<p>In this study novel composite electrodes were developed, in which the catalytic components were deposited in nanoparticulate form. The efficiency of the nanophase catalysts and membrane electrodes were tested in an important electrocatalytic process, namely hydrogen production by water electrolysis, for renewable energy systems. The activity of electrocatalytic nanostructured electrodes for hydrogen production by water electrolysis were compared with that of more conventional electrodes. Development of the methodology of preparing nanophase materials in a rapid, efficient and simple manner was investigated for potential application at industrial scale. Comparisons with industry standards were performed and electrodes with incorporated nanophases were characterized and evaluated for activity and durability.</p>

The proton exchange membrane fuel cell (PEMFC) is a potential electrochemicalpower device for vehicles, auxiliary power units and small-scale power plants. In themembrane electrode assembly (MEA), which is the core of the PEMFC single cell,oxygen in air and hydrogen electrochemically react on separate sides of a membraneand electrical energy is generated. The main challenges of the technology are associatedwith cost and lifetime. To meet these demands, firstly, the component expensesought to be reduced. Secondly, enabling system operation at elevated temperatures,i.e. up to 120 °C, would decrease the complexity of the system and subsequentlyresult in decreased system cost. These aspects and the demand for sufficientlifetime are the strong motives for development of new materials in the field.In this thesis, MEAs based on alternative materials are investigatedwith focus on hydrocarbon proton-conducting polymers, i.e. ionomers, and newcatalyst supports. The materials are evaluated by electrochemical methods, such ascyclic voltammetry, polarisation and impedance measurements; morphological studiesare also undertaken. The choice of ionomers, used in the porous electrodes andmembrane, is crucial in the development of high-performing stable MEAs for dynamicoperating conditions. The MEAs are optimised in terms of electrode compositionand preparation, as these parameters influence the electrode structure andthus the MEA performance. The successfully developed MEAs, based on the hydrocarbonionomer sulfonated polysulfone (sPSU), show promising fuel cell performancein a wide temperature range. Yet, these membranes induce mass-transportlimitations in the electrodes, resulting in deteriorated MEA performance. Further,the structure of the hydrated membranes is examined by nuclear magnetic resonancecryoporometry, revealing a relation between water domain size distributionand mechanical stability of the sPSU membranes. The sPSU electrodes possessproperties similar to those of the Nafion electrode, resulting in high fuel cell performancewhen combined with a high-performing membrane. Also, new catalystsupports are investigated; composite electrodes, in which deposition of platinum(Pt) onto titanium dioxide reduces the direct contact between Pt and carbon, showpromising performance and ex-situ stability. Use of graphitised carbon as catalystsupport improves the electrode stability as revealed by a fuel cell degradation study.The thesis reveals the importance of a precise MEA developmentstrategy, involving a broad methodology for investigating new materials both as integratedMEAs and as separate components. As the MEA components and processesinteract, a holistic approach is required to enable successful design of newMEAs and ultimately development of high-performing low-cost PEMFC systems. / QC 20100922

Hydrogen and oxygen or air polymer electrolyte membrane fuel cell is one of the most promising electrical energy conversion devices for a sustainable future due to its high efficiency and zero emission. Membrane electrode assembly (MEA), in which electrochemical reactions occur, is stated to be the heart of the fuel cell. The aim of this study was to develop methods for preparation of MEA with alternative polymer electrolyte membranes and compare their performances with the conventional Nafion&reg / membrane. The alternative membranes were sulphonated polyether-etherketone (SPEEK), composite, blend with sulphonated polyethersulphone (SPES), and polybenzimidazole (PBI). Several powder type MEA preparation techniques were employed by using Nafion&reg / membrane. These were GDL Spraying, Membrane Spraying, and Decal methods. GDL Spraying and Decal were determined as the most efficient and proper MEA preparation methods. These methods were tried to improve further by changing catalyst loading, introducing pore forming agents, and treating membrane and GDL. The highest performance, which was 0.53 W/cm2, for Nafion&reg / membrane was obtained at 70 0C cell temperature. In comparison, it was about 0.68 W/cm2 for a commercial MEA at the same temperature. MEA prepared with SPEEK membrane resulted in lower performance. Moreover, it was found that SPEEK membrane was not suitable for high temperature operation. It was stable up to 80 0C under the cell operating conditions. However, with the blend of 10 wt% SPES to SPEEK, the operating temperature was raised up to 90 0C without any membrane deformation. The highest power outputs were 0.29 W/cm2 (at 70 0C) and 0.27 W/cm2 (at 80 0C) for SPEEK and SPEEK-PES blend membrane based MEAs. The highest temperature, which was 150 0C, was attained with PBI based MEA during fuel cell tests.

Fuel cells are electricity generators which convert chemical energy of hydrogen directly to electricity by means of electrochemical oxidation and reduction reactions. A single proton exchange membrane (PEM) fuel cell can only generate electricity with a potential between 0.5V and 1V. The useful potential can be achieved by stacking cells in series to form a PEM fuel cell stack. There is a potential to utilize 100W class fuel cells. Fuelling is the major problem of the portable fuel cells. The aim of this thesis is to design and manufacture a PEM fuel cell stack which can be used for portable applications. The PEM fuel cell stack is planned to be incorporated to a NaBH4 hydrolysis reactor for H2 supply. Within the scope of this thesis a new coating technique called &ldquo / ultrasonic spray coating technique&rdquo / is developed for membrane electrode assembly (MEA) manufacturing. New metal and graphite bipolar plates are designed and manufactured by CNC technique. A fuel cell controller hardware is developed for fuel supply and system control. The power densities reached with the new method are 0.53, 0.74, 0.77, and 0.88 W/cm2 for 20%, 40%, 50%, 70% Pt/C catalyst by keeping 0.4mg Pt/cm2 platinum loading constant, respectively. The power density increase is 267% compared to &ldquo / spraying of catalyst ink with air pressure atomizing spray gun&rdquo / . All parts of the PEM fuel cell stack designed were produced, assembled, and tested. The current density reached is 12.9A at 12 V stack potential and the corresponding electrical power of the stack is 155W.

Fuel cells are expected to play a major role in the economy of this century and for the foreseeable future. The use of hydrogen and fuel cells can address critical challenges in all energy sectors like commercial, residential, industrial, and transportation. Fuel cells are electrochemical devices that convert energy of a chemical reaction directly into electrical energy by combining hydrogen fuel with oxygen from air. If hydrogen is used as fuel, only byproducts are heat and water. The objective of this thesis is to investigate the effect of operating temperature and relative humidity (RH) of reactant gases on proton exchange membrane (PEM) fuel cell performance by adjusting the operation temperature of the fuel cell and humidification temperature of the reactant gases. In this study, the effect of the different operating parameters on the performance of single proton exchange membrane (PEM) fuel cell have been studied experimentally using pure hydrogen on the anode side and air on the cathode side. Experiments with different fuel cell operating temperatures, different air and hydrogen humidification temperatures have been carried out. The experimental results are presented in the form of polarization curves, which show the effects of the various operating parameters on the performance of the PEM fuel cell. The polarization curves data have been fit to a zero dimensional model, and the effect of the fuel cell operation and humidification temperatures on the kinetic parameters and the cell resistance have been determined. The fuel cell has been operated with 1.2 and 2 stoichiometry ratio for hydrogen and air, respectively. Fuel cell performance was detected at different fuel cell operation temperatures changing from 60 to 80 &ordm / C, and relative humidity of the entering gases changing from 20 to 100 % for air and 50 % and 100 % for hydrogen. Tests were performed in a PEM fuel cell test station. The highest performance of 275 mA/cm2 at 0.6 V and 650 mA/cm2 at 0.4 V was obtained for 50 % RH air with a constant 100 % relative humidity of hydrogen for working at atmospheric pressure and 60 oC fuel cell temperature. However, the highest performance of 230 mA/cm2 at 0.6 V for 50 % RH of air with a constant 100 % relative humidity of hydrogen and the highest performance of 530 mA/cm2 at 0.4 V for both 70 % RH and 100% RH air with a constant 100 % relative humidity of hydrogen was obtained for working at atmospheric pressure and 70 oC fuel cell temperature. Besides, the highest performance of 200 mA/cm2 at 0.6 V and 530 mA/cm2 at 0.4 V was obtained for 100 % RH air with a constant 100 % RH of hydrogen for working at atmospheric pressure and 80 oC fuel cell temperature.

<p>In this study novel composite electrodes were developed, in which the catalytic components were deposited in nanoparticulate form. The efficiency of the nanophase catalysts and membrane electrodes were tested in an important electrocatalytic process, namely hydrogen production by water electrolysis, for renewable energy systems. The activity of electrocatalytic nanostructured electrodes for hydrogen production by water electrolysis were compared with that of more conventional electrodes. Development of the methodology of preparing nanophase materials in a rapid, efficient and simple manner was investigated for potential application at industrial scale. Comparisons with industry standards were performed and electrodes with incorporated nanophases were characterized and evaluated for activity and durability.</p>

Made available in DSpace on 2014-10-09T12:42:20Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:42Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:42:20Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:42Z (GMT). No. of bitstreams: 0 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Sistemas de PEMFC são capazes de gerar energia elétrica com alta eficiência e baixa ou nenhuma emissão de poluentes, porém questões de custo e durabilidade impedem sua ampla comercialização. Nesse trabalho foi desenvolvido um MEA com eletrocatalisadores à base de paládio. Foram sintetizados e caracterizados eletrocatalisadores Pd/C, Pt/C e Ligas PdPt/C com diferentes razões entre metais e carbono. Foi realizado um estudo da razão entre ionômero de Nafion e eletrocatalisador para formação de triplas fases reacionais de máximos desempenhos, criado um modelo matemático para transpor esse ajuste para eletrocatalisadores com diferentes razões entre metal e suporte, considerando os aspectos volumétricos da camada catalisadora, e então realizado um estudo da espessura da camada catalisadora. Para as caracterizações foram utilizadas as técnicas de Difração de Raios-X, Microscopias Eletrônicas de Transmissão e de Varredura, Energia Dispersiva de Raios-X, Picnometria a Gás, Porosimetria por Intrusão de Mercúrio, Adsorção de Gás, segundo as equações de BET e BJH, Análise Termo Gravimétrica e feitas as determinações de diâmetros de partículas, de áreas de superfície específica e de parâmetros de rede. Todos os eletrocatalisadores foram usados no preparo de MEAs que foram avaliados em célula unitária de 5 cm2 entre 25 e 100 °C a 1 atm; e a melhor composição foi avaliada também a 3 atm. No estudo dos metais para as reações, visando reduzir a platina aplicada aos eletrodos, sem perdas de desempenho, foram selecionados Pd/C para ânodos e PdPt/C 1:1 para cátodos. A estrutura de MEA desenvolvida utilizou 0,25 mgPt.cm-2 e resultou em densidades de potência de até 550 mW.cm-2 e potências de até 2,2 kWe por grama de platina. A estimativa realizada mostrou que houve uma redução de até 64,5 % nos custos em relação à estrutura de MEA previamente conhecida. Em função da temperatura e pressão de operação foram obtidos valores a partir de R$ 3.540,73 para o preparo de MEAs para cada quilowatt instalado. Com base em estudos recentes, concluiu-se que o custo do MEA desenvolvido é compatível às aplicações estacionárias de PEMFC. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP / FAPESP: 10/10028-1

Doctor Scientiae - DSc / In this study novel composite electrodes were developed, in which the catalytic components were deposited in nanoparticulate form. The efficiency of the nanophase catalysts and membrane electrodes were tested in an important electrocatalytic process, namely hydrogen production by water electrolysis, for renewable energy systems. The activity of electrocatalytic nanostructured electrodes for hydrogen production by water electrolysis were compared with that of more conventional electrodes. Development of the methodology of preparing nanophase materials in a rapid, efficient and simple manner was investigated for potential application at industrial scale. Comparisons with industry standards were performed and electrodes with incorporated nanophases were characterized and evaluated for activity and durability. / South Africa

In a previous study, we reported that polymer electrolyte fuel cells prepared by direct membrane deposition (DMD) produced power densities in excess of 4 W/cm2. In this study, the underlying origins that give rise to these high power densities are investigated and reported. The membranes of high power, DMD-fabricated fuel cells are relatively thin (12 μm) compared to typical benchmark, commercially available membranes. Electrochemical impedance spectroscopy, at high current densities (2.2 A/cm2) reveals that mass transport resistance was half that of reference, catalyst-coated-membranes (CCM). This is attributed to an improved oxygen supply in the cathode catalyst layer by way of a reduced propensity of flooding, and which is facilitated by an enhancement in the back diffusion of water from cathode to anode through the thin directly deposited membrane. DMD-fabricated membrane-electrode-assemblies possess 50% reduction in ionic resistance (15 mΩcm2) compared to conventional CCMs, with contributions of 9 mΩcm2 for the membrane resistance and 6 mΩcm2 for the contact resistance of the membrane and catalyst layer ionomer. The improved mass transport is responsible for 90% of the increase in power density of the DMD fuel cell, while the reduced ionic resistance accounts for a 10% of the improvement.