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A Novel Process for Fabricating Membrane-electrode Assemblies with Low Platinum Loading for Use in Proton Exchange Membrane Fuel CellsKarimi, Shahram 31 August 2011 (has links)
A novel method based on pulse current electrodeposition (PCE) employing four different waveforms was developed and utilized for fabricating membrane-electrode assemblies (MEAs) with low platinum loading for use in low-temperature proton exchange membrane fuel cells. It was found that both peak deposition current density and duty cycle control the nucleation rate and the growth of platinum crystallites. Based on the combination of parameters used in this study, the optimum conditions for PCE were found to be a peak deposition current density of 400 mA cm-2, a duty cycle of 4%, and a pulse generated and delivered in the microsecond range utilizing a ramp-down waveform. MEAs prepared by PCE using the ramp-down waveform show performance comparable with commercial MEAs that employ ten times the loading of platinum catalyst. The thickness of the pulse electrodeposited catalyst layer is about 5-7 µm, which is ten times thinner than that of commercial state-of-the-art electrodes.
MEAs prepared by PCE outperformed commercial MEAs when subjected to a series of steady-state and transient lifetime tests. In steady-state lifetime tests, the average cell voltage over a 3000-h period at a constant current density of 619 mA cm-2 for the in-house and the state-of-the-art MEAs were 564 mV and 505 mV, respectively. In addition, the influence of substrate and carbon powder type, hydrophobic polymer content in the gas diffusion layer, microporous layer loading, and the through-plane gas permeability of different gas diffusion layers on fuel cell performance were investigated and optimized.
Finally, two mathematical models based on the microhardness model developed by Molina et al. [J. Molina, B. A. Hoyos, Electrochim. Acta, 54 (2009) 1784-1790] and Milchev [A. Milchev, “Electrocrystallization: Fundamentals of Nucleation And Growth” 2002, Kluwer Academic Publishers, 189-215] were refined and further developed, one based on pure diffusion control and another based on joint diffusion, ohmic and charge transfer control developed by Milchev [A. Milchev, J. Electroanal. Chem., 312 (1991) 267-275 & A. Milchev, Electrochim. Acta, 37 (12) (1992) 2229-2232]. Experimental results validated the above models and a strong correlation between the microhardness and the particle size of the deposited layer was established.
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A Novel Process for Fabricating Membrane-electrode Assemblies with Low Platinum Loading for Use in Proton Exchange Membrane Fuel CellsKarimi, Shahram 31 August 2011 (has links)
A novel method based on pulse current electrodeposition (PCE) employing four different waveforms was developed and utilized for fabricating membrane-electrode assemblies (MEAs) with low platinum loading for use in low-temperature proton exchange membrane fuel cells. It was found that both peak deposition current density and duty cycle control the nucleation rate and the growth of platinum crystallites. Based on the combination of parameters used in this study, the optimum conditions for PCE were found to be a peak deposition current density of 400 mA cm-2, a duty cycle of 4%, and a pulse generated and delivered in the microsecond range utilizing a ramp-down waveform. MEAs prepared by PCE using the ramp-down waveform show performance comparable with commercial MEAs that employ ten times the loading of platinum catalyst. The thickness of the pulse electrodeposited catalyst layer is about 5-7 µm, which is ten times thinner than that of commercial state-of-the-art electrodes.
MEAs prepared by PCE outperformed commercial MEAs when subjected to a series of steady-state and transient lifetime tests. In steady-state lifetime tests, the average cell voltage over a 3000-h period at a constant current density of 619 mA cm-2 for the in-house and the state-of-the-art MEAs were 564 mV and 505 mV, respectively. In addition, the influence of substrate and carbon powder type, hydrophobic polymer content in the gas diffusion layer, microporous layer loading, and the through-plane gas permeability of different gas diffusion layers on fuel cell performance were investigated and optimized.
Finally, two mathematical models based on the microhardness model developed by Molina et al. [J. Molina, B. A. Hoyos, Electrochim. Acta, 54 (2009) 1784-1790] and Milchev [A. Milchev, “Electrocrystallization: Fundamentals of Nucleation And Growth” 2002, Kluwer Academic Publishers, 189-215] were refined and further developed, one based on pure diffusion control and another based on joint diffusion, ohmic and charge transfer control developed by Milchev [A. Milchev, J. Electroanal. Chem., 312 (1991) 267-275 & A. Milchev, Electrochim. Acta, 37 (12) (1992) 2229-2232]. Experimental results validated the above models and a strong correlation between the microhardness and the particle size of the deposited layer was established.
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Experimental Methods and Mathematical Models to Examine Durability of Polymer Electrolyte Membrane Fuel Cell CatalystsDhanushkodi, Shankar Raman 07 June 2013 (has links)
Proton exchange membrane fuel cells (PEMFC) are attractive energy sources for power trains in vehicles because of their low operating temperature that enables fast start-up and high power densities. Cost reduction and durability are the key issues to be solved before PEMFCs can be successfully commercialized. The major portion of fuel cell cost is associated with the catalyst layer which is typically comprised of carbon-supported Pt and ionomer. The degradation of the catalyst layer is one of the major failure modes that can cause voltage degradation and limit the service life of the fuel cell stack during operation. To develop a highly durable and better performing catalyst layer, topics such as the causes for the degradation, modes of failure, different mechanisms and effect of degradation on fuel cell performance must be studied thoroughly.
Key degradation modes of catalyst layer are carbon corrosion and Pt dissolution. These two modes change the electrode structure in the membrane electrode assembly (MEA) and result in catalyst layer thinning, CO2 evolution, Pt deposition in the membrane and Pt agglomeration. Alteration of the electrode morphology can lead to voltage degradation.
Accelerated stress tests (ASTs) which simulate the conditions and environments to which fuel cells are subject, but which can be completed in a timely manner, are commonly used to investigate the degradation of the various components. One of the current challenges in employing these ASTs is to relate the performance loss under a given set of conditions to the various life-limiting factors and material changes. In this study, various degradation modes of the cathode catalyst layer are isolated to study their relative impact on performance loss ‗Fingerprints‘ of identifiable performance losses due to carbon corrosion are developed for MEAs with 0.4 mg cm−2 cathode platinum loadings. The fingerprint is used to determine the extent of performance loss due to carbon corrosion and Pt dissolution in cases where both mechanisms operate. This method of deconvoluting the contributions to performance loss is validated by comparison to the measured performance losses when the catalyst layer is subjected to an AST in which Pt dissolution is predominant. The limitations of this method
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are discussed in detail. The developed fingerprint suggests that carbon loss leading to CO2 evolution during carbon corrosion ASTs contributes to performance loss of the cell. A mechanistic model for carbon corrosion of the cathode catalyst layer based on one appearing in the literature is developed and validated by comparison of the predicted carbon losses to those measured during various carbon corrosion ASTs. Practical use of the model is verified by comparing the predicted and experimentally observed performance losses. Analysis of the model reveals that the reversible adsorption of water and subsequent oxidation of the carbon site onto which water is adsorbed is the main cause of the current decay during ASTs.
Operation of PEM fuel cells at higher cell temperatures and lower relative humidities accelerates Pt dissolution in the catalyst layer during ASTs. In this study, the effects of temperature and relative humidity on MEA degradation are investigated by applying a newly developed AST protocol in which Pt dissolution is predominant and involves the application of a potentiostatic square-wave pulse with a repeating pattern of 3s at 0.6 V followed by 3s at 1.0 V. This protocol is applied at three different temperatures (40°C, 60°C and 80°C) to the same MEA. A diagnostic signature is developed to estimate kinetic losses by making use of the effective platinum surface area (EPSA) obtained from cyclic voltammograms. The analysis indicates that performance degradation occurs mainly due to the loss of Pt in electrical contact with the support and becomes particularly large at 80°C.
This Pt dissolution AST protocol is also investigated at three different relative humidities (100%, 50% and 0%). Electrochemical impedance spectroscopy measurements of the MEAs show an increase in both the polarization and ohmic resistances during the course of the AST. Analysis by cyclic voltammetry shows a slight increase in EPSA when the humidity increases from 50% to 100%. The proton resistivity of the ionomer measured by carrying out impedance measurements on MEAs with H2 being fed on the anode side and N2 on the cathode side is found to increase by the time it reaches its end-of-life state when operated under 0 % RH conditions.
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Fabrication de piles à combustible par procédés d'impression / Fuel cells active layers realisation by printing processesBois, Chloé 26 October 2012 (has links)
Les piles à combustibles sont une alternative à l’utilisation de ressources fossiles. Cependant, l’énergie qu’elles produisent reste chère et les procédés de fabrication actuels ne sont pas adaptés à des productions à grande échelle. Une piles de type PEMFC (Proton Exchange Membrane Fuel Cell) essont un système constitué de cinq couches dans lequel la membrane et les deux couches de diffusion peuvent être considértestées comme support d’impression et les deux couches actives peuvent être imprimées par des procédés continus.Ce travail démontrea la pertinence du procédé d’impression appelé flexographiquee dans la fabrication de composants de PEMFC. La flexographieCe procédé offre permet de produire de grandes surfaces de production avec peu de perte de matière fonctionnelle. Malgré la faible imprimabilité des supports choisis, elle permit la fabrication des couches actives aux performances similaires à celles fabriquéesites par procédés conventionnels ont pu être réalisées grâce à la flexogaphie. / In a context of fossil fuel shortage and hydrocarbon emission reduction, fuel cells are a promising solution for energy production. However, the cost of the energy they produce remains too expensive to be competitive and the conventional manufacturing processes used limit the scaling up of the production. The core of Proton Exchange Membrane Fuel Cells (PEMFCs) is a stack composed of five constituents, in which the proton exchange membrane and the two gas diffusion layers have potential for being can be considered as used a a printing substrates, and the two catalyst layers can be printed by continuous printing processes.This work demonstrated the relevance of the printing process called flexography for manufacturing fuel cell components. It offers allows larger production with low waste of expensive elements. Despite of the poor printability of the both chosen substrates, the achieved catalyst layers printed by flexography reached similar electrochemical properties than those made by conventional processes.
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Etude computationnelle de la formation d'un film ultra-mince de Nafion à l'intérieur d'une couche catalytique de PEMFC / Computational studies of the formation of Nafion ultra-thin films inside PEMFC catalyst layerDamasceno Borges, Daiane 12 April 2013 (has links)
Le Nafion dans la couche catalytique des PEMFCs peut former un revêtement de film ultra-mince enrobant la surface du catalyseur et ses supports. La morphologie du Nafion se révèle être très sensibles à la nature du matériau sur lequel le film est déposé, et en particulier le caractère hydrophobe/phile de ces matériaux. Notre travail consiste à effectuer une enquête complète sur les effets hydrophiles du substrat sur les propriétés physiques du film ultra-mince de Nafion à des niveaux différents d'hydratation. Par conséquent, nous étudions selon un cadre unique une variété d'environnements spécifiques de la couche du catalyseur de la PEMFC, pouvant aller d'un substrat hydrophobe (carbone) à hydrophile (platine). La méthode numérique choisie pour ce travail est une simulation par Dynamique Moléculaire classique. Les configurations de films ultra-minces correctement thermalisés ont été décrites en détail en fonction de leurs propriétés structurales et dynamiques. / Nafion inside Polymer Electrolyte Membrane Fuel Cells (PEMFC) catalyst layers can be found as an ultra-thin film coating the catalyst and the catalyst support surfaces. Nafion morphology shows to be strongly sensitive to the type of material where the film is deposited, especially the hydrophobic/philic character of these materials. Our work consists in performing a complete investigation of the substrate hydrophilicity effects on the physical properties of Nafion ultra-thin film at different hydration levels. We investigate in a unique framework a variety of environments peculiar of the PEMFC catalyst layer, ranging from hydrophobic (carbon) to hydrophilic (platinum) substrates. The numerical method chosen for this work is classical Molecular Dynamics simulations. The well-thermalized thin-film configurations were described in details in terms of their structural and dynamical properties.
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Desenvolvimento de processo de produção de conjuntos eletrodo-membrana-eletrodo para células a combustível baseadas no uso de membrana polimérica condutora de prótons (PEMFC) por impressão a tela / Development of a membrane electrode assembly production process for proton exchange membrane fuel cell (PEMFC) by sieve printingBonifacio, Rafael Nogueira 30 March 2010 (has links)
Energia é um recurso que historicamente apresenta tendência de crescimento de demanda. Projeções indicam que, para suprir as necessidades energéticas do futuro, será necessário um uso massivo do hidrogênio como combustível. O uso de sistemas de célula a combustível baseada no uso de membrana polimérica condutora de prótons (PEMFC) tem características que permitem sua aplicação para geração de energia elétrica em aplicações estacionárias, automotivas e portáteis. O uso de hidrogênio como combustível para PEMFC apresenta a vantagem de resultar em baixa emissão de poluentes quando comparado às dos combustíveis fósseis. Para que ocorram as reações em uma PEMFC é necessária a construção de conjuntos eletrodo-membrana-eletrodo (MEA), sendo o processo de produção de MEAs e os materiais utilizados, relevantes no custo final do kW instalado para geração de energia por sistemas de célula a combustível, o que é, atualmente, uma barreira tecnológica e financeira para a aplicação em grande escala desta tecnologia. Nesse trabalho foi desenvolvido um processo de produção de MEAs por impressão a tela que apresenta alta reprodutibilidade, rapidez e baixo custo. Foram desenvolvidos o processo de impressão a tela e a composição de uma tinta precursora da camada catalisadora (TPCC), que permitem o preparo de eletrodos para confecção de MEAs com a aplicação da massa exata de eletrocatalisador adequada para cátodos 0,6 miligramas de platina por centímetro quadrados (mgPt.cm-2) e ânodos 0,4 mgPt.cm-2 em apenas uma aplicação por eletrodo. A TPCC foi desenvolvida, produzida, aplicada e caracterizada, apresentando características semelhantes a de tintas de impressão a tela para outras aplicações. Os MEAs produzidos apresentaram desempenho de até 712 mA.cm-2 a 600 mV para MEAs de 25 cm2 e o custo para produção de MEAs de 247,86 cm2 capazes de gerar 1 kW de energia foi estimado em R$ 13.939,45, considerando custo de equipamentos, materiais e mão de obra. / Energy is a resource that presents historical trend of growth in demand. Projections indicate that future energy needs will require a massive use of hydrogen as fuel. The use of systems based on the use of proton exchange membrane fuel cell (PEMFC) has features that allow its application for stationary applications, automotive and portable power generation. The use of hydrogen as fuel for PEMFC has the advantage low pollutants emission, when compared to fossil fuels. For the reactions in a PEMFC is necessary to build membrane electrode assembly (MEA). And the production of MEAs and its materials are relevant to the final cost of kW of power generated by systems of fuel cell. This represent currently a technological and financial barriers to large-scale application of this technology. In this work a process of MEAs fabrication were developed that showed high reproducibility, rapidity and low cost by sieve printing. The process of sieve printing and the ink composition as a precursor to the catalyst layer were developed, which allow the preparation of electrodes for MEAs fabrication with the implementation of the exact catalyst loading, 0.6 milligrams of platinum per square centimeters (mgPt.cm-2) suitable for cathodes and 0.4 mgPt.cm-2 for anode in only one application step per electrode. The ink was developed, produced, characterized and used with similar characteristics to ink of sieve printing build for other applications. The MEAs produced had a performance of up to 712 mA.cm-2 by 600 mV to 25 cm2 MEA area. The MEA cost production for MEAs of 247.86 cm2, that can generate 1 kilowatt of energy was estimated to US$ 7,744.14 including cost of equipment, materials and labor.
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Desenvolvimento de processo de produção de conjuntos eletrodo-membrana-eletrodo para células a combustível baseadas no uso de membrana polimérica condutora de prótons (PEMFC) por impressão a tela / Development of a membrane electrode assembly production process for proton exchange membrane fuel cell (PEMFC) by sieve printingRafael Nogueira Bonifacio 30 March 2010 (has links)
Energia é um recurso que historicamente apresenta tendência de crescimento de demanda. Projeções indicam que, para suprir as necessidades energéticas do futuro, será necessário um uso massivo do hidrogênio como combustível. O uso de sistemas de célula a combustível baseada no uso de membrana polimérica condutora de prótons (PEMFC) tem características que permitem sua aplicação para geração de energia elétrica em aplicações estacionárias, automotivas e portáteis. O uso de hidrogênio como combustível para PEMFC apresenta a vantagem de resultar em baixa emissão de poluentes quando comparado às dos combustíveis fósseis. Para que ocorram as reações em uma PEMFC é necessária a construção de conjuntos eletrodo-membrana-eletrodo (MEA), sendo o processo de produção de MEAs e os materiais utilizados, relevantes no custo final do kW instalado para geração de energia por sistemas de célula a combustível, o que é, atualmente, uma barreira tecnológica e financeira para a aplicação em grande escala desta tecnologia. Nesse trabalho foi desenvolvido um processo de produção de MEAs por impressão a tela que apresenta alta reprodutibilidade, rapidez e baixo custo. Foram desenvolvidos o processo de impressão a tela e a composição de uma tinta precursora da camada catalisadora (TPCC), que permitem o preparo de eletrodos para confecção de MEAs com a aplicação da massa exata de eletrocatalisador adequada para cátodos 0,6 miligramas de platina por centímetro quadrados (mgPt.cm-2) e ânodos 0,4 mgPt.cm-2 em apenas uma aplicação por eletrodo. A TPCC foi desenvolvida, produzida, aplicada e caracterizada, apresentando características semelhantes a de tintas de impressão a tela para outras aplicações. Os MEAs produzidos apresentaram desempenho de até 712 mA.cm-2 a 600 mV para MEAs de 25 cm2 e o custo para produção de MEAs de 247,86 cm2 capazes de gerar 1 kW de energia foi estimado em R$ 13.939,45, considerando custo de equipamentos, materiais e mão de obra. / Energy is a resource that presents historical trend of growth in demand. Projections indicate that future energy needs will require a massive use of hydrogen as fuel. The use of systems based on the use of proton exchange membrane fuel cell (PEMFC) has features that allow its application for stationary applications, automotive and portable power generation. The use of hydrogen as fuel for PEMFC has the advantage low pollutants emission, when compared to fossil fuels. For the reactions in a PEMFC is necessary to build membrane electrode assembly (MEA). And the production of MEAs and its materials are relevant to the final cost of kW of power generated by systems of fuel cell. This represent currently a technological and financial barriers to large-scale application of this technology. In this work a process of MEAs fabrication were developed that showed high reproducibility, rapidity and low cost by sieve printing. The process of sieve printing and the ink composition as a precursor to the catalyst layer were developed, which allow the preparation of electrodes for MEAs fabrication with the implementation of the exact catalyst loading, 0.6 milligrams of platinum per square centimeters (mgPt.cm-2) suitable for cathodes and 0.4 mgPt.cm-2 for anode in only one application step per electrode. The ink was developed, produced, characterized and used with similar characteristics to ink of sieve printing build for other applications. The MEAs produced had a performance of up to 712 mA.cm-2 by 600 mV to 25 cm2 MEA area. The MEA cost production for MEAs of 247.86 cm2, that can generate 1 kilowatt of energy was estimated to US$ 7,744.14 including cost of equipment, materials and labor.
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2-d Modeling Of A Proton Exchange Membrane Fuel CellAgar, Ertan 01 February 2010 (has links) (PDF)
In this thesis, a Proton Exchange Membrane Fuel Cell is modeled with COMSOL Multiphysics software. A cross-section that is perpendicular to the flow direction is modeled in a 2-D, steady-state, one-phase and isothermal configuration. Anode, cathode and membrane are used as subdomains and serpentine flow channels define the flow field . The flow velocity is defined at the catalyst layers as boundary conditions with respect to the current density that is obtained by using an agglomerate approach at the catalyst layer with the help of fundamental electrochemical equations. Darcy&rsquo / s Law is used for modeling the porous media flow. To investigate the effects of species depletion along the flow channels, a different type of cross-section that is parallel to the flow direction is modeled by adding flow channels as a subdomain to the anode and cathode. Differently, Brinkman Equations are used to define flow in the porous electrodes and the free flow in the channels is modeled with Navier-Stokes equations. By running parallel-to-flow model, mass fractions of species at three different locations (the inlet, the center and the exit of the channel) are predicted for different cell po- tentials. These mass fractions are used as inputs to the perpendicular-to-flow model to obtain performance curves. Finally, by maintaining restricted amount of species by having a very low pressure difference along the channel to represent a single mid-cell of a fuel cell stack, a species depletion problem is detected. If the cell potential is decreased beyond a critical value, this phenomenon causes dead places at which the reaction does not take place. Therefore, at these dead places the current density goes to zero unexpectedly.
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Computational modeling and optimization of proton exchange membrane fuel cellsSecanell Gallart, Marc 13 November 2007 (has links)
Improvements in performance, reliability and durability as well as reductions in production costs, remain critical prerequisites for the commercialization of proton exchange membrane fuel cells. In this thesis, a computational framework for fuel cell analysis and optimization is presented as an innovative alternative to the time consuming trial-and-error process currently used for fuel cell design. The framework is based on a two-dimensional through-the-channel isothermal, isobaric and single phase membrane electrode assembly (MEA) model. The model input parameters are the manufacturing parameters used to build the MEA: platinum loading, platinum to carbon ratio, electrolyte content and gas diffusion layer porosity. The governing equations of the fuel cell model are solved using Netwon's algorithm and an adaptive finite element method in order to achieve quadratic convergence and a mesh independent solution respectively. The analysis module is used to solve two optimization problems: i) maximize performance; and, ii) maximize performance while minimizing the production cost of the MEA. To solve these problems a gradient-based optimization algorithm is used in conjunction with analytical sensitivities. The presented computational framework is the first attempt in the literature to combine highly efficient analysis and optimization methods to perform optimization in order to tackle large-scale problems. The framework presented is capable of solving a complete MEA optimization problem with state-of-the-art electrode models in approximately 30 minutes. The optimization results show that it is possible to achieve Pt-specific power density for the optimized MEAs of 0.422 $g_{Pt}/kW$. This value is extremely close to the target of 0.4 $g_{Pt}/kW$ for large-scale implementation and demonstrate the potential of using numerical optimization for fuel cell design.
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Computational modeling and optimization of proton exchange membrane fuel cellsSecanell Gallart, Marc 13 November 2007 (has links)
Improvements in performance, reliability and durability as well as reductions in production costs, remain critical prerequisites for the commercialization of proton exchange membrane fuel cells. In this thesis, a computational framework for fuel cell analysis and optimization is presented as an innovative alternative to the time consuming trial-and-error process currently used for fuel cell design. The framework is based on a two-dimensional through-the-channel isothermal, isobaric and single phase membrane electrode assembly (MEA) model. The model input parameters are the manufacturing parameters used to build the MEA: platinum loading, platinum to carbon ratio, electrolyte content and gas diffusion layer porosity. The governing equations of the fuel cell model are solved using Netwon's algorithm and an adaptive finite element method in order to achieve quadratic convergence and a mesh independent solution respectively. The analysis module is used to solve two optimization problems: i) maximize performance; and, ii) maximize performance while minimizing the production cost of the MEA. To solve these problems a gradient-based optimization algorithm is used in conjunction with analytical sensitivities. The presented computational framework is the first attempt in the literature to combine highly efficient analysis and optimization methods to perform optimization in order to tackle large-scale problems. The framework presented is capable of solving a complete MEA optimization problem with state-of-the-art electrode models in approximately 30 minutes. The optimization results show that it is possible to achieve Pt-specific power density for the optimized MEAs of 0.422 $g_{Pt}/kW$. This value is extremely close to the target of 0.4 $g_{Pt}/kW$ for large-scale implementation and demonstrate the potential of using numerical optimization for fuel cell design.
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