Neste trabalho foram estudadas ligas La0,7-xPrxMg0,3Al0,3Mn0,4Co0,5Ni3,8 (x= 0 a 0,7) no estado bruto de fusão, para utilização em eletrodos negativos de baterias de níquel-hidreto metálico (Ni-HM). A caracterização das ligas foi realizada através das seguintes técnicas: microscopia eletrônica de varredura (MEV), espectroscopia de energia dispersiva (EDS) e difração de raios X. Foi também determinada capacidade de absorção de hidrogênio destas ligas. A hidrogenação do material foi realizada em dois processos sendo: o primeiro denominado de baixa pressão (0,2 MPa de hidrogênio e temperatura de 500ºC) e o segundo de alta pressão (1 MPa e de hidrogênio e temperatura de 25ºC). Foi observado que com o aumento do teor de Pr a capacidade de absorção de hidrogênio diminui. Para o estudo da capacidade de descarga das baterias foi utilizado um analisador digital de quatro canais e observou-se um decréscimo na capacidade de descarga das baterias com adição de praseodímio para as composições La0,7-xPrxMg0,3Al0,3Mn0,4Co0,5Ni3,8 (x= 0 a 0,3). A maior capacidade de descarga (386 mAhg-1) e estabilidade cíclica foi obtida para a liga La0,2Pr0,5Mg0,3Al0,3Mn0,4Co0,5Ni3,8. Esta capacidade obtida pode estar relacionada com a maior proporção da fase LaMg2Ni9 encontrada na liga com adição de 0,5 % at. de Pr. / The La0,7-xPrxMg0,3Al0,3Mn0,4Co0,5Ni3,8 (x= 0 a 0.7) as-cast alloys to apply in negative electrodes for nickel-metal hydride batteries (Ni-MH). The characterizations of the alloys were realized by: scanning electron microscope (SEM), energy dispersive spectrometry (EDS) and X-ray diffraction techniques. A study of hydrogen absorption capacity of the alloys realized. The hydrogenation of the material was performed in two processes: the low pressure (0.2 MPa of hydrogen and temperature of the 773 K) and high pressure (1 MPa of hydrogen and temperature of the 298 K). It was observed that with increasing Pr content occurred a decrease the hydrogen absorption capacity. The capacity of discharge of the batteries was determined utilizing an analyzer digital computerized composed of four channels. It was observed decreases of the discharge capacity of the batteries when increase praseodymium content in La0,7-xPrxMg0,3Al0,3Mn0,4Co0,5Ni3,8 (x= 0 a 0.3) alloys. The highest discharge capacity (386 mAhg-1) and stability cyclic were obtained to La0.2Pr0.5Mg0.3Al0.3Mn0.4Co0.5Ni3.8 alloy. This capacity can be related to the higher proportion of phase LaMg2Ni9 in the alloy with the addition of 0.5 at.% Pr.

O aumento no consumo energético e a crescente preocupação ambiental frente à emissão de gases poluentes criam um apelo mundial favorável para pesquisas de novas tecnologias não poluentes de fontes de energia. Baterias recarregáveis de lítio-ar em solventes não aquosos possuem uma alta densidade de energia teórica (5200 Wh kg-1), o que as tornam promissoras para aplicação em dispositivos estacionários e em veículos elétricos. Entretanto, muitos problemas relacionados ao cátodo necessitam ser contornados para permitir a aplicação desta tecnologia, por exemplo, a baixa reversibilidade das reações, baixa potência e instabilidades dos materiais empregados nos eletrodos e dos solventes eletrolíticos. Assim, neste trabalho um modelo cinético foi empregado para os dados experimentais de espectroscopia de impedância eletroquímica, para a obtenção das constantes cinéticas das etapas elementares do mecanismo da reação de redução de oxigênio (RRO), o que permitiu investigar a influência de parâmetros como o tipo e tamanho de partícula do eletrocatalisador, o papel do solvente utilizado na RRO e compreender melhor as reações ocorridas no cátodo dessa bateria. A investigação inicial se deu com a utilização de sistemas menos complexos como uma folha de platina ou eletrodo de carbono vítreo como eletrodos de trabalho em 1,2-dimetoxietano (DME)/perclorato de lítio (LiClO4). A seguir, sistemas complexos com a presença de nanopartículas de carbono favoreceu o processo de adsorção das moléculas de oxigênio e aumentou ligeiramente (uma ordem de magnitude) a etapa de formação de superóxido de lítio (etapa determinante de reação) quando comparada com os eletrodos de platina e carbono vítreo, atribuída à presença dos grupos laterais mediando à transferência eletrônica para as moléculas de oxigênio. No entanto, foi observada uma rápida passivação da superfície eletrocatalítica através da formação de filmes finos de Li2O2 e Li2CO3 aumentando o sobrepotencial da bateria durante a carga (diferença de potencial entre a carga e descarga > 1 V). Adicionalmente, a incorporação das nanopartículas de platina (Ptnp), ao invés da folha de platina, resultou no aumento da constante cinética da etapa determinante da reação em duas ordens de magnitude, o qual pode ser atribuído a uma mudança das propriedades eletrônicas na banda d metálica em função do tamanho nanométrico das partículas, e estas modificações contribuíram para uma melhor eficiência energética quando comparado ao sistema sem a presença de eletrocatalisador. Entretanto, as Ptnp se mostraram não específicas para a RRO, catalisando as reações de degradação do solvente eletrolítico e diminuindo rapidamente a eficiência energética do dispositivo prático, devido ao acúmulo de material no eletrodo. O emprego de líquido iônico como solvente eletrolítico, ao invés de DME, promoveu uma maior estabilização do intermediário superóxido formado na primeira etapa de transferência eletrônica, devido à interação com os cátions do líquido iônico em solução, o qual resultou em um valor de constante cinética da formação do superóxido de três ordens de magnitude maior que o obtido com o mesmo eletrodo de carbono vítreo em DME, além de diminuir as reações de degradação do solvente. Estes fatores podem contribuir para uma maior potência e ciclabilidade da bateria de lítio-ar operando com líquidos iônicos. / The increasing in energetic consumption and environmental concerning toward rising in the emission of pollutant gases create a favorable scenario to develop non-pollutant technologies and more efficient energy storages. Rechargeable non-aqueous lithium-air batteries possess high theoretical energy density (5200 Wh kg-1), characterizing as a promising system to stationary and electric vehicles applications. However, many issues on the cathode electrode should be addressed to enable this technology, for example, low reversibility of the reactions, low rate-capability and instabilities issues from cathode materials and electrolytic solvents. Here, a kinetic model was employed for modulate the experimental impedance data in order to obtain the rate constants of elementary steps from oxygen reduction reaction (ORR), which allows the investigation of the role of some parameters such as, type and grain size of electrocatalysts, and the solvent influence. The initial investigation were with less complexes systems of platinum bulk or glassy carbon as the working electrode in 1,2-dimethoxyethane (DME)/lithium perchlorate (LiClO4). Based on that, the role of carbon nanoparticles in the ORR was an increasing the oxygen adsorption process, and by slightly increasing (one order of magnitude) the superoxide formation (rate determining step) as when compared with platinum and glassy carbon electrodes due to the presence of side groups acting as mediators to the electron transfer. Nonetheless, a fast surface passivation was observed in function of Li2O2 and Li2CO3 thin films formations, and these films increase the battery overpotential during the charge process (potential difference between charge/discharge >1V). In addition, dispersed platinum nanoparticles (Ptnp) resulted in an increase of two orders of magnitude on the rate constant of the rate determining step when compared to platinum bulk. This can be explained due to changes in electronic properties of metallic d-bands in function of nanometric size. These changes contributed to enhance the energetic efficiency of the practical device when compared to the non-catalyzed system. However, the Ptnp were non-specific toward the ORR catalyzing the electrolyte degradation reactions, and decreasing the energy efficiency faster than the non-catalyzed system. The ionic liquid rather than DME promoted better stabilization process for intermediary superoxide due to interaction between cations present in solution, resulting in an outstanding enhancement of the rate constant for rate determining step (three orders of magnitude) when compared to the same working electrode in DME. In addition, decrease the electrolyte degradation reaction. These factors can improve a higher rate-capability and cycle life of the practical lithium-air batteries.

Les accumulateurs graphite/LiNi0,5Mn1,5O4 (LNMO) permettent d’atteindre des densités d’énergie élevées grâce à leur tension de 5V. Toutefois, une dégradation des électrodes et des électrolytes à base d’alkylcarbonates et de LiPF6 a lieu à haut potentiel reste un problème qu’il est nécessaire de résoudre. L’ajout d’additifs fonctionnels à l’électrolyte comme l’AS, l’AM, le FEC ou le LiBOB forme des films de passivation aux interfaces électrode/électrolyte. Ces films réduisent la dégradation des matériaux et de l’électrolyte de l’accumulateur Gr/LNMO. Pour étudier le mécanisme d’action de ces additifs, les interfaces graphite/électrolyte et LNMO/électrolyte ont été caractérisées au moyen de cellules symétriques Gr/Gr et LNMO/LNMO et de cellules complètes. Les interfaces ont été étudié par spectroscopie d’impédance électrochimique (EIS) et photoélectronique à rayons X (XPS). De plus, l’électrolyte a été analysé par chromatographie en phase gazeuse liée à la spectrométrie de masse (GC-MS). / Gr/LiNi0.5Mn1.5O4 (LNMO) accumulators achieve higher energy densities than current commercial batteries. However, degradation of electrodes and electrolytes based on alkylcarbonates and LiPF6 takes place at high potential remains a problem which it needs to be resolved. The addition of functional additives to the electrolyte such as AS, AM, FEC or LiBOB which form passivation films at the electrode/electrolyte interfaces is a possible solution to these issues. These films reduce the degradation of materials and the oxidation of electrolyte in the Gr/LNMO accumulator. In order to study action mechanism of these additives, graphite/electrolyte and LNMO/electrolyte interfaces were characterized by symmetric Gr/Gr and LNMO/LNMO cells and full cells. Interfaces were investigated by electrochemical impedance spectroscpoy (EIS) and X-ray photoelectron spectroscopy (XPS) while the electrolyte was analyzed by mass spectrometric gas chromatography (GC-MS).

The decarbonization of the energy system is one of the most complex and consequential challenges of the 21st century. Meeting this challenge will require the deployment of existing low carbon technologies at unprecedented scales and rates and will necessitate the development of new technologies that have the ability to transform variable renewable energy into high energy density products. Reversible Solid Oxide Cells (RSOCs) are electrochemical devices that can function both as fuel cells or electrolyzers: in fuel cell mode, RSOCs consume a chemical fuel (H₂, CO, CH₄, etc.) to produce electrical power, while in electrolysis mode they consume electric power and chemical inputs (H₂O, CO₂) to produce a chemical fuel (H₂, CO, CH₄, etc.). As such, RSOC systems can be thought of as flexible “energy hubs” that have unique potential to bridge the low power density renewable infrastructure with that of high energy density fuels in an efficient, dynamic, and bidirectional fashion. This dissertation explores the different operational sensitivities and design trade-offs of a methane based RSOC system, investigates the optimum operating strategies for a system that adapts to variations in the hourly spot electricity and fuel prices in Western Denmark, and provides an economic analysis of the system under a wide variety of design assumptions, operational strategies, and fuel and electricity market structures. In order to perform such comprehensive analyses, a 0-D computational model of a methane based RSOC system was developed in Python. In fuel cell mode, the system generates power by consuming natural gas, while in electrolysis mode the system generates synthetic natural gas (SNG) by electrolyzing steam and catalytically hydrogenating recycled CO₂ into CH₄ downstream of the RSOC. The model's flexibility enables the simulation of “part-load” operation, allowing the user to assess the changes in output, efficiency, and operating cost as the system is operated across multiple points. The model has the ability to evaluate the impact that changes in design choices and operating parameters (Area Specific Resistance, temperatures, current density, etc.) have on the system as it interfaces with time varying exogenous factors such as fuel and electricity prices. As such, one of the main contributions of this model is the ability to run simulations in which the operating strategy of the RSOC system responds and adapts to varying market signals. The computational model is used to develop a series of hourly optimizations for finding the optimal operating strategy for an RSOC system that can buy or sell electricity and gas in the spot electricity and natural gas markets in Western Denmark. After receiving an electricity and gas price signal, the optimization determines the operating mode (fuel cell, electrolysis or idle) and operating point (e.g., current density) that maximize the operating profits every hour for the given electricity and gas price pair. In order to avoid the speculation associated with traditional energy storage simulations, the system is “opened” at both ends, allowing it to instantaneously buy and sell any electricity or gas that is generated. Thus, the system never stores any of the products and it buys and sells them at the instantaneously available market price. By assuming that market prices reflect all existing information, this design choice removes the necessity of having to speculate about the future in order to determine the optimum operating strategy. This approach is one of the innovations presented in this work. The optimizations aim at maximizing the operating profits at each hour of the year, and decisions of operating mode and point are based on marginal operating costs for each electricity and natural gas price pair. The full economic analysis, however, requires the understanding of how design choices (e.g. operating limits, heat management, gas recycling systems, etc.) affect the investment costs, and therefore a Total Plant Cost (TPC) model is developed. For each design choice, the TPC model is used to compute a cost of the system per m² of active electrode area or kW of output. This value, assumed to be a sunk cost that does not affect the operating decision, together with the operating profits resulting from the optimization is used to assess the overall profitability of the system. For a system with 100m² of active electrode area, conventional costing metrics suggest that the balance of plant (BoP) components for managing the system's heat (Heat exchangers, evaporators, condensers) are the main cost drivers and represent roughly 50% of the TPC. The cost of the electrochemical RSOC stack, assembly, power inverter and piping represent 35% of the cost, with the other 15% coming from pumps, compressors and the methanation system. Twenty different optimization scenarios are developed in order to quantify the effect that system design choices, operating limits, and market prices have on the operating profile and on the overall economics of the system. The first 12 case studies are based on real hourly spot electricity and natural gas prices for the years 2009-2014 in Western Denmark. For the last 8 scenarios, a forecasted hourly time-series for electricity in the Danish grid for the year 2050 and two fixed SNG prices (high and a low) are used. The 2050 prices, which assume a fossil fuel free system, are used to understand the role and value that RSOC systems can offer in deeply decarbonized energy systems. For each optimization, different parameters such as the initial ASR and the operating limits (maximum current densities for each mode of operation) are varied in order to find the impact that these changes have on the system's design (balance of plant components), hourly operating mode, investment costs, hourly operating profits, and overall plant profits. For the 2009-2014 optimizations, it is found that the sale of electricity (fuel cell mode) and fuel (electrolysis mode) is not large enough to cover the fixed costs associated with the plant. Fuel cell mode dominates the operation (61% of the time) with electrolysis representing only ~ 4% of the operating hours. ASR is found to have an important impact on the system's economics, due to the fact that a lowering of the ASR leads to a reduction in the size of the heat management system, which in turn reduces the Total Plant Cost. For the 2050 dataset, it is found that under the high gas price scenario electrolysis mode dominates (50% of the time), and fuel cell operation represents 15% of the hours in the year. For the low SNG price, electrolysis still dominates (48% of the time), and fuel cell operation increases to 30% of the operating hours. Furthermore, for the high SNG scenario, the sale of fuel and electricity are large enough to cover the system's fixed cost, making the system attractive from an investment perspective. For the low SNG price, the system also becomes profitable when using ASR values of 0.4 ASR or below.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / O presente trabalho apresenta o estudo de um conversor CC/CC com dois estÃgios para aplicaÃÃo no desenvolvimento de sistemas autÃnomos de energia elÃtrica. O conversor sob estudo consiste basicamente da associaÃÃo de dois conversores CC/CC, em que entre eles à inserido um banco de baterias para dar continuidade ao fornecimento de energia em perÃodos em que nÃo hà radiaÃÃo solar. Todos os conversores utilizados para a composiÃÃo do sistema sÃo do tipo boost utilizando a cÃlula de comutaÃÃo de trÃs estados (CCTE). O primeiro conversor tem a funÃÃo enviar energia desde os painÃis fotovoltaicos a um banco de baterias de 48 V e permitir a operaÃÃo dos painÃis fotovoltaicos no ponto de mÃxima potÃncia (MPP- Maximum Power Point). O segundo estÃgio à constituÃdo por um conversor de alto ganho de tensÃo, cujo papel à elevar a tensÃo do banco de baterias de 48 V para uma tensÃo de 400 Vcc, formando assim o barramento de saÃda do sistema em tensÃo contÃnua. Para garantir a regulaÃÃo da tensÃo em 400 Vcc, foi implementada a tÃcnica de controle LQR (Linear Quadratic Regulator). Para o projeto do controle LQR à utilizado uma metodologia simplificada para a obtenÃÃo de um modelo reduzido do conversor de alto ganho de tensÃo. Para cada estÃgio à apresentado seu estudo teÃrico, anÃlise de perdas e dimensionamento dos componentes para o atendimento das especificaÃÃes de projeto. Para verificar a anÃlise teÃrica foi montado um protÃtipo para cada estÃgio e os resultados experimentais sÃo apresentados neste trabalho. / This work presents a study of a DC/DC converter with two stages for implementation of a stand-alone photovoltaic power system. The converter under study consists of two DC/DC converters, in which between them is inserted a battery bank to give continuity to the energy supply in periods when there isnât solar radiation. All converters used for the composition of the system are of type boost based on the three-state switching cell (TSSC). The first converter has function of to send energy from photovoltaic panels to a battery bank of 48 V formed by four batteries of 12V connected in series, and its function is to allow the photovoltaic panels operation at the maximum power point (MPP). The second stage consists of a converter of high voltage gain, whose role is to raise the 48 V battery bank voltage to 400V DC output bus voltage. To ensure the regulation of voltage at 400 V DC, was implemented the control LQR (Linear Quadratic Regulator). To design the controller LQR, a simplified methodology to obtain a model of the high-gain voltage converter is used. For each stage is presented its theoretical study, analysis and the components were designed and specified. To verify the theoretical analysis, was developed a prototype for each stage and the experimental results are presented in this work.

Neste trabalho foi desenvolvida uma metodologia para realizar a gestão ativa da demanda de energia elétrica de consumidores, providos de armazenamento de energia elétrica e geração solar fotovoltaica, inseridos em redes inteligentes. Tal metodologia pode ser utilizada em instalações residenciais e comerciais. Utilizando estratégias de otimização e inteligência artificial, a metodologia configura um sistema de tomada de decisão para o gerenciador do conversor da bateria, que realiza a gestão da energia armazenada, visando reduzir o custo com energia elétrica para o consumidor final. Esta gestão propicia contribuição com a distribuidora em forma de aumento da reserva de capacidade da rede elétrica nos casos em que a tarifa de energia elétrica for mais cara no horário de pico. De qualquer forma, há potencial postergação da necessidade de expansão da rede elétrica e redução de impactos ambientais advindos da geração convencional de energia elétrica, uma vez que tal gestão de energia propicia redução de consumo de energia elétrica da rede. O mesmo sistema de tomada de decisão do gerenciador do conversor da bateria pode ser utilizado em vários consumidores com características semelhantes (mesmo tipo, localização e tarifação de energia elétrica, e perfil de consumo similar), uma vez que tal sistema é composto por uma rede neural treinada com dados locais. Estudo de caso foi conduzido considerando consumidor residencial na cidade de São Paulo. Foram construídos quinze perfis de consumo, que foram combinados com três perfis de geração solar. A metodologia apresentou desempenho satisfatório, tanto na avaliação da etapa de otimização quanto de treinamento da rede neural, uma vez que as curvas de armazenamento de energia apresentaram comportamentos próximos aos esperados. O sistema de tomada de decisão também respondeu de forma adequada, alterando a curva de carga do consumidor vista pela rede de forma a reduzir o custo diário com energia elétrica e o consumo de energia no horário de pico da residência em todos os casos estudados. A análise econômica apontou a necessidade de encontrar formas de tornar a iniciativa positiva do ponto de vista econômico no estudo de caso realizado. / This work presents a methodology developed to perform the active demand side management for consumers, provided with energy storage and solar photovoltaic power, inserted in smart grids. Such methodology can be used in residential and commercial installations. Using optimization and artificial intelligence strategies, the methodology sets up a decision-making system for the battery converter manager, which performs energy storage management, in order to reduce the cost with electricity for the final consumer. This management contributes with the utility increasing the grid reserve capacity when the electricity tariff is more expensive during peak hours. Anyway, there is potential postponement of the need to expand the grid, and environmental impacts reduction from conventional power generation, since such power management provides a reduction of the grid electricity consumption. The same decision-making system of the battery converter manager can be used in several consumers with similar characteristics (same type, location and electricity tariff, and similar consumption profile), since this system is composed by a neural network trained with local data. A case study was conducted considering household in the city of São Paulo. Fifteen consumption profiles were built, which were combined with three solar generation profiles. The methodology presented satisfactory performance both in the evaluation of the optimization stage and the neural network training stage, since the energy storage curves presented behaviors close to those expected. The decision-making system also responded adequately, changing the consumer load curve seen by the grid in order to reduce the daily electricity cost, and energy consumption at peak hours of the household in all cases studied. The economic analysis pointed to the need to find ways to make the initiative positive from an economic point of view in the case study carried out.

Este trabalho apresenta um estudo exploratório do potencial do Paraguai e da Bolívia para o desenvolvimento de uma indústria de mobilidade elétrica, avaliando a viabilidade de substituição da frota convencional de veículos leves, propulsados atualmente por motores à combustão interna (VCI), por veículos elétricos (VE) equivalentes. O estudo leva em consideração critérios econômicos, energéticos, ambientais, geopolíticos e disponibilidade de recursos naturais. Por tanto, são consideradas duas situações de substituição. No primeiro, por veículos elétricos disponíveis no mercado internacional (VE) e, alternativamente, por veículos elétricos com baterias de Li-ion, resultado da implantação e desenvolvimento de uma indústria de VE`s e outra de baterias de íons de lítio (Li-ion). Aproveitando assim, as vantagens estratégicas de recursos naturais proveniente do Salar de Uyuni Bolívia e da disponibilidade de energia elétrica no Paraguai, considerando a utilização de parte da potência da usina de Itaipu, propriedade do Paraguai e atualmente cedida a seu sócio no empreendimento, o Brasil, bem como a partir das abundantes reservas de gás natural boliviano e o potencial de ambos os países para o desenvolvimento de projetos de fontes renováveis. A indústria de baterias para os automóveis elétricos pode ser localizada na Bolívia, perto dos recursos e com grandes avanços tecnológicos e investimentos do governo na área nos últimos anos, enquanto a de VEL pode ser sediada no Paraguai que na atualidade possui um grande interesse de investidores estrangeiros. Os governos poderiam fomentar o projeto com iniciativas, como subsídios no custo da energia utilizada para o abastecimento de VE`s, ou no custo de investimento inicial do veículo. Poderia também fornecer financiamento para a aquisição de VE`s a taxas menores as do mercado. As estimativas conduzidas neste trabalho mostram que uma eventual substituição da frota de veículos leves VCI por VE no período de 10 anos, geraria benefícios econômicos cumulativos para o Paraguai de US$ 1.031 milhões e para Bolívia de US$ 1.373 milhões. Essa substituição permitiria uma redução das emissões de Gases de Efeito estufa (GEE) de 8.398 GgCO2 para o Paraguai e 9.420 7 GgCO2 para a Bolívia. Inicialmente seriam produzidos 40 mil veículos por ano em cada país para atingir a escala necessária para a redução dos custos das BIL`s. A ideia subjacente é ganhar escala local para a cadeia de produção inicial e, em seguida, acessar os mercados de América latina e o mundo. / This document presents an exploratory study of the potential of Paraguay and Bolivia for the development of an electric mobility industry, assessing the viability of replacing conventional light vehicle fleet, currently driven by internal combustion engines (ICE), for electric vehicles (EV) equivalent. The study takes into account economic, energy, environmental, geopolitical, and availability of natural resources criteria. Therefore, two replacement situations are considered. In the first, for EV`s currently available in the international market and, alternatively, for electric vehicles with Li-ion batteries, due to the implementation and development of both, an electric vehicle and a lithium-ion batteries industry. Leveraging so, the strategic advantages of natural resources from the Salar de Uyuni - Bolivia and the availability of electricity. This considering the use of part of the over-potential of the Itaipu power plant, owned by Paraguay and currently assigned to his associated in the undertaken, Brazil, and from Bolivian natural gas abundant reserves and the potential of both countries for the development of renewable projects. The battery industry for electric cars could be located in Bolivia, because of the proximity of the lithium resources and the technological breakthroughs and investments in the area of the Bolivian government in recent years, while the LEV industry could be based in Paraguay, which currently has a great appeal for foreign investors. Governments could promote the project with incentives such as subsidies in the cost of energy used to supply EV`s, or the cost of the initial investment vehicle, it also could provide funding for the acquisition of EV`s at lower rates. Estimates conducted in this study in a ten year basis show that any replacement of the ICE light vehicle fleet for EV would generate cumulative economic benefits to Paraguay for US$ 1,031 million, and for Bolivia US$ 1,373 million. This substitution would reduce Greenhouse Gases emissions (GHG) in 8,398 GgCO2 for Paraguay and 9,420 GgCO2 for Bolivia. Initially, 40,000 vehicles per year in each country would be produced to achieve the scale required for reducing BIL`s costs. The underlying idea is to make local scale for initial production chain and then access the Latin America markets and the world.

Les accumulateurs Ni-MH (Nickel-Métal-Hydrure) sont un sujet prometteur et largement étudié dans les recherches d’une énergie propre et durable. Trouver le matériau idéal pour l'électrode négative à haute densité volumétrique et gravimétrique est la clé pour l’application de cette technologie. Les hydrures métalliques à base de Ti-Ni ont des propriétés équilibrées entre la capacité d’hydrogène et les performances électrochimiques.L’objectif de cette thèse est d’étudier les effets de substitutions/additions d’éléments et de la mécanosynthèse sur la structure et les propriétés d’hydrogène des alliages Ti-Ni. Dans cette étude, une série d’alliages à base de Ti-Ni avec des substitutions/additions de Mg ou de Zr ont été systématiquement étudiés.Les alliages (TiNi)1-xMgx, (TiH2)1.5Mg0.5Ni, and Ti2-xZrxNi ont été synthétisés par mécanosynthèse à partir de poudres élémentaires. Dans un premier temps, l’influence du temps de broyage et les effets de substitutions/additions sur les microstructures ont été caractérisés par des techniques telles que la DRX, le MEB et le MET. Dans un second temps, les propriétés d’hydrogénation des différents alliages ont été mesurées par des réactions solid-gaz et par cyclage électrochimique.La théorie de la fonctionnelle de la densité (DFT) en utilisant le programme CASTEP a permis de calculer les enthalpies de formation afin de comparer la stabilité thermodynamique des alliages obtenus. Dans ces travaux de recherche, nous avons identifié les priorités d’alliage des ternaires Ni-Ti-Mg et Ti-Ni-Zr dans des conditions de broyage. La transformation structurale du Ti en phase CFC, induite par l’introduction d’éléments étrangers, a été mise en évidence.Les courbes PCI (Pression-Composition-Isothermes) et les capacités de décharge en fonction du nombre de cycles indiquent les propriétés d’hydrogène des alliages obtenus, y compris TiNi, Ti2Ni (amorphe), Ti-Mg et Ti-Zr. / Ni-MH (Nickel-Metal-Hydride) batteries have been a promising and extensively studied topic among clean and sustainable energy researches. Finding the ideal material for the negative electrode with high volumetric and gravimetric densities is the key to apply this technology on broader applications. Metal hydrides based on Ti-Ni have balanced properties between hydrogen capacity and electrochemical performances in cycling.The objective of this thesis is to study the effects of element substitution/doping and mechanical alloying on the structural and hydrogen properties of Ti-Ni alloys. In this study, a series of Ti-Ni based systems with Mg or Zr doping/substitution have been systematically investigated.The metallic compounds (TiNi)1-xMgx, (TiH2)1.5Mg0.5Ni, and Ti2-xZrxNi were synthesized by mechanically alloying from elemental powders.The milling time and effects of Mg, Zr substitution/doping were studied firstly in respect of their microstructures, using characterization techniques including XRD, SEM, TEM (EDX support), followed by the hydrogen properties measurements of the samples by hydrogen solid-gas reaction and electrochemical cycling.A first principle calculation tool based on DFT (Density Functional Theory) was carried out to further investigate the enthalpy of formation in order to compare the thermodynamical stability of the obtained compounds. In the study, we have found the alloying priorities in the ternary alloys Ti-Ni-Mg and Ti-Ni-Zr under milling conditions.A structure transformation of Ti to FCC induced by foreign elements is reported and investigated. Enthalpy of formation per atom of the compounds were obtained by DFT calculations, which helped interpreting the experimental results. PCI (Pressure Composition Isotherms) curves and discharge capacities as the function of cycling numbers revealed the hydrogen properties of the obtained compounds, including TiNi, Ti2Ni (amorphous), Ti-Mg and Ti-Zr.

Le stockage de l'hydrogène est l'un des plus grands problèmes techniques qui restreignent l'application pratique de l'hydrogène. Les hydrures métalliques sont considérés comme la solution principale à ce problème puisqu'ils peuvent absorber et désorber de façon réversible une grande quantité d'hydrogène sous une température et une pression modérées. Par ailleurs, les hydrures métalliques utilisés comme électrodes négatives dans les accumulateurs Nickel-Métal Hydrure (Ni-MH) sont également les composants clés des performances de ces derniers.Dans cette thèse, les alliages métalliques TiMgNix, MgTi1-xNix et TiMg1-xNix ont été synthétisés par broyage mécanique à partir de poudres élémentaires. La microstructure et les transformations de phase des échantillons préparés ont été caractérisées par DRX, MEB et MET (avec microanalyse EDS).Les propriétés d'hydrogénation ont été mesurées par réaction d'hydrogène solide-gaz et par des essais électrochimiques. Un diagramme de composition-capacité 3D a été établi sur la base du diagramme de phase ternaire Ti-Mg-Ni. Un procédé de broyage en deux étapes a été mis en œuvre pour améliorer les performances électrochimiques des alliages Ti-Mg-Ni.De plus, les alliages TiNi1-xCux ont été synthétisés par broyage mécanique et ensuite recuits. L 'influence de la substitution du nickel par le cuivre sur la structure et les propriétés électrochimiques est étudiée en utilisant une double approche: expérimentale et par simulation.Les résultats obtenus par la théorie de la fonctionnelle de la densité (DFT) en utilisant le programme CASTEP montrent que l'enthalpie de formation et l'énergie d'adsorption de l¿hydrogène de la phase pseudo-binaire Ti(Ni, Cu) sont en bon accord avec les résultats expérimentaux. / The storage of hydrogen is one of the biggest technical problem that restrict the practical application of hydrogen. Metal hydrides are mainly regarded as the solution facing to this issue since it can reversibly absorb and desorb big amount of hydrogen under moderate temperature and pressure. Meanwhile, metal hydrides used as the negative electrodes of Ni-MH batteries are also the key components to the battery performance.In this thesis, the metallic composite TiMgNix, MgTi1-xNix and TiMg1-xNix were synthesized by mechanical alloying from elemental powder. The microstructure and phase transformation of prepared samples were characterized by XRD, SEM, TEM (EDS support). The hydrogenation properties were measured by hydrogen solid-gas reaction and electrochemical tests. Based on the Ti-Mg-Ni ternary phase diagram, a 3D composition-capacity diagram have been established. Two-step mill process was proposed for meliorating the electrochemical performance of Ti-Mg-Ni alloys.Additionally, TiNi1-xCux alloys had been synthesized by mechanical alloying and subsequent annealing and studied using experimental and computational approaches. The influence of Cu substitution for Ni on the phase structure and electrochemical properties are investigated. The first principle calculation was carried out to study the formation enthalpy and hydrogen adsorption energy of pseudo-binary Ti(Ni, Cu) phase. The computational results are in good agreement with experimental results.

L’hydrogène est la solution potentielle pour réussir la transition énergétique d’un système actuel basé en grande partie sur les combustibles fossiles vers un système non émetteur de gaz toxiques et respectueux de l’environnement. Cependant, le stockage de l’hydrogène est un grand défi qui freine son application pratique dans les différents domaines. Les hydrures métalliques permettent de stocker une grande quantité d’hydrogène de façon réversible dans de bonnes conditions (Température, pression, sécurité…) comparée aux autres modes de stockage (gazeux et liquide). En plus, ces mêmes matériaux sont utilisés comme électrode négative dans les batteries Nickel-Métal Hydrure.Dans la première partie de cette thèse, les alliages Ti-Fe ont été synthétisés parmécanosynthèse pour différents temps de broyage et différents rapports massiquesbilles/poudre. Afin d’optimiser les paramètres d’élaboration, ces alliages ont été caractérisés par différentes techniques telles que la diffraction des rayons X, la microscopie électronique à balayage, la chronopotentiométrie, la chronoampérométrie et la voltamétrie cyclique.Dans une seconde partie, les alliages TiFe+4%MWNTs, TiFe0.95-xMx, TiFe0.90M0.10 etTiFe0.90Mn0.05V0.05 (x=0.05, 0.15) (M : Mn ou V) ont été élaborés selon les paramètres optimaux déterminés précédemment. L’influence de l’additif Nanotubes de Carbone à multiparois (MWNTs), de la substitution partielle du Fe par Mn et/ou V et de l’excès de Titane sur les propriétés structurales, morphologiques et électrochimiques telles que l’activation, la capacité de décharge électrochimique, la réversibilité, la tenue au cyclage, le coefficient de diffusion ont ensuite été étudiés. Les propriétés redox des électrodes, le potentiel de Nernst et la densité du courant d’échange, ont été déterminés, en se basant sur la première loi de Sternet le modèle théorique de Bulter -Volmer.Les résultats électrochimiques obtenus montrent que l’alliage TiFe+4 wt.% MWNTs présente les meilleures performances : une activation rapide (au 1er cycle) et une meilleure capacité maximale de décharge (266 mAh g-1) avec une réversibilité qui reste inchangée. / Hydrogen is the potential solution to make a success of the energy transition of a current system basically based on fossil fuels towards a system friendly to environment. However, the storage of hydrogen is a big challenge that hinders its practical application in different areas.. Metal hydrides can store a large amount of hydrogen reversibly under good conditions (temperature, pressure, safety ...) compared to other storage modes (gaseous and liquid). In addition, these same materials are used as negative electrode in Nickel-Metal Hydride batteriesIn the first part of this thesis, Ti-Fe alloys were synthesized using mechanical alloying (MA) under argon atmosphere at room temperature, with different ball to powder weight ratio and at different milling times. In order to determine the optimal parameters of the elaboration the metallic composite were investigated using different techniques such as X-ray diffraction, scanning electron microscopy (EDS support), chronopotentiometry, chronoamperometry and cyclic voltammetry,In the second part, the metallic compounds, TiFe+4%MWNTs, TiFe0.95-xMx, TiFe0.90M0.10 and TiFe0.90Mn0.05V0.05 (x=0.05, 0.15) (M : Mn or V), which are used as the negative electrode material for Ni-MH secondary batteries, were synthesized by mechanical alloying according to optimal parameters, previously determined.The effect of MWNT addition, the Mn and/or V partial substitution for Fe and the excess of titanium on the structural, morphological and electrochemical parameters such as activation, electrochemical discharge capacity, reversibility, cycle life time and hydrogen diffusion coefficient were investigated.The redox properties of the electrodes such as the Nernst potential and the exchange current density were studied based on Stern’s first law and the theoretical model of Bulter-Volmer.The electrochemical properties of studied samples show the best performance for TiFe+4% MWNTs alloy. Indeed, this alloy presents a rapid activation (1st cycle) and a best discharge capacity (266 mAhg-1) with a reversibility remaining unchanged