The thesis studies the sintering behaviours and mechanical properties of perovskite-structured Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) ceramics. The sintering behaviours of BSCF are studied by sintering BSCF powder using a series of sintering temperatures and dwell times. Under all circumstances, only a cubic perovskite structure is identified in as-sintered samples. The relative density of BSCF increases with increasing sintering temperature and dwell time, but shows a more significant increase with increasing temperature. While the grain size increases with increasing sintering temperature and dwell time, it is found that the increasing temperature contributes much more significantly than increasing dwell time in grain growth. The shape of grain size distribution profile is independent of sintering temperature and dwell time, but the profile shifts with different sintering conditions. The grain maintains an aspect ratio of 1.8 irrespective of sintering conditions. Similar findings are also made on the Ni-doped BSCF, but it is found that Ni doping inhibits the grain growth and retards the densification of BSCF while it has little influence on the grain size distributions and grain aspect ratio distributions. The grain growth exponent (n) and apparent activation energy (Q) are also systematically studied. It is found that grain boundary diffusion is the dominant controlling mechanism for BSCF while both grain boundary and lattice diffusions are the equally dominant controlling mechanisms for BSCF-Ni8. The fracture stress of BSCF is measured by both three-point and ring-on-ring bending tests at room and high temperatures. The fracture stress determined by three-point bending tests is consistently higher than that value measured by ring-on-ring tests for a given temperature. By utilising Weibull statistics a close prediction is made of the three-point values from the ring-on-ring values. Compared with the Young’s modulus of BSCF obtained from three-point bending tests between RT and 800 °C, the values determined from ring-on-ring tests shows a fairly good agreement. However, the Young’s modulus measured by both bending tests is lower than that value determined by micro-indentation tests. Hardness and fracture toughness are independent of grain size and grain orientation. Porosity is the dominant factor in Young’s modulus, hardness and fracture toughness of BSCF. The intrinsic hardness, intrinsic Young’s modulus and intrinsic fracture toughness of BSCF are also determined. The subcritical crack growth (SCG) of BSCF is also studied using constant load method at RT and constant stress rate method at 800 °C. It is found that that BSCF is not susceptible to SCG at RT but becomes relatively sensitive to SCG at 800 °C. The results are subsequently used as a basis for a strength–probability–time (SPT) lifetime prediction. Ni doping increases the Young’s modulus, hardness and fracture toughness of BSCF determined micro-indentation tests at RT. Both hardness and Young’s modulus show a non-monotonic trend with Ni doping content, which is attributed to the porosity and secondary phase. The intrinsic hardness, intrinsic Young’s modulus and intrinsic fracture toughness of 8 mol% Ni-doped BSCF are determined. Dopants have little influence on grain orientation and the distribution of grain boundary misorientation angles of BSCF.

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.

O óxido misto de Ba0,50Sr0,50Co0,80Fe0,20O3-δ (BSCF) apresenta propriedades funcionais para ser usado como material catódico de Células a Combustível de Óxido Sólido de Temperatura Intermediária (ITSOFCs). O BSCF, preparado a partir de nitratos, por reação em fase líquida, pelo método de complexação EDTA-Citratos em condições variadas de pH, foi calcinado para obtenção de particulados cristalinos e monofásicos, e posteriormente sinterizados. A caracterização dos particulados e corpos cerâmicos foi realizada utilizando as técnicas de Análise física, química e microestrutural, visando à avaliação do comportamento e das propriedades do composto para utilização como cátodo de ITSOFCs. O comportamento térmico dos particulados indicou estabilidade composicional após tratamento térmico acima de 850°C, a estequiometria real dos particulados ficou próxima da estequiometria teórica, a presença de carbono residual, após tratamento térmico acima de 800°C dos particulados, foi inferior a 0,5% em massa, foi encontrada presença de resíduos de carbonato nos particulados, com exceção daqueles obtidos em pH 4, os particulados com estrutura cristalina monofásica, de menor área de superfície específica e maior porosidade foram obtidos com tratamento térmico a 900°C por 5h. As cerâmicas apresentaram coeficiente de expansão térmica próximo dos eletrólitos de Céria dopada com Gadolínia (GDC) e Céria dopada com Samária (SDC), comumente utilizados em ITSOFCs, densificação e porosidades adequadas, quando sinterizadas a 1000°C por 1h. A condutividade elétrica foi maior para as cerâmicas, sinterizadas a 1000°C por 1h, originadas dos particulados obtidos em pH 6 de síntese, calcinados a 900°C por 5h. / The mixed oxide of Ba0,50Sr0,50Co0,80Fe0,20O3-δ (BSCF) present functional properties to be used as cathode material of Intermediate Temperature Solid Oxide Fuel Cell (ITSOFC). The BSCF, prepared from nitrates by liquid phase reaction with complexing method EDTA-Citrates, under conditions of varying pH, was calcined to obtain a particulate crystalline single-phase and, subsequently sintered. The characterization of particulate and ceramic bodies was performed using the physical, chemical and microstructure analysis, in order to evaluate the behavior and properties of the compound for use as a cathode for ITSOFCs. The thermal behavior of particulate indicated compositional stability after heat treatment above 850°C, the actual stoichiometry of the particles was close to theoretical stoichiometry, the presence of residual carbon after thermal treatment above 800°C of particulates was less than 0.5% in weight, was found residues of carbonate in particulate, except those obtained at pH 4, the particulates with monophasic crystalline structure, with lower specific surface area and greater porosity were obtained with thermal treatment at 900°C for 5h. The ceramics exhibited thermal expansion coefficient close to the electrolyte Gadolinia doped Ceria (GDC) and Samaria doped Ceria (SDC), commonly used in ITSOFCs, porosity and adequate densification when sintered at 1000°C for 1h. The electrical conductivity was higher for ceramics sintered at 1000°C for 1h, originating from particulates obtained at pH 6 synthesis, calcined at 900°C for 5h.

O óxido misto de Ba0,50Sr0,50Co0,80Fe0,20O3-δ (BSCF) apresenta propriedades funcionais para ser usado como material catódico de Células a Combustível de Óxido Sólido de Temperatura Intermediária (ITSOFCs). O BSCF, preparado a partir de nitratos, por reação em fase líquida, pelo método de complexação EDTA-Citratos em condições variadas de pH, foi calcinado para obtenção de particulados cristalinos e monofásicos, e posteriormente sinterizados. A caracterização dos particulados e corpos cerâmicos foi realizada utilizando as técnicas de Análise física, química e microestrutural, visando à avaliação do comportamento e das propriedades do composto para utilização como cátodo de ITSOFCs. O comportamento térmico dos particulados indicou estabilidade composicional após tratamento térmico acima de 850°C, a estequiometria real dos particulados ficou próxima da estequiometria teórica, a presença de carbono residual, após tratamento térmico acima de 800°C dos particulados, foi inferior a 0,5% em massa, foi encontrada presença de resíduos de carbonato nos particulados, com exceção daqueles obtidos em pH 4, os particulados com estrutura cristalina monofásica, de menor área de superfície específica e maior porosidade foram obtidos com tratamento térmico a 900°C por 5h. As cerâmicas apresentaram coeficiente de expansão térmica próximo dos eletrólitos de Céria dopada com Gadolínia (GDC) e Céria dopada com Samária (SDC), comumente utilizados em ITSOFCs, densificação e porosidades adequadas, quando sinterizadas a 1000°C por 1h. A condutividade elétrica foi maior para as cerâmicas, sinterizadas a 1000°C por 1h, originadas dos particulados obtidos em pH 6 de síntese, calcinados a 900°C por 5h. / The mixed oxide of Ba0,50Sr0,50Co0,80Fe0,20O3-δ (BSCF) present functional properties to be used as cathode material of Intermediate Temperature Solid Oxide Fuel Cell (ITSOFC). The BSCF, prepared from nitrates by liquid phase reaction with complexing method EDTA-Citrates, under conditions of varying pH, was calcined to obtain a particulate crystalline single-phase and, subsequently sintered. The characterization of particulate and ceramic bodies was performed using the physical, chemical and microstructure analysis, in order to evaluate the behavior and properties of the compound for use as a cathode for ITSOFCs. The thermal behavior of particulate indicated compositional stability after heat treatment above 850°C, the actual stoichiometry of the particles was close to theoretical stoichiometry, the presence of residual carbon after thermal treatment above 800°C of particulates was less than 0.5% in weight, was found residues of carbonate in particulate, except those obtained at pH 4, the particulates with monophasic crystalline structure, with lower specific surface area and greater porosity were obtained with thermal treatment at 900°C for 5h. The ceramics exhibited thermal expansion coefficient close to the electrolyte Gadolinia doped Ceria (GDC) and Samaria doped Ceria (SDC), commonly used in ITSOFCs, porosity and adequate densification when sintered at 1000°C for 1h. The electrical conductivity was higher for ceramics sintered at 1000°C for 1h, originating from particulates obtained at pH 6 synthesis, calcined at 900°C for 5h.

Ba0.5Sr0.5Co0.8Fe0.2O3-delta (BSCF) and SrCo0.48Fe0.12Ti0.4O3-delta (SCFT) were synthesised by co-precipitation. BSCF was pressed and sintered at 1100℃ for 10 hours to pellets (relative density: 93%) from which X-ray diffraction (XRD) revealed single Pm-3m phase (a=3.9782 A). Scanning electron microscopy (SEM) revealed clear equiaxed grains (grain size 33 ± 16 micro metre). The pellets were decomposed in 7 ± 1 % CO2/N2 at 800℃ for 1 to 30 minutes. XRD confirmed secondary phases: R-3mH phase (a=b=5.1397 A, c=9.4847 A) and Fm-3m phase (a=4.2490 A). Electron backscattered diffraction (EBSD) ascribed R-3mH and Fm-3m phases to the surface and part of the cross-section precipitates, respectively as revealed by SEM. Energy dispersive X-ray spectroscopy (EDX) revealed the compositions of R-3mH and Fm-3m phases to be Ba0.65±0.03Sr0.35±0.03CO3 (BSC) and CoO, respectively. Transmission electron microscopy (TEM) and EDX revealed the structure (15R, R3m and R-3mH) and composition (Ba0.20Sr0.10Co0.59Fe0.10Ox) of lamellar precipitates in cross-section, suggesting Ba and Sr diffuse from the lamellae to BSC. A unique orientation relation (BSCF {111} // BSC {0001}) was uncovered by EBSD. TEM revealed high symmetry contact planes of lamellae and BSCF, suggesting nucleation energy governs decomposition. Fresh BSCF pellets were decomposed in N2 at 800℃. Fm-3m and P63/mmc phases were confirmed by XRD and lamellae were observed by SEM, followed by decomposition in 7±1 % N2/CO2 at 800℃. XRD revealed higher weight % of BSC and CoO. SEM revealed BSC preferring lamellae, hence hexagonal phases accelerated BSC formation. BSCF pellets were dip coated in SCFT propan-2-ol suspension (3:10), followed by sintering at 1165℃ for 10 hours. XRD revealed a Pm-3m phase (a=3.885 A) and SEM revealed a grain size of 65 ± 9 micro metre and open porosity of 1.6 ± 1 %. They were annealed in 7 ± 1 % CO2/N2 at 800℃. XRD revealed no secondary phases, suggesting enhanced stability. However, oxygen permeability was reduced (1.2 ml/cm2 to 0.8 ml/cm2) because the coating composition changed to Ba0.20Sr0.27Co0.40Fe0.10Ti0.04Ox; this was revealed by EDX.

En esta tesis se estudiaron las propiedades electroquímicas y la estabilidad de fases de los compuestos La1-xBaxCoO3-g con 0.0 ≤ x ≤ 1.0 para su utilización como material de cátodo. Se determinó el diagrama de fases y la estabilidad de la estructura cristalina perovskita cúbica en aire. Medidas de conductividad eléctrica, dilatometría, termogravimetría y espectroscopía de impedancia compleja se utilizaron para evaluar y relacionar las distintas propiedades con el rendimiento catódico. La muestra con x = 0.7 presentó el mejor desempeño como electrodo con un valor de resistencia de polarización de Rp = 0.065 Ωcm2 a 600 ºC, en aire, cuando se utiliza una configuración de electrodo con gradiente de composición. La estructura perovskita cúbica de las muestras del sistema La1-xBaxCoO3-g con alto contenido de Ba resultaron tener una transformación de fase hacia una estructura hexagonal a temperatura intermedia. Con el objetivo de estabilizar la estructura cristalina cúbica se realizó el reemplazo de Co por Fe en el sitio B de la perovskita. De esta manera se estudio el diagrama de fase del sistema La1-xBaxCo1-yFeyO3-g con 0.7 ≤ x ≤ 0.9 y 0.1 ≤ y ≤ 0.6. Se observó que el contenido necesario para estabilizar la fase con estructura perovskita cúbica aumenta desde y = 0.3 hasta y = 0.6 cuando el contenido de Ba aumenta desde x = 0.7 hasta x = 0.9. Sobre las muestras estabilizadas se evaluaron los coeficientes de expansión, el contenido de oxígeno y la respuesta electroquímica en función de la temperatura y la presión parcial de oxígeno. Finalmente se estudió la influencia en la Rp de la microestructura, configuración y composición del electrodo mediante el uso de las cobaltitas del sistema La1-xBaxCoO3-g con x = 0.5, 0.7 y 1.0, Ba0.5Sr0.5Co0.8Fe0.2O3-g y BaCo0.7Fe0.2Nb0.1O3-g y el uso de electrodos con gradientes de composición y material compuesto, con Ce0.9Gd0.1O1.95 como material de electrolito. El valor de Rp mostró mayor dependencia con la configuración del electrodo que de la composición y microestructura del material utilizado. Los menores valores de Rp se obtuvieron para las cobaltitas de La0.5Ba0.5CoO3-g y Ba0.5Sr0.5Co0.8Fe0.2O3-g con la configuración de electrodo con gradiente de composición, con Rp = 0.036 y 0.039 Ω cm2 a 600 ºC, en aire, respectivamente. / In this thesis, the electrochemical properties and phase stability of La1-xBaxCoO3-g system with 0.0 ≤ x ≤ 1.0 as cathode material for IT-SOFC were studied. The phase diagram and the stability of the cubic perovskite crystal structure were determined in air. Measurements of electrical conductivity, dilatometry, thermogravimetry and complex impedance spectroscopy were used to evaluate the different properties and relate with the cathode performance. The samples with x = 0.7 have shown the best performance as electrode with a polarization resistance value of Rp = 0.065 Ωcm2 at 600 °C, in air, when a graded cathode configuration was used. The cubic perovskite phases in the La1-xBaxCoO3-g system with high Ba content (x > 0.5) were found to have a phase transformation to a hexagonal structure at intermediate temperature. In order to stabilize the cubic crystal structure, the substitution of Co for Fe was performed in the B site of the perovskite. Thus the phase diagram of La1-xBaxCo1-yFeyO3-g system with 0.7 ≤ x ≤ 0.9 and 0.1 ≤ y ≤ 0.6 was studied. It was observed that the content needed to stabilize the perovskite phase with cubic structure increases from y = 0.3 to y = 0.6 when the Ba content increases from x = 0.7 to x = 0.9. The expansion coefficients, the oxygen content and the electrochemical response as a function of temperature and oxygen partial pressure were evaluated for the stable cubic perovskites. Finally, the effect of the microstructure, composition and electrode configuration on the polarization resistance of the compounds La1-xBaxCoO3-g with x = 0.5, 0.7 and 1.0, and Ba0.5Sr0.5Co0.8Fe0.2O3-g and BaCo0.7Fe0.2Nb0.1O3-g was studied using a graded electrode configuration with Ce0.9Gd0.1O1.95 as electrolyte. The results indicate that the electrode configuration is more important than the composition and the microstructure of the material in order to reduce the polarization resistance. The lower values of Rp were obtained for the cobaltites La0.5Ba0.5CoO3-g and Ba0.5Sr0.5Co0.8Fe0.2O3-g using the graded cathode electrode configuration. The values were Rp = 0.036 and 0.039 Ωcm2 at 600 °C in air, respectively.

This thesis focuses on developing an appropriate cathode material throughnanotechnology as a key component for a promising alternative of renewable energygenerating systems, Intermediate Temperature Solid Oxide Fuel Cells (IT-SOFC).Aiming at a working cathode material for IT-SOFC, a recently reported capable oxideperovskite material has been synthesized through two different chemical methods.BaxSr1-xCoyFe1-yO3−δ (BSCF) with y =0.8 and x =0.2 was fabricated in nanocrystallineform by a novel chemical alloying approach, co-precipitation- as well as conventionalsol-gel method to produce oxide perovskites. The thermal properties, phase constituents,microstructure and elemental analysis of the samples were characterized by TG-DSC,XRD, SEM and EDS techniques respectively. Thermodynamic modeling has beenperformed using a KTH-developed software (Medusa) and Spark Plasma Sintering (SPS)has been used to obtain pellets of BSCF, preserving the nanostructure and generatingquite dense pellets for electrical conductivity measurements.The results show that the powders synthesized by solution co-precipitation have cubicperovskite-type structure with a high homogeneity and uniform distribution and meanparticle size of 50-90 nm range, while sol-gel powders are not easy to form a pure phaseand mostly the process ends up with large particle containing two or three phases.Finer resultant powder compared to sol-gel technique and earlier research works onBSCF has been achieved in this project using oxalate co-precipitation method. Topreserve nanoscaled features of BSCF powder which possess a significant increase ofelectrical conductivity due to decrease the electrical resistivity of grain boundaries, forthe sample synthesized through co-precipitation, ~92% dense pellet sintered by SPS atV1080 °C and under 50 MPa pressure and its electrical conductivity has been measuredfrom room temperature to 900 °C.Specific conductivity values were precisely measured and the maximum of 63 S.cm-1 at430 °C in air and 25 S.cm-1 at 375°C in N2 correspondingly are two times higher thanconventional BSCF implying a high pledge for nano-BSCF as a strong candidate ascathode material in IT-SOFC.

Preparation and performance of the perovskite-type barium strontium cobalt iron oxide (Ba_0.5 Sr_0.5 Co_0.8 Fe_0.2 O_(3-δ), BSCF) and its doped compositions were studied in this dissertation. Three transition metals (copper, nickel and niobium) were substituted into the parent BSCF at various ratios to create the formula Ba_0.5 Sr_0.5 (Co_0.8 Fe_0.2)_(1-x) M_x O_(3-δ) (0.02≤x≤0.30; M=Cu,Ni or Nb). Two synthetic methods (solid-state reaction and wet chemical co-precipitation) were developed for the preparation of starting powders. In the previous reports [1, 2], BSCF ceramics suffered from insufficient densification and severe cracking; these problems were resolved in this study by optimising the ceramic processing conditions. The phase transition sequences from starting powders to single-phase cubic perovskite were studied by SEM, XRD, TGA, EDS and Raman spectroscopy. The powders prepared by solid-state method were found to require higher calcination temperature to form pure perovskite phase, and an extra intermediate structure (Ba,Sr)Fe_2 O_4 was detected in the reaction sequence. The materials performance was examined from five aspects: thermal stability, chemical stability, oxygen permeability, electronic conductivity and mechanical performance. The secondary phases of thermal/chemical degradation were investigated, and a needle-like intragranular precipitate was originally discovered in this work. It was discovered that the niobium substitution could significantly improve BSCF’s thermal stability and chemical stability. The oxygen permeability and mechanical performance were also improved by niobium when the substitution ratios are small (< 10%). Although the electronic conductivity was lowered by niobium substitution as a trade-off, it does not become a drawback to restrict the materials’ potential applications as mixed ionic-electronic conductors (MIEC).Furthermore, the material system’s “composition - lattice structure - performance” relationships were systematically investigated in this work; the oxygen deficiency value (δ) and the average bond energy (ABE) were found to have strong correlations with the materials performance.

Cette étude est dédiée au développement de piles à combustible de type SOFC en configuration monochambre. L'originalité de ce type de pile SOFC est l'absence de séparation physique entre les compartiments anodique et cathodique. Un mélange d'hydrocarbure et d'air est injecté sur l'ensemble du dispositif comportant l'électrolyte et les deux électrodes de la pile SOFC. Le principe de fonctionnement de ce type de pile repose sur la différence d'activité catalytique entre les deux électrodes. L'anode doit être sélective pour l'oxydation des hydrocarbures et la cathode pour la réduction de l'oxygène. Cette configuration originale permet de s'affranchir des problèmes d'étanchéité des configurations conventionnelles deux atmosphères, ainsi que d'éviter les contraintes sur l'épaisseur de l'électrolyte suivant la disposition des électrodes (coplanaires ou de part et d'autre de l'électrolyte). Cette configuration conduit à des dispositifs simplifiés du point de vue technologique, et donc moins coûteux.<br />Dans cette étude, les électrodes ont été déposées en couches épaisses par la technologie de sérigraphie sur des pastilles support d'électrolyte. Au niveau matériaux, des électrolytes à base de cérine (en particulier GDC et SDC) ont été utilisés afin de diminuer la température de fonctionnement des piles de type SOFC (par rapport à celles avec un électrolyte YSZ). Des électrodes à propriétés catalytiques bien spécifiques vis à vis du mélange gazeux, ont été aussi étudiés : cermets Ni - GDC ou Ni - SDC pour l'anode, cathodes à base de LSM, BSCF ou SSC. Les poudres initiales ainsi que les couches sérigraphiées ont été caractérisées (analyse de phase, microstructure, stabilité chimique, conductivité électrique...) par diverses méthodes physico-chimiques. Différentes piles ont été élaborées et testées dans un réacteur monochambre sous des mélanges air-propane. L'influence des conditions gazeuses (débit, composition) ainsi que de la température de fonctionnement sur les performances des piles a été étudiée. Compte tenu de nos conditions de test, les performances se sont avérées relativement modestes (densité de puissance maximale de l'ordre de 12 mW.cm-2). Néanmoins, cette étude confirme la validité du concept des piles SOFC monochambres, et a aussi permis de développer un savoir-faire au niveau du laboratoire pour poursuivre les études sur cette thématique.