Orientador: Carlos Alberto Canesin / Resumo: Uma das principais dificuldades para a adoção dos veículos elétricos (VE) é o tempo de abastecimento (carregamento elétrico), considerado elevado quando comparado com o tempo requerido para abastecer um veículo com motor a combustão interna. O carregamento do VE típico de passageiros é geralmente realizado na residência do proprietário, ligando o carregador interno do VE em uma tomada convencional monofásica. Este método de carregamento é conhecido como de Corrente Alternada (CA), requer, tipicamente pelo menos 7 horas para fornecer uma carga completa. Por outro lado, o método de carregamento por Corrente Continua (CC) oferece tempos de carregamento entre 10 e 80 minutos. Contudo, para obter este nível de desempenho, são empregados carregadores externos de alta potência ligados de forma direta ao banco de baterias do VE. Devido ao custo e aos requerimentos de alimentação, estes carregadores rápidos são usados principalmente em aplicações públicas e comerciais. As pesquisas pelas melhores topologias a serem empregadas nos carregadores rápidos ainda são, neste ano de 2017 objeto de estudos em escala mundial. Neste contexto, este trabalho descreve a análise e implementação de um protótipo de carregador externo rápido para VE, o qual é composto por um retificador híbrido trifásico com correção ativa do fator de potência (Etapa CA-CC), seguido de um conversor tipo Buck entrelaçado (Etapa CC-CC). Na etapa CA-CC são impostas correntes de entrada senoidais, obtendo desta forma uma r... (Resumo completo, clicar acesso eletrônico abaixo) / Mestre

Submitted by CAMILO ALEXEY SUAREZ BUITRAGO null (camiloalexey@gmail.com) on 2017-05-05T23:51:03Z No. of bitstreams: 1 CAMILO ALEXEY SUAREZ BUITRAGO.pdf: 4865572 bytes, checksum: e8593c9e425def26a441b4b919b9d371 (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-05-08T16:36:05Z (GMT) No. of bitstreams: 1 suarezbuitrago_ca_me_ilha.pdf: 4865572 bytes, checksum: e8593c9e425def26a441b4b919b9d371 (MD5) / Made available in DSpace on 2017-05-08T16:36:05Z (GMT). No. of bitstreams: 1 suarezbuitrago_ca_me_ilha.pdf: 4865572 bytes, checksum: e8593c9e425def26a441b4b919b9d371 (MD5) Previous issue date: 2017-03-13 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Uma das principais dificuldades para a adoção dos veículos elétricos (VE) é o tempo de abastecimento (carregamento elétrico), considerado elevado quando comparado com o tempo requerido para abastecer um veículo com motor a combustão interna. O carregamento do VE típico de passageiros é geralmente realizado na residência do proprietário, ligando o carregador interno do VE em uma tomada convencional monofásica. Este método de carregamento é conhecido como de Corrente Alternada (CA), requer, tipicamente pelo menos 7 horas para fornecer uma carga completa. Por outro lado, o método de carregamento por Corrente Continua (CC) oferece tempos de carregamento entre 10 e 80 minutos. Contudo, para obter este nível de desempenho, são empregados carregadores externos de alta potência ligados de forma direta ao banco de baterias do VE. Devido ao custo e aos requerimentos de alimentação, estes carregadores rápidos são usados principalmente em aplicações públicas e comerciais. As pesquisas pelas melhores topologias a serem empregadas nos carregadores rápidos ainda são, neste ano de 2017 objeto de estudos em escala mundial. Neste contexto, este trabalho descreve a análise e implementação de um protótipo de carregador externo rápido para VE, o qual é composto por um retificador híbrido trifásico com correção ativa do fator de potência (Etapa CA-CC), seguido de um conversor tipo Buck entrelaçado (Etapa CC-CC). Na etapa CA-CC são impostas correntes de entrada senoidais, obtendo desta forma uma reduzida distorção harmônica total (DHT). Nesta etapa são empregados retificadores SEPIC comutados sob corrente nula (Zero Current Switching, ZCS) controlados por uma simples modulação por histerese, em paralelo com um retificador trifásico a diodos de seis pulsos. O estágio SEPIC processa apenas uma fração da potência total entregue pelo retificador híbrido, reduzindo deste modo os esforços de corrente dos semicondutores empregados, permitindo o uso desta topologia em elevados níveis de potência. Na etapa CC-CC o conversor Buck entrelaçado é controlado por modulação de largura de pulso (Pulse-Width Modulation, PWM), permitindo assim a implantação da técnica de carregamento por corrente constante e tensão constante (Constant Current-Constant Voltage, CC-CV), comumente empregada em baterias de íons de lítio e supercapacitores (SC). Como principal resultado foi obtido o carregamento de um banco de supercapacitores de 2,54 F, com corrente constante de 20 A, variando sua tensão de 180 V a 270 V com uma duração de 40 s, obtendo uma distorção harmônica total de 3,52% na corrente de entrada, ajustando-se ao padrão IEEE 2030.1.1-2015. / One of the main barriers against electric vehicle (EV) adoption is related to the battery recharging time, which is relatively high when compared to the time required to fill up a gasoline/diesel internal combustion engine vehicle. EV charging generally is done at home, using the on-board EV charger tied to conventional single phase power inlet, this charging method is known as Alternating Current (AC) and takes at least 7 hours to provide a full charge. On the other hand, the Direct Current (DC) method offers charging times from 1.2 hours to 10 minutes. However, to reach this performance, high power off-board chargers also known as fast-chargers (FC), directly charge the EV battery bank. Due to its cost and power supply requirements FC are used only in public or commercial applications. The researches for the best FC topologies are an active area of studies over the world. This work describes the analysis and implementation of an off-board electric vehicle (EV) Fast Charger prototype. It is composed by a three-phase hybrid rectifier with power factor correction (AC/DC stage), followed by an interleaved buck converter (DC/DC stage). At AC/DC stage, sinusoidal input phase currents are imposed, and consequently low Total Harmonic Distortion (THD) is obtained by the use of Zero Current Switching (ZCS) SEPIC rectifiers, applying a simple hysteresis control technique, in parallel with a conventional three-phase six pulses diode rectifier. The SEPIC converters manage only a fraction of the total power delivered by the hybrid rectifier, reducing the semiconductors current stresses, and allowing the use of this topology for high power levels. At DC/DC stage, the interleaved buck converter is controlled by Pulse Width Modulation (PWM), allowing Constant Current–Constant Voltage (CC-CV) charging technique, typically used for Lithium-ion (Li) batteries and Supercapacitors (SC). As main result of this implementation was obtained a charging process using constant a constant current of 20A over a supercapacitor bank of 2,54 F, raising its voltage from 180V to 270V in less than 40s, having a input phase current THD of 3,52%, fulfilling the requirements of IEEE 2030.1.1-2015 standard.

Advances in the biomedical field require functional materials and processes that can lead to devices that are biocompatible, and biodegradable while maintaining high performance and mechanical conformability. In this context, a current shift in focus is towards natural polymers as not only the structural but also functional components of such devices. This poses material-specific functionalization and fabrication related questions in the design and fabrication of such systems. Silk protein biopolymers from the silkworm show tremendous promise in this regard due to intrinsic properties: mechanical performance, optical transparency, biocompatibility, biodegradability, processability, and the ability to entrap and stabilize biomolecules. The unique ensemble of properties indicates opportunities to employ this material into numerous biomedical applications. However, specific processing, functionalization, and fabrication techniques are required to make a successful transition from the silk cocoon to silk-based devices. This research is focused on these challenges to form silk-based functional material and devices for application in areas of therapeutics, bio-optics, and bioelectronics. To make silk proteins mechanically conformable to biological tissues, the first exploration is directed towards the realization of precisely micro-patterned silk proteins in flexible formats. The optical properties of silk proteins are investigated by showing the angle-dependent iridescent behavior of micropatterned proteins, and developing soft micro-optical devices for light concentration and focusing. The optical characteristics and fabrication process reported in the work can lead to the future application of silk proteins in flexible optics and electronics. The microfabrication process of silk proteins is further extended to form shape-defined silk protein microparticles. Here, the specificity of shape and the ability to form monodisperse shapes can be used as shape encoded efficient cargo and contrast agents. Also, these particles can efficiently entrap and stabilize biomolecules for drug delivery and bioimaging applications. Next, a smart confluence of silk sericin and a synthetic functional polymer PEDOT:PSS is shown. The composite materials obtained have synergistic effects from both polymers. Silk proteins impart biodegradability and patternability, while the intrinsically conductive PEDOT:PSS imparts electrical conductivity and electrochemical activity. Conductive micro architectures on rigid as well as flexible formats are shown via a green, water-based fabrication process. The applications of the composite are successfully demonstrated by realizing biosensing and energy storage devices on rigid or flexible forms. The versatility of the approach will lead to the development of a variety of applications such as in bio-optics, bioelectronics, and in the fundamental study of cellular bio electrogenic environments. Finally, to expand the applicability of reported functional polymers and composites beyond the microscale, a method for silk nano-patterning via electron beam lithography is explored. The technique enables one-step fabrication of user defined structures at the submicron and nano-scales. By virtue of acrylate chemistry, a very low energetic beam and dosage are required to form silk nano-architectures. Also, the process can form both positive and negative features depending on the dosage. The fabrication platform can also form nano scale patterns of the conductive composite. The conductive measurements confirm the formation of conductive nanowires and the ability of silk sericin to entrap PEDOT:PSS particles in nanoscale features.

Cette thèse a pour objectif de proposer une modélisation performante des supercondensateurs à électrodes à base de carbone activé, composants de puissance présents dans un nombre croissant d’applications de stockage d’énergie. La première étape des travaux a consisté à mettre en évidence les phénomènes physico-chimiques, qu’ils soient électrostatiques ou électrochimiques grâce à des essais de caractérisation spécifiques et de vieillissement. L’analyse des résultats associée à la connaissance des matériaux constitutifs a conduit à attribuer le comportement non linéaire du supercondensateur aux phénomènes d’adsorption-désorption (électrosorption) et de diffusion anomale des espèces adsorbées dans le réseau microporeux de l’électrode. La prise en compte de ces phénomènes et de la capacité de double couche a permis de définir un modèle non linéaire fractionnaire dont les paramètres dépendent des grandeurs physico-chimiques de la cellule. La procédure proposée pour l’identification des paramètres du modèle repose sur la réponse en tension du supercondensateur à des profils de charges-décharges. Malgré la simplicité de l’identification, le modèle traduit fidèlement le comportement du supercondensateur soumis à des profils en courant typiques d’applications véhicules électriques et hybrides. / This work aim is an efficient modelling proposal for supercapacitors made of activated carbon electrodes which are power components used in many energy storage applications. In the first part of this study, the purpose is to evidence physico-chemical phenomena, electrostatic or electrochemical as well, thanks to characterization and aging tests. The results analysis combined with materials knowledge leads to suppose that the supercapacitor non linear behavior is due to adsorption-desorption processes and also to anomalous diffusion of adsorbed species into the electrode microporous network. These mechanisms in addition with the double layer capacitor principle allow us to define a non linear fractional model with parameters that depend on physic0-chemical characteristics of the cell. The proposed identification procedure is based on the voltage response to charges-discharge current profiles. In spite of the simplicity of this identification method, the model matches very well the behavior of the supercapacitor under current profiles that are typical of hybrid and electric vehicle applications.

Des carbones dérivés de carbures à porosité monodisperse et nanocentrée autour de 0,6 nm ont été préparés par fluoration de carbures via l’arrachement sélectif de l’élément métallique et le maintien de l’empreinte carbonée initiale. Les carbures précurseurs ont été choisis parmi deux des classes de carbures à savoir interstitiels pour le carbure de titane et de niobium et covalents pour le carbure de silicium. La fluoration directe procédant sous flux d’une atmosphère de fluor pur apparait comme étant la seule méthode de fluoration apte à déstabiliser les poudres cristallisées. Appliquée au carbure de titane, des matériaux à teneur variable en carbone et en trifluorure de titane ont été obtenus et caractérisés structuralement par Diffraction des Rayons X quantitative, spectroscopies IR et Raman et leur texture sondée par Microscopie Electronique à Balayage et à Transmission et isothermes d’adsorption à l’azote à 77K. Ils ont aussi été évalués comme matériau d’électrode de supercondensateurs. La fluoration du carbure de silicium pour la stabilisation d’une phase carbonée est plus difficile et seule l’abaissement de la cristallinité du carbure par l’utilisation d’une mise en forme de type couche mince combinée à une méthode de fluoration alternative par décomposition de l’agent fluorant XeF2 ont permis d’obtenir une couche mince de carbone nanostructurée valorisable comme lubrifiant solide et aux propriétés de mouillabilité modulables. / Carbide-derived Carbons (CDC) with monodisperse ultramicroporosity have been prepared by carbide fluorination thanks to selective etching of metallic element. The chosen carbides precursors were titanium and niobium carbides, and silicon carbides from interstitial and covalent carbide family, respectively. Direct fluorination proceeding by a pure flow of 1 atm. of molecular fluorine is the only fluorination way which leads to the transformation of the powdered and highly crystallized carbide into some carbons. Materials with different ratio of carbon and solid titanium trifluoride were successfully obtained by direct fluorination of titanium carbide, characterized by quantitative XRD, IR and Raman spectroscopies and Scanning and Transmission Electronic Microscopies and used in supercapacitors. The direct fluorination of silicon carbide in order to form carbon is more difficult because of the competition between carbon formation and its degradation into gaseous carbon fluorides. To success in our goal, thin film morphology was used as precursor. However, an accurate fluorination way is needed and decomposition of XeF2 fluorinating agent was chosen. Thin films with variable thickness of nanostructured carbon at the surface were obtained and used as solid lubricant with tunable wettability properties.

This master´s thesis deals different types of the aprotic electrolytes for supercapacitors and investigates by impedance spectroscopy to conductivity and method cyclic voltametry to measure dimension potential windows. Used aprotic solvents: propylencarbonate, dimethylsulfoxide, N, N dimethylformamide, ethylencarbonate, dimethylcarbonate, diethylcarbonate and acetonitrile. In the aprotic solvents were appended salts: LiClO4, NaClO4, KClO4, LiBF4, LiPF6, TEABF4 and TMABF4. From these compounds were prepared solutions with the different molar concentrations.

This master’s thesis deals with supercapacitors and polymer gel electrolytes. The practical part deals with the preparation of samples of polymer gel electrolyte with addition of alkali salts by measuring their electrical conductivity and evaluation potential windows.

Dissertation thesis is focused on using alternative energy sources called energy harvesting. This thesis offers a solution to problems with autonomous powering of sensor networks if primary power source recovery is impossible. In these cases, energy of the external power (e.g. temperature, light, motion) should be used. Proposed solution should be especially used in the field of medical applications (e.g. cochlear implants, pacemakers, insulin pumps). Long time monitoring of the personal health status is also possible when employing automated sensor systems. In this work, there is state of art review relating to the low power energy sources for an alternative powering of sensor systems. It was observed that existing systems are almost prepared for the implementation of energy harvesting power sources. The energy harvesting power sources have been developed by numerous researcher teams around the world, but there are only a few variants of power management circuits for effective energy gaining, storing and using. This area has a huge potential for the next research. The issues regarding to the distribution of gained energy are solved on the complex level in the thesis. For these purposes, a new simulation model of the whole system (fully implantable artificial cochlea) including its subcircuits was developed in the SPICE environment. It connects independent subcircuits into a single comprehensive model. Using this model, a few novel principles for energy distribution (e.g. Charge Push Through technique) was developed. In the near future, these techniques are also applicable to the design of versatile sensor systems.

Philosophiae Doctor - PhD / Energy storage technologies are rapidly being developed due to the increased awareness of global warming and growing reliance of society on renewable energy sources. Among various electrochemical energy storage technologies, high power supercapacitors and lithium ion batteries with excellent energy density stand out in terms of their flexibility and scalability. However, supercapacitors are handicapped by low energy density and batteries lag behind in power. Supercapatteries have emerged as hybrid devices which synergize the merits of supercapacitors and batteries with the likelihood of becoming the ultimate power sources for multi-function electronic equipment and electric/hybrid vehicles in the future. But the need for new and advanced electrodes is key to enhancing the performance of supercapatteries. Leading-edge technologies in material design such as nanoarchitectonics become very relevant in this regard. This work involves the preparation of vanadium pentoxide (V2O5), pristine and zinc doped lithium manganese silicate (Li2MnSiO4) nanoarchitectures as well as their composites with hydroxylated graphene (G-ol) and carbon nanotubes (CNT). / 2023-12-01

Les travaux de cette thèse ont porté sur l'élaboration, l'optimisation et l'étude d'électrodes composites de nanotubes de carbone verticalement alignés (VACNT) sur un collecteur d'aluminium et modifiés par l'oxyde de manganèse (MnO₂). Les VACNT synthétisés par voir CVD à basse température (580°C:) directement sur le collecteur ont permis d'obtenir des tapis de NTC parfaitement alignés d'une épaisseur allant de 20 à 80 µm et possédant des densités de 10¹¹ NTC.cm² et dont le taux de catalyseur (Fe) est inférieur à 1%. Leur modification par du MnO2 permet d’accroître leur capacité de stockage électrochimique. Afin de réaliser un enrobage optimal des VACNT par le MnO₂, différents précurseurs de l'oxyde ainsi que diverses méthodes(dépôts électrochimiques, chimiques, CVD) ont été utilisées et optimisées. Les composites élaborés ont ensuite été étudiées en tant que matériau d'électrode pour la réalisation de supercondensateurs asymétriques eu milieux aqueux. / This thesis was focused on the development, optimization and study of composite electrodes of vertically aligned carbon nanotubes (VACNT) on an aluminum collector and modified with manganese oxide (MnO₂).VACNT were synthesized by a CVD process at low temperature (580° C) directly on the collector. Perfectly aligned CNT forest with a thickness of 20 to 80 μm were obtained with high densities of 10¹¹ NTC.cm² and whose catalyst (Fe) content is less than 1%. Their modification with MnO₂ increase their electrochemical storage capacity. In order to achiew optimal coating of VACNT by MnO₂, different precursors of the oxide and various methods ( electrochemical, chemical, CVD) were used and optimized. Composites were studied as electrode material for the realization of asymmetric supercapacitors in aqueous media. In addition, structurals, morphologicals and electrochemicals analyzes carried out on the different materials allowed a better understanding of the role of the elaboration's conditions on the properties of the VACNT/MnO₂ composites obtained.