京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第19754号 / 農博第2150号 / 新制||農||1038(附属図書館) / 学位論文||H28||N4970(農学部図書室) / 32790 / 京都大学大学院農学研究科食品生物科学専攻 / (主査)教授 安達 修二, 教授 入江 一浩, 教授 保川 清 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

京都大学 / 0048 / 新制・論文博士 / 博士(農学) / 乙第13074号 / 論農博第2844号 / 新制||農||1046(附属図書館) / 学位論文||H29||N5030(農学部図書室) / 33225 / (主査)教授 安達 修二, 教授 谷 史人, 教授 橋本 渉 / 学位規則第4条第2項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

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Photodynamic therapy (PDT) has been investigated over the past three decades and is currently an approved therapeutic modality for skin cancer, the treatment of superficial bladder, early lung and advanced esophageal cancers, and age-related macular degeneration in a number of countries. In PDT, the absorption of light by a chromophore generates cytotoxic species such as reactive singlet oxygen, leading to irreversible destruction of the treated tissue. The measurement of the singlet oxygen quantum yield is an important determinant used to evaluate the efficiency of new photodynamic therapy agents developed in the laboratory, to screen potential photosensitizers in aqueous media.The singlet oxygen quantum yield is a quantitative measurement of the efficiency in which photosensitizers are able to use energy, in the form of light, to convert oxygen in the ground state to the reactive species singlet oxygen useful in photodynamic therapy. Singlet oxygen quantum yields of photosensitizers differ when measured in different solvents. The majority of the existing quantum yield values found in literature for various photosensitizers are documented with the sensitizers in organic solvents though values in aqueous media are more valuable for actual applications. Determination of accurate and precise quantum yield values in aqueous solution is a much more difficult problem than in organic media. Problems in aqueous solution arise primarily from the physicochemical properties of singlet oxygen in water. Singlet oxygen has a much shorter lifetime in water than it does in organic solvents, causing challenges with respect to quantitative detection of singlet oxygen.The ensuing pages are an attempt to explore the theory and document the procedures developed to provide the accurate measurement of singlet oxygen in aqueous media. Details of this experimental method and singlet oxygen quantum yield results of new compounds relative to established photosensitizers will be presented.

This dissertation describes a new vinyl-acrylic copolymer that displays great potential for applications in lithium ion batteries by enabling processes that are novel, faster, safer, and less costly than existing manufacturing methods. Overall, the works presented are based on tailored chemical synthesis directly applied to lithium ion battery manufacturing. Current manufacturing methods still have many flaws such as toxic processes and other time consuming if not costly steps. Understanding the chemistry of materials and processes related to battery manufacturing allows the design of techniques and methods that can ultimately improve the performance of existing batteries while reducing the cost. Chapter 1 provides an introduction to lithium batteries in terms of energy output, standard electrode and electrolyte materials, and processes for fabricating battery components. In this chapter, slightly more emphasis is placed on the electrolyte aspects of lithium battery technology, namely the plasticization of gel polymer hosts by liquid electrolyte and the standalone solid polymer electrolytes. Chapter 2 focuses on the free radical polymerization of poly(ethylene glycol) methyl ether methacrylate (PEGMA), methyl methacrylate (MMA), and isobutyl vinyl ether (IBVE) monomers to afford a vinyl-acrylic poly(PEGMA-co-MMA-co-IBVE) random copolymer and its detailed properties as a soluble, amorphous, and adhesive electrolyte that is able to permanently hold 800 times its own weight. Such material properties envision a printable battery manufacturing procedure, since existing electrolytes lack adhesion at a single macromolecular level. Without adhesion, the cathode and anode layers easily delaminate from the cell assembly, not to mention weak interfacial contact and poor mass transfer with the electrolyte. Many soft matter type electrolytes have been reported, but they lack either adhesive strength or ease of solubility. Obtaining both properties in iv a single material is a rarity. Chapter 3 aims at improving the ionic conductivity of the poly(PEGMA-co-MMA-co-IBVE) copolymer electrolyte by studying the effect of internal and external plasticizers, molecular weight of PEGMA monomer, and addition of inorganic solid state electrolytes. The inorganic electrolyte additives include Li(1+x+y)AlxTi(2-x)SiyP(3-y)O12, LiILi2WO4 mixture, Li7La3Zr2O12, and Li2S-P2S5 as part of an organic-inorganic hybrid approach. Electrolytes can also be used as an electrode binder so long as it has structural integrity and allows ion transfer to and from the active electrode material during insertion/extraction processes. In Chapter 4, the use of this electrolyte as a water-soluble binder for the aqueous fabrication of LiCoO2 cathodes is presented. Results of this study demonstrated the first aqueous process fabrication of thick, flexible, and fully compressed lithium ion battery electrodes by using commercial nickel foam as a supporting current collector. This feat is rather impressive because these properties are far superior to other aqueous binders in terms of material loading per electrode, specific area capacity, durability, and cell resistance. Finally, Chapter 5 expands on this concept by using the poly(PEGMA-co-MMA-co-IBVE) copolymer for the aqueous fabrication of a low voltage Li4Ti5O12 anode type electrode. Each component of a lithium ion battery serves a distinct role and undergoes unique electrochemical processes during cycling. The fact that this poly(PEGMA-co-MMA-co-IBVE) copolymer can be used in all three components, albeit for only about 50 cycles in a liquid half cell setup, demonstrates as a proof of concept that switching the current toxic manufacturing of lithium-ion batteries to an aqueous process is highly feasible. Furthermore, new electrode manufacturing techniques are also deemed possible. A conclusive summary along with directions for future work concerning the v novelties of this unique multifunctional vinyl-acrylic copolymer as an electrolyte, a cathode binder, and an anode binder are discussed in Chapter 6.

<p> A brief review of the theoretical and experimental aspects of liquid droplet nucleation from vapours and of crystal nucleation from aqueous solution is presented. In order to study the nucleation and crystal growth of several analytically important metal chelates, methods were developed to measure the size distribution of crystals growing in a supersaturated solution. These methods involved rapid mixing techniques followed by measurement of the size distribution of the precipitated particles using a Coulter counter and multichannel analyser. The size distributions were dumped from the analyser onto magnetic tape and recovered using computer methods. The mixing and counting techniques were calibrated and tested using barium sulphate and spheres of known size distribution. </p> <p> From the size distributions obtained for the metal chelates, conclusions were made regarding the nucleation step, and the parameters important in the classical Volmer-Weber-Becker-Doring theory of nucleation were calculated. The validity of the values were evaluated and comparisons made with values obtained by other workers. </p> <p> The laws controlling the crystal growth of the metal chelates and their importance in elucidating the type of nucleation process were also investigated. </p> / Thesis / Doctor of Philosophy (PhD)

<p> The mechanism by which PVC particles remained stable in n-butylchloride was investigated.</p> <p> The PVC particles were made by aqueous emulsion polymerization with benzoyl peroxide initiator and polyvinyl alcohol surfactant. The particles were cleaned by ion exchange and their surface charge was found to be 0.068 ± 0.005 C/m^2. Dispersions of PVC in n-butylchloride were prepared by two methods. In the first, the particles were dried in an oven. The dried particles were redispersed in n-butylchloride via sonication. This produced a dispersion consisting of 0.26 kg/m^3 of PVC particles with an arithmetic volume average diameter of 317 nm and a standard deviation of 93 nm. The second method involved dialyzing the cleaned aqueous latex with methanol and then with n-butylchloride. The dialysis method was inferior to the sonication method. The dialysis method was time consuming, it produced a dispersion with large particle diameter, the dispersion was contaminated with water and methanol and surface species were removed by the methanol.</p> <p> The particles were found to be stabilized by an electrostatic mechanism. This was verified by observing that the particles migrated to the positive electrode when exposed to a potential difference of 1000 V. A surface potential of 0.203 V was calculated for the particles from mobility measurements and the Huckel equation.</p> <p> The charge separation that must occur to allow the particles to have the negative charge is hypothesized to be a result of organic molecules such as PVC-PVA oligomers that dissolve from the particles and form micelles. These molecules were readily soluble in methanol and only slightly soluble in n-butylchloride. As a result, when the dispersion was washed with methanol, the particles flocculated. The presence of these species in the dispersant was supported by evidence from ultra-violet, infra-red and nuclear magnetic resonance spectroscopy. The electronegative groups in the micelles provide a reasonably polar environment for hydrogen ions to exist. These hydrogen ions became the countercharge for the negatively charged particles.</p> / Thesis / Master of Engineering (MEngr)

The following Thesis is comprised of two separate and individual parts, both of which relate to the disposal of hydrogen sulfide. Section One is an investigation into the possibility of developing a hydrogen sulfide decomposition process which would produce both hydrogen and elemental sulfur. Section Two deals with the speciation study of a catalyst used in a traditional process which converts hydrogen sulfide gas into elemental sulfur. / Section 1: <p> The disposal of hydrogen sulfide by electrolysis to produce both hydrogen and sulfur appears to an interesting alternative to the conventional Claus process which wastes the hydrogen content of hydrogen sulfide. The electrolysis at room temperature has been reported in the literature, however, the investigation was somewhat limited by the low conductivity displayed by the electrolysis solution (pyridine/hydrogen sulfide mixture). </p> <p> The primary goal of this research was to construct a suitable apparatus and carry out a series of conductivity measurements of liquid hydrogen sulfide at room temperature with and without the addition of possible electrolytes. The objective was to determine if an electrolyte could be found that would increase the conductivity to a suitably high level to warrant the further investigation of the electrolysis process. </p> <p> Of the six possible electrolytes, only tetrapropyl ammonium iodide increased the conductivity to a desirable level. A 0.4034 M solution of this alkyl ammonium iodide in liquid hydrogen sulfide increased the conductivity (at 23 C) from 7.00 X 10-8 ohm-1cm-1 for the pure solvent to 1.13 X 10-2 ohm-1cm-1. This increase was attributed to the formation of the corresponding hydrogen sulfide adduct and its subsequent dissociation in liquid hydrogen sulfide. </p> </p> Now that it has clearly been established that appropriately high conducting solutions of hydrogen sulfide can be prepared, the further investigation of the electrolysis of hydrogen sulfide as a viable industrial process is warranted. </p> Section 2: <p> This section deals with the investigation of species present in vanadium(IV): citrate solutions over a wide range of pH values. Various spectroscopic methods (UV/VIS, ESR, vanadium Sl FT-NMR) were used to probe this specific system. The accumulated spectroscopic data were rationalized on the basis of thirteen vanadium(IV) containing species, four of which were proposed to be vanadium(IV): citrate species. Based on the observed spectroscopic data an equilibrium diagram was prepared which illustrates the vanadium(IV) species present as a function of pH. </p> / Thesis / Master of Science (MSc)

The invention of Li-ion batteries (LIBs) marks a new era of energy storage and allows for the large-scale industrialization of electric vehicles. However, the flammable organic electrolyte in LIBs raises significant safety concerns and has resulted in numerous fires and explosion accidents. In the pursuit of more reliable and stable battery solutions, interests in aqueous batteries composed of high-energy cathodes and water-based electrolytes are surging. Limited by the narrow electrochemical stability window (ESW) of water, conventional aqueous batteries only achieve inferior energy densities. Current development mainly focuses on manipulating the properties of aqueous electrolytes through introducing excessive salts or secondary solvents, which enables an unprecedentedly broad ESW and more selections of electrode materials while also resulting in some compromises. On the other hand, the interaction between electrodes and aqueous electrolytes and associated electrode failure mechanism, as the key factors that govern cell performance, are of vital importance yet not fully understood. Owing to the high-temperature calcination synthesis, most electrode materials are intrinsically moisture-free and sensitive to the water-rich environment. Therefore, compared to the degradation behaviors in conventional LIBs, such as cracking and structure collapse, the electrode may suffer more severe damage during cycling and lead to rapid capacity decay. Herein, we adopted multi-scale characterization techniques to identify the failure modes at cathode–electrolyte interface and provide strategies for improving the cell capacity and life during prolonged cycling. In Chapter 1, we first provide a background introduction of conventional non-aqueous and aqueous batteries. We then show the current development of modern aqueous batteries through electrolyte modification and their merits and drawbacks. Finally, we present typical electrode failure mechanism in non-aqueous electrolytes and discuss how water can further impact the degradation behaviors. In Chapter 2, we prepare three types of aqueous electrolytes and systematically evaluate the electrochemical performance of LiNixMnyCo1-x-yO2, LiMn2O4 and LiFePO4 in the aqueous electrolytes. Combing surface- and bulk-sensitive techniques, we identify the roles played by surface exfoliation, structure degradation, transition metal dissolution and interface formation in terms of the capacity decay in different cathode materials. We also provide fundamental insights into the materials selection and electrolyte design in the aqueous batteries. In Chapter 3, we select LiMn2O4 as the material platform to study the transition metal dissolution behavior. Relying on the spatially resolved X-ray fluorescence microscopy, we discover a voltage-dependent Mn dissolution/redeposition (D/R) process during electrochemical cycling, which is confirmed to be related to the Jahn–Teller distortion and surface reconstruction at different voltages. Inspired by the findings, we propose an approach to stabilize the material performance through coating sulfonated tetrafluoroethylene (i.e., Nafion) on the particle, which can regulate the proton diffusion and Mn dissolution behavior. Our study discovers the dynamic Mn D/R process and highlights the impact of coating strategy in the performance of aqueous batteries. In Chapter 4, we investigate the diffusion layer formed by transition metals at the electrode–electrolyte interface. With the help of customized cells and XFM technique, we successfully track the spatiotemporal evolution of the diffusion layer during soaking and electrochemical cycling. The thickness of diffusion layer is determined to be at micron level, which can be readily diminished when gas is generated on the electrode surface. Our approach can be further expanded to study the phase transformation and particle agglomeration at the interfacial region and provide insights into the reactive complexes. In Chapter 5, we reveal the correlation between the electrolytic water decomposition and ion intercalation behaviors in aqueous batteries. In the Na-deficient system, we discover that overcharging in the formation process can introduce more cyclable Na ions into the full cell and allows for a boosted performance from 58 mAh/g to 124 mAh/g. The mechanism can be attributed to the water oxidation on the cathode and Na-ion intercalation on the anode when the charging voltage exceeds the normal oxidation potential of cathode. We emphasize the importance of unique formation process in terms of the cell performance and cycle life of aqueous batteries. In Chapter 6, we summarize the results of our work and propose perspectives of future research directions. / Doctor of Philosophy / Li-ion batteries (LIBs) have dominated the market for portable devices and electric vehicles owing to their high energy density and good cycle life. However, frequent battery explosion accidents have raised significant safety concerns for all customers. The root cause can be attributed to the flammable organic electrolytes in conventional LIBs. To address this issue, aqueous batteries based on water-rich electrolytes attract intensive attention recently. Recent research progress has dramatically improved the energy density of aqueous batteries dramatically by modifying the properties of electrolytes. However, most electrode materials are incompatible with water, leading to severe side reactions and an unstable cycle life. Therefore, understanding the failure mechanism of electrode materials in the presence of water is crucial while not fully studied yet. Our projects systematically evaluate the degradation behavior of various electrodes in aqueous electrolytes and uncover the root cause of transition metal dissolution in the electrodes. Our studies shed light on improving battery capacity and cycle life through a specialized formation cycle and polymer coating process. Furthermore, we also provide new approaches to investigate the dynamic process occurring at electrode–electrolyte interface, which is applicable to other solid–liquid systems. In summary, our research reveals the correlation between the failure mechanism and the capacity decay in various electrode materials, proposing effective approaches to enhance the battery performance.

The traditional paradigm declares tetravalent uranium to be immobile under reducing conditions – an assumption widely employed for nuclear waste management strategies. In contrast, experiments presented here demonstrate this assumption, although valid for low temperatures, can be erroneous for high temperature natural systems. This project focuses on the ability of sulfate-bearing solutions to transport uranium at reduced conditions and elevated temperatures, identifies the new species U(OH)2SO4, derives thermodynamic constants necessary for modeling, and expands the quantifiable range of U4+ mobility to more neutral pH conditions. The data obtained enable more accurate assessment of uranium mobility by updating the existing uranium thermodynamic databases and is applicable to uranium fluid transport in oreorming systems and nuclear waste repositories.