accelerate with the introduction of H2O, while oxygen adsorption/transport seem to slow down due to adsorbed H2O. Furthermore, CO2 was shown to cause poisoning on the BSCF cathode, yet the poisoning was significantly reduced with the co-presence of water. The results suggest that although BSCF seem to display mixed proton-electronic conduction, its strong affinity to H2O may inhibit the oxygen reduction reaction on the cathode and new cathode materials still need to be designed.

Cette thèse vise à évaluer le potentiel d'un nouveau couple cathode / électrolyte pour une application en IT-SOFC (700°C), par le biais de l’élaboration et du test de cellules à anode support de configuration planaire. Les matériaux concernés sont l'électrolyte BaIn0.3Ti0.7O2.85 (BIT07), de structure perovskite, et les nickelates de terres rares Ln2-xNiO4+ (LnN, Ln = La, Nd, Pr) en tant que cathodes ; ces matériaux ont montré des propriétés prometteuses dans des travaux préliminaires effectués à l'IMN et l'ICMCB. La première partie de cette thèse porte sur la mise en place d'un protocole d'élaboration de cellules complètes utilisant des techniques bas coûts et industrialisables (cellules de taille 3 x 3 cm2) : l’anode Ni / BIT07 a été élaborée par coulage en bande, l'électrolyte BIT07 par vacuum slip casting et les cathodes par sérigraphie. Les mesures électrochimiques réalisées sur une première génération de cellules ont mis en évidence la nécessité d'ajouter une couche barrière de GDC entre les cathodes LnN et l'électrolyte BIT07. Les meilleures performances ont été obtenues pour une cellule BIT07 / Ni | BIT07 | GDC | PrN, avec une densité de puissance à 700°C et 0.7 V de 176 mW cm-2 pour une faible résistance de polarisation de 0. 29 Ω cm2. La principale limitation des performances a été identifiée comme étant la résistance interne du banc de test, donnant lieu à des valeurs de résistances séries anormalement élevées. Cette cellule a été opérée avec succès durant plus de 500 heures sous courant, avec néanmoins une vitesse de dégradation extrapolée élevée de l’ordre de 27% / kh. / This thesis aimed at assessing the potential of a novel cathode / electrolyte couple for IT-SOFC applications (700°C), through the elaboration and testing of planar anode-supported cells. The materials involved were the perovskite-structured BaIn0.3Ti0.7O2.85 (BIT07) electrolyte and the rare earth nickelate Ln2-xNiO4+ (LnN, Ln = La, Nd, Pr) cathodes, both materials having shown promising properties in preliminary work done at the IMN and the ICMCB. The first part of this thesis concerned the implementation of a cell elaboration protocol using low-cost and scalable shaping techniques (cell size 3 x 3 cm2); namely, the Ni / BIT07 anodes were elaborated by tape casting, the BIT07 electrolyte by vacuum slip casting and the cathodes by screen printing. Comparison of electrochemical results for a first and second generation of cells highlighted the usefulness of adding a GDC buffer layer in between the LnN cathodes and the BIT07 electrolyte. The best performance has been obtained for a cell BIT07 / Ni | BIT07 | GDC | PrN, with a power density at 700°C and 0.7 V of 176 mW cm-2 for a competitive polarisation resistance of 0.29 Ω cm2. The main limitation of the performance has been determined to be related to the internal resistance of the test setup, giving anomalously high series resistances. This cell has been successfully operated beyond 500 hours under current, although with a fairly high extrapolated degradation rate of 27% / kh.

Climate change and environmental degradation, in addition to the challenges of limited fossil fuel resources, have driven governments to pursue creative renewable energy sources. Natural gas and biofuels are limitless energy sources produced from both fossil fuels and biomass that is renewable. SOFCs (Solid Oxide Fuel Cells) are a type of renewable energy system that can convert biofuels into power and heat whenever needed. They often operate at high temperatures (> 850 °C), which allows for fuel flexibility; nevertheless, such high temperatures are associated by rapid material deterioration and performance loss, usually before 40,000 hours of operation. As a result, many recent studies and activities have concentrated on lowering the operating temperature of SOFCs. Lowering the temperature causes decreased ionic conductivity, decreased catalytic activity, and increased carbon deposition on the anode side catalysts. This project aimed at developing an innovative cathode-supported SOFC to be fed by biofuels and operating at low-intermediate temperatures. Colloidal processes and co-sintering were selected to fabricate the final SOFC owing to their flexibility in optimizing the final desired properties and saving more manufacturing costs. The first chapter of this thesis provides an introduction to the essential concepts as well as professional specifics and previous work. The cell design and component materials are defined, as are additional requirements for lowering the operating temperature in SOFCs. Commercialization challenges and recommended solutions are also discussed, which involve the development of both new anode materials and production procedures. The project's goal is detailed at the end of Chapter 1, along with the reasons why various approaches were chosen. Molybdenum was chosen as a suitable anodic material to be doped into LSCF, and tape casting was developed further to create the cathode. The cathode support layer should have a consistent thickness, balanced flexibility and mechanical strength, and better shrinkage qualities. The plasticizer is a high molecular weight polyethylene glycol (PEG 4000), which improves these characteristics. Chapter 2 covers the steps involved in creating the button SOFC, starting with powder synthesis and ending with cathode tape casting. SOFC performance and anode catalytic activity are investigated to assess SOFC durability while fed by biogas. In Chapter 3, the findings are presented and explored in various contexts. Meanwhile, the anode material performance and cathode design and structure receive the greatest attention. Molybdenum was doped into LSCF via auto-combustion, yielding a fine and porous powder form. X-ray diffraction patterns demonstrated that increasing the Mo dopant increases anodic stability. In parallel, flat and crack-free green cathodes with 47% solid loading can be obtained by adjusting the PEG 4000 to binder quantity ratio at 1.00 wt% and drying the tapes at 70% relative humidity. The tapes had an excellent mechanical strength to flexibility ratio, which allowed them to be readily handled and rolled. The tapes benefited from a strong balance of flexibility and mechanical strength, allowing them to be easily handled and rolled while also exhibiting very low residual stresses during subsequent lamination and co-sintering procedures. The final manufactured SOFC revealed a porous anode structure and a less porous cathode layer using electron microscopy. Whereas the electrolyte was dense enough to ensure gas tightness. There was no delamination throughout the cell. The cells were then electrochemically measured, and the reactivity of LSCFMo to various fuels and temperatures was investigated. LSCFMo performed best when fed by methanol at 700 °C, leaving no carbon traces after operation. The very low ohmic resistance of the electrodes indicates a very good design and manufacture technique. A conclusion is presented in the final section of this thesis to highlight the most significant achievements of this research.

Cette thèse vise à évaluer le potentiel d'un nouveau couple cathode / électrolyte pour une application en IT-SOFC (700°C), par le biais de l'élaboration et du test de cellules à anode support de configuration planaire. Les matériaux concernés sont l'électrolyte BaIn0.3Ti0.7O2.85 (BIT07), de structure perovskite, et les nickelates de terres rares Ln2-xNiO4+ (LnN, Ln = La, Nd, Pr) en tant que cathodes ; ces matériaux ont montré des propriétés prometteuses dans des travaux préliminaires effectués à l'IMN et l'ICMCB. La première partie de cette thèse porte sur la mise en place d'un protocole d'élaboration de cellules complètes utilisant des techniques bas coûts et industrialisables (cellules de taille 3 x 3 cm2) : l'anode Ni / BIT07 a été élaborée par coulage en bande, l'électrolyte BIT07 par vacuum slip casting et les cathodes par sérigraphie. Les mesures électrochimiques réalisées sur une première génération de cellules ont mis en évidence la nécessité d'ajouter une couche barrière de GDC entre les cathodes LnN et l'électrolyte BIT07. Les meilleures performances ont été obtenues pour une cellule BIT07 / Ni | BIT07 | GDC | PrN, avec une densité de puissance à 700°C et 0.7 V de 176 mW cm-2 pour une faible résistance de polarisation de 0. 29 Ω cm2. La principale limitation des performances a été identifiée comme étant la résistance interne du banc de test, donnant lieu à des valeurs de résistances séries anormalement élevées. Cette cellule a été opérée avec succès durant plus de 500 heures sous courant, avec néanmoins une vitesse de dégradation extrapolée élevée de l'ordre de 27% / kh.