A cinética da reação de redução de oxigênio (RRO) foi estudada em eletrólito alcalino em diferentes eletrocatalisadores. As atividades eletrocatalíticas medidas experimentalmente em metais puros foram correlacionadas com propriedades eletrônicas do eletrocatalisador, como o centro em energia da banda d (εd). A RRO também foi investigada em Pt e Ag modificados pela formação de liga com outros metais de transição. Por fim, a RRO foi conduzida em diferentes óxidos de manganês sintetizados em laboratório, com o objetivo de se determinar a fase mais ativa e o mecanismo da reação nos diferentes óxidos. A atividade eletrocatalítica frente à RRO dos metais puros ou das monocamadas de platina suportadas em diferentes substratos metálicos monocristalinos apresentou uma dependência tipo “vulcão" em função da energia do centro da banda d do metal eletrocatalisador. Estes resultados indicam que tanto a quebra da ligação O-O como a hidrogenação dos intermediários reacionais têm que ser facilitados, de forma que a cinética das duas reações, as quais são aceleradas por propriedades antagônicas, seja otimizada. O ganho de atividade para a RRO observado para as ligas de Pt em relação à Pt pura foi associado à menor reatividade da Pt na ligas, o que leva à uma menor força da adsorção Pt-O- e, consequentemente, maior cinética de eletroredução dos intermediários oxigenados. A maior atividade das ligas de Ag comparada com a Ag pura foi atribuída à uma mais forte adsorção Ag-O-, o que resulta em maior cinética da quebra da ligação O-O. Os resultados para os diferentes óxidos de Mn mostraram que a ativação para a RRO é maior para os materiais com alto conteúdo de MnO2. A atividade eletrocatalítica dos óxidos de manganês foi associada com um mecanismo acoplado envolvendo uma mudança do estado de oxidação de Mn (IV) para Mn (III), com a transferência de elétrons do Mn (III) para o O2 adsorvido [], em processo via 2 elétrons, com subsequente reação de desproporcionamente do intermediário HO2-, recirculando O2 no sistema, tendendo à um mecanísmo global via 4 elétrons por molécula de O2. / The oxygen reduction reaction (ORR) was studied on electrodes formed by Pt monolayers deposited on different metallic substrates, and on carbon-supported electrocatalysts composed by PtM/C (M = V, Cr e Co) and AgPt/C alloys, and on different Mn oxides (Mn3O4/C, Mn2O3/C and MnO2/C) in alkaline electrolyte. The experimentally measured electrocatalytic activities of the different metal catalysts and of the Pt monolayers were plotted against the metal d-band center values (_d). In all cases, the electronic features of the metal electrocatalysts were used for understanding the catalytic activities, and trying to establish the electronic/ORR kinetics relationship. The XANES results for the PtM/C alloys at high electrode potentials have shown lower vacancy of the Pt 5d band compared to pure Pt/C, indicating lower Pt reactivity for adsorbates. The enhanced catalytic activity of Pt in the alloys was attributed to a faster electroreduction of oxygenated intermediates. For the AgPt/C alloys, the XANES results have shown a emptying of the Ag orbitals due to a charge transfer to Pt, and the increased activity of the Ag atoms was ascribed to an electronic effect induced by the presence of Pt, increasing the Ag-O adsorption strength For the manganese oxide materials, the XANES results indicated a chance of the Mn oxidation state as a function of the electrode potential, and higher electrocatalytic activity was observed for MnO2/C. This was explained based on the activation for the ORR, which is higher for the material with higher MnO2 contents and the occurrence of a mediation processes involving the reduction of Mn(IV) to Mn(III), followed by the electron transfer of Mn(III) to oxygen.

Direct methanol fuel cell (DMFC) is considered as a highly promising power source. It is based on polymer electrolytes membrane (PEM) fuel cell technology. It posses a number of advantages such as a liquid fuel, quick refueling, low cost of methanol and the compact cell, design making it suitable for various potential applications including stationary and portable applications. DMFCs are also environmentally friendly. Although carbon dioxide is produced, there is no production of sulfur or nitrogen oxides. The development of commercial DMFCs has nevertheless been hindered by some important issues. The most important are the low power density caused by the slow electrochemical methanol oxidation at the anode and methanol crossover through PEM, which is responsible for inhibiting the activity of the cathode catalyst as well. With the eventual goal of improving the overall performance of the DMFC, this study has been concerned with an investigation of the issues and effect of various parameters on its performance. First of all, the electrode preparation methodology and the effect of the catalyst were investigated. The most efficient membrane electrode assembly (MEA) was prepared with Pt/Ru black at anode and Pt black cathode on either side of a Nafion 117 membrane. Performance was however limited by current oscillations observed at low cell voltage and high current density attributed to carbon dioxide removal. Consequently, the effect of flow rate was investigated. Higher flow rates eliminated these oscillations. Then attention was focused on the management of the two-phase flow that occurs in the diffusion layer of the electrode as well as in the anode bipolar plate flow channels. Removal of carbon dioxide formed during methanol oxidation was thus found to be an important issue in DMFC. There is a competition between methanol diffusion to the catalyst layer and CO2 removal in the opposite direction. The two fluxes needed to be balanced in order to optimize performance. To accomplish this, the ratio of hydrophilic and hydrophobic pores respectively formed in the catalytic layer by Nafion and PTFE (Teflon) was altered. It also had an effect on crossover. The effect of a barrier layer was investigated to reduce crossover. Finally, zirconia and silica nano-composite membranes were tested instead of Nafion and found to reduce crossover. Developing a good understanding of what happens on the catalyst surface is important to develop a strategy on how improve DMFC performance. Thus is why a dynamic model based on a simplified mechanism for methanol electro-oxidation reaction was developed. It shows, amongst other insights, how the intermediate species coverage evolves with time. The mechanism was however too simple to provide an idea of which poisoning species are formed on the catalyst surface. A more exhaustive mechanism is thus being developed using Reaction Route analysis.

Direct methanol fuel cell (DMFC) is considered as a highly promising power source. It is based on polymer electrolytes membrane (PEM) fuel cell technology. It posses a number of advantages such as a liquid fuel, quick refueling, low cost of methanol and the compact cell, design making it suitable for various potential applications including stationary and portable applications. DMFCs are also environmentally friendly. Although carbon dioxide is produced, there is no production of sulfur or nitrogen oxides. The development of commercial DMFCs has nevertheless been hindered by some important issues. The most important are the low power density caused by the slow electrochemical methanol oxidation at the anode and methanol crossover through PEM, which is responsible for inhibiting the activity of the cathode catalyst as well. With the eventual goal of improving the overall performance of the DMFC, this study has been concerned with an investigation of the issues and effect of various parameters on its performance. First of all, the electrode preparation methodology and the effect of the catalyst were investigated. The most efficient membrane electrode assembly (MEA) was prepared with Pt/Ru black at anode and Pt black cathode on either side of a Nafion 117 membrane. Performance was however limited by current oscillations observed at low cell voltage and high current density attributed to carbon dioxide removal. Consequently, the effect of flow rate was investigated. Higher flow rates eliminated these oscillations. Then attention was focused on the management of the two-phase flow that occurs in the diffusion layer of the electrode as well as in the anode bipolar plate flow channels. Removal of carbon dioxide formed during methanol oxidation was thus found to be an important issue in DMFC. There is a competition between methanol diffusion to the catalyst layer and CO2 removal in the opposite direction. The two fluxes needed to be balanced in order to optimize performance. To accomplish this, the ratio of hydrophilic and hydrophobic pores respectively formed in the catalytic layer by Nafion and PTFE (Teflon) was altered. It also had an effect on crossover. The effect of a barrier layer was investigated to reduce crossover. Finally, zirconia and silica nano-composite membranes were tested instead of Nafion and found to reduce crossover. Developing a good understanding of what happens on the catalyst surface is important to develop a strategy on how improve DMFC performance. Thus is why a dynamic model based on a simplified mechanism for methanol electro-oxidation reaction was developed. It shows, amongst other insights, how the intermediate species coverage evolves with time. The mechanism was however too simple to provide an idea of which poisoning species are formed on the catalyst surface. A more exhaustive mechanism is thus being developed using Reaction Route analysis.

Electrochemical impedance spectroscopy (EIS) is a technique consisting of the application of a small perturbing current or voltage to an electrochemical system and measuring the response of the system. The response of the system can be described through the notion of impedance, Z, which is defined as the transfer function between the voltage and the current signal. By describing the impedance, one can gain insight into the interpretation of EIS experiments for the measurement of fundamental physical properties (eg diffusion coefficients). The impedance responses of electrochemical systems have been described in the past as an arrangement of ideal equivalent-circuit elements. Simple lumped-parameter circuits and more complex finite-transmission-line circuits have been used in the past, but the disadvantage of this approach is the difficulty in interpreting the equivalent-circuit parameters in terms of fundamental properties. It is then interesting to determine impedance by describing mathematically the fundamental physical processes that govern the response of the system. By describing and predicting analytically the impedance response induced by the perturbing current signal, one can: (i) gain considerable insight into the electrochemical process of interest, (ii) make explicit use of the modeling approach to address operational issues such as process design optimization, monitoring, diagnostics and control, and (iii) offer an interpretation to carefully designed EIS experiments for the measurement of fundamental physical properties such as diffusion coefficients or surface of active catalyst.

In recognition of the shortcomings inherent to the operating temperature ranges of current fuel cell systems, namely the“temperature gap" between 200C and 600C, an effort to develop an intermediate-temperature molten-salt electrolyte fuel cell (IT-MSFC) was undertaken. In this type of fuel cell, the molten salt electrolyte is supported on a porous support, in a planar or other geometry similar to that used in existing fuel cell technologies, such as phosphoric acid fuel cell (PAFC) and molten carbonate fuel cells (MCFC). Such a fuel cell using a molten hydroxide electrolyte and Pt/C catalyst was constructed and tested using hydrogen and oxygen as fuel. The performance was comparable to that which has been obtained from PEM fuel cells at the low end of the voltage range, reaching 950ma/cm2 at 0.4 V in the highest performing test. Performance was superior to PEM fuel cells at the high end of the voltage range, due to the more favorable kinetics at the higher temperatures, with an open circuit voltage (OCV) of 1.0 V with a linear performance curve between 1.0 V and 0.6 V, which is characteristic of fuel cells with low kinetic overpotentials. Longevity of the fuel cell was very poor, however a number of experiments were undertaken to improve it, enabling extension of operating life from 5 minutes to 30 minutes, which is still far too low for practical use. The key problem was identified as electrolyte retention by the support matrix and possible degradation of the gas diffusion layer and catalyst. Experiments were also conducted using methanol vapor as fuel, and it was found to provide performance close to that recorded with pure hydrogen. Experiments were also conducted using several alternative molten salts, including nitrate and chloride eutectics. Combinations of nitrates with hydroxides added to act as a charge carrier produced a working fuel cell, however performance was greatly reduced. Though preliminary, the work described herein demonstrates the great potential of IT-MSFC, and outlines the work needed to make this type of fuel cell practical.

For fuel cells to become commercially viable in a wider range of applications, the amount of catalyst must be reduced. One crucial area of the fuel cell assembly is the anode and cathode; these layers allow fuel and exhaust gases to diffuse, provide conduction paths for both protons and electrons, and house sites for electrocataytic reactions. Despite their multi-functionality and importance, these layers have received little attention in the way of engineering design. While Nafion and catalyst loading has been studied, the electrode layer is still considered a two-dimensional structure. By understanding the current electrode limitations, available materials, and interactions at the sites reaction sites, an intelligent, deliberate design of the anode and cathode layer can be undertaken. A three-dimensional, fibrous mat of continuous, networked proton-conducting fibers can decrease mass diffusion limitations while maintaining proton conductivity. Nafion can be formed into these types of fibers via the fabrication technique of electrospinning. By forcing a solution of Nafion, solvent, and carrier polymer through a small nozzle under high electric voltage, the polymer can be extruded into fibers with nanometer-scale diameters. The ability to control the fiber morphology lies with solution, environmental and equipment properties. In order to successfully fabricate Nafion nanofibers, we looked to both existing methodologies as well as mathematical models to try to predict behavior and fabricate our own nanofibers. Once fabricated, these mats are assembled in a membrane-electrode assembly and tested with both methanol and hydrogen as fuel, with performance compared against known data for conventional MEAs. We have been able to successfully electrospin Nafion® nanofibers continuously, creating fiber mats with fiber diameters near 400nm as verified by SEM. These mats were tested in a direct methanol fuel cell (DMFC) application as cathodes, and showed improved performance with a dilute methanol feed compared to conventional MEAs with equivalent Nafion and catalyst loading. An MEA fabricated with twin electrospun electrodes was compared against an equivalent conventional MEA, showing the same performance enhancement using a dilute methanol fuel.

O alto índice de emissões gasosas tem impulsionado cada vez mais pesquisas com células a combustível com membrana trocadora de prótons (PEMFC), dispositivo eletroquímico capaz de produzir energia gerando apenas vapor de água como resíduo. Atualmente, entre os desafios que impossibilitam a popularização deste tipo de dispositivo estão o aperfeiçoamento da gestão da água e a diminuição dos índices de crossover de reagentes do ânodo para o cátodo. Este trabalho teve como meta utilizar a biomimética como ferramenta para criar novos designs de canais em placas de distribuição de reagentes, para melhor gestão da água e minimização do crossover do combustível em PEMFCs. Foram realizados experimentos em laboratório utilizando-se protótipos de PEMFC e experimentos computacionais de modelagem fluidodinâmica utilizando software SolidWorks. Pelos resultados constatou-se que a variação sincronizada da profundidade dos canais de fluxo em ambos os lados da placa bipolar possibilita minimizar a queda de pressão dos reagentes, sem a necessidade de aumento da espessura desta mantendo-se a densidade de potência do stack. Verificou-se que placas de distribuição de reagentes parcialmente interdigitadas são uma ferramenta eficaz no controle da umidade da célula durante a operação, evitando o uso de dispositivos periféricos para umidificação, e maior transferência de energia térmica entre placas e reagente. Numa célula a combustível alimentada com etanol sem periféricos para melhor balanço do decréscimo do crossover de etanol e remoção eficiente da água produzida no cátodo, a melhor combinação de placas de distribuição de reagentes foi obtida quando usado no ânodo uma placa com canais de distribuição de reagentes contínuos, e no cátodo uma placa com canais parcialmente interdigitados. Para melhor gestão da água, transferência de energia térmica e crossover em função do design dos canais de distribuição de reagentes nas placas bipolares, neste trabalho, foram propostas placas com canais de distribuição bioinspirados. O uso da biomimética mostrou ser uma abordagem diferenciada em busca da melhora de desempenho de PEMFCs. A biomimética possibilitou a criação de múltiplos subsistemas com características de autossimilaridade dentro de uma mesma estrutura física, e permitiu ampliar a proporção de área ativa do MEA, mantendo-se as mesmas dimensões das placas bipolares, através do uso de canais em fractais. As placas bipolares bioinspiradas propostas, tendo canais com configurações em fractais padronizadas, mostraram através de ensaios simulados serem altamente eficientes na gestão da água e do crossover. / The high gas emissions content has driving more attention on proton exchange membrane fuel cells (PEMFC), an electrochemical device that generates energy producing only water vapor as waste. Among the challenges that reduces the use of this type of device are a better water management and the fuel crossover reduction. The aim of this work is the use of biomimetics as a tool to create new flow field plate designs for improving water management and minimizing fuel crossover in a PEMFC. A serie of lab experiments were carried out in a single PEMFC prototype and others computational fluid dynamic using SolidWorks. The results have shown that a synchronized variation in the depth of the flow field channels on both sides of a bipolar plate allows minimize the reagent pressure loss without increasing the plate thickness or decreasing the stack power density. The baffle flow field plates have shown be an effective tool for controlling the cell humidification operated without periphericals or humidifiers devices and for a better transferring thermal energy between the plate and reagent. For a better balance between ethanol crossover and efficient removal of water produced in a direct ethanol proton exchange membrane fuel cell without peripherals, the best flow field plate combination obtained was a continuous channels plate at the anode side, and partially discontinuous channels plate at the cathode. For a better water management, thermal energy transfer management and crossover management in this work, flow field plates with designs bioinspired were investigated. The biomimetic was a strong tool to optimizing the performance of PEMFC. The biomimetic has enabled the creation of numerous similar self-subsystems optimizing the MEA active area by using fractals channels without changing the bipolar plate dimensions. The bipolar plate’s bioinspired having configured channels in fractal standard showed through SolidWorks simulated experiments be highly efficient in controlling water or ethanol crossover in a PEMFC.

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Nuclear Engineering; and, (M.S.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 1975. / Includes bibliographical references. / by George Doumet. / M.S.

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 1979. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Includes bibliographical references. / by Roger Dean Farr. / M.S.

Thesis (Ocean.E)--Massachusetts Institute of Technology, Dept. of Ocean Engineering, 1979. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING. / Includes bibliographical references. / Ocean.E