The desire for pure diatomic hydrogen gas, H2(g), has been on the rise since the concept of the hydrogen economy system was proposed back in 1970. The production of hydrogen has been extensively examined over 40 + years as the need to replace current fuel sources, hydrocarbons, has become more prevalent. Currently there are only two practical and renewable production methods of hydrogen; landfill gas and power to gas. This study focuses on the later method; using various renewable energy sources, such as photovoltaics, to provide off-peak energy to perform water electrolysis. Efficient electrolysis takes place in electrochemical cells which maximize performance efficiency with the use of noble metal electrocatalyst. Optimizing these electrocatalyst to be less material dependent, highly durable, and more efficient will support the implementation of power to gas electrolysis into the energy infrastructure. The main focus of this study is to explore RuO2 nanorods as a possible electrocatalyst for Proton Exchange Membrane (PEM) water electrolysis. A PEM electrolyzer cell has been constructed and fitted with a RuO2 nanorod decorated, mixed metal oxide (MMO) ribbon mesh anode catalyst structure. The current density-voltage characteristics were measured for the RuO2 nanorod electrocatalyst while under water feed operation. The electrocatalytic behavior was compared to that of ribbon mesh anode catalyst structures not decorated with RuO2 nanorods; one coated with a Ir/Ta MMO catalyst, the other was stripped of the MMO coating resulting in a Ti ribbon mesh anode. The results of these experiments show increased activity with the RuO2 nanorod electrocatalyst corresponding to a decrease in electrochemical overpotential. Through the collection of experimental data from various electrolyzer cell configurations, these overpotenials were able to be identified, resulting in categorical attributions of the enhanced catalytic behavior examined.

This study describes the development of a novel thin membrane exchange assembly (MEA) from a solid acid material, cesium hydrogen sulfate (CsHSO4), and from a composite anode electrocatalyst for electrolytic splitting of (100 %) H2S feed content gas operating at 135 kPa and 150 °C. A new class of anode electrocatalyst with the general composition, RuO2/CoS2, and an improved proton conductor, CsHSO4, have shown great stability and desired properties at typical operating conditions. This configuration demonstrated stable electrochemical operation for 24 h with a (100 %) H2S fuel stream at 423 K. This same system showed a maximum current density of (19 mA/cm²) at 900 mV. The performance of this new anode electrocatalyst when compared to that of Pt black investigated in a previous study showed an overall superiority in application. We have achieved a 30 % reduction in the overall system performance by fabricating a thin (200 µm) CsHSO4 electrolyte, which reduced the whole MEA thickness from 2.3 mm to 500 µm. The result of permeability measurements proved that this thin solid electrolyte is impermeable to H2S gas and physical integrity was preserved throughout the experimental period. Further resistance losses were compensated by using a high energy planetary milling system to enhance the ionic conductivity of CsHSO4. The difference in stability and electrochemical performance of these cells compared to that of Pt anode based systems is directly attributable to the anode materials developed in this project. Factorial experiments were used to characterize the effect of controllable process variables (electrolyte thickness, time, age of the electrolyte) on the cell current density and interfacial polarization resistances. As expected, cell current density and interfacial polarization resistances were a function of electrolyte thickness and age. Nevertheless, the effect of electrolyte thickness has a more prominent effect on the measured parameters. In addition, these experiments were used to identify regions of optimum system performance. Tafel plots were constructed to investigate the kinetic behavior of various anode based electrocatalysts. Exchange current densities, which are directly a measure of the electrochemical reaction, increased with RuO2/CoS2-based anodes. These experiments also suggested that high levels of feed utilization were possible using these materials. This was an impressive result considering the drastic improvement in electrochemical performance, current density, and sulfur tolerance compared to the other anode configurations.

The decrease in thermal decomposition temperature led to the amorphization of RuO2, and nano RuO2 particles were uniformly dispersed in amorphous Ta2O5 matrix. Such nano particles induced the increase in effective surface area for oxygen evolution and change in rate determining step, resulting in a significant decrease in oxygen overpotential. This excellent achievement induced a significant decrease in cell voltage of 0.7 V compared to lead alloy anodes and a voltage reduction of 37 % was achieved for copper electrowinning. Another distinct feature of the amorphous anodes is that nano RuO2 particles increase the overpotential of the unwanted side reaction on the anode, so that the anodic deposition of PbO2 can be completely inhibited. Therefore, the amorphous RuO2-Ta2O5/Ti anodes developed in this thesis have a high possibility to improve the purity of electrowon metal, reduce the maintenance of electrolysis process, prolong the lifetime of the anode, and make a low impact to environment. / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University

Σε αυτή την μελέτη παρασκευάστηκαν ηλεκτρόδια Pt-RuO2-TiO2 και χαρακτηρίστηκαν με περίθλαση ακτίνων Χ (X-ray diffraction - XRD), φασματοσκοπία φωτοηλεκτρονίων από ακτίνες Χ (X-ray photoelectron spectroscopy - XPS), ηλεκτροχημικές τεχνικές και πειράματα ρόφησης-οξείδωσης μονοξειδίου του άνθρακα (CO stripping). Ερευνήθηκε η μείωση της περιεκτικότητας σε Pt και RuO2 χωρίς απώλειες της ηλεκτροκαταλυτικής ενεργότητας. Το TiO2 επιλέχθηκε λόγω της χημικής του σταθερότητας και του χαμηλού κόστους. Βρέθηκε ότι περιεκτικότητα σε TiO2 μέχρι 50% οδηγεί σε αύξηση της ηλεκτροχημικά ενεργής επιφάνειας (EAS) του ηλεκτροδίου. Η ηλεκτροχημικά ενεργή επιφάνεια (EAS) του ηλεκτροδίου Pt(25%)-RuO2(25%)-TiO2(50%) ήταν μεγαλύτερη του ηλεκτροδίου Pt(50%)-RuO2(50%), ενώ για περιεκτικότητα σε TiO2 μεγαλύτερη από 65% η EAS μειώνεται δραματικά. Το παραπάνω συμπέρασμα στηρίχθηκε σε μετρήσεις του φορτίου της αναγωγικής κορυφής των κυκλικών βολταμογραφημάτων και σε πειράματα ρόφησης-οξείδωσης του CO (CO stripping). Όλα τα δείγματα χρησιμοποιήθηκαν και ως άνοδοι κατά τη διάρκεια ηλεκτροχημικής οξείδωσης μεθανόλης, αιθανόλης και γλυκερόλης. Και στις τρεις περιπτώσεις το ηλεκτρόδιο Pt(25%)-RuO2(25%)-TiO2(50%) παρουσίασε τη μεγαλύτερη ηλεκτροκαταλυτική ενεργότητα. Η παρατηρούμενη αυξημένη απόδοση των ηλεκτροδίων που παρασκευάστηκαν αποδόθηκε στην αυξημένη διασπορά της Pt και του RuO2, στο σχηματισμό μικρότερων κρυσταλλιτών Pt και RuO2 με την πρόσθεση TiO2, καθώς επίσης και σε ηλεκτρονιακές αλληλεπιδράσεις μεταξύ των μετάλλων και του TiO2. / In this study Pt-RuO2-TiO2 electrodes were prepared and characterised by X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), electrochemical techniques and CO stripping. The minimization of the Pt and RuO2 loading without electrocatalytic activity losses was explored. TiO2 was chosen due to its chemical stability and low cost. It was found that TiO2 loading up to 50% resulted in an increase of the Electrochemically Active Surface (EAS). The EAS of Pt(25%)-RuO2(25%)-TiO2(50%) was higher than that of Pt(50%)-RuO2(50%) while for TiO2 loadings higher than 50% the EAS diminished. The above conclusion has been confirmed by following the charge of the platinum reduction peak on cyclic voltammograms and by CO stripping experiments. All samples were used as anodes during electrochemical oxidation of methanol, ethanol and glycerol. In all cases the Pt(25%)-RuO2(25%)-TiO2(50%) electrode exhibited better electrocatalytic activity than the Pt(50%)-RuO2(50%) anode. The observed higher performance of this electrode has been attributed to the enhanced dispersion of Pt and RuO2 particles, the formation of smaller crystallites of Pt and RuO2 by the addition of TiO2 and the electronic interactions between metals and TiO2.

In this study, we used UV-ozone Ar sputtering, X-ray photoelectron and ultra-violet photoelectron spectroscopies and sputtering based depositions of RuO2 and Se nano-layers on indium tin oxides (ITOs). We elucidated the effect of Ar sputtering on the composition and chemistry of Sn rich ITO surface. We demonstrated that while a combination of UV-ozone radiation and Ar sputtering removes most of the hydrocarbons responsible for degrading the work function of ITO, it also removes significant amount of the segregated SN at the ITO surface that's responsible for its reasonable work function of 4.7eV. We also demonstrated for the first time that sputtering cleaning ITO surface leads to the reduction of the charge state of Sn from Sn4+ to Sn2+ that adds to the degradation of the work function. For the nano-layers coverage of ITO studies, we evaluated both RuO2 and Se. For RuO2 coated ITO, XPS showed the formation of a Ru-Sn-O ternary oxide. The RuO2 nano-layer reduced the oxidation state of Sn in the Sn-rich surface of ITO from +4 to +2. The best work function obtained for this system is 4.98eV, raising the effective work function of ITO by more than 0.5 eV. For the Se coated ITO studies, a systematic study of the dependence of the effective work function on the thickness of Se overage and its chemistry at the Se/ITO interface was undertaken. XPS showed that Se reacts with Sn at the Sn-rich surface of ITO determined the presence of both negative and positive oxidation state of Se at the Se/ITO interface. The Se also reduced the oxidation state of Sn from Sn4+ to Sn2+ in the Sn-rich ITO surface. The highest effective work function obtained for this system is 5.06eV. A combination of RuO2/Se nanoscale coating of optimally cleaned ITO would be a good alternative for device applications that would provide work function tuning in addition to their potential ability to act as interface stabilizers and a barrier to reaction and inter-diffusion at ITO/active layers interfaces responsible for long term stability of devices and especially organic solar cells and organic light emitting diodes.

Thèse en cotutelle (avec l'Université Toulouse 3 - Paul Sabatier) en Science des matériaux et Electrochimie / Avec le développement des systèmes électroniques embarqués se pose la question de la miniaturisation des dispositifs de stockage d’énergie. De nos jours, cette fonction est principalement assurée par des micro-batteries. Ces composants possèdent cependant une faible puissance disponible, une durée de vie limitée et un domaine de fonctionnement en température restreint. Les “micro-supercondensateurs” sur puce permettraient de s’affranchir de ces limitations, mais ils ne sont aujourd’hui qu’au stade de la recherche universitaire avec des densités d’énergie bien inférieures à celles des micro-batteries. L’énergie et la puissance stockées dans un supercondensateur sont proportionnelles au carré de la fenêtre de potentiel, qui dépend elle-même de la stabilité électrochimique de l’électrolyte utilisé. L’électrolyte joue ainsi un rôle prépondérant sur les propriétés des supercondensateurs (tension, gamme de température, courant de fuite, durée de vie…). Cette thèse vise à développer des liquides ioniques protiques et aprotiques dédiés aux micro-supercondensateurs pseudocapacitifs à base d'oxydes métalliques (RuO2, MnO2). Les électrolytes à base de liquides ioniques présentent des propriétés intéressantes, notamment une faible pression de vapeur saturante, une stabilité aux hautes températures, ainsi qu’une large fenêtre de potentiel. Ils contribuent ainsi à améliorer la densité d’énergie surfaciques, principal problème rencontré par les micro-supercondensateurs actuels. Les liquides ioniques étudiés ont été conçus sur la base de leurs structures et leurs propriétés physico-chimiques. Des caractérisations électrochimiques ont été réalisées avec des micro-supercondensateurs à base d’oxyde de ruthénium et d’oxyde de manganèse. De très bonnes performances ont été obtenus en utilisant des collecteurs de courant poreux à grande surface spécifique. Les électrolytes liquides constituant cependant un verrou technologique à la réalisation de micro-supercondensateurs fonctionnels compatible avec les procédés de microfabrication, des ionogels composés d’une matrice solide dans laquelle a été confinée le liquide ionique ont également été réalisés. / The rising growth of smart and autonomous microelectronic devices in the IoT (Internet of Things) era urges the development of advanced microscale energy sources with tailor-made features and customized energy/power requirements. Micro-supercapacitors (MSCs) emerged as potential energy storage devices complementing micro-batteries to power ubiquitous sensor networks needed to foster the development of IoT. However, the low cell voltage and low energy density remain major bottleneck that prevents their application at a large scale in real devices. To mitigate this issue, several studies have been devoted to the engineering of MSC electrode materials and structural architecting of current collectors to enhance the surface area and areal energy density by considering the limited available footprint area. This, however, has associated challenges such as a complex synthesis route, poor interfacial and mechanical stability of the electrode, and electrolyte compatibility issues, among others. Another key challenge to solve for reaching high energy density values in MSCs is the limited electrochemical stability window (ESW) of the electrolytes used as energy stored is directly related to the square of the cell voltage. The electrolytes play a major role in deciding the ESW and liquid-state electrolytes commonly used are troublesome for the microfabrication process due to leakage, evaporation, and safety issues. Therefore, it’s imperative to develop alternative electrolytes including solid-state electrolytes reconcilable to the target application of MSCs. This thesis aims at developing novel ionic-liquid (IL)-based electrolytes (both protic and aprotic) suitable for pseudocapacitive metal oxide (e.g., RuO2, MnO2)-based micro-supercapacitors (MSCs). IL-based electrolytes exhibit key properties including low vapor pressure, high temperature stability, low melting point, etc. with a wide ESW and help improve energy density performance, overcoming the major bottleneck faced by current MSCs. During this project, ILs are rationally designed based on their physicochemical properties. The detailed structure-property and electrochemical characterization studies were done using RuO2 and MnO2-based MSCs. We demonstrate state-of-the-art performance by developing high surface area porous current collectors with enhanced mass loading and solid-state devices using ionogel electrolytes, enabling their feasible integration with microelectronics to power connected IoT sensor networks.

The thesis consists of eight chapters of which the first chapter presents a brief overview of inorganic nanostructures. Synthesis and magnetic properties of MnO and NiO nanocrystals are described in Chapter 2, with emphasis on the low-temperature ferromagnetic interactions in these antiferromagnetic oxides. Chapter 3 deals with the synthesis and characterizations of nanocrystals of ReO3, RuO2 and IrO2 which are oxides with metallic properties. Pressure-induced phase transitions of ReO3 nanocrystals and the use of the nanocrystals for carrying out surface-enhanced Raman spectroscopy of the molecules form Chapter 4. Use of ionic liquids to synthesize different nanostructures of semiconducting metal sulfides and selenides is described in Chapter 5. Synthesis of Mn-doped GaN nanocrystals and their magnetic properties are described in Chapter 6. A detailed investigation has been carried out on the growth kinetics of nanostructures of a few inorganic materials by using small-angle X-ray scattering and other techniques (Chapter 7). The study includes the growth kinetics of nanocrystals of Au, CdS and CdSe as well as of nanorods of ZnO. Results of a synchrotron X-ray study of the formation of nanocrystalline gold films at the organic-aqueous interface are also included in this chapter. Chapter 8 discuses the use of the organic-aqueous interface to generate Janus nanocrystalline films of inorganic materials where one side of the film is hydrophobic and other side is hydrophilic. This chapter also includes the formation of nanostructured peptide fibrils at the organic-aqueous interface and their use as templates to prepare inorganic nanotubes.

Dans son ensemble, cette thèse porte sur la synthèse, l’étude structurale et l’étude des propriétés magnétiques et de transport de différentes familles d’oxydes de ruthénium, présentant des comportements électroniques et magnétiques variés, de structure rutile, hexaferrite de type R et hollandite. Le but de ce travail était l’étude des particularités des oxydes de ruthénium sondées par l’effet Seebeck dans les matériaux suivants : RuO2 de structure rutile (chaînes d’octaèdres de RuO6 liés par leurs arêtes, interconnectées par leurs sommets) à transport de type Boltzmann dominé par les interactions électron-phonon, les hexaferrites de type R BaCo2Ru4O11 et BaMn2Ru4O11 (octaèdres de RuO6 liés par les arêtes, formant des plans kagomé, et octaèdres de RuO6 liés par une face) ferromagnétiques doux et mauvais métaux, et deux nouvelles hollandites Sr1.5Ru6.1Cr1.9O16 et Ba1.5Ru6.1Cr1.9O16 (doubles chaînes de RuO6 liés par les arêtes, interconnectées par les sommets) avec agglomérats de spins localisés. La synthèse de ces deux nouvelles hollandites par réaction à l’état solide a permis de mettre en évidence l’existence de magnétorésistance négative dans cette famille de composés. Cette thèse montre que le comportement du coefficient Seebeck S d'oxydes de ruthénium à structures constituées d'octaèdres RuO6 majoritairement liés par leurs arêtes présente deux comportements différents. À basse T, S dépend fortement de la structure cristallographique et de la structure électronique associée. Par contre, dans la limite haute T, S tend vers une valeur commune indépendamment de la structure comme rapporté ici pour les hexaferrites de type R et les hollandites, et comme observé précédemment dans la pérovskite SrRuO3 (octaèdres RuO6 liés par les sommets) ferromagnétique métallique et dans la quadruple pérovskite LaCu3Ru4O12 (octaèdres RuO6 liés par les sommets) métallique présentant un magnétisme de type Pauli. Dans ces hexaferrites de type R BaCo2Ru4O11 et BaMn2Ru4O11 et dans ces deux nouvelles hollandites Sr1.5Ru6.1Cr1.9O16 et Ba1.5Ru6.1Cr1.9O16, le coefficient Seebeck à haute température atteint une valeur dominée par l’entropie de spin du ruthénium. / This thesis deals with the synthesis, the structural study and the magnetic properties and electronic transport studies of different ruthenium oxide families, presenting various magnetic and electronic behaviors, with rutile, R-type hexaferrite and hollandite structures. The goal of this thesis was the study of the ruthenium oxide peculiarities probed by the Seebeck effect in the following materials: RuO2 rutile (edge-shared RuO6 chain interconnected by their vertices) with Boltzmann type transport dominated by electron-phonon interactions, BaCo2Ru4O11 et BaMn2Ru4O11 R-type hexaferrites (edge-shared RuO6 octahedra, forming kagome planes, and face-shared RuO6 octahedra) soft ferromagnetic bad metals, and two new hollandites Sr1.5Ru6.1Cr1.9O16 et Ba1.5Ru6.1Cr1.9O16 (double chains of edge-shared RuO6 octahedra, interconnected by their vertices) with localized transport and cluster-glass behavior. The synthesis of both new hollandites by solid state reaction allowed us to show the existence of negative magnetoresistance in this compound family. This thesis shows that the behavior of the Seebeck coefficient of ruthenium oxides with structures mainly consisting of edge-shared RuO6 octahedra presents two different behaviors. At low T, S strongly depends on the crystallographic structure and on the associated electronic structure. On the other hand, in the high T limit, S tends a common value independently of the structure as reported here for the R-type hexaferrites and the hollandites and as previously observed in the ferromagnetic metal SrRuO3 perovskite (apex-shared RuO6 octahedra) and in the metallic with Pauli-type magnetism quadruple perovskite LaCu3Ru4O12 (apex-shared RuO6 octahedra). In these R-type hexaferrites BaCo2Ru4O11 and BaMn2Ru4O11 and these two new hollandites Sr1.5Ru6.1Cr1.9O16 and Ba1.5Ru6.1Cr1.9O16, the high temperature Seebeck coefficient reaches a value dominated by the Ru spin entropy term.

The Antimatter Experiment: Gravity, Interferometry, Spectroscopy (AEGIS) at the European Organization for Nuclear Research (CERN) is an experiment investigating the influence of earth’s gravitational force upon antimatter. To perform precise measurements the antimatter needs to be cooled to a temperature of 100 mK. This will be done in a Penning trap, formed by several electrodes, which are charged with several kV and have to be individually electrically insulated. The trap is thermally linked to a mixing chamber of a 3He-4He dilution refrigerator. Two link designs are examined, the Rod design and the Sandwich design. The Rod design electrically connects a single electrode with a heat exchanger, immersed in the helium of the mixing chamber, by a copper pin. An alumina ring and the helium electrically insulate the Rod design. The Sandwich uses an electrically insulating sapphire plate sandwiched between the electrode and the mixing chamber. Indium layers on the sapphire plate are applied to improve the thermal contact. Four differently prepared test Sandwiches are investigated. They differ in the sapphire surface roughness and in the application method of the indium layers. Measurements with static and sinusoidal heat loads are performed to uncover the behavior of the thermal boundary resistances. The thermal total resistance of the best Sandwich shows a temperature dependency of T-2,64 and is significantly lower, with roughly 30 cm2K4/W at 50 mK, than experimental data found in the literature. The estimated thermal boundary resistance between indium and sapphire agrees very well with the value of the acoustic mismatch theory at low temperatures. In both designs, homemade heat exchangers are integrated to transfer the heat to the cold helium. These heat exchangers are based on sintered structures to increase the heat transferring surface and to overcome the significant influence of the thermal resistance (Kapitza resistance). The heat exchangers are optimized concerning the adherence of the sinter to the substrate and its sinter height, e.g. its thermal penetration length. Ruthenium oxide metallic resistors (RuO2) are used as temperature sensors for the investigations. They consist of various materials, which affect the reproducibility. The sensor conditioning and the resulting good reproducibility is discussed as well.

The Antimatter Experiment: Gravity, Interferometry, Spectroscopy (AEGIS) at the European Organization for Nuclear Research (CERN) is an experiment investigating the influence of earth’s gravitational force upon antimatter. To perform precise measurements the antimatter needs to be cooled to a temperature of 100 mK. This will be done in a Penning trap, formed by several electrodes, which are charged with several kV and have to be individually electrically insulated. The trap is thermally linked to a mixing chamber of a 3He-4He dilution refrigerator. Two link designs are examined, the Rod design and the Sandwich design. The Rod design electrically connects a single electrode with a heat exchanger, immersed in the helium of the mixing chamber, by a copper pin. An alumina ring and the helium electrically insulate the Rod design. The Sandwich uses an electrically insulating sapphire plate sandwiched between the electrode and the mixing chamber. Indium layers on the sapphire plate are applied to improve the thermal contact. Four differently prepared test Sandwiches are investigated. They differ in the sapphire surface roughness and in the application method of the indium layers. Measurements with static and sinusoidal heat loads are performed to uncover the behavior of the thermal boundary resistances. The thermal total resistance of the best Sandwich shows a temperature dependency of T-2,64 and is significantly lower, with roughly 30 cm2K4/W at 50 mK, than experimental data found in the literature. The estimated thermal boundary resistance between indium and sapphire agrees very well with the value of the acoustic mismatch theory at low temperatures. In both designs, homemade heat exchangers are integrated to transfer the heat to the cold helium. These heat exchangers are based on sintered structures to increase the heat transferring surface and to overcome the significant influence of the thermal resistance (Kapitza resistance). The heat exchangers are optimized concerning the adherence of the sinter to the substrate and its sinter height, e.g. its thermal penetration length. Ruthenium oxide metallic resistors (RuO2) are used as temperature sensors for the investigations. They consist of various materials, which affect the reproducibility. The sensor conditioning and the resulting good reproducibility is discussed as well.