Poisoning of the catalyst seems to be one of the most serious problems preventing a widespread commercialization of fuel cell technology. This thesis focuses on the effect of CO poisoning and hydrogen dilution by nitrogen on performance of fuel cells with low platinum content. Catalysts were deposited by magnetron sputtering directly on membrane etched by plasma. Alloys with different platinum-ruthenium ratio were used to mitigate the CO poisoning. We found that presence of nitrogen has almost negligible effect on the fuel cell performance. On the other hand, CO, even in small concentrations, caused a significant drop in power density. PtRu with atomic ratio 2:1 and 1:1 showed the best CO tolerance.

A energia é o combustível do crescimento e um requisito essencial para o desenvolvimento sócio-econômico. No entanto, o atual modelo de produção baseado em combustíveis fósseis é considerado ameaçador para o homem e a natureza. Desta forma, as preocupações relacionadas às atividades antrópicas e os seus efeitos no meio ambiente são traduzidos pela implementação de padrões mais rígidos de controle ambiental e pela mobilização da sociedade em favor das tecnologias energéticas menos impactantes. Diante desse cenário, a Célula a Combustível de Membrana Trocadora de Prótons - PEMFC tem sido reconhecida como a resposta para a premente necessidade de energia limpa e eficiente. Em relação aos sistemas convencionais de geração de energia, suas vantagens durante o uso a configuram como candidata ideal para diversas aplicações, em especial as móveis. Entretanto, embora o foco de diversas avaliações ambientais em sistemas de energia seja voltado para a etapa da sua utilização, os estágios relacionados à produção do sistema e destinação final devem ser considerados já que estes também apresentam impactos. No caso da PEMFC, nas fases anteriores e posteriores ao uso, os aspectos relacionados aos catalisadores de platina apontam cargas ambientais que não podem ser negligenciadas. Neste sentido, a Avaliação do Ciclo de Vida tem sido utilizada para entender e questionar os riscos e oportunidades que acompanham um determinado produto, a partir de uma visão sistêmica das suas relações com o meio ambiente. É precisamente nesse contexto que o presente trabalho pretende dar sua maior contribuição, a partir de um estudo exploratório almeja-se prover uma análise ambiental dessa tecnologia na etapa pós-uso do conjunto eletrodo membrana, nomeadamente em relação aos catalisadores de platina, sob o enfoque da Avaliação do Ciclo de Vida - ACV. Para atingir tal propósito, são apresentadas e discutidas as relações entre energia, meio ambiente e desenvolvimento, bem como a tecnologia de Células a Combustível e os atuais estudos sobre ACV da PEMFC. As contribuições das questões levantadas foram utilizadas para o desenvolvimento de um método de recuperação dos catalisadores da PEMFC e, especialmente, para a sua posterior avaliação ambiental. Dentre os resultados significativos destaca-se a importância da ACV como ferramenta útil para compreender o peso das questões ambientais relacionadas à platina e, para subsidiar as estratégias relacionadas ao desenvolvimento, consolidação e inovação da PEMFC. / The energy is the fuel of growth and an essential requirement for the socioeconomic development. However, the current production model is based on fossil fuels, considered as threat to man and nature. As for, the relating to the human activities and their effects on the environment, they are handled by the implementation of a more rigid model of environmental control and the mobilization of the society in favor of technologies with less energy impact. In view of this scenario, the Proton Exchange Membrane Fuel Cell - PEMFC has been recognized as a key for the vital need of a clean and efficient energy. Considering the conventional power generation system, their advantages during usage configure its application as an ideal option for several utilities, especially in the mobile sector. Even though, the focus on several environmental evaluations in energy systems is referred back to the initial stage of it use, the employment relating to production of the system and to final destination should be considered, since these also present impacts. In the case of PEMFC, their previous and subsequent phases of use are issues related to the platinum catalysts, which indicates an environmental importance that cannot be overlooked. In this sense, the Life Cycle Assessment has been used to understand and to question the risks and opportunities that are associated to certain product, starting from a systemic concept of their relationships with the environment. It is precisely in this context that the present research intends to present its major contribution, starting from an exploratory study towards the its objectives to provide an environmental analysis of such technology linked to post stage of powder-use of the membrane electrode assembly - MEA, concerning the platinum catalysts, on the subject of Life Cycle Assessment - LCA. To attain such aim, the relationships between energy, environment and development are presented and discussed, as well as, the Fuel Cell technology and the current studies on LCA of PEMFC. Several questions raised up on this issues have conthbuted in the development of a method of recuperating the PEMFC catalysts and, particularly, for its subsequent environmental evaluation. Among significant results are the importance of LCA, out lined as useful tool for perceiving the weight of environmental matters concerning the platinum and its subsidy strategies relating to the development, consolidation and to the innovation of PEMFC.

A energia é o combustível do crescimento e um requisito essencial para o desenvolvimento sócio-econômico. No entanto, o atual modelo de produção baseado em combustíveis fósseis é considerado ameaçador para o homem e a natureza. Desta forma, as preocupações relacionadas às atividades antrópicas e os seus efeitos no meio ambiente são traduzidos pela implementação de padrões mais rígidos de controle ambiental e pela mobilização da sociedade em favor das tecnologias energéticas menos impactantes. Diante desse cenário, a Célula a Combustível de Membrana Trocadora de Prótons - PEMFC tem sido reconhecida como a resposta para a premente necessidade de energia limpa e eficiente. Em relação aos sistemas convencionais de geração de energia, suas vantagens durante o uso a configuram como candidata ideal para diversas aplicações, em especial as móveis. Entretanto, embora o foco de diversas avaliações ambientais em sistemas de energia seja voltado para a etapa da sua utilização, os estágios relacionados à produção do sistema e destinação final devem ser considerados já que estes também apresentam impactos. No caso da PEMFC, nas fases anteriores e posteriores ao uso, os aspectos relacionados aos catalisadores de platina apontam cargas ambientais que não podem ser negligenciadas. Neste sentido, a Avaliação do Ciclo de Vida tem sido utilizada para entender e questionar os riscos e oportunidades que acompanham um determinado produto, a partir de uma visão sistêmica das suas relações com o meio ambiente. É precisamente nesse contexto que o presente trabalho pretende dar sua maior contribuição, a partir de um estudo exploratório almeja-se prover uma análise ambiental dessa tecnologia na etapa pós-uso do conjunto eletrodo membrana, nomeadamente em relação aos catalisadores de platina, sob o enfoque da Avaliação do Ciclo de Vida - ACV. Para atingir tal propósito, são apresentadas e discutidas as relações entre energia, meio ambiente e desenvolvimento, bem como a tecnologia de Células a Combustível e os atuais estudos sobre ACV da PEMFC. As contribuições das questões levantadas foram utilizadas para o desenvolvimento de um método de recuperação dos catalisadores da PEMFC e, especialmente, para a sua posterior avaliação ambiental. Dentre os resultados significativos destaca-se a importância da ACV como ferramenta útil para compreender o peso das questões ambientais relacionadas à platina e, para subsidiar as estratégias relacionadas ao desenvolvimento, consolidação e inovação da PEMFC. / The energy is the fuel of growth and an essential requirement for the socioeconomic development. However, the current production model is based on fossil fuels, considered as threat to man and nature. As for, the relating to the human activities and their effects on the environment, they are handled by the implementation of a more rigid model of environmental control and the mobilization of the society in favor of technologies with less energy impact. In view of this scenario, the Proton Exchange Membrane Fuel Cell - PEMFC has been recognized as a key for the vital need of a clean and efficient energy. Considering the conventional power generation system, their advantages during usage configure its application as an ideal option for several utilities, especially in the mobile sector. Even though, the focus on several environmental evaluations in energy systems is referred back to the initial stage of it use, the employment relating to production of the system and to final destination should be considered, since these also present impacts. In the case of PEMFC, their previous and subsequent phases of use are issues related to the platinum catalysts, which indicates an environmental importance that cannot be overlooked. In this sense, the Life Cycle Assessment has been used to understand and to question the risks and opportunities that are associated to certain product, starting from a systemic concept of their relationships with the environment. It is precisely in this context that the present research intends to present its major contribution, starting from an exploratory study towards the its objectives to provide an environmental analysis of such technology linked to post stage of powder-use of the membrane electrode assembly - MEA, concerning the platinum catalysts, on the subject of Life Cycle Assessment - LCA. To attain such aim, the relationships between energy, environment and development are presented and discussed, as well as, the Fuel Cell technology and the current studies on LCA of PEMFC. Several questions raised up on this issues have conthbuted in the development of a method of recuperating the PEMFC catalysts and, particularly, for its subsequent environmental evaluation. Among significant results are the importance of LCA, out lined as useful tool for perceiving the weight of environmental matters concerning the platinum and its subsidy strategies relating to the development, consolidation and to the innovation of PEMFC.

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.

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.

The need for sustainable energy use has motivated the exploration of renewable alternative fuels and fuel conversion technology on a global scale. Fuel cells, which convert chemical energy directly into electrical energy with high efficiency and low emissions, provide a promising strategy for achieving energy sustainability. The current progress in fuel cell commercialization is mainly in portable and stationary applications, but fuel cell technology for transportation applications, which make up a substantial portion of the global energy market, have seen little commercial success. Proton exchange membrane fuel cells (PEMFCs) have high potential for addressing the future energy needs of the transportation energy sector. However, one of the prevailing limitations of the PEMFC is the availability of high-performance, cost-effective electrolyte materials. These materials may be realized in the near future by developing multi-functional polymer blends targeted at specific performance capabilities. Due to the near-infinite possibilities of polymer combinations and processing techniques high-throughput polymer characterization techniques are necessary to effectively and systematically screen for optimal materials and relevant structure-property relationships. In this work, a high-throughput mass transport assay (HT-MTA) has been developed to characterize water flux and permeability at multiple sample locations in parallel. The functionality of HT-MTA was evaluated using standard Nafion® films and a model semi-interpenetrated polymer network with commercial polyvinylidine fluoride as the host matrix for a proprietary polyelectrolyte supplied by Arkema, Inc. To further demonstrate the utility of HT-MTA, the instrument was incorporated into the lab's current high-throughput characterization toolset and used to investigate the mechanisms and effects of rapid free radical degradation of Nafion® membranes based on various concentrations of hydrogen peroxide and iron(II) sulfate in solution. The results have been used suggest the effects of these regent components on preferential degradation pathways and will prove to be useful in later simulating the membrane performance during in-situ fuel cell lifetime which is both time-intensive and costly. The high-throughput toolset was also used to develop a novel optimized blend consisting of polyetherimide (PEI), a low-cost high performance resin, and sulfonated PEI (S-PEI) made using a relatively mild post sulfonation reaction with trimethylsilyl chlorosulfonate. The effects of blend composition and thermal annealing on film performance were evaluated and the polymer system was shown to have optimal performance properties that should prove to be useful in other high-performance applications where mechanical strength is critical. In general, this work shows promising results for efficiently developing advanced polymer materials using high-throughput screening techniques.

A new type of fuel cell that combines the advantages of a proton exchange membrane fuel cells and anion exchange membrane fuel cells operated with methanol is demonstrated. Two configurations: one with a high pH anode and low pH cathode (anode hybrid fuel cell (AHFC)),and another with a high pH cathode and a low pH anode (cathode hybrid fuel cell (CHFC)) have been studied in this work. The principle of operation of the hybrid fuel cells were explained. The two different hybrid cell configurations were used in order to study the effect of the electrode fabrication on fuel cell performance. Further, the ionomer content and properties such as the ion exchange capacity and molecular weight were optimized for the best performance. A comparison of the different ionomers with similar properties is carried out in order to obtain the best possible ionomer for the fuel cell. An initial voltage drop was observed at low current density in the AHFC, this was attributed to the alkaline anode and the effect of the ionomers with the new cationic groups were studied on this voltage drop was studied. These ionomers with the different cationic groups were studied in the CHFC design as well. Finally, the use of non platinum catalyst cathode with the CHFC design was also demonstrated for the first time.

First- principles modeling is used to predict hydrogen permeability through Palladium (Pd)-rich binary alloy membranes as a function of temperature and H2 pressure. We introduce a simplified model that incorporates only a few factors and yields quantitative prediction. This model is used to predict hydrogen permeability in a wide range of binary alloy membranes and to find promising alloys that have high hydrogen permeability. We show how our efficient Density Functional Theory (DFT)-based model predicts the chemical stability and proton conductivity of doped barium zirconate (BaZrO3), barium stannate (BaSnO3), and barium hafnate (BaHfO3). Our data is also used to explore the physical origins of the trends in chemical stability and proton conductivity among different dopants. We also study potassium tantalate (KTaO3), which is a prototype perovskite, to examine the characteristics of undoped perovskites. Specifically, we study the impacts of isotope effects, tunneling effects, and native point defects on proton mobility in KTaO3. It is important to find and develop solid-state Li-ion electrolyte materials that are chemically stable and have high ionic conductivities for high performance Li-ion batteries. We show how we predict the chemical stability of Li7La3Zr2O12, Li7La3Sn2O12, and Li7La3Hf2O12 with respect to carbonate and hydroxide formation reactions.

Dealloying refers to the partial, selective dissolution of the less noble component(s) of a binary or ternary alloy precursor, resulting in a noble-rich, porous structure that has high surface area. Such surface structure is beneficial for fuel cells (FC) because FC uses platinum (Pt), a scarce metal, to catalyze the oxygen reduction reaction (ORR) at the cathode surface. In order to characterize the benefit of the dealloying process in FC ORR catalysts with the rotating disk electrode (RDE) technique, a high surface area catalyst support, namely 3M Co’s nanostructured thin film (NSTF), was incorporated into the RDE measurements. NSTF-coated glassy carbon (GC) disks were used in RDE experiments on a Pt/Pt1-xIrx (0.05 < x < 0.3) composition spread. ORR measurements using NSTF-coated GC disks measure the catalytic properties with the same morphology, composition and surface structure as would be found in a fuel cell. A series of Pt1-xCox and Pt1-xNix (0.5 < x < 0.8) dealloy catalyst precursor films were tested using NSTF-coated GC disks in RDE studies. The value of x in Pt1-xMx (M = Ni, Co) was selected to be high in order to examine the dealloying process. The catalyst films were examined by a RDE test protocol that tracked the surface enhancement factor (SEF) and ORR current densities over a large number of test cycles. The aim was to measure the catalytic performance of the Pt-M materials as dealloying took place. The SEF of the PtCo and PtNi materials increased rapidly at the beginning and reached a plateau as high as 50 cm2/cm2 while the specific ORR activities increased as the initial M content in the catalyst precursor increased. The impact of the dealloying process on morphology was examined by completely dealloying a Pt3Ni7 precursor, deposited on mirror-polished GC disks, at a constant potential. As the dealloying process continued, the SEF of the material increased from about 1 cm2/cm2 to > 30 cm2/cm2 and resulted in the formation of whisker-like structures.

Polymer electrolyte membrane fuel cells (PEMFCs) have been looked as potential alternative energy conversion devices to conventional energy conversion systems such as combustion engines. Proton conducting membranes (PEMs) are one critical component of PEMFCs. The development of novel electrolyte membranes with dense structure, good mechanical flexibility, and high proton conductivity, but with little or no dependence on humidity at temperatures above 100¡ãC remains an important challenge to the realization of practical PEM fuel cells. In this thesis, to solve the technical difficulties existing in current high temperature PEM systems based on phosphoric acid and imidazole, a new type of proton conducting species 1H-1,2,3-triazole has been explored, and proved to have high proton conductivity and also enough electrochemical stability for fuel cell applications. In further experiments, effective methods have been developed to synthesize triazole derivatives and polymers. The properties of the synthesized polymers have studied and reported in this thesis. Preliminary computational simulations have also been performed to study the proton conducting mechanism to provide intrinsic information of the proton conducting process in 1H-1,2,3-triazole. In the final part, research works on other proton conducting species including H3PO4 and other heterocycles have been reported.