O presente trabalho utilizou a técnica de automontagem camada-por-camada para produzir eletrodos híbridos de poli(o-metoxianilina) e nanopartículas de pentóxido de vanádio. Foram obtidos filmes acusticamente rígidos, homogêneos com relação à massa depositada e com crescimento linear com o número de bicamadas depositadas. A caracterização eletroquímica foi realizada por voltametria cíclica, onde esse filme apresentou alta capacidade de intercalação/desintercalação de íons lítio e de forma reversível. A capacidade eletroquímica desse filme foi então comparada com filmes automontados de poli(dialildimetilamônio)/V2O5 e polialilamina/V2O5. O filme de Poli(dialildimetilamônio) apresentou um crescimento irregular com dissolução das nanopartículas, o que resultou em uma capacidade eletroquímica extremamente inferior ao filme de poli(o-metoxianilina). O filme de polialilamina apresentou uma deposição mais eficiente de V2O5 que o filme de poli(o-metoxianilina), entretanto essa maior quantidade de pentóxido de vanádio não refletiu em um aumento da capacidade do eletrodo. Os resultados de espectroscopia de impedância eletroquímica mostram que o filme de polialilamina é significativamente mais resistivo que o filme de poli(o-metoxianilina). Essa diminuição da condutividade, associada ao fato de que a poli(o-metoxianilina) também participa do processo de eletrointercalação, explicam seu melhor desempenho frente a intercalação de lítio. A difusão iônica do lítio nos filmes automontados foi estudada por varredura linear a diferentes velocidades, foi observado que o coeficiente de difusão no filme com polialilamina é uma ordem de grandeza menor que no filme de poli(o-metoxianilina). Por fim, o desempenho eletroquímico do filme de poli(o-metoxianilina)/V2O5 foi comparado no eletrólito composto por um líquido iônico hidrofóbico [bis(trifluorometanosulfonil)imideto de 1-butil-2,3-dimetil-imidazólio] com um solvente orgânico convencional (carbonato de propileno). O eletrodo se mostrou estável no líquido iônico, com maior capacidade específica e menor perda de capacidade. O desempenho superior ao eletrólito convencional está relacionado com a natureza iônica do líquido iônico e com a dissolução do filme em carbonato de propileno. Esses resultados, associados com o fato de que o líquido iônico estudado é compatível com ânodos de lítio metálico, indicam cátodos de poli(o-metoxianilina)/V2O5 em eletrólitos de (bis(trifluorometanosulfonil)imideto de 1-butil-2,3-dimetil-imidazólio podem desenvolver baterias de lítio de alta capacidade, durabilidade e segurança. / The present work used layer-by-layer technique to assemble hybrid electrodes of poly(o-methoxyaniline) and vanadium pentoxide nanoparticles. The film obtained was acoustically rigid, with homogeneous mass deposition and linear growth over the bilayer deposition. The electrochemical characterization was performed by cyclic voltammetry and the film showed high capacity for lithium intercalation and high reversibility in the extraction process. This film\'s capacity was compared with self-assembled poly(diallyldimetylammonium)/V2O5 and polyallylamine/V2O5. In the poly(diallyldimetylammonium) film, dissolution of the nanoparticles was observed, which reflected on a very low electrochemical capacity. The deposition of vanadium pentoxide was more efficient in polyallylamine, but even with a higher amount of V2O5, this electrode presented a smaller electrochemical capacity than poly(o-methoxyaniline)/ V2O5. Electrochemical impedance spectroscopy measurements showed that the film with polyallylamine was much more resistive than the film with poly(o-methoxyaniline). The smaller conductivity and the fact that poly(o-methoxyaniline) also participates in the electroinsertion processes explains the higher performance of poly(o-methoxyaniline)/ V2O5 electrode. Linear sweep experiments with different scan rates were performed to study the chemical diffusion of lithium in the layer-by-layer films. It was observed that the diffusion coefficient in the polyallylamine film is ten times smaller than in the poly(o-methoxyaniline) film. The capacity poly(o-methoxyaniline)/V2O5 electrode was also compared in different electrolytes; a hydrophobic ionic liquid [1-butyl- 2,3-dimethyl-imidazolium bis(trifluoromethanesulfonyl)imide] and an organic solvent (propylene carbonate). In ionic liquid the film was stable, had higher capacity and better cyclability, which is related to the ionic nature of the electrolyte and the fact that in propylene carbonate, dissolution of the film was observed. These results, and the possibility of using metallic lithium as anode in [1-butyl-2,3-dimethyl-imidazolium bis(trifluoromethanesulfonyl)imide], indicates the feasibility of using ionic liquids and poly(o-methoxyaniline)/V2O5 cathodes in safe, durable and high performance lithium batteries.

No description available.

<p>This thesis evaluates several solid-state NMR spectroscopy approaches to studying lithium ion dynamics in solid-state electrolytes. With the goal of reducing the risks associated with current liquid electrolytes, solid-state electrolytes provide non-flammable materials that are also stable against attack by cathode and anode materials. Solid-state NMR spectroscopy offers a versatile method to determine structural details and can also provide information about ion mobility in solid-state electrolytes. Challenges involved in the study of solid-state electrolytes include the difficulty in distinguishing between ^6,7Li resonances due to the small chemical shift range of diamagnetic lithium species. The NMR methods selected in this thesis aim to circumvent some of these issues in order to determine structural and dynamic properties in solid-state electrolytes. Several different electrolytes have been examined including LaLi_0.5Fe_0.2O_2.09 and related materials, which exhibit intricate structural properties. ¹³⁹La NMR spectroscopy, in combination with ⁷Li MAS NMR spectroscopy, was used to determine the nature of this disorder. In addition, studies of the quadrupolar framework ⁸⁷Rb nucleus, which take advantage of its large electric field gradient, have been used to indirectly probe the activation energy for Ag⁺ ion hopping in the solid-state silver ion electrolyte RbAg₄I₅. Alternatively, dipolar coupling between ⁶Li and ⁷Li has been used to compare lithium ion hopping rates in Li₆BaLa₂M₂O₁₂ (M = Ta, Nb) using ⁶Li{⁷Li}-REDOR NMR studies. Finally, T₂ relaxation studies have been used to probe ion dynamics in Li₃V₂(PO₄)₃ and LiVO₃ in order to determine if this is a viable method to study dynamics in these materials.</p> / Doctor of Philosophy (PhD)

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.

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.

Le composite LiF-Cu fonctionnant selon la réaction de conversion : Cu + 2 LiF →CuF2 + 2 Li+ + 2 e- a été synthétisé afin d’être étudié comme matériau d’électrode positivepour batterie au lithium. Pour faire réagir ces phases à l’état solide, les îlots de LiF nedoivent pas excéder quelques nanomètres et la percolation électrique dans l’épaisseur doitêtre établie. La technique retenue pour obtenir cette nanostructuration est la co-pulvérisationcathodique RF alternée. Afin de contrôler la synthèse du nanocomposite, la vitesse de dépôtet le flux d’adatomes pour chaque matériau ont été mesurés par profilométrie et ICP-OES.Leur composition et leur morphologie ont été caractérisées par microscopie électronique(SEM, TEM, STEM, HRTEM, AFM), diffraction (XRD, SAED) et spectroscopie (EELS, XPS).Les résultats ont montré que la morphologie obtenue était bien faite d’îlots nanométriques deCu et de LiF. La conductivité électrique du nanocomposite est de 5 ordres de grandeursupérieure à celle du LiF seul. Des premiers tests en batterie ont montré une fortepolarisation typique des matériaux de conversion et une faible cyclabilité. / The LiF-Cu nanocomposite reacting through the conversion reaction: Cu + 2 LiF→ CuF2 + 2 Li+ + 2 e- has been synthesized in order to be studied as positive electrodematerial for lithium battery. In order to perform this reaction in the solid state, the size of theLiF islands mustn't exceeds a few nanometers an the electric percolation through thethickness must be achieved. The technique used to obtain this nanostructuration is thealternated RF co-sputtering. In order to control the nanocomposite synthesis, the rate ofdeposition and the adatoms flux for each material have been measured using profilometryand ICP-OES. Their composition and morphology have been characterised by electronicalmicroscopy (SEM, TEM, STEM, HRTEM, AFM), diffraction (XRD, SAED) and spectroscopy(EELS, XPS). Results have shown that the morphology was indeed made of nanometricislands of Cu and LiF. The nanocomposite electric conductivity is 5 order of magnitudehigher than the LiF one. The first tests have shown a high polarization typical of conversionmaterials and a poor cyclability.

Les piles au lithium tiennent une place importante dans de nombreuses applications, notamment dans le secteur industriel à forte valeur ajoutée. Les oxyfluorures de graphites et graphènes, ainsi que leurs précurseurs oxydes, ont été identifiés comme des matériaux de cathode pouvant permettre d’augmenter la densité d'énergie de ces piles. Durant cette thèse, afin d’obtenir des nouveaux oxyfluorures de graphite, deux voies de synthèse ont été prospectées. Lors de la synthèse enchainant oxydation de Hummers puis fluoration gaz-solide, le paramètre température d’oxydation a été modulé et a donné lieu à des composés contenant des proportions différentes de fonctions oxygénées de type OH, COOH, COC. Lors de la synthèse débutant par la fluoration, différentes méthodes de fluoration ont été mise en oeuvre faisant agir soit le fluor moléculaire soit le fluor radicalaire à deux échelles de synthèse (laboratoire et micropilote). Une caractérisation minutieuse des matériaux issus de chaque voie, croisant les analyses structurales (DRX, ATG, diffusion Raman...) et analyses chimiques (IR, RMN, XPS...) a permis de cerner les modularités sur les effets de structure et de distribution de fonctions à l'échelle locale. Ce panel de composés a été testé en décharge galvanostatique en pile au lithium afin de corréler activité électrochimique des fonctions et gain en performances. / Primary Lithium Batteries are substantial in many applications, particularly in industrial niche sectors. Graphite oxifluorides and their precursors, graphite oxides, are promising materials for the cathodes. We explored two-step synthesis combining Hummers' oxidation and solid-gas fluorination. Temperature of oxidation was key parameter to control OH, COC and COOH ratio. Direct fluorination and controlled fluorination were processed at laboratory and scaled-up. Because of complexity of the materials and specificity at each scale, we cross-checked the data from several techniques for structure (XRD, TGA, Raman spectroscopy...) and chemistry (IR, MAS NMR, XPS...) for an accurate picture. We tested the broad set of materials. Galvanostatic discharges enabled us to understand the electrochemical activity of functions at stake and key factors of design for better performances.

Dans une vision de développement durable et d'indépendance énergétique visant l'intégration massive des énergies renouvelables à moyen terme dans le mix énergétique, les travaux menés au cours de cette thèse se sont axés sur deux thématiques :- d'une part, la comparaison de la production de trois technologies différentes de panneaux solaires (silicium, silicium avec concentration, CdTe) en fonctionnement réel dans une centrale photovoltaïque au sol dotée du suivi deux axes de la course du soleil ;- d'autre part et étant donné la nature intermittente de l'énergie photovoltaïque et son non-synchronisme avec la consommation, le développement et l'intégration de batteries à base de lithium comme moyen de stockage électrochimique de l'énergie photovoltaïque. L'approche est novatrice et a permis l'étude de nouveaux composés d'électrodes étudiés sous contraintes photovoltaïques réelles et utilisant différentes stratégies de restitution de l'énergie en vue du déploiement prochain des réseaux intelligents. Les simulations portent sur des accumulateurs de petites tailles classiquement utilisés dans les laboratoires de recherche mais préfigurant ce qui pourra être construit à plus grande taille. / In a vision of sustainable development and energy independence aiming at the massive integration of the medium-term renewable energies in the energy mix, the research works are centered on two themes:- On one hand, the comparison of the production of three technologies different from solar panels (silicon, silicon with concentration, CdTe) installed into a photovoltaic power plant with 2-axes sun tracking;- On the other hand and given the intermittent nature of the photovoltaic energy and its non-simultaneity with the consumption, the development and the integration of batteries with lithium as means of electrochemical storage of the photovoltaic energy. The approach is innovative and allowed the study of new compounds of electrodes studied under real photovoltaic constraints and using various strategies of return of the energy with the aim of the next deployment of the intelligent networks. The simulations concern batteries of small sizes classically used in research laboratories but prefiguring what can be built in bigger size.

Physikalische und chemische Charakterisierung von Lithiumionenzellen

Rapporten är skriven för ett högskoleingenjörsexamensarbete på kungliga tekniska högskolan, inom programmet maskinteknik, med inriktning industriell ekonomi och produktion. Bakgrunden av detta arbete ska ge läsaren en grund för de olika modellerna, elbilar och vätgasbilar samt väcka ett intresse för att bevara säkerheten med valet av bil. Syftet och målet med denna studie har varit att presentera en jämförelsestudie, gällande elbilar och vätgasbilar, samt svara på frågeställningarna som arbetet tagit fram. Resultatet av arbetet bygger på både FMEA- analyser för vätgasbilar och elbilar, samt jämförelsematris som ger en förtydligad bild på skillnader mellan elbilar och vätgasbilar, ur vissa valda funktioner. En förtydligad bild av FMEA analysen har byggt, genom att tillämpa ett paretodiagram som beskriver de olika risker och prioritering som finns för respektive modell. Rekommendationer och ytterligare säkerhetsarbeten för att minimera dessa risker beskrivs i FMEA analysen, utifrån indata och beskrivningar från tidigare rapporter, samt kunskap från studier. Resultatet från FMEA- analysen, paretodiagrammet, samt jämförelsematrisen visar att vätgasbilar är en säkrare modell och har en framtid eftersom utvecklingsmöjligheterna fortfarande finns, då dessa är nya på marknaden. Vätgasbilen är även mindre riskbenägen modell jämfört med elbilar, detta kan man visa med hjälp av RPN-talet, som är lägre för vätgasbilar, i jämförelse med elbilarnas RPN-tal. / The background of this thesis will give the reader the basis for the models of electric and hydrogen fueled vehicles. The purpose and goal of this study has been to present a comparative study regarding electric and hydrogen vehicles, and to answer the questions that the study has raised. The results of the work are based on both FMEA analysis for hydrogen and electric vehicles, as well as a comparison matrix that provides a clarified picture of the differences between electric vehicles and hydrogen vehicles, through certain selected factors. A clarified picture of the FMEA analysis results has been built by applying a pareto diagram that describes the different risks of each model and also what their priorities are. Recommendations and additional safety work to minimize these risks are suggested and described in the FMEA analysis, based on input data and descriptions from previous reports, as well as gained knowledge from studies. The results from the FMEA analysis, pareto-diagram and the comparison matrix shows that hydrogen vehicles are a less risk-prone model compared to electric vehicles and have a bright future as development opportunities still exist, this due to the fact that they are still new in the automotive industry. This can be proved with the help of the RPN number for hydrogen vehicles, which is lower compared to the RPN number of electric vehicles.