京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第17887号 / 工博第3796号 / 新制||工||1581(附属図書館) / 30707 / 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 酒井 明, 教授 邑瀬 邦明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21756号 / 工博第4573号 / 新制||工||1713(附属図書館) / 京都大学大学院工学研究科機械理工学専攻 / (主査)教授 蓮尾 昌裕, 教授 木村 健二, 教授 江利口 浩二 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21787号 / 工博第4604号 / 新制||工||1717(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 作花 哲夫, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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Conventional primary Li/CFx batteries employ graphite and polyvinylidene fluoride additives in the cathodes. These additives usher in some un-desired side-effects, such as lower battery capacities (mAh/g) and smaller current densities (mA/g). An innovative pretreatment was developed in this research in which CFx was subject to a “solvated electron” reduction to obtain a thin layer graphitic carbon coating on the CFx particle surfaces. Resistivity tests revealed that these partially reduced CFx particles have a higher conductivity at comparable graphitic carbon contents. Electrochemical discharge reactions demonstrated that batteries made from the reduced CFx were superior to the conventional batteries with higher current densities and higher capacities achieved. Impedance spectroscopy (EIS) studies found out that the reduced CFx particles have smaller cell reaction resistances, smaller double layer/intercalation capacitances and smaller mass transport resistances. It appears that use of reduced CFx has the potential to replace the conventional CFx plus additives as a cathode material in Li/CFx batteries.

We have designed a new type of plasma gun ion source for a Malmberg-Penning trap based on Metal Vapor Vacuum Arc (MeVVA) ion source designs. Our primary intent with this MeVVA-type source is to create a confinable beryllium-7 (7-Be) plasma. 7-Be is a peculiar isotope due to its varying radioactive decay half-life in different electro-chemical configurations. It is also found in an unexpected abundance at high altitudes of the Earth's atmosphere. It is possible ioniziation affects the radioactivity of the isotope, partly explaining this discrepancy with atmospheric models. The short half-life of 7-Be requires us to replace the sample inside the ion source on a regular basis. Our design makes it possible to easily remove the cathode of the ion source from an ultra-high vacuum trap and exchange 7-Be samples while only needing to repressurize a small chamber rather than the entire trap. This design has an added benefit of being capable of generating plasmas from a wide variety of metals by simply exchanging the source target in the removable cathode. Because of this wide compatibility, we will be able to use our trap for studying any number of different plasmas, including other radioactive types. Testing of the ion source design shows we are able to extract more than a sufficient number of ions at reasonable energies for confinement.

This dissertation investigates the possibility of using compact and heaterless calcium aluminate electride hollow cathodes in different electric propulsion systems for space applications. As conventional hollow cathodes generally require a heater to reach the high operating temperatures necessary to thermally emit electrons, research on low temperature heaterless hollow cathodes as electron sources has been increasing. Efforts at Technische Universität Dresden have resulted in an operational hollow cathode design that can be reliably used for low current plasma discharges. Hollow cathodes are crucial components in electric propulsion systems to ionize the propellant and neutralize the extracted ion beam. The successful development of an operational hollow cathode opens the possibility of using the design in different low-power electric propulsion systems. As the electron emission properties of C12A7:e- are still not well understood, a volume-averaged hollow cathode model has been developed as part of this thesis to obtain an improved insight into the plasma processes governing the cathode discharge. The model consists of two computational domains in which the plasma properties are volume-averaged. A lumped-node thermal model coupled with the plasma model provides the cathode temperature distribution for different operating points. The model moreover provides the discharge voltage which can be directly compared to experimental data. The thermal model was compared to thermal measurements to derive adequate values for free model parameters. The discharge voltage fits well for a 1 A discharge but diverges from measurement data at higher currents. The model is a starting point for further modeling efforts and needs to be verified using extensive plasma diagnostics. The first electric propulsion system developed as part of this thesis is an electrothermal device that takes advantage of high particle temperatures in a hollow cathode discharge. A performance model and preliminary test series were used to derive design parameters for a prototype that was used for an extensive parameter study. The thruster reliably generates thrust over a current range between 1 A – 3 A. The thrust achieved with this device is in the high micronewton to low millinewton range. The specific impulse is on the order of 100 s, which is low for electric propulsion systems, and the high discharge voltages of approximately 50 V limit the achievable efficiency to <1%. The second thruster concept is a DC discharge gridded ion thruster using a C12A7:e- hollow cathode as the discharge cathode and the neutral gas inlet. An analytical discharge model combined with a particle-in-cell simulation for ion extraction by electrostatically biased grids was used to design a modular testing prototype. The concept requires a low discharge current on the order of 200 mA. Operating the cathodes in a milliamp discharge current range proved to be difficult and was accompanied by high discharge voltages. Extracting an ion beam from the testing prototype was not successful. The third propulsion system is a magnetoplasmadynamic thruster (MPDT) that takes advantage of a strong magnetic field generated by permanent magnets and an orthogonal current in a plasma discharge using a C12A7:e- hollow cathode. Conventional MPDTs require high current discharges to generate a sufficiently strong self-induced magnetic field. The developed concept is a design alternative to expand the operational envelope to lower powers. A major advantage is the comparatively easy scalability of the device. One prototype for the low amp current range was developed and successfully operated. The generated thrust is in the low millinewton range with a specific impulse up to 1,200 s. The test series highlighted thermal problems with the design. Consequently, a sub-amp version of the concept was developed. The thruster was successfully operated but required high mass flow rates, lowering the specific impulse and efficiency.

Fuel cells are promising candidates for converting chemical energy into electrical energy. The Molten Carbonate Fuel Cell (MCFC) is a high temperature fuel cell that produces electrical energy from a variety of fuels containing hydrogen, hydrocarbons and carbon monoxide. Since the waste heat has a high temperature it can also be used leading to a high overall efficiency. Material degradation and the cost of the components are the problems for the commercialisation of MCFC. Although there are companies around the world starting to commercialise MCFC some further cost reduction is needed before MCFC can be fully introduced at the market. In this work, alternative materials for three different components of MCFC have been investigated. The alternative materials should have a lower cost compared to the state-of-the-art materials but also meet the life-time goal of MCFC, which is around 5 years. The nickel dissolution of the cathode is a problem and a cathode with lower solubility is needed. The dissolution of nickel for three alternative cathode materials was investigated, where one of the materials had a lower solubility than the state-of-the-art nickel oxide. This material was also tested in a cell and the electrochemical performance was found to be comparable with nickel oxide and is an interesting candidate. An inexpensive anode current collector material is also desired. For the anode current collector, the contact resistance should be low and it should have good corrosion properties. The two alternative materials tested had low contact resistance, but some chromium enrichment was seen at the grain boundaries. This can lead to a decreased mechanical stability of the material. In the wet-seal area, the stainless steel used as bipolar/separator plate should be coated. An alternative process to coat the stainless steel, that is less expensive, was evaluated. This process can be a suitable process, but today, when the coating process is done manually there seems to be a problem with the adherence. This work has been a part of the IRMATECH project, which was financed by the European Commission, where the partners have been universities, research institutes and companies around Europe. / QC 20101123

Solid oxide fuel cells are used as stationary power plants for electricity production. Despite having a very high efficiency of 90% they haven’t gained a world-wide commercial usage, due to their very high operating temperatures, and high production cost. However, there is a lot of ongoing research with the aim of developing intermediate-temperature solid oxide fuel cells (IT-SOFCs) that could operate at temperatures below 800°C. Cathodes are the most studied components of IT-SOFCs, since decreasing operating temperature results in slow oxygen reduction reaction(ORR) kinetics and large polarization losses. Perovskite related metal oxides have become very popular materials that could make suitable cathodes for IT-SOFCs. In this work an evaluation of several materials belonging to three different material groups have been studied: single layer perovskites, with a general formula of ABO3, double layer perovskites, with a general formula of AA’B2O6 and Ruddlesden-Popper phase, with a general formula of An+1BnO3n+1. Power generating capabilities of those materials have been studied on an electrolyte supported cell, cathode/LSGM9182/Ni-Fe. IR drop and overpotential of the cathode was measured and activation energy of the ORR for each material has been calculated. The double layer perovskite cobaltites offer a significant drop in overpotential, increase in conductivity compared to their single layer counterpart, while being able to generate significant amount of power. Ruddlesden-Popper phase materials offer the lowest activation energy values amongst the researched materials, but offer limited power generation values in the setup they were tested. Both of double layer perovskites and Ruddlesden-Popper based materials have opportunities for their performance to be improved. / Fastoxidbränsleceller används som stationära kraftverk för elproduktion. Trots att de har en mycket hög effektivitet på 90% har de inte fått en världsomspännande kommersiell användning på grund av deras mycket höga driftstemperaturer och hög produktionskostnad. Det är emellertid mycket pågående forskning med sikte på att utveckla intermediär temperatur fastoxidbränsleceller (IT-SOFC) som kan fungera vid temperaturer under 800 ° C. Katod är de mest studerade komponenterna i IT-SOFC, eftersom minskad driftstemperatur resulterar i kinetik med långsam syrereduktion (ORR) och stora polarisationsförluster. Perovskite-relaterade metalloxider har blivit mycket populära material som kan göra lämpliga katoder för IT-SOFC. I detta arbete har en utvärdering av flera material som hör till tre olika materialgrupper studerats: singelskikt perovskiter, med en generell formel för ABO3, dubbelskikt perovskiter, med en generell formel av AA'B2O6 och Ruddlesden-Popper-fasen med en allmän formel för An + 1BnO3n + 1. Effektgenereringskapaciteten hos dessa material har studerats på en elektrolytbärbar cell, katod / LSGM9182 / Ni-Fe. IR-droppe och överpotential hos katoden mättes och aktiveringsenergin för ORR för varje material har beräknats. Dubbelskiktet perovskit koboltiter ger en signifikant minskning av överpotentialen, ökad ledningsförmåga jämfört med deras enkelskikt motpart, samtidigt som man kan generera betydande mängden kraft. Ruddlesden-Popper-fasmaterial erbjuder de lägsta aktiveringsenergivärdena bland de undersökta materialen, men erbjuder begränsade kraftproduktionsvärden i den inställning de testades. Både av dubbelskiktet perovskiter och Ruddlesden-Popper-baserade material har möjligheter att förbättra deras prestanda.

In order to support UCLA’s development of the 3 cm Miniature Xenon Ion (MiXI) thruster, Cal Poly has a 3 cm thruster under development. This version, called MiXI Cal Poly Version 1 (MiXI-CPv1), is complete and has been utilized in vacuum chamber thermal validation testing. Testing on this version was used to check the validity of heat transfer simulations modeled in SolidWorks. Investigations of the 3 cm ion thruster configuration were intended to discover the driving factors affecting the thermal behavior of the discharge chamber and surrounding design space. Numerical simulations indicate that the heating of the samarium cobalt permanent magnets can be mitigated through the implementation of two proposed modifications. The first modification is to implement a 2% thoriated tungsten filament cathode. This design exhibited maximum permanent magnet temperatures of 325°C, twenty-five degrees below the maximum upper temperature of 350°C. Since some magnetic degaussing effects have been observed at temperatures above 300°C, the aforementioned solution can be combined with a thruster design modification to achieve a reduced permanent magnet temperature of 298°C. This modification would involve increase the anode wall thickness from approximately 0.7 mm to 2 mm below the permanent magnet ring, creating a stepped anode design. Additionally, less effective solutions were proposed and modeled and are presented for completeness.