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On-device synthesis of customized carbon nanotube structuresPitkänen, O. (Olli) 19 July 2019 (has links)
Abstract
Carbon nanotubes (CNTs) are known for their excellent mechanical, electrical and thermal properties, that have fostered a vast number of applications during the last two decades, from composites, electrodes and nanoelectonics components, to sensors and biological scaffolds. Direct integration of CNTs into devices is not straightforward, as high growth temperatures (above 600 °C) challenge the chemical and thermal stability of substrates, catalysts and other nearby materials or components. However, by decreasing growth temperature and/or working out protocols that take into account the thermal stability of the materials involved, it is possible to create several new types of architectures and devices with functionalities not shown before.
In this work, we show that, with selection of the appropriate substrate, diffusion barrier and catalyst materials, direct growth of functional CNT films and their micropatterns may be achieved, not only on Si chips, but also on other atypical surfaces, using chemical vapor deposition. This thesis explores low-temperature CNT synthesis over bi- and trimetallic catalysts, and investigates the effect of diffusion barrier layers on the electrical properties of substrate-to-CNT contacts. On one hand, the lowest achieved CNT synthesis temperature (400 °C) is compatible with most silicon technologies, thus enabling direct integration of CNTs with materials and devices with low thermal budgets. On the other hand, the results of diffusion barrier studies helped us in designing and demonstrating on-chip micropatterned CNT structures for super and pseudocapacitor electrodes. In addition, we also show a method for maskless growth of CNT micropatterns using laser-treated steel and superalloy surfaces, whose surface diffusion properties change as a result of barrier-type metal oxide formation. Furthermore, we present CNT growth on carbon materials and demonstrate entirely carbon-based hierarchical composites for electromagnetic interference shielding applications, exhibiting outstanding absorption-based shielding performance.
The results presented in this thesis are expected to contribute to a further expansion of CNT-based technologies, in particular with potential for future advances in high-frequency devices (arrays, amplifiers and shielding materials), energy materials (electrodes and scaffolds), as well as in nanoelectromechanical systems (sensors and actuators). / Tiivistelmä
Hiilinanoputket tunnetaan niiden erinomaisista mekaanisista, sähköisistä ja termisistä ominaisuuksista, joita on hyödynnetty lukuisissa sovelluksissa viimeisen kahden vuosikymmenen aikana alkaen komposiiteista, elektrodeista, nanoelektroniikkakomponenteista ja sensoreista aina biologisiin tukirakenteisiin. Nanoputkien synteesi suoraan laitteessa ei ole suoraviivaista, sillä korkeat, yli 600 °C synteesilämpötilat asettavat haasteita substraatin, katalyytin sekä muiden lähellä olevien materiaalien ja komponenttien kemialliselle ja termiselle vakaudelle. Alentamalla synteesilämpötilaa ja/tai kehittämällä termisen vakauden huomioivia menetelmiä on mahdollista luoda uudenlaisia arkkitehtuureja ja sovelluksia ennennäkemättömillä ominaisuuksilla.
Tässä työssä osoitetaan, että sopivan substraatin, diffuusiosuojan ja katalyyttimateriaalin valitsemalla funktionaalisten hiilinanoputkien synteesi on mahdollista piin lisäksi myös muille, epätavallisille pinnoille käyttäen kemiallista kaasufaasipinnoitusta. Väitöstyössä käsitellään hiilinanoputkien matalan lämpötilan synteesiä hyödyntäen kaksi- ja kolmimetallisia katalyyttejä sekä tutkitaan diffuusiosuojakerroksen sähköistä vaikutusta substraatin ja hiilinanoputkien väliseen kontaktiin. Alin saavutettu synteesilämpötila (400 °C) on yhteensopiva useimpien piiteknologioiden kanssa, mikä mahdollistaa nanoputkien suoran integroinnin matalaa lämpötilaa edellyttäville materiaaleille. Työssä tutkitun diffuusiosuojakerroksen kehitys mahdollisti myös piisirun päälle toteutettujen hiilinanoputkipohjaisten super- ja pseudokondensaattorielektrodien demonstroinnin. Lisäksi työssä esitetään menetelmä, jossa laserkäsittelemällä teräs- ja supermetalliseospinta, jonka avulla mikrokuvioitu hiilinanoputkien kasvu ilman litografiaprosessia on mahdollista.
Viimeisenä työssä esitetään hiilinanoputkien synteesi suoraan toiselle hiilimateriaalille ja demonstroidaan täysin hiilipohjainen, hierarkkinen komposiittimateriaali erinomaisella absorptioon perustuvalla suojauskyvyllä sähkömagneettisiin häiriösuojaussovelluksiin.
Väitöstyössä esitettyjen tulosten odotetaan osaltaan edistävän hiilinanoputkipohjaisten teknologioiden kehitystä erityisesti korkean taajuuden laitteissa, energiamateriaaleissa sekä nanosähkömekaanisissa järjestelmissä.
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Estratégias de estabilização e efeitos sinérgicos em nanomateriais multifuncionais baseados em hidróxidos de níquel / Stabilization strategies and synergistic effects in multifunctional nanomaterials based on nickel hydroxidesGonçalves, Josué Martins 25 April 2019 (has links)
Nesta tese de doutorado foram desenvolvidos e caracterizados nanomateriais eletroativos, explorando estratégias de estabilização e os efeitos sinérgicos em nanomateriais multifuncionais baseados em alfa-hidróxido de níquel, com potencial aplicação nas mais essências e urgentes áreas de atuação científica e tecnológicas, como por exemplo na conversão e armazenamento de energia, e sensores amperométricos. Nesse sentido, foram desenvolvidos nanopartículas (NPs) de alfa-hidróxidos de níquel (α-Ni(OH)2) estabilizados pela formação de nanocompósitos com óxido de grafeno (GO), denominados de α-Ni(OH)2@GO. Analogamente, foram preparados NPs de sais de hidróxido duplo de níquel e cobalto (α- NiCo(OH)2), estabilizados pela incorporação cátions Co2+ na estrutura do α-Ni(OH)2, e o correspondente nanocompósito com óxido de grafeno reduzido (rGO) denominado de α- NiCo(OH)2@rGO. De modo geral, os nanocompósitos exibiram alta capacidade de carga em elevadas densidades de corrente, alta capacidade de retenção de carga e elevada estabilidade como consequência da interação sinergística de seus componentes, com potencial aplicação em dispositivos de armazenamento de energia de alto desempenho, como por exemplo em supercapacitores híbridos. Por outro lado, um dos principais desafios no campo da conversão de energia, concentra-se no desenvolvimento de eletrocatalisadores eficientes e robustos para impulsionar a cinética intrinsecamente lenta da reação de evolução de oxigênio (OER), que envolve etapas de transferência de elétrons acopladas a de prótons. Para isso, foram preparados nanocompósitos ternários baseados em NPs de αNi(OH)2 de diferentes tamanhos, octacarboxiftalocianina de ferro (FeOCPc) e rGO (α-NiFeOCPc@rGO). As NPs de α- Ni@rGO-K maiores e mais cristalinas e seus respectivos nanocompósitos mostraram propriedades eletrocatalíticas superiores para a OER quando comparados com os respectivos derivados de α-Ni(OH)2-Na, indicando a relevância do tamanho do nanocristal de α-Ni(OH)2 na estrutura do nanocompósito e consequente efeitos sinérgicos nas propriedades eletroquímicas e eletrocatalíticas dos nanocompósitos ternários. Além disso, foram desenvolvidos eletrodos modificados com NPs de hidróxido duplo lamelar de NiCe (α-NiCe) como sensores de alta sensibilidade, e de fundamental importância para detecção e quantificação de prednisona, uma droga proibida pelo Comitê Olímpico Internacional (COI). Em resumo, a incorporação de 20% em mols de íons Ce(III/IV) em nanopartículas de α- Ni(OH)2 aumentou a estabilidade deste material na fase alfa, conferindo melhores propriedades eletrocatalíticas responsáveis pela rápida oxidação da prednisona e de seus subprodutos de degradação, permitindo a preparação de sensores amperométricos com elevada sensibilidade e baixo limite de detecção (LOD) em comparação aos eletrodos modificados já reportando na literatura. Em suma, as estratégias no design de nanomateriais foram exploradas com sucesso para gerar novos nanomateriais e nanocompósitos com propriedades eletrocatalíticas e de armazenamento de carga aprimoradas, com potencial de aplicação em sensores e supercapacitores híbridos. / In this doctoral thesis, nanomaterials design strategies were explored in order to improve the stability of alpha-nickel hydroxide nanoparticles while developing synergistic effects, generating multifunctional electrochemically active nanomaterials and nanocomposites with potential application in amperometric sensors and energy conversion and storage devices. In this context, the α-Ni(OH)2 NPs were stabilized by generating double hydroxide salts, by interaction with octacarboxyphthalocyanine molecules and graphene oxide (GO) generating hybrid and nanocomposite materials, for example α-Ni(OH)2@GO. Nickel hydroxide NPs was stabilized by incorporation of Co2+ cation to produce α-NixCoy(OH)2 double hydroxide salts and the corresponding nanocomposite with reduced graphene oxide (rGO) designated - NiCo(OH)2@rGO. In this way, nanocomposites with potential application in high performance energy storage devices such as hybrid supercapacitors were produced, since exhibited large charge capacities at high current densities and great stability as a consequence of the synergistic interaction of their componentes. One of the main challenges in the field of energy conversion, the development of efficient and robust electrocatalysts to boost the intrinsically slow multielectronic multiprotonic transfer kinetics of the oxygen evolution reaction (OER) was also addressed using ternary nanocomposites based on α-Ni(OH)2 NPs, iron octacarboxyphthalocyanine (FeOCPc) and rGO (α-NiFeOCPc@rGO). The more crystalline - Ni@rGO-K NPs and their respective nanocomposites showed superior electrocatalytic properties when compared to the respective α-Ni(OH)2-Na derivatives, indicating the relevance of the α-Ni(OH)2 nanocrystal size and synergistic effects on their electrochemical and electrocatalytic properties. In addition, amperometric sensors based on NiCe layered doublehydroxide NPs (α-NiCe) were developed for determination of prednisone, a drug forbidden by the International Olympic Committee (IOC). The incorporation of 20 m% of Ce3+/4+ ions in α- Ni(OH)2 nanoparticles increased its stability in the alpha phase, conferring improved electrocatalytic properties responsible for the rapid oxidation of prednisone and its degradation byproducts, responsible for the higher sensitivity and lower detection limits (LOD) than similar devices reported in the literature. In short, nanomaterials design strategies were successfully explored to generated new nanomaterials and nanocomposites with enhanced electrocatalytic and charge storage properties with potential application in sensors and hybrid supercapacitors.
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Intégration de micro-supercondensateurs à hautes performances sur puce de silicium et substrats flexibles / Integration of high performance micro-supercapacitors on silicon chip and flexible substratesBrousse, Kevin 09 March 2018 (has links)
Le développement de l'internet des objets au service des " Smart Cities " requière des sources d'énergie miniaturisées. Ces travaux concernent la préparation de micro- supercondensateurs à hautes performances par voies sèches. Des films minces de carbure de titane ont été déposés sur wafer de silicium par pulvérisation, puis convertis par chloration partielle en films de carbone dérivé de carbure microporeux adhérents. 205 mF.cm-2 / 410 F.cm-3 ont été délivrés en milieu 1M H2SO4, et 170 F.cm-3 dans un mélange de liquide ionique et d'acétonitrile en contrôlant la taille des micropores. Les micro-supercondensateurs préparés sur wafer par cette voie, compatible avec les techniques de microfabrication utilisées dans l'industrie des semi-conducteurs, surpassent les performances des micro-supercondensateurs sur puce rapportées jusqu'alors. Enfin, l'écriture laser d'oxydes commerciaux sur polyimide s'est avérée prometteuse pour la préparation de micro-supercondensateurs flexibles. / The development of the internet of things, serving the concept of Smart Cities, demands miniaturized energy storage devices. Electrochemical double layer capacitors (or so called EDLCs) are a good candidate as they can handle fast charge and discharge over 1,000,000 cycles. This work focuses on the preparation of high performance micro- supercapacitors using non wet processing routes. Titanium carbide (TiC) thin films were first deposited on silicon wafer by non-reactive DC magnetron sputtering. The deposition parameters, such as pressure and temperature, were optimized to prepare dense and thick TiC films. Then, microporous carbide-derived carbon (CDC) films with sub-nanometer pore diameters were obtained by removing the metallic atoms of the TiC films under chlorine atmosphere. Partial chlorination led to strongly adherent TiC-CDC films which could be used as electrode in aqueous electrolyte. Capacitance values of 205 mF.cm-2 / 410 F.cm-3 were delivered in 1M H2SO4, and were stable over 10,000 cycles. In order to increase the energy density of the on-chip electrodes, the pore sizes were increased to accommodate the larger ions of organic electrolytes, by performing chlorination at higher temperatures. The 700°C chlorinated TiC-CDC electrodes delivered up to 72 mF.cm-2 within a 3 V potential window in an ionic liquid / acetonitrile mixture. Another strategy consisted in the grafting of anthraquinone (AQ) molecules, which brought additional faradic contribution to the capacitive current. Electrochemical grafting by pulsed chronoamperometry allowed to double the TiC-CDC capacitance in aqueous electrolyte (1M KOH). On-chip CDC-based micro-supercapacitors were successfully prepared via reactive ion etching/ inductive coupled plasma procedure followed by chlorination. This non-wet processing route is fully compatible with the microfabrication techniques used in the semi-conductor industry, and the as-prepared micro-devices outperforms the current state of art of on-chip micro-supercapacitors. Aside, the preparation of flexible micro-supercapacitors was achieved via direct laser-writing, which provided a facile and scalable engineering with low cost. Ruthenium oxide (RuO2)-based interdigitated electrodes were obtained from laser-writing of a commercial RuO2.xH2O / cellulose acetate mixture spin-coated onto KaptonTM. Capacitance values of ~30 mF.cm-2 were recorded in 1M H2SO4 for the flexible device. This work open the way for the design of high performance micro-devices at a large scale.
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Estudo das características elétricas e microestruturais de supercapacitores para armazenamento de energia / Study of electrical and microstructural characteristics of supercapacitors for energy storageFernandez, Antonio Paulo Rodrigues 05 August 2016 (has links)
Esta dissertação tem por objetivo reportar dados relativos às características elétricas e microestruturais de eletrodos aplicadas em dispositivos armazenadores de energia, especificamente supercapacitores constituídos por eletrodos de carvão ativado. Os parâmetros elétricos estudados foram a resistência em série equivalente obtida pelo método da interrupção de corrente (ESR(Inst)) (sendo que a sigla ESR é oriunda do termo inglês Equivalent Series Resistance), a resistência em paralelo equivalente (EPR(Dep)) obtida pelo método do valor dependente (sendo que a sigla EPR é oriunda do termo inglês Equivalent Parallel Resistance) e a capacitância (C(DC)) obtida pelo método da corrente contínua (sendo que a sigla DC oriunda do termo inglês Direct Current). Tais parâmetros foram escolhidos devido ao impacto que causam no tempo de vida útil, na capacidade de armazenamento de cargas elétricas, na velocidade de carga e descarga, na perda por efeito termoiônico nos processos de carga e descarga e na perda de cargas armazenadas devido à autodescarga em supercapacitores. Os dados microestruturais reportam por meio de imagens a homogeneidade da porosidade e por meio de valores correlacionados a composição química e eventuais contaminações presentes nos eletrodos. Os dados e valores coletados possuem a intenção de servir como referência comparativa de qualidade e apontar qual parâmetro afeta mais a qualidade do supercapacitor. Para tanto foram realizados testes a fim de coletar valores de C(DC), ESR(Inst) e EPR(Dep) após a exposição de supercapacitores de 1F/5,5V a temperaturas de 50ºC, 75ºC, 100ºC e 125ºC por 672 horas, sendo os dados coletados ao inicio dos testes, à temperatura ambiente, e posteriormente a cada 168 horas. Feitos os experimentos concluiu-se que o parâmetro que sofreu maior deterioração com o acréscimo de energia térmica foi a EPR(Dep), em seguida a C(DC), que de fato pouco sofreu alteração e a ESR(Inst), em que a mudança dentro do erro de medição foi imperceptível. / This paper aims to report information on electrical and microstructural characteristics of electrodes applied at devices that store energy, specifically supercapacitors made of activated carbon electrodes. The studied electrical parameters were the equivalent series resistance obtained by the method of the instantaneous value of the voltage drop (ESR(Inst)), where the acronym ESR has the meaning Equivalent Series Resistance, the equivalent parallel resistance (EPR(Dep)) obtained by the method of dependent value, where the acronym EPR has the meaning Equivalent Parallel Resistance, and the capacitance (C(DC)) obtained by the method of direct current. These parameters were chosen because of the impact they have on lifetime, the storage capacity of electric charge, the speed of loading and unloading, the loss thermionic effect on the charge and discharge processes and loss of stored charge due to self-discharge in supercapacitors. The data given by microstructural images of the homogeneity and porosity values correlated by the chemical composition and possible contaminations present in the electrodes. The collected data and values are intended to serve as a comparative reference point and quality parameter which most affects the quality of the supercapacitor. For both tests were carried out in order to collect values of C(DC), ESR(Inst) and EPR(Dep) after supercapacitors of the 1F/5.5V are exposure at temperatures of 50, 75, 100 and 125°C for 672 hours, and the data collected at the beginning of the tests (room temperature) and subsequently every 168 hours. Made experiments it was concluded that the parameter further deterioration suffered with the increase of thermal energy is EPR(Dep), then C(DC), which in fact little changed and ESR(Inst), in which the change in the measurement error was are noticeable.
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Composition, structure et comportement électrochimique d'Hydroxydes Doubles Lamellaires au cobalt : vers des applications en tant que matériaux d'électrodes / Composition, Structure and electrochemical behaviour of cobalt-containing Layered Double Hydroxides : towards applications as electrode materialsVialat, Pierre 02 October 2014 (has links)
Les Hydroxydes Doubles Lamellaires (HDL) sont des matériaux en couches à forte potentialité pour de nombreux domaines d’applications, cependant, leur caractère d’isolants électriques limite les possibilités d’applications en électrochimie. Il est donc intéressant de chercher des moyens d’améliorer leurs propriétés conductrices. Dans ce but, trois approches ont été envisagées : - l’insertion de cations de métaux de transition 3d dans les feuillets, - l’intercalation de médiateurs redox entre les feuillets ou - l’ajout de percolant électronique dans le système afin d’obtenir des HDL « électroactifs ». Même si les combinaisons possibles de cations divalents et trivalents dans le feuillet HDL sont nombreuses, toutes les études ont été centrées sur le rôle d’un élément principalement, le cobalt. La composition chimique des matériaux ainsi que leurs propriétés physico-chimiques en termes de morphologie et de structure globale et locale ont été étudiées par le couplage de différentes techniques d’analyse (DRX, IRTF, MEB, ATG, XAS, PDF, XPS) avant de réaliser la caractérisation des propriétés électrochimiques par voltammétrie cyclique et spectroscopie d’impédance électrochimique. Ces analyses ont alors montré les potentialités applicatives de certaines compositions des matériaux HDL choisis. Les propriétés capacitives des phases CoIICoIII-CO3 ont été étudiées pour une utilisation en tant que matériaux d’électrodes de supercondensateurs alors que la présence d’un médiateur redox ainsi que les propriétés d’immobilisation d’enzymes de la phase hybride Co2Al-ABTS ont permis d’élaborer des bioélectrodes potentiellement adaptables dans une biopile. / Layered Double Hydroxides (LDH) are lamellar materials with strong potentiality for numerous fields of application, however, their insulating electric character limits the possibilities for electrochemical applications. It is thus necessary to investigate for ways to improve their conductive properties. In this purpose, three approaches were envisaged: - insertion of cations of 3d transition metals into the lamellar sheets, - insertion of redox mediators between the layers or - addition of electronic percolants in the system to obtain “electroactive” LDH. Even if the possibilities of combination of divalent and trivalent metal cations within the LDH layer are tunable, all the studies were centered on the role of an element mainly, the cobalt. The chemical compositions of materials as well as their physico-chemical properties, in terms of morphology and global and local structure, were then studied by coupling various analytical techniques before realizing the characterization of the electrochemical properties by cyclic voltammetry and electrochemical impedance spectroscopy. These analyses then showed the application potentialities of certain type of LDH materials. The capacitive properties of CoIICoIII-CO3 phases were studied as supercapacitor electrode materials while the presence of a redox mediator as well as the immobilization properties for enzymes of the hybrid phase Co2Al-ABTS allowed constructing bioelectrodes potentially applicable in biofuel cell.
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Organosulphur compounds for electrochemical energy storage applications : supercapacitors and lithium-sulphur batteries / Composés organo-soufrés pour application au stockage électrochimique de l'énergie : supercondensateurs et batteries lithium-soufreCoadou, Erwan 07 July 2016 (has links)
Les travaux presentés dans ce manuscrit ont été consacrés à l’étude de composés organo-soufrés comme composants d’électrolyte pour systèmes électrochimiques de stockage d’énergie, en particulier dans les batteries lithium-soufre. Des liquides ioniques originaux, basés sur des cations sulfonium fonctionnalisés par des chaînes de type glyme ont été synthétisés et caractérisés, puis testés en tant qu’électrolytes dans des supercondensateurs symétriques avec électrodes en carbone activé. Il est apparu que l’adaptation de la structure des liquides ioniques à la porosité du carbone activé est d’importance fondamentale pour le développement de systèmes plus performants. L’ étude menée sur les batteries lithium-soufre a permis une meilleure compréhension des mécanismes de fonctionnement d’un système redox soufre/diphenyl disulfure dans des solvants glymes. L’influence des solvants sur les équilibres chimiques entre polysulfures organiques et minéraux et sur le fonctionnement du système a été étudiée. D’après les premiers résultats obtenus, cette stratégie semble particulièrement prometteuse pour améliorer les performances des batteries lithium-soufre. / The work presented in this manuscript concentrates on investigating the use of organosulfur compounds as potential electrolyte components for electrochemical energy storage systems, in particular in lithium-sulfur batteries. Novel glyme-functionalised sulfonium-based ionic liquids were synthesised and characterised before being tested as pure electrolytes for symmetrical supercapacitors based on activated carbon electrodes. The adaptation of the structure of the ionic liquids to the porosity of activated carbon was found to be of fundamental importance for the design of more efficient systems. For lithium-sulfur batteries, the study has enabled a better understanding of the mechanisms involved during the operation of the sulfur/diphenyl disulfide redox couple in a range of glyme-based solvents. Similarly, the influence of the glyme-based solvents on the chemical equilibria between organic and mineral polysulfides and on the system operation has been investigated. The initial results demonstrated that this is a particularly promising strategy in order to significantly improve the performances of lithium-sulfur batteries.
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Etude de Polyanilines et de nanocomposites Polyaniline/Graphène en milieu liquide ionique protique pour la réalisation de supercondensateurs / Study of polyanilinen and nanocomposites polyaniline / graphene in protic ionic liquid for energy storageAl Zohbi, Fatima 16 December 2016 (has links)
Les travaux réalisés dans le cadre de cette thèse ont porté sur la réalisation de polymères conducteurs de type polyaniline et de leurs composites associés à du graphène en vue d’une utilisation en tant que matériaux d’électrodes dans des dispositifs de stockage d’énergie de type supercondensateurs. Les travaux se sont tout d’abord orientés sur la synthèse de nouveaux liquides ioniques protiques (LIP) associant des cations pyrrolidinium (Pyrr+) et imidazolium (Imi+) avec des anions p-toluène sulfonate (PTS-), hydrogénosulfate (HSO4-) ou (+)-camphre-10-sulfonate (Cs-), et de l’étude de leur propriétés physico-chimiques (conductivité, viscosité) dans des mélanges binaires LIP/eau. Après avoir déterminé les formulations permettant d’atteindre les propriétés de transport optimales, les capacitances spécifiques de la Pani/HCl dans ces milieux LIP ont été déterminées et nous avons montré que les performances de dispositifs symétriques sont améliorées en capacitance, énergie et en puissance (400 F/g, 7 Wh.kg-1 et 4 kW.kg-1 pour les valeurs les plus élevées) par rapport à un milieu H2SO4 1M. Ces milieux LIP ont également été utilisés comme milieu de synthèse de la Pani. Nous avons ainsi montré que la nature des LIP, qui sont des milieux nanostructurants, pouvait modifier les propriétés électroniques, morphologiques et thermiques des Pani. Un optimum de conductivité électronique de la Pani (22 S/cm) a été atteint avec une synthèse réalisée dans le mélange binaire [Imi][HSO4]/eau 70/30 (pourcentage massique) générant une morphologie fibrillaire et une bonne cyclabilité (93% de rétention de capacitance sur 1000 cycles dans H2SO4 1M. Des valeurs de près de 400 F/g ont été obtenues dans le mélange [Pyrr][HSO4]/eau 41/59 optimisé. Dans le cas de la synthèse de la Pani réalisée dans [Pyrr][PTS]/eau, un gain en stabilité thermique (360°C) est obtenu grâce au dopage par l’anion PTS-. Finalement, une étude exploratoire sur la préparation de composites Pani/graphène et Pani/oxyde de graphène a été réalisée. Les synthèses des nanocomposites ont été effectuées dans les mélanges LIP/eau. L’optimisation de la composition du composite a été étudiée et indique que des rapports massiques de graphène ou oxyde de graphène d’environ 15% permettent d’atteindre des performances de stockage prometteuses et exaltées par rapport à celles obtenues pour des Pani sans graphène. / The work carried out during this PhD thesis is based on the preparation of conducting polymers such as polyaniline (Pani) and their composites associated with graphene for use as electrode materials for supercapacitors application. This work was first dedicated to the synthesis of new protic ionic liquids (PILs) combining pyrrolidinium (Pyrr+) or imidazolium (Imi+) cations with p-toluene sulfonate (PTS-), hydrogen sulfate (HSO4-) or (+)-camphor-10-sulfonate (Cs-) anion, and the study of their physico-chemicals properties (conductivity, viscosity) in binary mixtures PILs/water. After determining the formulations needed to achieve the optimum of transport properties, the specific capacitance of Pani/HCl in these PILs medium was determined, and we have shown that the performance of symmetrical devices are improved in capacitance, specific energy and specific power (400F/g, 7Wh/kg and 4kW/kg for the higher values) in comparison to those obtained in a H2SO4 1M medium. These PILs mediums were also used as a synthesis medium of Pani. We have shown that the nature of PILs, acting as soft template, could change the electronic, morphological and thermal properties of Pani. An optimum of electronic conductivity of Pani (22 S/cm) was obtained with a synthesis realized in the binary mixture [Imi][HSO4]/water 70/30 generating a fibrillar morphology and a good cyclability (93% capacitance retention over 1000 cycles in H2SO4 1M at 2 A/g). For Pani synthesis in [Pyrr][PTS]/water, a thermal stability gain (360 °C) is obtained thanks to a PTS- doped Pani. Finally, a preliminary study on the preparation of composite Pani/graphene and Pani/graphene oxide was performed. The syntheses of nanocomposites were realized in PILs/water mixtures. The optimization of the composition of the Pani nanocomposites was studied and it was found that a mass ratio of about 15% in weight of graphene or graphene oxide enables to obtain promising nanomaterials with higher electrochemical performances compared with pristine Pani.
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Estudo das características elétricas e microestruturais de supercapacitores para armazenamento de energia / Study of electrical and microstructural characteristics of supercapacitors for energy storageAntonio Paulo Rodrigues Fernandez 05 August 2016 (has links)
Esta dissertação tem por objetivo reportar dados relativos às características elétricas e microestruturais de eletrodos aplicadas em dispositivos armazenadores de energia, especificamente supercapacitores constituídos por eletrodos de carvão ativado. Os parâmetros elétricos estudados foram a resistência em série equivalente obtida pelo método da interrupção de corrente (ESR(Inst)) (sendo que a sigla ESR é oriunda do termo inglês Equivalent Series Resistance), a resistência em paralelo equivalente (EPR(Dep)) obtida pelo método do valor dependente (sendo que a sigla EPR é oriunda do termo inglês Equivalent Parallel Resistance) e a capacitância (C(DC)) obtida pelo método da corrente contínua (sendo que a sigla DC oriunda do termo inglês Direct Current). Tais parâmetros foram escolhidos devido ao impacto que causam no tempo de vida útil, na capacidade de armazenamento de cargas elétricas, na velocidade de carga e descarga, na perda por efeito termoiônico nos processos de carga e descarga e na perda de cargas armazenadas devido à autodescarga em supercapacitores. Os dados microestruturais reportam por meio de imagens a homogeneidade da porosidade e por meio de valores correlacionados a composição química e eventuais contaminações presentes nos eletrodos. Os dados e valores coletados possuem a intenção de servir como referência comparativa de qualidade e apontar qual parâmetro afeta mais a qualidade do supercapacitor. Para tanto foram realizados testes a fim de coletar valores de C(DC), ESR(Inst) e EPR(Dep) após a exposição de supercapacitores de 1F/5,5V a temperaturas de 50ºC, 75ºC, 100ºC e 125ºC por 672 horas, sendo os dados coletados ao inicio dos testes, à temperatura ambiente, e posteriormente a cada 168 horas. Feitos os experimentos concluiu-se que o parâmetro que sofreu maior deterioração com o acréscimo de energia térmica foi a EPR(Dep), em seguida a C(DC), que de fato pouco sofreu alteração e a ESR(Inst), em que a mudança dentro do erro de medição foi imperceptível. / This paper aims to report information on electrical and microstructural characteristics of electrodes applied at devices that store energy, specifically supercapacitors made of activated carbon electrodes. The studied electrical parameters were the equivalent series resistance obtained by the method of the instantaneous value of the voltage drop (ESR(Inst)), where the acronym ESR has the meaning Equivalent Series Resistance, the equivalent parallel resistance (EPR(Dep)) obtained by the method of dependent value, where the acronym EPR has the meaning Equivalent Parallel Resistance, and the capacitance (C(DC)) obtained by the method of direct current. These parameters were chosen because of the impact they have on lifetime, the storage capacity of electric charge, the speed of loading and unloading, the loss thermionic effect on the charge and discharge processes and loss of stored charge due to self-discharge in supercapacitors. The data given by microstructural images of the homogeneity and porosity values correlated by the chemical composition and possible contaminations present in the electrodes. The collected data and values are intended to serve as a comparative reference point and quality parameter which most affects the quality of the supercapacitor. For both tests were carried out in order to collect values of C(DC), ESR(Inst) and EPR(Dep) after supercapacitors of the 1F/5.5V are exposure at temperatures of 50, 75, 100 and 125°C for 672 hours, and the data collected at the beginning of the tests (room temperature) and subsequently every 168 hours. Made experiments it was concluded that the parameter further deterioration suffered with the increase of thermal energy is EPR(Dep), then C(DC), which in fact little changed and ESR(Inst), in which the change in the measurement error was are noticeable.
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Hybrid Electrochemical Capacitors: Materials, Optimization, and MiniaturizationAgrawal, Richa 11 January 2018 (has links)
With the ever-advancing technology, there is an incessant need for reliable electrochemical energy storage (EES) components that can provide desired energy and power. At the forefront of EES systems are electrochemical capacitors (ECs), also known as supercapacitors that typically have higher power and superior cycle longevity but lower energy densities than their battery counterparts. One of the routes to achieve higher energy density for ECs is using the hybrid EC configuration, which typically utilizes a redox electrode coupled with a counter double-layer type electrode.
In this dissertation, both scale-up (coin-cell type) as well as scale-down (on-chip miniaturized) hybrid ECs were designed, constructed and evaluated. The first part of the dissertation comprised material identification, syntheses, and electrochemical analyses. Lithium titanate-anatase titanium oxide (Li4Ti5O12-TiO2) composites were synthesized via electrostatic spray deposition (ESD) and characterized in both half-cell and full-cell assembly against lithium and nanostructured carbon based counter electrodes, respectively. The second redox type material studied for hybrid electrochemical capacitors was ESD derived manganese oxide (MnOx). The MnOx electrodes exhibited a high gravimetric capacitance of 225F g-1 in aqueous media. Further improvement in the rate handling of the MnOx electrodes was achieved by using CNT additives. The MnOx-CNT composites were tested in full-cell assembly against activated carbon counter electrodes and tested for different anode and cathode mass ratios in order to achieve the best energy-power tradeoff, which was the second major goal of the dissertation. The optimized hybrid capacitor was able to deliver a high specific energy density of 30.3 Wh kg-1 and a maximal power density of 4kW kg-1. The last part of the dissertation focused on a scale-down miniaturized hybrid microsupercapacitor; an interdigitated electrode design was adopted in order to shorten the ion-transport pathway, and MnOx and reduced graphene oxide (rGO) were chosen as the redox and double layer components, respectively. The hybrid microsupercapacitor was able to deliver a high stack energy density of 1.02 mWh cm-3 and a maximal stack power density of 3.44 W cm-3, both of which are comparable with thin-film batteries and commercial supercapacitor in terms of volumetric energy and power densities.
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Electrochemical characterization of nanostructured SnO2 and TiO2 forpotential application as dielectric materials in sulfonated-polyaniline based supercapacitorsNgqongwa, Lundi Vincent January 2010 (has links)
<p>In this research project, nanostructured composites based on Tin dioxide (SnO2) and Titanium dioxide (TiO2) with poly-4-styrene sulfonic acid (PSSA) doped polyaniline (PANI) conducting polymer has been investigated based on their structural, electrical and electrochemical properties. The synthesis of conducting polymers and their metal oxide or composites have been carried out chemically or electrochemically according to methods modified from the literature. Layer-by-layer construction of nano-Metal Oxide/PSSA doped polyaniline composites were successfully constructed by electroanalytical methods on the surface of a glassy carbon working electrode (GCE).</p>
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