Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第16852号 / 工博第3573号 / 新制||工||1540(附属図書館) / 29527 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 乾 晴行, 准教授 宇田 哲也 / 学位規則第4条第1項該当

Doctor of Philosophy / Department of Electrical and Computer Engineering / Medhat M. Morcos / Characterized by variable impedances, DC power sources normal operation, reliability, and life-time is negatively affected by the sequential switching within any DC power system. The impedances of Nickel-Cadmium (NiCd) storage batteries and Direct Ethanol Fuel Cells (DEFC) vary nonlinearly; therefore, existing DC power system models, that employ averaging of the sequential switching process, are inaccurate in describing the system output voltage. In this research, Fourier-series models of DC–DC converters are developed and evaluated, through numerical computations and computer simulations. Both NiCd-DC converter and DEFC-DC converter power systems are experimentally evaluated over a selected switching frequency range. Input voltage and output voltage characteristics of two types of DEFC-DC converter systems (Nickel-mesh and Nickel-foam electrode assembly) are determined. Experimental results are compared to computer simulations, thus validating the Fourier-series models. Experimental results show a correlation between the DC converter switching frequency and the output of the DC power system. Sequential switching operation, along with the type of DC converter employed, are factors determining the maximum power transfer of the system. The models developed in this work are flexible over a large switching frequency range, and for any desired duty cycle. Correction factors, accounting for the source-converter impedance matching, are easily implemented in Fourier-series models. The research demonstrates the advantages of Fourier-series models, as compared to both large-signal and small-signal models, with regard to accuracy and ease of implementation to any DC–DC converter-driven power system.

The maximum theoretical energy efficiency of fuel cells is much larger than those of the steam-power-turbine cycles that are currently used for generating electrical power. Similarly, direct hydrocarbon fuel cells, DHFCs, can theoretically be much more efficient than hydrogen fuel cells. Unfortunately the current densities (overall reaction rates) of DHFCs are substantially smaller than those of hydrogen fuel cells. The problem is that the exchange current density (catalytic reaction rate) is orders of magnitude smaller for DHFCs. Other work at the University of Ottawa has been directed toward the development of polymer electrolytes for DHFCs that operate above the boiling point of water, making corrosion rates much slower so that precious metal catalysts are not required. Propane (liquefied petroleum gas, LPG) was the hydrocarbon chosen for this research partly because infrastructure for its transportation and storage in rural areas already exists. In this work nickel based catalysts, an inexpensive replacement for the platinum based catalysts used in conventional fuel cells, were examined using density functional theory, DFT. The heats of propane adsorption for 3d metals, when plotted as a function of the number of 3d electrons in the metal atom, had the shape of a volcano plot, with the value for nickel being the peak value of the volcano plot. Also the C-H bond of the central carbon atom was longer for propane adsorbed on nickel than when adsorbed on any of the other metals, suggesting that the species adsorbed on nickel was less likely to desorb than those on other metals. The selectivity of the propyl radical reaction was examined. It was found that propyl radicals

This thesis focuses on developing an alternative system for membrane electrode assembly (MEA) formation to use with a direct methanol fuel cell (DMFC). The approach involves incorporating inorganic fillers with an industry standard Nafion polymer as part of a methanol resistant composite barrier layer at the anode/membrane interface of MEA featuring Nafion 117 membranes. This procedure is used to reduce the fuel cell losses related to the crossover of un-oxidised methanol through the membrane and prevent its subsequent reaction at the cathode. The inorganic filler used within this study was mordenite that has Si/Al ratio of 5 and by incorporating this into the barrier layer a superior DMFC performance has been achieved in comparison to a standard MEA featuring a Nafion 117 membrane. The voltage, current density and power density used as a measure of DMFC performance under a range of methanol molarities (1M-4M) and cell temperatures (40°C-70°C) have been taken for both the novel and standard MEA. Linear sweep voltammetry (LSV) and AC impedance spectroscopy (ACIS) were used to give some insight into what was occurring within the MEA with regards to methanol crossover current and the proton conductivity within the DMFC. To obtain the best possible DMFC performance a range of mordenite loadings from 0wt%1.0wt% were utilised and an optimum loading of 0.5wt% was reached. MEA which featured mordenite that had undergone ion exchange into a protonated form (from the sodium form) and had a silane functional group (glycidoxypropyltrimethoxysilane) grafted onto the surface, gave DMFC performances that were as much as 50% better than the standard. The highest power density obtained with this MEA was 43.6mW/cm-2 compared to the 35mW/cm-2 obtained using the standard. Values obtained for the methanol crossover current and proton conductivity under working DMFC operating conditions showed that this novel MEA had as much as 16% lower methanol permeability compared to the standard combined with comparable proton conductivity when using a 1M methanol feed. The durability of a novel MEA featuring the 0.5wt% functionalised H-mordenite composite barrier layer was tested in the DMFC and compared to a standard MEA at a constant current of 50mA/cm-2 over 100 hours. The cell potential fell by 0.1mV/h in comparison to a 0.23mV/h loss observed with the standard. The work reported within this study aims to show that by incorporating a thin Nafion/mordenite composite layer at the anode/membrane interface within an MEA will result in improvements in DMFC performance. The development of this technology has led to the application for a patent due to the potential for the commercial development of DMFC using this novel approach.

Ce travail concerne la mise au point d’une cellule électrochimique de technologie PEM pour l’appauvrissement en oxygène d’un flux d’air. L’idée de départ consiste à répondre aux problématiques des photo-bioréacteurs en ce qui concerne le contrôle de la quantité d’oxygène nécessaire pour la croissance des micro-organismes. Deux axes principaux sont indispensables pour notre étude. Au début, nous avons étudié l’aspect technologique vu que la cellule électrochimique à concevoir n’est que le fruit de la combinaison d’une demi-pile à combustible au niveau de la cathode (réduction de l’oxygène) avec un demi-électrolyseur de l’eau à l’anode. De ce fait, le choix des matériaux des différents constituants de cette cellule passe par l’étude des systèmes pile à combustible et électrolyseurs de même type PEM. Cette étude nous a permis ensuite de concevoir notre cellule et de la valider expérimentalement. En parallèle, la cellule électrochimique, sujet de cette étude, est conçue pour fonctionner principalement en tant que cellule d’appauvrissement en oxygène de l’air. La réaction électrochimique clé qui contrôle ce mode de fonctionnement est la RRO. Néanmoins, l’étude cinétique de cette réaction passe par l’étude de deux autres réactions se passant lorsque notre cellule fonctionne en mode électrolyseur de l’eau. Ce dernier mode de fonctionnement a été pris en compte lors de notre conception du banc d’essai. En électrolyse, un dégagement d’hydrogène s’effectue à la cathode et un dégagement d’oxygène à l’anode aura lieu. Le relevé des paramètres des deux réactions a été utile pour déterminer les paramètres cinétiques de la réaction principale; réaction de réduction de l’O2 à la cathode / This work concerns the conception of a PEM electrochemical cell for oxygen depletion from an air flow. The starting idea consists in finding solution for the problem of photo-bioreactors regarding the control of the oxygen amount necessary for the growth of microorganisms. Two main areas are essential for our study. At first, we studied the technological aspect since the electrochemical cell design is the result of a combination of a half-fuel cell at the cathode compartment (reduction of oxygen) with a half-water electrolyzer at the anode. Therefore, the choice of materials for the different constituents of the cell passes through the study of PEM fuel cell systems and electrolyzers as well. This study allowed us to design and experimentally validate our cell. In parallel, the electrochemical cell, subject of this study, is designed to function primarily as cell of oxygen depletion. The reaction key which control mode is the ORR. However, the kinetic study of this reaction involves the study of two other reactions when our cell operates in the water electrolyser mode. The latter mode has been taken into account in our design of the test bench. In electrolysis, hydrogen evolution takes place at the cathode and oxygen evolution at the anode will occur. The survey of the kinetic parameters of these two reactions was useful for determining the kinetic parameters of the main reaction; reduction reaction of O2 at the cathode

Le travail de cette thèse s’inscrit dans une thématique qui concerne le dimensionnement optimal et la gestion d’énergie résiliente aux défauts d’un système multi-sources (hybride) pour l’alimentation d’un véhicule électrique. Dans notre cas, le système de stockage est composé d’une pile à combustible comme source principale et une source secondaire à base d’une batterie Li-ion. L’étude réalisée sur le dimensionnement montre l’intérêt de l’hybridation par rapport à un système mono-source batterie seule ou bien pile à combustible seule. L’intérêt de cette hybridation en termes de masse, de volume et de coût devient de plus en plus important en augmentant l’autonomie du véhicule. Après avoir dimensionné la source hybride pour une autonomie de 700 km, on s’est intéressé à l’influence de la technologie de la batterie et les méthodes de gestion sur les performances de la source (le volume, la masse, le cout, les contraintes électriques appliquées sur les composants et la consommation d’hydrogène du système PàC/Batterie). La partie dimensionnement est suivie par le développement d’une stratégie de gestion d’énergie originale basée sur la prise en compte de l’état de charge de la batterie (SOC) pour adapter les limites de fonctionnement de la pile à combustible. Les résultats obtenus avec cette méthode sont comparés avec deux autres stratégies de gestion d’énergie en ligne à savoir, la méthode de découpage fréquentiel et l’utilisation d’un superviseur floue. La stratégie développée a donné des bons résultats expérimentaux en termes de contraintes vues par les cellules et de consommation d’hydrogène. Malgré un bon dimensionnement de la source embarquée et une bonne optimisation de la méthode de gestion d’énergie, le système n’est pas à l’abri du défaut et peut être le siège de plusieurs défauts qui peuvent apparaitre au niveau de capteurs de tension et de courant. Afin d’assurer la continuité de service du système hybride en présence de ces défauts, une stratégie de commande tolérante aux fautes a été développée afin de garantir la stabilité de système hybride PàC/Batterie et assurer des performances acceptables en mode dégradé. / The work of this thesis is part of a theme that concerns the optimal sizing and energy management resilient to the faults of a multi-source system (hybrid) for the power supply of an electric vehicle. In our case, the storage system consists of a fuel cell as the main source and a secondary source based on a Li-ion battery. The study carried out on the sizing shows the interest of the hybridization compared to a mono-source single battery or fuel cell only system. The interest of this hybridization in terms of weight, volume and cost becomes more and more important by increasing the autonomy of the vehicle. After scaling the hybrid source for a 700 km drive range, we investigated the influence of battery technology and management methods on the performance of the source (volume, mass, cost, electrical stress applied to the components and the hydrogen consumption of the Fuel Cell / Battery system).The sizing part is followed by the development of an original energy management strategy based on the state of charge of the battery (SOC) to adapt the operating limits of the fuel cell. The results obtained with this method are compared with two other online energy management strategies namely, the frequency division method and the use of a fuzzy supervisor. The strategy developed gave good experimental results in terms of constraints seen by cells and hydrogen consumption. Despite a good sizing of the on-board source and a good optimization of the energy management method, the system is not immune from the fault and can be the seat of several faults that can appear at voltage sensors. and current. In order to ensure the service continuity of the hybrid system in the presence of these faults, a fault-tolerant control strategy has been developed in order to guarantee the stability of the hybrid Fuel Cell/ Battery system and to ensure acceptable performance in degraded mode.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22773号 / 工博第4772号 / 新制||工||1746(附属図書館) / 京都大学大学院工学研究科航空宇宙工学専攻 / (主査)教授 岩井 裕, 教授 吉田 英生, 教授 江口 浩一 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Proton Exchange Membrane Fuel Cell (PEMFC) is the most commonly used type of hydrogen fuel cell and a promising solution for vehicular and stationary power applications. This research starts with an extensive review of the PEMFC research, including experimental testing, and performance modeling, and performance degradation modeling using relatively accurate and easy-to-use mechanistic models. Next, a new PEMFC performance degradation model is introduced by amending the semi-empirical, mechanistic performance model to support the design and control of PEMFC systems and fuel cell electric vehicles (FCEVs). The new model takes into account critical factors impacting PEMFC performance. The performance degradation due to the oxidation of catalyst platinum (Pt) and loss of active surface area is captured by fitting the degradation model parameters using experimental data to capture the observed PEMFC performance fading. The new performance degradation model is then tested and further improved under the four typical load modes that a PEMFC system experiences in a vehicular application under regular driving cycles. The model is also fitted with PEMFC experimental degradation data under different load modes to improve modeling accuracy. The new model is applied and tested using simulations of a representative FCEV. The actual power load on an 80 kW PEMFC system in the modeled FCEV was obtained using the Advanced Vehicle Simulator (ADVISOR) under the US EPA Urban Dynamometer Driving Schedule (UDDS). With the ability to predict the operation life of the PEMFC, the appropriate sizes of the PEMFC system and the energy storage system (ESS) can be determined. Improved power control and energy management can be developed to extend the operation life of the PEMFC and lower the lifecycle cost of the FCEV. / Graduate

This project deals with the design and realisation of a set that will work as a power supply point with electricity generated from renewable energy sources. The theoretical part deals with information about renewable energy sources and energy storage options. In the practical part, a mobile kit for powering variable message traffic signs is designed. It uses photovoltaic panels and stores energy in a lead-acid battery. A methanol fuel cell is used for backup power. The device is adapted for use in road traffic and meets the requirements of the relevant authorities. To verify the stability of the structure, there were performed static calculations, which proved the ability of the device to withstand wind stress. Part of the work was to draw a complete production documentation, which was used to create a test sample. Long-term measurements of energy flows in the system were performed on that sample. These measurements confirmed the ability of the device to operate autonomously and the possibility of using it for the required purpose.

The Master’s thesis reviews the topic of hydrogen in within European and Czech energy industry. Hydrogen’s usage in gas industry, heating industry and power engineering may play a significant role in meeting European Union’s ambitious goals aiming to reduce emission production. This work identifies specifications of technologies used to produce, transport, and use of hydrogen and their impact on today’s energy systems and safety. The technical, economic, and political context is emphasized. The technical part covers the topic of injecting hydrogen into natural gas and it’s impact on physico-chemical properties of gas. The work analyses concentrations of 0, 5, 10, 15, 20 and 25 molar percent of hydrogen in real composition of natural gas measured on a handover point of transition system. Furthermore, calculations for these mixtures have been done to determine a change in characteristics of a heat exchanger. The results show, that with higher concentrations of hydrogen, the power of heat exchanger rises, while the power of a burner decreases due to lower calorific value of gas mixture. The last chapter follows up on a economical analysis of fuel and emission allowance costs for above-mentioned concentrations of hydrogen in gas mixture. Specific values of combined cycle gas plant Počerady from year 2019 were used for calculations. The results show, that in all of the three considered scenarios of emission allowance price predictions, replacing hydrogen with natural gas did not have a positive economic impact.