Síntese e caracterização da cerâmica de [BaZr0,1Ce0,7Y0,1Yb0,1O3-δ] para uso como eletrólito de Células a Combustível de Cerâmicas Protônicas (PCFCs)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Sistema de instrumentação e controle para células a combustível

Este trabajo presenta un estudio sobre el funcionamiento y aplicaciones de las células de combustible de membrana tipo PEM, o de intercambio de protones, alimentadas con hidrógeno puro y oxigeno obtenido de aire comprimido. Una vez evaluado el proceso de dichas células y las variables que intervienen en el mismo, como presión, humedad y temperatura, se presenta una variedad de métodos para la instrumentación de tales variables así como métodos y sistemas para la estabilidad y control de las mismas, en torno a los valores óptimos para una mayor eficacia en el proceso. Tomando como variable principal a controlar la temperatura del proceso, y exponiendo los valores concretos en torno a 80 grados centígrados entre los que debe situarse, es realizado un modelo del proceso de calentamiento y evolución de la temperatura en función de la potencia del calentador resistivo en el dominio de la frecuencia compleja, y a su vez implementado un sistema de medición mediante sensores termopar de tipo K de respuesta casi lineal. La señal medida por los sensores es amplificada de manera diferencial mediante amplificadores de instrumentación INA2126, y es desarrollado un algoritmo de corrección de error de unión fría (error producido por la inclusión de nuevos metales del conector en el efecto termopar). Son incluidos los datos de test referentes al sistema de medición de temperatura , incluyendo las desviaciones o error respecto a los valores ideales de medida. Para la adquisición de datos y implementación de algoritmos de control, es utilizado un PC con el software Labview de National Instruments, que permite una programación intuitiva, versátil y visual, y poder realizar interfaces de usuario gráficas simples. La conexión entre el hardware de instrumentación y control de la célula y el PC se realiza mediante un interface de adquisición de datos USB NI 6800 que cuenta con un amplio número de salidas y entradas analógicas. Una vez digitalizadas las muestras de la señal medida, y corregido el error de unión fría anteriormente apuntado, es implementado en dicho software un controlador de tipo PID ( proporcional-integral-derivativo) , que se presenta como uno de los métodos más adecuados por su simplicidad de programación y su eficacia para el control de este tipo de variables. Para la evaluación del comportamiento del sistema son expuestas simulaciones mediante el software Matlab y Simulink determinando por tanto las mejores estrategias para desarrollar el control PID, así como los posibles resultados del proceso. En cuanto al sistema de calentamiento de los fluidos, es empleado un elemento resistor calentador, cuya potencia es controlada mediante un circuito electrónico compuesto por un detector de cruce por cero de la onda AC de alimentación y un sistema formado por un elemento TRIAC y su circuito de accionamiento. De manera análoga se expone el sistema de instrumentación para la presión de los gases en el circuito, variable que oscila en valores próximos a 3 atmosferas, para ello es empleado un sensor de presión con salida en corriente mediante bucle 4-20 mA, y un convertidor simple corriente a tensión para la entrada al sistema de adquisición de datos. Consecuentemente se presenta el esquema y componentes necesarios para la canalización, calentamiento y humidificación de los gases empleados en el proceso así como la situación de los sensores y actuadores. Por último el trabajo expone la relación de algoritmos desarrollados y un apéndice con información relativa al software Labview. ABTRACT This document presents a study about the operation and applications of PEM fuel cells (Proton exchange membrane fuel cells), fed with pure hydrogen and oxygen obtained from compressed air. Having evaluated the process of these cells and the variables involved on it, such as pressure, humidity and temperature, there is a variety of methods for implementing their control and to set up them around optimal values for greater efficiency in the process. Taking as primary process variable the temperature, and exposing its correct values around 80 degrees centigrade, between which must be placed, is carried out a model of the heating process and the temperature evolution related with the resistive heater power on the complex frequency domain, and is implemented a measuring system with thermocouple sensor type K performing a almost linear response. The differential signal measured by the sensor is amplified through INA2126 instrumentation amplifiers, and is developed a cold junction error correction algorithm (error produced by the inclusion of additional metals of connectors on the thermocouple effect). Data from the test concerning the temperature measurement system are included , including deviations or error regarding the ideal values of measurement. For data acquisition and implementation of control algorithms, is used a PC with LabVIEW software from National Instruments, which makes programming intuitive, versatile, visual, and useful to perform simple user interfaces. The connection between the instrumentation and control hardware of the cell and the PC interface is via a USB data acquisition NI 6800 that has a large number of analog inputs and outputs. Once stored the samples of the measured signal, and correct the error noted above junction, is implemented a software controller PID (proportional-integral-derivative), which is presented as one of the best methods for their programming simplicity and effectiveness for the control of such variables. To evaluate the performance of the system are presented simulations using Matlab and Simulink software thereby determining the best strategies to develop PID control, and possible outcomes of the process. As fluid heating system, is employed a heater resistor element whose power is controlled by an electronic circuit comprising a zero crossing detector of the AC power wave and a system consisting of a Triac and its drive circuit. As made with temperature variable it is developed an instrumentation system for gas pressure in the circuit, variable ranging in values around 3 atmospheres, it is employed a pressure sensor with a current output via 4-20 mA loop, and a single current to voltage converter to adequate the input to the data acquisition system. Consequently is developed the scheme and components needed for circulation, heating and humidification of the gases used in the process as well as the location of sensors and actuators. Finally the document presents the list of algorithms and an appendix with information about Labview software.

Estudo e desenvolvimento de catalisadores para células a combustível visando o aumento de escala e avaliação da distribuição de corrente

O trabalho visa o desenvolvimento do sistema para medidas de distribuição de corrente e ampliação de escala (50 cm²) buscando aperfeiçoar as condições de preparação do conjunto eletrodo membrana (MEA) quanto às condições de operação da célula e avaliar a melhor geometria. Foram realizados estudos de síntese de catalisadores de Pt-M e avaliação do desempenho desses materias e das rotas de síntese utilizadas com objetivo de aplicar estes materias em sistemas de maior escala. A insuficiência do desempenho e estabilidade dos catalisadores são fatores que ainda inviabilizam o uso em larga escala das células a combustível de eletrólito polimérico sólido, destacando-se as perdas associadas ao desempenho do cátodo. Os catalisadores preparados foram nanopartículas bimetálicas PtM/C (M = Fe, Co e Ni) suportadas em carbono de elevada área superficial, por duas rotas sintéticas. Foram utilizadas as rotas: ácido fórmico e etilenoglicol modificado (EG). Em ambas as rotas se buscou catalisadores com alto grau de incorporação do segundo metal, tamanho de partícula pequeno e bom desempenho catalítico do cátodo. Observou-se que pela rota do ácido fórmico com modificações no processo de síntese é possível obter a incorporação nominal do segundo metal no catalisador, porém há desvantagem de o tamanho de partícula ser elevado. Pela rota do EG obteve-se catalisadores com pequeno tamanho de partícula, porém a incorporação do segundo metal mostrou-se ineficiente. Os estudos de ampliação de escala foram realizados em células de 50 cm2 variando-se as condições de operação; i) diferentes placas de distribuição de gás, e ii) diferentes valores de fluxo dos gases reagentes. Foi observado que a baixos fluxos de gases a quantidade de reagente é insuficiente para ser difundida por todo eletrodo, o que ocasiona reação apenas na região de entrada de gases no sistema, ocasionando uma rápida limitação em obter-se densidades de corrente alta. Pode-se observar que a diferença de desempenho entre as placas é pequena, porém a placa serpentina 6 apresentou melhor desempenho. O desempenho dos cátodos preparados com catalisadores comerciais e os sintetizados no laboratório nas células de 50 cm² mostrou sofrer bastante influência das condições de operação comparada com as células de 4,6 cm².

Síntese e caracterização de PSFC (Pr0,5Sr0,5Fe1-xCuxO3-δ, sendo x=0,2 e x=0,4) para aplicação como catodo de células a combustível de óxido sólido

The PSFC (Pr0.5Sr0.5Fe1-xCuxO3-δ) is a new mixed oxide perovskite and has been studied and evaluated the cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs), mainly due to its good compatibility with the electrolyte (CGO) and its high ionic conductivity and electronic in intermediate temperature. In this work, PSFC powders with two different compositions (Pr0,5Sr0,5Fe0,8Cu0,2O3- PSFC5582 and Pr0,5Sr0,5Fe0,6Cu0,4O3-PSFC5564) were synthesized by the citrate method using a new route. The powders obtained were characterized by thermal analysis (Differential Scanning Calorimetry and Thermogravimetry), and the material calcined at 800, 900 and 1000 °C for 5h were analyzed by X-ray diffractometry (XRD), with the Rietveld refinement of the diffraction data and dilatometry. PSFC5582 composite films were obtained by screen printing of powder calcined at 1000 °C. The films were deposited on substrate ceria doped with gadolinia (CGO) and then sintered at 1050 °C for 2h. The electrochemical performance of the electrodes was evaluated by impedance spectroscopy and the interface electrode/electrolyte was observed by scanning electron microscopy (SEM). The specific resistance area (ASR) was 0.44 Ω.cm² at 800 °C, slightly lower than those reported in the literature for cathodes containing cobalt. The thermal expansion coefficients of both the PSFC compositions were obtained and varied between 13 and 15 x 10-6 °C-1 , in a temperature range of 200 to 650 °C, demonstrating the good thermal compatibility of cathodes with Ce0,9Gd0,1O1,95 electrolytes (CET = 12 x 10-6 °C).

Sinterização de Ce1-XEuXO2-(X/2) para aplicação como eletrólito sólido em células a combustível de temperaturas intermediárias

Given the environmental concern over global warming that occurs mainly by emission of CO2 from the combustion of petroleum, coal and natural gas research focused on alternative and clean energy generation has been intensified. Among these, the highlight the solid oxide fuel cell intermediate temperature (IT-SOFC). For application as electrolyte of the devices doped based CeO2 with rare earth ions (TR+ 3) have been quite promising because they have good ionic conductivity and operate at relatively low temperatures (500-800 ° C). In this work, studied the Ce1-xEuxO2-δ (x = 0,1, 0,2 and 0,3), solid solutions synthesized by the polymeric precursor method to be used as solid electrolyte. It was also studied the processing steps of these powders (milling, compaction and two step sintering) in order to obtain dense sintered pellets with reduced grain size and homogeneous microstructure. For this, the powders were characterized by thermal analysis, X-ray diffraction, particle size distribution and scanning electrons microscopy, since the sintered samples were characterized by dilatometry, scanning electrons microscopy, density and grain size measurements. By x-ray diffraction, it was verified the formation of the solid solution for all compositions. Crystallites in the nanometric scale were found for both sintering routes but the two step sintering presented significant reduction in the average grain size

Influência do método de síntese e caracterização de pós compósitos de NiO- Ce1-xEuxO2-δ para anodos catalíticos de células a combustível

Fuel cells are electrochemical devices that convert chemical energy into electricity. Due to the development of new materials, fuel cells are emerging as generating clean energy generator. Among the types of fuel cells, categorized according to the electrode type, the solid oxide fuel cells (SOFC) stand out due to be the only device entirely made of solid particles. Beyond that, their operation temperature is relatively high (between 500 and 1000 °C), allowing them to operate with high efficiency. Another aspect that promotes the use of SOFC over other cells is their ability to operate with different fuels. The CeO2 based materials doped with rare earth (TR+3) may be used as alternatives to traditional NiO-YSZ anodes as they have higher ionic conductivity and smaller ohmic losses compared to YSZ, and can operate at lower temperatures (500-800°C). In the composition of the anode, the concentration of NiO, acting as a catalyst in YSZ provides high electrical conductivity and high electrochemical activity of reactions, providing internal reform in the cell. In this work compounds of NiO - Ce1-xEuxO2-δ (x = 0.1, 0.2 and 0.3) were synthesized from polymeric precursor, Pechini, method of combustion and also by microwave-assisted hydrothermal method. The materials were characterized by the techniques of TG, TPR, XRD and FEG-SEM. The refinement of data obtained by X-ray diffraction showed that all powders of NiO - Cex-1EuxO2-δ crystallized in a cubic phase with fluorite structure, and also the presence of Ni. Through the characterizations can be proved that all routes of preparation used were effective for producing ceramics with characteristics suitable for application as SOFC anodes, but the microwave-assisted hydrothermal method showed a significant reduction in the average grain size and improved control of the compositions of the phases

Preparação e caracterização de filmes cerâmicos para cátodos de células a combustível de óxido sólido

Alternative and clean energy generation research has been intensified in last decades. Among the alternatives, fuel cells are one of the most important. There are different types of fuel cells, among which stands out intermediate temperature solid oxide fuel cell (IT-SOFC) matter of the present work. For application as cathode on this type of devices, the ceramic Ba0.5Sr0.5C0.8Fe0.2O3-δ doped with rare earth ions (Nd, Sm) have been quite promising because they show good ionic conductivity and operate at relatively low temperatures (500 - 800°C). In this work, Ba0.5Sr0.5Co0.8Fe0.2O3-δ, (BaSr)0.5Sm0.5Co0.8Fe0.2O3-δ and (BaSr)0.5Nd0.5C0.8Fe0.2O3-δ were obtained by modified Pechini method, making use of gelatin as polymerizing agent. The powders were characterized by X-Ray Diffraction (XRD), Temperature Programmed Reduction (TPR) and Scanning Electron Microscopy (SEM). The perovskite phase was observed in all X-ray patterns for the materials Ba0.5Sr0.5C0.8Fe0.2O3-δ doped with rare earth ions (Nd, Sm). The SEM images showed that the materials have a characteristics porous, with very uniform pore distribution, which are favorable for application as cathodes. Subsequently, screen-printed assymmetrical cells were studied by impedance spectroscopy, to assess the kinetics of the cathode for the reduction reaction of oxygen. The best resistance to the specific area was found for the cathode BSSCF sintered at 1050 °C for 4 hours with around 0.15 Ω.cm2 at 750 °C as well as cathodes BSNCF and BSCF obtained resistances specific area of 0.2 and 0.73 Ω.cm2, respectively, for the same conditions. The polarization curves showed similar behavior to the best cathodes BSSCF and BSNCF, such combination of properties indicates that the film potentially depict good performance as IT-SOFC cathodes

Síntese e caracterização de intermetálicos ordenados binários de ouro: potenciais eletrocatalisadores de reações em células à combustível

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Síntese citrato-hidrotermal e caracterização eletroquímica de LSCF para aplicação como catodo em célula a combustível de temperatura intermediária

The lanthanum strontium cobalt iron oxide (La1-xSrxCo1-yFeyO3 LSCF) is the most commonly used material for application as cathode in Solid Oxide Fuel Cells (SOFCs), mainly due to their high mixed ionic electronic conductivity between 600 and 800ºC. In this study, LSCF powders with different compositions were synthesized via a combination between citrate and hydrothermal methods. As-prepared powders were calcined from 700 to 900°C and then characterized by X-ray fluorescence, X-ray diffraction, thermal analyses, particle size analyses, nitrogen adsorption (BET) and scanning electronic microscopy. Films of composition La0,6Sr0,4Co0,2Fe0,8O3 (LSCF6428), powders calcined at 900°C, were screen-printed on gadolinium doped ceria (CGO) substrates and sintered between 1150 and 1200°C. The effects of level of sintering on the microstructure and electrochemical performance of electrodes were evaluated by scanning electronic microscopy and impedance spectroscopy. Area specific resistance (ASR) exhibited strong relation with the microstructure of the electrodes. The best electrochemical performance (0.18 ohm.cm2 at 800°C) was obtained for the cathode sintered at 1200°C for 2 h. The electrochemical activity can be further improved through surface activation by impregnation with PrOx, in this case the electrode area specific resistance decreases to values as low as 0.12 ohm.cm2 (800°C), 0.17 ohm.cm2 (750°C) and 0.31 ohm.cm2 (700°C). The results indicate that the citrate-hydrothermal method is suitable for the attainment of LSCF particulates with potential application as cathode component in intermediate temperature solid oxide fuel cells (IT-SOFCs)

Análise econômica do uso de célula a combustível para acionamento de ônibus urbano

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)