Philosophiae Doctor - PhD / Fuel cells are long term solution for global energy needs. In current fuel cell technologies, Proton Exchange Membrane (PEM) fuel cells are known for quick start-up and ease of operation compared to other types of fuel cells. Operating PEM fuel cells at high temperature show promising applications for stationary combined heat and power application (CHP). The high operating temperature up to 160°C allows waste heat to be recovered for co-generation or tri-generation purposes. The commercially available PEM fuel cells operating at 160⁰C can tolerate up to 3% CO without significant loss of performance, making HT-PEM fuel cell viable choice when reformate is used. In reality these advantages convert to very little balance-of-plant compared to Nafion® based fuel cells operating at 60°C. However, there are some problems that prevent high temperature fuel cells from large scale commercialization. The cathode is said to have sluggish reaction kinetics and high cell potentials and operating temperature during fuel cell start-up may cause severe degradation. The formation of liquid water during the shut-down can cause the phosphoric acid to leach from the cell during operation. Efforts are being made to reduce the cost and increase the durability of fuel cell components (such as catalyst and membrane) at high temperatures. Apart from degradation issues, the problems are related to cost and performance. The performance of the PEM fuel cells depends on a lot of factors such as fuel cell design and assembly, operating conditions and the flow field design used on the cathode and anode plates. The flow field geometry is one important factor influencing the performance of fuel cells. The flow fields have significant effect on pressure and flow distribution inside the fuel cell. A homogeneous distribution of the reactant gases over the active catalyst surface leads to improved electrochemical reactions and thus enhances the performance of the fuel cell. So, the design of flow fields is one of the important issues for performance improvement of PEM fuel cell in terms of power density and efficiency. There are different types of flow fields available for PEM fuel cells such as serpentine, pin, interdigitated and straight flow fields but the most obvious choice is multiple serpentine. The same can be used for high temperature PEM fuel cell (HT-PEMFC) application with ease because of absence of liquid water during the high temperature operation and no need for complex water management.

Philosophiae Doctor - PhD / Proton exchange membrane fuel cells (PEMFC) converts chemical energy from the electrochemical reaction of oxygen and hydrogen into electrical while emitting heat, oxygen depleted air (ODA) and water as by-products. The by-products have useful functions in aircrafts, such as heat that can be used for ice prevention, deoxygenated air for fire retardation and drinkable water for use on board. Consequently, the PEMFC is also studied to optimize recovery of the useful products. Despite the progress made, durability and reliability remain key challenges to the fuel cell technology. One of the reasons for this is the limited understanding of PEMFC behaviour in the aeronautic environment. The aim of this thesis was to define a comprehensive non-intrusive diagnostic technique that provides real time diagnostics on the PEMFC State of Health (SoH). The framework of the study involved determining factors that have direct influence on fuel cell life in aeronautic environment through a literature survey, examining the effects of the factors by subjecting the PEMFC to simulated conditions, establishing measurable parameters reflective of the factors and defining the diagnostic tool based on literature review and this thesis finding.

The incorporation of an ejector refrigeration cycle with a high temperature PEM fuel cell (HT-PEMFC) presents a novel approach to combined heat and power (CHP) applications. An ejector refrigeration system (ERS) can enhance the flexibility of a CHP system by providing an additional means of utilizing the fuel cell waste heat besides domestic hot water (DHW) heating. This study looks into the performance gains that can be attained by incorporating ejector refrigeration with HT-PEMFC micro-CHP (mCHP) systems (1 to 5kWe). The effectiveness of the ERS in utilizing fuel cell waste heat is studied as is the relulting enhancement to overall system efficiency. A test rig specially constructed to evaluate an ERS under simulated HT-PEMFC conditions is used to test the concept and verify modeling predictions. In addition, two separate analytical models were constructed to simulate the ERS test rig and a HT-PEMFC/ERS mCHP system. The ERS test rig was simulated using a Matlab based model, while two residential sized HT-PEMFC/ERS mCHP systems were simulated using a Simulink model. Using U.S. Energy Information Administration (EIA) air conditioning and DHW load profiles, as well as data collected from a large residential monitoring study in Florida, the Simulink model provides the results in system efficiency gain associated with supporting residential space cooling and water heating loads. It was found that incorporation of an ERS increased the efficiency of a HT-PEMFC mCHP system by 8 t0 10 percentage points over just using the fuel cell waste heat for DHW. In addition, results from the Matlab ERS test rig model were shown to match well with experimental results. / by Michel Fuchs. / Thesis (Ph.D.)--Florida Atlantic University, 2012. / Includes bibliography. / Mode of access: World Wide Web. / System requirements: Adobe Reader.

O objetivo desse trabalho foi investigar as relações entre a durabilidade e as diversas configurações dos componentes de uma célula a combustível do tipo PEM por meio de Testes de Durabilidade de Longa Duração. Foram comparados três tipos de geometria de fluxo, duas espessuras de membranas poliméricas e dois níveis de cargas de platina. Em diversos aspectos, a geometria de canais de fluxo do tipo serpentina se mostrou superior aos demais. Em relação às membranas, as do tipo Nafion 212 se mostraram bastante frágeis e suscetíveis ao crossover de H2, apesar de fornecerem maior potência elétrica que as membranas Nafion 115, as quais exibiram maior durabilidade. No que diz respeito à carga de platina nos eletrodos, verificou-se que os eletrodos preparados com 0,1 mg Pt cm-2 perderam, proporcionalmente, mais área eletroquimicamente ativa que aqueles preparados com 0,4 mg Pt cm-2, mas, ao mesmo tempo, apresentaram as menores taxas de perdas irreversíveis de desempenho. As análises por diversas técnicas eletroquímicas indicaram que os aumentos das resistências ôhmicas e de transporte de massas são os fatores que mais contribuem para as perdas irreversíveis de desempenho, enquanto que o aumento da resistência de transporte de cargas devido ao encharcamento dos eletrodos é o principal responsável pelas perdas reversíveis de desempenho. A proporção de ionômero na camada catalítica foi investigada e verificou-se que, apesar de facilitar para que ocorram perdas reversíveis de desempenho, a maior proporção de ionômero na camada catalítica contribuiu em mitigar a degradação do MEA. Por fim, observou-se que a qualidade do contato entre os eletrodos e a membrana tem grande contribuição na durabilidade das células a combustível do tipo PEM. / The aim of this work was to investigate the relations between durability and the several Proton Exchange Membrane Fuel Cell (PEMFC) setups via long-term durability tests. Comparisons were made with three types of flow field designs, two polymeric membranes thicknesses and two platinum loadings. In many aspects, the serpentine flow field design has presented better results than the others. Regarding the membranes, Nafion 212 has shown to be very fragile and susceptible to H2 crossover, although it provides more electrical power than the Nafion 115 membrane which exhibited better durability. Concerning the platinum loading, the electrodes prepared with 0.1 mg Pt cm-2 have lost proportionally more electrochemical surface area than the ones prepared with 0.4 mg Pt cm-2 but at the same time, the electrodes with the lowest platinum load presented lower irreversible performance loss rate. The analyses made by several electrochemical techniques have indicated that the raise of the ohmic and mass transport resistances are the factors that most contribute to the irreversible performance loss, meanwhile the charge transport resistance due to the electrodes flooding is the main responsible for the reversible performance loss. The proportion of ionomer in the catalytic layer was studied and it was possible to infer that the highest ionomer proportion contributes to mitigate the MEA degradation, although it facilitates the reversible performance loss occurrence. Finally, it was observed that the contact quality of the electrodes and the membrane has remarkable influence on the PEMFCs durability.

Pulsing the flow of reactants in proton exchange membrane fuel cells (PEMFC) is a new frontier in the area of fuel cell research. Although power performance losses resulting from water accumulation also referred to as flooding, and power performance recovery resulting from water removal or purging, have been studied and monitored, the nexus between pulsing of reactants and power performance has yet to be established. This study introduces pulsing of reactants as a method of improving power performance. This study investigates how under continuous supply of reactants, pressure increase due to water accumulation, and power performance decay in PEMFCs. Furthermore, this study shows that power performance can be optimized through pulsing of reactants, and it investigates several variables affecting the power production under these conditions. Specifically, changes in frequency, duty cycle, and shifting of reactants as they affect performance are monitored and analyzed. Advanced data acquisition and control software allow multi-input monitoring of thermo-fluid and electrical data, while analog and digital controllers make it possible to implement optimization techniques for both discrete and continuous modes. / by Aquiles Perez. / Thesis (Ph.D.)--Florida Atlantic University, 2009. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2009. Mode of access: World Wide Web.

O objetivo desse trabalho foi investigar as relações entre a durabilidade e as diversas configurações dos componentes de uma célula a combustível do tipo PEM por meio de Testes de Durabilidade de Longa Duração. Foram comparados três tipos de geometria de fluxo, duas espessuras de membranas poliméricas e dois níveis de cargas de platina. Em diversos aspectos, a geometria de canais de fluxo do tipo serpentina se mostrou superior aos demais. Em relação às membranas, as do tipo Nafion 212 se mostraram bastante frágeis e suscetíveis ao crossover de H2, apesar de fornecerem maior potência elétrica que as membranas Nafion 115, as quais exibiram maior durabilidade. No que diz respeito à carga de platina nos eletrodos, verificou-se que os eletrodos preparados com 0,1 mg Pt cm-2 perderam, proporcionalmente, mais área eletroquimicamente ativa que aqueles preparados com 0,4 mg Pt cm-2, mas, ao mesmo tempo, apresentaram as menores taxas de perdas irreversíveis de desempenho. As análises por diversas técnicas eletroquímicas indicaram que os aumentos das resistências ôhmicas e de transporte de massas são os fatores que mais contribuem para as perdas irreversíveis de desempenho, enquanto que o aumento da resistência de transporte de cargas devido ao encharcamento dos eletrodos é o principal responsável pelas perdas reversíveis de desempenho. A proporção de ionômero na camada catalítica foi investigada e verificou-se que, apesar de facilitar para que ocorram perdas reversíveis de desempenho, a maior proporção de ionômero na camada catalítica contribuiu em mitigar a degradação do MEA. Por fim, observou-se que a qualidade do contato entre os eletrodos e a membrana tem grande contribuição na durabilidade das células a combustível do tipo PEM. / The aim of this work was to investigate the relations between durability and the several Proton Exchange Membrane Fuel Cell (PEMFC) setups via long-term durability tests. Comparisons were made with three types of flow field designs, two polymeric membranes thicknesses and two platinum loadings. In many aspects, the serpentine flow field design has presented better results than the others. Regarding the membranes, Nafion 212 has shown to be very fragile and susceptible to H2 crossover, although it provides more electrical power than the Nafion 115 membrane which exhibited better durability. Concerning the platinum loading, the electrodes prepared with 0.1 mg Pt cm-2 have lost proportionally more electrochemical surface area than the ones prepared with 0.4 mg Pt cm-2 but at the same time, the electrodes with the lowest platinum load presented lower irreversible performance loss rate. The analyses made by several electrochemical techniques have indicated that the raise of the ohmic and mass transport resistances are the factors that most contribute to the irreversible performance loss, meanwhile the charge transport resistance due to the electrodes flooding is the main responsible for the reversible performance loss. The proportion of ionomer in the catalytic layer was studied and it was possible to infer that the highest ionomer proportion contributes to mitigate the MEA degradation, although it facilitates the reversible performance loss occurrence. Finally, it was observed that the contact quality of the electrodes and the membrane has remarkable influence on the PEMFCs durability.

In order to achieve a more stable and highly proton conducting membrane that is also cost effective, the perfluoroalkyl benzenesulfonylimides (PFSI) polymers are proposed as electrolyte for Proton Exchange Membrane Fuel Cells. 4-(trifluoromethyl)-2-diazonium perfluoro-3, 6-dioxa-4-methyl-7-octene benzenesulfonyl imide (I) is synthesized from Nafion monomer via a 5-step schematic reaction at optimal reaction conditions. This diazonium PFSI zwitterionic monomer can be further subjected to polymerization. The loss of the diazonium N2+ functional group in the monomer is believed to form the covalent bond between the PFSI polymer electrolyte and carbon electrodes support. All the intermediates and final products were characterized using 1H NMR, 19F NMR and IR spectrometry.

Remote area power supply (RAPS) is a potential early market for renewable energy - hydrogen systems because of the relatively high costs of conventional energy sources in remote regions. Solar-hydrogen RAPS systems commonly employ photovoltaic panels, a Proton Exchange Membrane (PEM) electrolyser, a storage for hydrogen gas, and a PEM fuel cell. Unitised Regenerative Fuel Cells (URFCs) use the same hardware for both electrolyser and fuel cell functions. Since both of these functions are not required simultaneously in a solar hydrogen RAPS system, URFCs based on PEM technology provide a promising opportunity for reducing the cost of the hydrogen subsystem used in renewable-energy hydrogen systems for RAPS. URFCs also have potential applications in the areas of aerospace, submarines, energy storage for central grids, and hydrogen cars. In this thesis, a general theoretical relationship between cell potential and current density of a single-cell PEM URFC operating in both fuel-cell (FC) and electrolyser (E) modes is developed using modified Butler-Volmer equations for both oxygen- and hydrogen-electrodes, and accounting for mass transport losses and saturation behaviour in both modes, membrane resistance to proton current, and membrane and electrode resistances to electron current. This theoretical relationship is used to construct a computer model based on Excel and Visual Basic to generate voltage-current (V-I) polarisation curves in both E and FC modes for URFCs with a range of membrane electrode assembly characteristics. The model is used to investigate the influence on polarisation curves of varying key parameters such charge transfer coefficients, exchange current densities, saturation currents, and membrane conductivity. A method for using the model to obtain best-fit values for electrode characteristics corresponding to an experime ntally-measured polarisation curve of a URFC is presented. The experimental component of the thesis has involved the design and construction of single PEM URFCs with an active area of 5 cm2 with a number of different catalyst types and loadings. V-I curves for all these cells have been measured and the performance of the cells compared. The computer model has then been used to obtain best-fit values for the electrode characteristics for the URFCs with single catalyst materials active in each mode on each electrode for the corresponding experimentally-measured V-I curves. Generally values have been found for exchange current densities, charge transfer coefficients, and saturation current densities that give a close fit between the empirical and theoretically-generated curves. The values found conform well to expectations based on the catalyst loadings, in partial confirmation of the validity of the modelling approach. The model thus promises to be a useful tool in identifying electrodes with materials and structures, together with optimal catalyst types and loadings that will improve URFC performance. Finally the role URFCs can play in developing cost-competitive solar- hydrogen RAPS systems is discussed, and some future directions for future URFC research and development are identified.

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Proton exchange membrane fuel cell (PEMFC) is a potential alternative energy conversion device for stationary and automotive applications. Wide commercialization of PEMFC depends on progress that can be achieved to enhance its reliability and durability along with cost reduction. It is desirable to operate the PEMFC at uniform local current density and temperature distributions over the surface of the membrane electrode assembly (MEA). Non-uniform distributions of both current and temperature over the MEA could result in poor reactant and catalyst utilization as well as overall cell performance degradation. Local current distribution in the PEMFC electrodes are closely related to operating conditions, but it is also affected by the organization of the reactant flow arrangements in PEMFCs. Reactant depletion and water formation along the flow channel leads to current variation from the channel inlet to the exit, which leads to non-uniformity of local electrochemical reaction activity, and degradation of the cell performance. Flow arrangements between the anode and cathode streams, such as co-, counter- and cross- flow can exacerbate the effect of the non-uniformity considerably, producing complex current distribution patterns over the electrode surfaces. Thus, understanding of the local current density and its spatial characteristics, as well as the temperature distributions under different physical and operating conditions, is crucially important in order to develop optimum design and operational strategies. Despite the importance of the influence of the flow arrangement on the local current and temperature distributions under various operating conditions, few systematic studies have been conducted experimentally to investigate this effect. In this research, an experimental setup with special PEMFC test cells are designed and fabricated in-house, in order to conduct in-situ mapping of the local current and temperature distributions over the electrode surfaces. A segmented flow field plate and the printed circuit board (PCB) technique is used to measure the current distribution in a single PEMFC. In situ, nondestructive temperature measurements are conducted using thermocouples to determine the actual temperature distribution. Experimental studies have been conducted to investigate the effect of different flow arrangements between the anode and cathode (co-, counter-, and cross- flow) on the local current density distribution over the MEA surface. Furthermore, local current distribution has been characterized for PEMFCs under various operating conditions such as reactant stoichiometry ratios, reactant backpressure, cell temperature, cell potentials, and relative humidity for each one of the reactant flow arrangements. The dynamic characteristics of the local current in PEMFC under different operating conditions also have been studied. Temperature distributions along the parallel and serpentine flow channels in PEMFs under various operating conditions are also investigated. All independent tests are conducted to identify and optimize the key design and operational parameters for both local current and temperature distributions. It has been found that the local current density distribution is strongly affected by the flow arrangement between the anode and cathode streams and the key operating conditions. It has also been observed that the counter-flow arrangement generates the most uniform distribution for the current density, whereas the co-flow arrangement results in a considerable variation in the current density from the reactant gas stream inlet to the exit. Low stoichiometry ratio of hydrogen at the anode side has a predominant effect on the current distribution and cell performance. Further, it has been found that the dynamic characteristics and the degree of fluctuation of local current density inside PEMFC are strongly influenced by the crucial operating conditions. In-situ, nondestructive temperature measurements indicate that the temperature distribution inside the PEMFC is strongly sensitive to the cell’s current density. The temperature distribution inside the PEMFC seems to be virtually uniform at low current density, while the temperature variation increases up to 2 oC at the high current density. Finally, the present work contribution related to the local current and temperature distributions is required to understand the effect of each individual or even several operating parameters combined together on the local current and temperature distributions. This will help to develop an optimum design, which leads to enhancing the reliability and durability in operational PEMFCs.