Made available in DSpace on 2014-10-09T12:26:31Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:25Z (GMT). No. of bitstreams: 0 / Este trabalho teve por objetivo avaliar a aplicação de diversas tecnologias de células a combustível tipo PEMFC desenvolvidas no IPEN para obtenção de um módulo de potência de 500 We. Foram estudados o aumento de escala na produção de MEAs de 25 cm2 para 144 cm2 pelo método de impressão a tela; a simulação por fluidodinâmica computacional de canais de fluxo de gases em placas bipolares utilizando o programa COMSOL e; o estudo de desempenho de eletrodos Pt/C desenvolvidos pelo método de redução por álcool, em células individuais de 144 cm2. Assim, desenvolveu-se um módulo de 500 We de potência nominal, produzido com tecnologia nacional, e com apoio da indústria para possíveis aplicações comerciais. A indústria nacional contribuiu com o hardware do módulo e os sistemas de vedação e refrigeração. Foi realizado um teste de 100 horas em célula unitária de 144 cm2 para observação do comportamento do MEA fabricado pelo processo de impressão à tela, bem como das outras tecnologias descritas, e a célula mostrou-se estável neste intervalo de tempo. O módulo desenvolvido com tecnologia nacional apresentou a potência máxima de 574 We à corrente de 100 A (694,4 mA cm-2). A potência de operação de 500 We foi obtida à corrente de 77,7 A (540,1 mA cm-2) ao potencial de 6,43 V, com uma eficiência de 43,3%. Em termos de cogeração, a potência térmica ou calor gerado pelo módulo foi de 652 Wt. Deste modo, foram consolidados os experimentos em P&D realizados no IPEN em células a combustível, para produção de potência elétrica. Uma estimativa inicial de custo para o módulo de 500 We estudado foi de R$ 4.500,00, baseando-se apenas nos materiais empregados em sua construção. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Le développement de lubrifiants à haute valeur ajoutée subissant des conditions opératoires de plus en plus draconiennes, économes en carburant et performants pendant une longue durée reste un défi considérable pour les fabricants d’huiles. Cette thèse concerne l’étude du rôle et des actions des améliorants d’indice de viscosité (ou Viscosity Index Improvers (VII)) dans les lubrifiants moteurs. Le premier objectif visé dans ce travail est la caractérisation des comportements rhéologiques et la modélisation de la viscosité en fonction de conditions réelles de température, pression et contrainte de cisaillement pour des solutions d’huile de base et de polymère sans additifs fonctionnels. Plusieurs polymères (PAMA, OCP et PISH) de masses moléculaires et conformations (peigne, linéaire et étoile) différentes sont utilisés à 1,2% en masse dans une huile de base minérale hydrocraquée. L’originalité de la thèse réside dans l’utilisation de rhéomètres non-commerciaux à haute pression (jusqu’à 800 MPa). Un deuxième défi réside dans la compréhension de la relation entre la réponse rhéologique des lubrifiants automobiles simplifiés et les mécanismes présents à l’échelle moléculaire en explorant les notions de conformation, de solubilité et de rayon hydrodynamique grâce à l’extension de la loi d’Einstein à haute pression. Enfin, l’étude se concentre sur le lien entre rhéologie et tribologie et par extension, entre la composition chimique du lubrifiant et la tribologie. Les épaisseurs de film sont mesurées et comparées avec les prédictions analytiques de Hamrock-Dowson et avec les simulations numériques basées sur l’équation de Reynolds généralisée en incluant les modèles rhéologiques. Les données expérimentales et numériques sont en adéquation. / The development of high value-added lubricants overcoming more and more drastic operating conditions, fuel-efficient and providing excellent performance during a long time remains a huge challenge for oil makers. This thesis is dedicated to the study of the role and the actions of Viscosity Index Improvers (VII) in engine lubricants. The first objective targeted in this work is the characterization of the rheological behaviors and the modeling of viscosity in function of realistic conditions of temperature, pressure and shear stress for polymer-thickened base oil solutions without functional additives. Several polymers (PAMA, OCP and PISH) with different molecular weights and conformations (comb, linear and star) are used with a concentration of 1.2% (w/w) in a hydrocracked mineral base oil. The originality of the thesis lies in the use of non-commercial rheometers under high pressure (up to 800 MPa). A second challenge is the understanding of the relationship between the rheological response of simplified engine lubricants and the mechanisms occurring at the molecular scale by exploring the notions of conformation, solubility and hydrodynamic radius by the extension of the Einstein’s law at high pressure. Finally, the study focuses on the link between rheology and tribology and by extrapolation, between the chemical composition of the lubricant and tribology. The film thickness is measured and compared with the Hamrock-Dowson analytical predictions and with the numerical simulations based on the generalized Reynolds’ equation including the rheological models. Both experimental and numerical data are in good agreement.

Harvesting solar energy can potentially be a promising solution to the energy crisis now and in the future. However, material and processing costs continue to be the most important limitations for the commercial devices. A key solution to these problems might lie within the development of bio-hybrid solar cells that seeks to mimic photosynthesis to harvest solar energy and to take advantage of the low material costs, negative carbon footprint, and material abundance. The bio-photoelectrochemical cell technologies exploit biomimetic means of energy conversion by utilizing plant-derived photosystems which can be inexpensive and ultimately the most sustainable alternative. Plants and photosynthetic bacteria harvest light, through special proteins called reaction centers (RCs), with high efficiency and convert it into electrochemical energy. In theory, photosynthetic RCs can be used in a device to harvest solar energy and generate 1.1 V open circuit voltage and ~1 mA cm-2 short circuit photocurrent. Considering the nearly perfect quantum yield of photo-induced charge separation, efficiency of a protein-based solar cell might exceed 20%. In practice, the efficiency of fabricated devices has been limited mainly due to the challenges in the electron transfer between the protein complex and the device electrodes as well as limited light absorption. The overarching goal of this work is to increase the power conversion efficiency in protein-based solar cells by addressing those issues (i.e. electron transfer and light absorption). This work presents several approaches to increase the charge transfer rate between the photosynthetic RC and underlying electrode as well as increasing the light absorption to eventually enhance the external quantum efficiency (EQE) of bio-hybrid solar cells. The first approach is to decrease the electron transfer distance between one of the redox active sites in the RC and the underlying electrode by direct attachment of the of protein complex onto Au electrodes via surface exposed cysteine residues. This resulted in photocurrent densities as large as ~600 nA cm-2 while still the incident photon to generated electron quantum efficiency was as low as %3 × 10-4. 2- The second approach is to immobilize wild type RCs of Rhodobacter sphaeroides on the surface of a Au underlying electrode using self-assembled monolayers of carboxylic acid terminated oligomers and cytochrome c charge mediating layers, with a preferential orientation from the primary electron donor site. This approach resulted in EQE of up to 0.06%, which showed 200 times efficiency improvement comparing to the first approach. In the third approach, instead of isolated protein complexes, RCs plus light harvesting (LH) complexes were employed for a better photon absorption. Direct attachment of RC-LH1 complexes on Au working electrodes, resulted in 0.21% EQE which showed 3.5 times efficiency improvement over the second approach (700 times higher than the first approach). The main impact of this work is the harnessing of biological RCs for efficient energy harvesting in man-made structures. Specifically, the results in this work will advance the application of RCs in devices for energy harvesting and will enable a better understanding of bio and nanomaterial interfaces, thereby advancing the application of biological materials in electronic devices. At the end, this work offers general guidelines that can serve to improve the performance of bio-hybrid solar cells.

Ce travail porte sur les composés semi-conducteurs à base de séléniures pour la conversion d'énergie par effet photovoltaïque ou thermoélectrique. Une nouvelle famille de céramiques Cu₂GeSe₃-Sb₂Se₃ avec une microstructure unique a été synthétise par un procédé de fusion-trempe. L'influence de la composition du matériau et de l'ajout de l’iode sur la microstructure et les propriétés photoélectriques a été étudiée. Le réseau d’hétérojonctions formé par deux semi-conducteurs à bande interdite relativement étroite a un effet évident sur les propriétés photoélectriques. Le système Cu₃SbSe₄-Sb₂Se₃ a également été étudié avec l'objectif d'éliminer le germanium qui est un élément relativement rare. Et les résultats indiquent que le Cu3SbSe4 peut remplacer le Cu2GeSe3 pour former des hétérojonctions avec Sb₂Se₃, en maintenant une séparation et un transport de charges efficaces. Une approche basée sur une injection à chaud a été utilisée pour la synthèse de matériaux semi-conducteurs à base de séléniures pour des applications photovoltaïque ou thermoélectrique. Des nanoparticules et nano-feuillets monocristallins bidimensionnels de CuSe de haute qualité et ont été obtenus. La structure des nanocristaux de Cu₃Sb₁₋ₓSnxSe₄ a été étudiée et le mécanisme de formation des nano-feuillets a été proposé. Des nanoparticules de Cu₃Sb₁₋ₓSnxSe₄ avec une distribution de taille étroite ont été également synthétisées avec le procédé d’injection à chaud. Ces nanoparticules ont été utilisées comme précurseurs pour la préparation de matériaux massifs par pressage à chaud. Leur performance thermoélectrique a été étudiée. / This work was focused on selenide semiconducting compounds for energy conversion by photovoltaic or thermoelectric effect. A totally new family of Cu₂GeSe₃-Sb₂Se₃ ceramics with a unique microstructure was fabricated directly by melt-quenching method. The influence of the material composition and the iodine addition on the microstructure and photoelectrical properties was investigated. The interpenetrating heterojunction network formed by two relatively narrow bandgap semiconductors has an obvious enhancement effect on the photoelectrical properties. The Cu₃SbSe₄-Sb₂Se₃ system has also been studied with the objective to eliminate the germanium which is a relatively rare element. And the results indicated that Cu₃SbSe₄ can substitute the Cu₂GeSe₃ to form heterojunctions with Sb₂Se₃, maintaining the efficient charge separation and transport. A hot-injection based-approach has been used for the synthesis of selenide semiconducting materials for photovoltaic or thermoelectric applications. CuSe nanoparticles and CuSe nanoplates with high quality single-crystals and two dimensional nanostructure were prepared. The structure of the nanocrystals has been studied and the mechanism of the nanoplates formation has been proposed. Cu₃Sb₁₋ₓSnxSe₄ nanoparticles with a narrow size distribution had also been synthesized through the hot-injection route. They have been used as precursors for the preparation of bulk materials by hot-pressing and their thermoelectric performances have been studied.

Please read the abstract in the section 00front of this document / Dissertation (M Eng (Electrical Engineering))--University of Pretoria, 2007. / Electrical, Electronic and Computer Engineering / unrestricted

In this dissertation, density functional theory calculations are performed to calculate the thermodynamic and electrochemical properties of metal coordinated frameworks for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Gibb's free energy, overpotential, charge transfer and ligands effect are evaluated. The charge transfer analysis shows the positive charges on the metal coordinated frameworks play an essential role in improving the electrochemical properties of the metal coordinated frameworks. Based on the calculations, design principles are introduced to rationally design and predict the electrochemical properties of metal coordinated frameworks as efficient catalysts for ORR and OER. An intrinsic descriptor is discovered for the first time, which can be used as a materials parameter for rational design of the metal coordinated frameworks for energy storage and conversion. The success of the design principles provides a better understanding of the mechanism behind ORR and OER and a screening approach for the best catalyst for energy storage and conversion.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21333号 / 理博第4429号 / 新制||理||1636(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 寺西 利治, 教授 倉田 博基, 教授 時任 宣博 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Highly active and durable oxygen reduction catalysts are needed to reduce the costs and enhance the service life of polymer electrolyte fuel cells (PEFCs). This can be accomplished by alloying Pt with a transition metal (e.g. Ni) and by eliminating the corrodible, carbon based catalyst support - however, materials combining both approaches have seldom been implemented in PEFC cathodes. In this work, an unsupported Pt-Ni alloy nanochain ensemble (aerogel) demonstrates high current PEFC performance commensurate with that of a carbon supported benchmark (Pt/C) following optimization of the aerogel\'s catalyst layer (CL) structure. The latter is accomplished using a soluble filler to shift the CL\'s pore size distribution towards larger pores which improves reactant and product transport. Chiefly, the optimized PEFC aerogel cathodes display ≈ 2.5-fold larger surface-specific ORR activity than Pt/C and maintain 90% of the initial activity after an accelerated stress test (vs. 40% for Pt/C).

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