京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第21876号 / 人博第905号 / 新制||人||216(附属図書館) / 2018||人博||905(吉田南総合図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 内本 喜晴, 教授 田部 勢津久, 教授 吉田 鉄平 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第22548号 / 人博第951号 / 新制||人||226(附属図書館) / 2019||人博||951(吉田南総合図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 内本 喜晴, 教授 田部 勢津久, 准教授 藤原 直樹 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

Fundamental advances in cathode materials are key to lowering the operating temperature of solid oxide fuel cells (SOFCs). Detailed understanding of the structural, electronic and defect formation characteristics are essential for rational design of cathode materials. In this thesis we employ first principles methods to study La(Mn/Co)O3 and LnBaCo2O5+δ (Ln = Pr, Gd; δ = 0.5, 1) as cathode for SOFCs. Specifically, factors affecting the O vacancy formation and migration are investigated. We demonstrate that for LaMnO3 the anisotropy effects often neglected at high operating temperatures become relevant when the temperature is lowered. We show that this fact has consequences for the material properties and can be further enhanced by strain and Sr doping. Tensile strain promotes both the O vacancy formation and migration in pristine and Sr doped LaMnO3, while Sr doping enhances the O vacancy formation but not the migration. The effect of A-site hole doping (Mg2+, Ca2+ or Ba2+) on the electronic and magnetic properties as well as the O vacancy formation and migration in LaCoO3 are studied. All three dopants are found to facilitate O vacancy formation. Substitution of La3+ with Ba2+/Mg2+ yields the lowest O vacancy formation energy for low/intermediate spin Co, implying that not only the structure, but also the spin state of Co is a key parameter. Only for low spin Co the ionic radius is correlated with the O migration barrier. Enhanced migration for intermediate spin Co is ascribed to the availability of additional space at the transition state. For LnBaCo2O5+δ we compare the O vacancy formation in GdBaCo2O5.5 (Pmmm symmetry) and GdBaCo2O6 (P4/mmm symmetry), and the influence of Sr doping. The O vacancy formation energy is demonstrated to be smaller in the already O deficient compound. This relation is maintained under Sr doping. It turns out that Sr doping can be utilized to significantly enhance the O vacancy formation in both compounds. The observed trends are explained on a microscopic level. Furthermore, we consider antisite defects as they may modify the electronic and O migration properties but are rarely studied in double perovskite oxides. It turns out that O vacancy formation is significantly easier in PrBaCo2O5.5 than in GdBaCo2O5.5, the difference in formation energy being hardly modified by antisite defects. Finally, having established that the O vacancy formation energy is significantly lower in PrBaCo2O5.5 than in GdBaCo2O5.5, we study the O Frenkel energy and migration of O ions in PrBa(Co/Fe)2O5.5. The electronic structure and charge redistribution during defect formation are analyzed. We demonstrate that Co↔Fe substitution strongly affects the formation of defects and, consequently, the O migration. The low O Frenkel energy points to a high concentration of O vacancies. The migration of the O ions shows a distinct anisotropy.

This research study talks about the possible influence of gray cast iron microstructure on the corrosion properties of the brake rotor and the effect of stiction. Three Gray cast iron rotors with fully pearlitic microstructure and below 5% volume content of ferrite were studied in this research to understand their microstructural influence over corrosion. The selected gray cast iron rotors were friction tested against a 2009 Original Equipment Manufacturer (OEM) Ford F150 brake pad using scaled-down SAE J2522 standard test. Tested samples were later subjected to GMW16696 standard test, to identify the breakaway forces indirectly defining the corrosion resistance of the friction material used. The results show that the degree of corrosion and breakaway forces observed are greatly influenced by the graphite content quantified from quantitative analysis techniques adopted. Rotor with higher graphite content observed higher breakaway force and higher oxygen content compared to the other two studied rotors. Higher graphite content is considered to provide more cathodes, it accelerates the corrosion of the iron element in the rotor. There is no reliable correlation between the pearlite and ferrite of the gray cast iron rotor stiction force. The poor correlation between stiction force and microstructure also shows that the size of stiction force is not determined by a single factor.

Téma doktorské práce se zabývá přípravou a popisem katod na bázi autoemise, jenž představují kvalitní a levný elektronový zdroj pro zařízení pracující s fokusovaným elektronovým svazkem. Pro přípravu kompozitní autoemisní katody byla využita elektrochemická metoda výroby. Kompozitní struktura katody zlepšuje proudovou stabilitu ve srovnání s čistě autoemisními katodami na bázi wolframu. Na základě charakterizace katody, jenž byla nově provedena metodou šumové spektroskopie, byla implementována technologická zlepšení stávající výroby. Metoda šumové spektroskopie je založena na analýze emisního proudu v časové a kmitočtové rovině, ale především poskytuje informace o nosiči náboje, o jeho pohyblivosti a dále o životnosti katody. Výsledky experimentální části byly rozšířeny teoretickými simulacemi, vedoucími k návrhu metodiky charakterizace vylepšené autoemisní katody.

Indiana University-Purdue University Indianapolis (IUPUI) / Developing alternative cathodes with high capacity is critical for the next generation rechargeable batteries to meet the ever-increasing desires of global energy storage market. This thesis is focused on two sulfur-based cathode materials ranging from inorganic lithium sulfide to organotrisulfide. For lithium sulfide cathode, we developed a nano-Li2S/MWCNT paper electrode through solution filtration method, which involved a low temperature of 100 °C. The Li2S nanocrystals with a size less than 10 nm were formed uniformly in the pores of carbon paper network. These electrodes show an unprecedented low overpotential (0.1 V) in the first charges, also show high discharge capacities, good rate capability, and excellent cycling performance. This superior electrochemical performance makes them promising for use with lithium metal-free anodes in rechargeable Li–S batteries for practical applications. For organotrisulfide cathode, we use a small organotrisulfide compound, e.g. dimethyl trisulfide, to be a high capacity and high specific energy organosulfide cathode material for rechargeable lithium batteries. Based on XRD, XPS, SEM, and GC-MS analysis, we investigated the cell reaction mechanism. The redox reaction of DMTS is a 4e- process and the major discharge products are LiSCH3 and Li2S. The following cell reaction becomes quite complicated, apart from the major product DMTS, the high order organic polysulfide dimethyl tetrasulfide (DMTtS) and low order organic polysulfide dimethyl disulfide (DMDS) are also formed and charged/discharged in the following cycles. With a LiNO3 containing ether-based electrolyte, DMTS cell delivers an initial discharge capacity of 720 mAh g-1 and retains 74% of the initial capacity over 70 cycles with high DMTS loading of 6.7 mg cm-2 at C/10 rate. When the DMTS loading is increased to 11.3 mg cm-2, the specific energy is 1025 Wh kg-1 for the active materials (DMTS and lithium) and the specific energy is 229 Wh kg-1 for the cell including electrolyte. Adjusting on the organic group R in the organotrisulfide can achieve a group of high capacity cathode materials for rechargeable lithium batteries.

この研究では、著者は分光学的調査を通じて、DCプラズマカソードシステムによって照射された固体表面から反射された励起種を研究しました。 著者はまた、プラズマカソードと正イオン源として使用することができる新しいデュオプラズマトロンイオン源を開発しています。 著者は、水素バルマー放出を検出するために以前に開発されたドップラー分光法を使用して反射された励起状態粒子を調査するための技術を採用しました。 / In this study, the author studied the excited species reflected from solid surfaces irradiated by DC Plasma cathode systems through spectroscopic investigation. The author also develops a new duoplasmatron ion source that can be used as a plasma cathode and positive ion source. The author employed the technique to investigate the excited states particle reflected using Doppler spectroscopy previously developed for detecting hydrogen Balmer emissions. / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University

No description available.

This thesis describes research to understand the relationships between materials, microstructure, transport processes, and battery performance for primary alkaline battery cathodes. Specifically, the effect of various carbon additives, with different physical properties, on electronic transport or conductivity within battery cathodes was investigated. Generally, the electronic conductivity increases with carbon additives that have higher aspect ratios, smaller particle diameters, higher surface areas, and lower bulk densities. Other favorable carbon aspects include more aggregated and elongated carbon domains which permit good particleto-particle contacts. Of the various carbon additives investigated, graphene nanopowder was the best performer. This graphene nanopowder had the smallest particle diameter, highest surface area, and one of the lowest Scott densities of the carbon additives investigated as well as well-connected, interspersed carbon pathways. Notably, a typical effective ionic conductivity is more than 50 times less than the electronic conductivity (5.7 S/m to 300 S/m, respectively) for a high-performance cathode. Thus, alkaline battery cathodes could be redesigned to improve ionic conductivity for optimal performance. This work expanded on previously published work by relating additional carbon-additive material properties--specifically, particle morphology, surface area and Scott density--and their corresponding cathode microstructure to the fundamental transport processes in alkaline battery cathodes.

Rechargeable lithium ion batteries are common materials in everyday applications. The most frequently used cathode material, LiCoO2, provides high energy density and stable charge/discharge performance. However, LiCoO2 is toxic and relatively expensive, therefore, other alternatives are being sought after in the development of battery materials, such as LiMn0.33Ni0.33Co0.33O2 (identified commonly as 333 compound). The 333 compound is now popular due to its comparable performance with LiCoO2, lower price, enhanced stability, and more environmentally friendly characteristics. In addition, Li1.2Mn0.54Ni0.13Co0.13O2 (HENMC) is still on the stage of testing and it attracts wide attention due to its higher rechargeable capacity and thermal stability. However, there are still challenges confronted: cycle stability and low rate capability. In order to verify all the roles played by different elements shown in NMC materials and explore the corresponding performance with different formula units, compositional analysis is needed. ICP-MS (inductively coupled plasma mass spectrometry) can provide bulk compositional information and has been used in recent work, giving a general idea of the composition of NMC materials. However, compositional inhomogeneity analysis has usually been neglected in these studies. Therefore, the objective of this work was to explore this variation in composition locally with higher spatial resolution, at the NMC particle level. This work was carried out through the use of scanning electron microscopy – energy dispersive spectroscopy (SEM-EDS) and Auger electron spectroscopy (AES). Furthermore, nano-scale quantitative analysis was done with transmission electron microscopy – energy dispersive spectroscopy (TEM-EDS). Moreover, an optimal approach and procedure of compositional analysis by using EDS and AES was explored with proper standards and operation conditions to provide consistent and stable results. The optimal quantification method was applied to investigate the compositions of 333 compound before and after ball milling and HENMC specimen before and after cycling. The results support the structural changes and in turn the electrochemical performance of the battery material. In the 333 compound, the electrochemical performance of the battery was deteriorated due to ball milling, during which Zr was introduced and particles were more compact. In HENMC, during cycling, the Mn distribution was homogeneous at the beginning, then inhomogeneous and homogeneous again, supporting the hypothesis of the transformation of phases: formation of spinel phase and potential SEI layer. In-depth structural analysis of different NMC materials has been reported previously by other groups. However, the structural effects due to cycling, within particles still needs investigation. Therefore, X-ray diffraction (XRD) was used to investigate the bulk material crystalline structure. Local nano-scale level structural variations amongst different isolated primary particles were investigated by the electron diffraction pattern based on TEM. The 333 compound and HENMC cycling was examined before and after cycling. After cycling, in the 333 compound, the O1 phase domains with P-3m1 space group appear inside the O3 phase with R-3m lattice. With more cycling, more domains appear. For HENMC, the original pristine samples exhibit the rhombohedral and monoclinic phases. After cycling, more and more spinel phase appear. Finally, after 100 cycles, we observe evidence of the potential solid electrolyte interphase (SEI) formation. In all, all the results above support the phase changes of 333 compound and HENMC. More investigations are needed to understand the degradation process of both compounds. / Thesis / Master of Materials Science and Engineering (MMatSE)