Modeling And Predicting The Performance Of Infiltrated Solid Oxide Fuel Cell Anodes

Fuel cells are a topic of high interest in the scientific community right now because of their ability to efficiently convert chemical energy into electrical energy. This thesis is focused on solid oxide fuel cells (SOFCs) because of their fuel flexibility, and is specifically concerned with the anode properties of SOFCs. The anodes are composed of a ceramic material (yttrium stabilized zirconia, or YSZ), and conducting material. Recent research has shown that an infiltrated anode may offer better performance at a lower cost. This thesis focuses on the creation of a model of an infiltrated anode that mimics the underlying physics of the production process. Using the model, several key parameters for anode performance are considered. These are the initial volume fraction of YSZ in the slurry before sintering, the final porosity of the composite anode after sintering, and the size of the YSZ and conducting particles in the composite. The performance measures of the anode, namely percolation threshold and effective conductivity, are analyzed as a function of these important input parameters. Simple two and three-dimensional percolation models are used to determine the conditions at which the full infiltrated anode would be investigated. These more simple models showed that the aspect ratio of the anode has no effect on the threshold or effective conductivity, and that cell sizes of 303 are needed to obtain accurate conductivity values. The full model of the infiltrated anode is able to predict the performance of the SOFC anodes and it can be seen that increasing the size of the YSZ decreases the percolation threshold and increases the effective conductivity at low conductor loadings. Similar trends are seen for a decrease in final porosity and a decrease in the initial volume fraction of YSZ.

Development And Use Of A Model To Predict Properties Of Infiltrated Solid Oxide Fuel Cell Anodes

Solid oxide fuel cells (SOFCs) provide a potentially clean way of using energy sources. One important aspect of a functioning fuel cell is the anode and its characteristics (e.g. conductivity). Using infiltration of conductor particles has been shown to be a method for production at lower cost with comparable functionality. While these methods have been demonstrated experimentally, there is a vast range of variables to consider. Because of the long time for manufacture, a model is desired to aid in the development of the desired anode formulation. This thesis aims to (1) use an idealized system to determine the appropriate size and aspect ratio to determine the percolation threshold and effective conductivity as well as to (2) simulate the infiltrated fabrication method to determine the effective conductivity and percolation threshold as a function of ceramic and pore former particle size, particle fraction and the cell¿s final porosity. The idealized system found that the aspect ratio of the cell does not affect the cells functionality and that an aspect ratio of 1 is the most efficient computationally to use. Additionally, at cell sizes greater than 50x50, the conductivity asymptotes to a constant value. Through the infiltrated model simulations, it was found that by increasing the size of the ceramic (YSZ) and pore former particles, the percolation threshold can be decreased and the effective conductivity at low loadings can be increased. Furthermore, by decreasing the porosity of the cell, the percolation threshold and effective conductivity at low loadings can also be increased

An Investigation of Two Ceramic Electron Conductors for Use in Solid Oxide Fuel Cell Anodes

Conducted work with two potential alternatives to Ni, La0.8Sr0.2Cr0.5Mn0.5 (LSCM) and Sr doped LaVO3 (LSV) to serve as the electron conductor in the anode of solid oxide fuel cells SOFCs.

Development of Solid Oxide Fuel Cell Electrodes with High Conductivity and Enhanced Redox Stability

The intent of this study was the development of new ceramic SOFC anode materials which possess electrical conductivity as well as redox stability.

Local degradation of structural, mechanical, electrical and chemical properties of membrane electrode assembly in polymer electrolyte fuel cell

Polymer electrolyte fuel cell (PEMFC) is promising source of clean power in many applications ranging from portable electronics to automotive and land-based power generation. However, widespread commercialization of PEMFC is primarily challenged by degradation. The mechanisms of fuel cell degradation are not well understood. Even though the numbers of installed units around the world continue to increase and dominate the pre-markets, the present lifetime requirements for fuel cells cannot be guarantee, creating the need for a more comprehensive knowledge of material’s ageing mechanism. The objective of this project is to conduct experiments on membrane electrode assembly (MEA) components of PEMFC to study structural, mechanical, electrical and chemical changes during ageing and understanding failure/degradation mechanism. The first part of this project was devoted to surface roughness analysis on catalyst layer (CL) and gas diffusion layer (GDL) using surface mapping microscopy. This study was motivated by the need to have a quantitative understanding of the GDL and CL surface morphology at the submicron level to predict interfacial contact resistance. Nanoindentation studies using atomic force microscope (AFM) were introduced to investigate the effect of degradation on mechanical properties of CL. The elastic modulus was decreased by 45 % in end of life (EOL) CL as compare to beginning of life (BOL) CL. In another set of experiment, conductive AFM (cAFM) was used to probe the local electric current in CL. The conductivity drops by 62 % in EOL CL. The future task will include characterization of MEA degradation using Raman and Fourier transform infrared (FTIR) spectroscopy. Raman spectroscopy will help to detect degree of structural disorder in CL during degradation. FTIR will help to study the effect of CO in CL. XRD will be used to determine Pt particle size and its crystallinity. In-situ conductive AFM studies using electrochemical cell on CL to correlate its structure with oxygen reduction reaction (ORR) reactivity

Fluidic oscillator design for water removal enhancement in a PEM fuel cell

This research initiative was triggered by the problems of water management of Polymer Electrolyte Membrane Fuel Cell (PEMFC). In low temperature fuel cells such as PEMFC, some of the water produced after the chemical reaction remains in its liquid state. Excess water produced by the fuel cell must be removed from the system to avoid flooding of the gas diffusion layers (GDL). The GDL is responsible for the transport of reactant gas to the active sites and remove the water produced from the sites. If the GDL is flooded, the supply gas will not be able to reach the reactive sites and the fuel cell fails. The choice of water removal method in this research is to exert a variable asymmetrical force on a liquid droplet. As the drop of liquid is subjected to an external vibrational force in the form of periodic wave, it will begin to oscillate. A fluidic oscillator is capable to produce a pulsating flow using simple balance of momentum fluxes between three impinging jets. By connecting the outputs of the oscillator to the gas channels of a fuel cell, a flow pulsation can be imposed on a water droplet formed within the gas channel during fuel cell operation. The lowest frequency produced by this design is approximately 202 Hz when a 20 inches feed-back port length was used and a supply pressure of 5 psig was introduced. This information was found by setting up a fluidic network with appropriate data acquisition. The components include a fluidic amplifier, valves and fittings, flow meters, a pressure gage, NI-DAQ system, Siglab®, Matlab software and four PCB microphones. The operating environment of the water droplet was reviewed, speed of the sound pressure which travels down the square channel was precisely estimated, and measurement devices were carefully selected. Applicable alternative measurement devices and its application to pressure wave measurement was considered. Methods for experimental setup and possible approaches were recommended, with some discussion of potential problems with implementation of this technique. Some computational fluid dynamic was also performed as an approach to oscillator design.

Characterization Of Porous Media In Proton Exchange Membrane Fuel Cell Based on Percolation Studies

Water management in the porous media of proton exchange membrane (PEM) fuel cells, catalyst layer and porous transport layers (PTL) is confronted by two issues, flooding and dry out, both of which result in improper functioning of the fuel cell and lead to poor performance and degradation. The data that has been reported about water percolation and wettability within a fuel cell catalyst layer is limited to porosimetry. A new method and apparatus for measuring the percolation pressure in the catalyst layer has been developed. The experimental setup is similar to a Hele-Shaw experiment where samples are compressed and a fluid is injected into the sample. Pressure-Wetted Volume plots as well as Permeability plots for the catalyst layers were generated from the percolation testing. PTL samples were also characterizes using a Hele-Shaw method. Characterization for the PTLs was completed for the three states: new, conditioned and aged. This is represented in a Ce-t* plots, which show a large offset between new and aged samples.

Multi-scale study of hydrogen isotopes structural properties in solid phase in the context of inertial fusion target manufacturing

Designing the ignition and high-gain targets for inertial confinement fusion (ICF) requires a condensed uniform layer of the hydrogen fuel on the inner surface of a spherical polymer shell. The fuel layers have to be highly uniform in thickness and roughness.

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.

Marine Practice Guidelines for Fuel Cell Applications

This paper focuses on the implementation of fuel cells in marine systems as a propulsion system and energy source. The objective is to provide an overview of the pertinent legislation for marine applications of fuel cells. This work includes a characterization of some guidelines for the safe application of fuel cell systems on ships. It also describes two ships that have implemented fuel cells to obtain energy, the Viking Lady, the first marine ship to include this technology, and Greentug, a reference for new tugs

Long Term Performance Study of a Direct Methanol Fuel Cell Fed with Alcohol Blends

The use of alcohol blends in direct alcohol fuel cells may be a more environmentally friendly and less toxic alternative to the use of methanol alone in direct methanol fuel cells. This paper assesses the behaviour of a direct methanol fuel cell fed with aqueous methanol, aqueous ethanol and aqueous methanol/ethanol blends in a long term experimental study followed by modelling of polarization curves. Fuel cell performance is seen to decrease as the ethanol content rises, and subsequent operation with aqueous methanol only partly reverts this loss of performance. It seems that the difference in the oxidation rate of these alcohols may not be the only factor affecting fuel cell performance.

Conceptual design of offshore platform supply vessel based on hybrid diesel generator-fuel cell power plant

Nowadays increasing fuel prices and upcoming pollutant emission regulations are becoming a growing concern for the shipping industry worldwide. While fuel prices will keep rising in future years, the new International Convention for the Prevention of Pollution from Ships (MARPOL) and Sulphur Emissions Control Areas (SECA) regulations will forbid ships to use heavy fuel oils at certain situations. To fulfil with these regulations, the next step in the marine shipping business will comprise the use of cleaner fuels on board as well as developing new propulsion concept. In this work a new conceptual marine propulsion system is developed, based on the integration of diesel generators with fuel cells in a 2850 metric tonne of deadweight platform supply vessel. The efficiency of the two 250 kW methanol-fed Solid Oxide Fuel Cell (SOFC) system installed on board combined with the hydro dynamically optimized design of the hull of the ship will allow the ship to successfully operate at certain modes of operation while notably reduce the pollutant emissions to the atmosphere. Besides the cogeneration heat obtained from the fuel cell system will be used to answer different heating needs on board the vessel

Steam reforming of ethanol over bimetallic RhPt/La2O3: Long-term stability under favorable reaction conditions

Recently, the steam reforming of biofuels has been presented as a potential hydrogen source for fuel cells. Because this scenario represents an interesting opportunity for Colombia (South America), which produces large amounts of bioethanol, the steam reforming of ethanol was studied over a bimetallic RhPt/La2O3 catalyst under bulk mass transfer conditions. The effect of temperature and the initial concentrations of ethanol and water were evaluated at space velocities above 55,000 h−1 to determine the conditions that maximize the H2/CO ratio and reduce CH4 production while maintaining 100% conversion of ethanol. These requirements were accomplished when 21 mol% H2O and 3 mol% C2H5OH (steam/ethanol molar ratio = 7) were reacted at 600 °C. The catalyst stability was assessed under these reaction conditions during 120 h on stream, obtaining ethanol conversions above 99% during the entire test. The effect of both H2 and air flows as catalyst regeneration treatments were evaluated after 44 and 67 h on stream, respectively. The results showed that H2 treatment accelerated catalyst deactivation, and air regeneration increased both the catalyst stability and the H2 selectivity while decreasing CH4 generation. Fresh and spent catalyst samples were characterized by TEM/EDX, XPS, TPR, and TGA. Although the Rh and Pt in the fresh catalyst were completely reduced, the spent samples showed a partial oxidation of Rh and small amounts of carbonaceous residue. A possible Rh–Pt–Rh2O3 structure was proposed as the active site on the catalyst, which was regenerated by air treatment.

Evidence of Local pH Changes during Ethanol Oxidation at Pt Electrodes in Alkaline Media

Local changes of the interfacial pH can significantly affect the rate and mechanism during the course of an electrodic reaction. For instance, different pH values will have a significant effect on the equilibrium properties of both solution and surface species, altering the reactions kinetics. Ethanol oxidation at platinum electrodes in alkaline media involves the fast consumption of OH− species that will change the local pH at the electrode surface, decreasing the reaction rate. In this study, the local pH change during ethanol oxidation in alkaline media is accomplished by using rotating ring-disc electrode (RRDE) experiments. The current at the ring when polarized at the onset of hydrogen evolution serves as a measure of the local pH in the vicinity of the electrode. The results show that the current at the ring at 0.1 V (vs. RHE) becomes more negative during ethanol oxidation, owing to a change in the equilibrium potential of the hydrogen evolution reaction caused by a change in the local pH.

Fuel cell benefits : the program management office viewpoint /

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