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The growing market of mobile electronic devices, renewable off-grid energy sources and electric vehicles requires high-performance energy storage devices. Rechargeable batteries are usually the first choice due to their high energy density. However, supercapacitors have a higher power density and longer life-time compared to batteries. For some applications supercapacitors are more suitable than batteries. They can also be used to complement batteries in order to extend a battery's life-time. The use of supercapacitors is, however, still limited due to their high costs. Most commercially available supercapacitors contain expensive electrolytes and costly electrode materials. In this thesis I will present the concept of cost efficient, paper-based supercapacitors. The idea is to produce supercapacitors with low-cost, green materials and inexpensive production processes. We show that supercapacitor electrodes can be produced by coating graphite on paper. Roll-to-roll techniques known from the paper industry can be employed to facilitate an economic large-scale production. We investigated the influence of paper on the supercapacitor's performance and discussed its role as passive component. Furthermore, we used chemically reduced graphite oxide (CRGO) and a CRGO-gold nanoparticle composite to produce electrodes for supercapacitors. The highest specific capacitance was achieved with the CRGO-gold nanoparticle electrodes. However, materials produced by chemical synthesis and intercalation of nanoparticles are too costly for a large-scale production of inexpensive supercapacitor electrodes. Therefore, we introduced the idea of producing graphene and similar nano-sized materials in a high-pressure homogenizer. Layered materials like graphite can be exfoliated when subjected to high shear forces. In order to form mechanical stable electrodes, binders need to be added. Nanofibrillated cellulose (NFC) can be used as binder to improve the mechanical stability of the porous electrodes. Furthermore, NFC can be prepared in a high-pressure homogenizer and we aim to produce both NFC and graphene simultaneously to obtain a NFC-graphene composite. The addition of 10% NFC in ratio to the amount of graphite, increased the supercapacitor's capacitance, enhanced the dispersion stability of homogenized graphite and improved the mechanical stability of graphite electrodes in both dry and wet conditions. Scanning electron microscope images of the electrode's cross section revealed that NFC changed the internal structure of graphite electrodes depending on the type of graphite used. Thus, we discussed the influence of NFC and the electrode structure on the capacitance of supercapacitors.

Present day electrical equipment is rapidly becoming more and more sensitive to power quality problems, especially voltage sags. Various voltage sag correction devices are avaliable. This thesis analyzes a two-switch, single-phase electronic voltage regulator for correcting voltage sags. The theory of this voltage regulator has been investigated. An analytical method for sizing the energy storage capacitors has been established. The voltage regulator has been modeled and its steady-state and dynamic behavior has been studied by means of detailed computer simulations. A 220-V, 50-Hz, 1-kW rated regulator has been designed, simulated, and built. The results on the performance of voltage regulator and conclusions are also given.

Depuis plus de dix ans les capacités MIM (Métal Isolant Métal) sont des composants passifs largement intégrés au niveau des interconnections des puces de microélectronique. A cause de la miniaturisation et de la réduction de la surface des puces, la densité de capacité des capacités MIM doit être constamment augmentée. Une solution est l'utilisation d'un isolant avec une constante diélectrique élevée dit « high-k ». Pour les prochaines générations de condensateurs, des densités de capacité supérieur à 30 fF/µm² sont visées. L'oxyde de zirconium (ou zircone) a été sélectionné pour remplacer de l'oxyde de tantale actuellement utilisé. Il possède une constante diélectrique qui dépend de sa structure cristalline. Elle est respectivement de 17, 47 et 37 dans les phases monoclinique, quadratique et cubique. Il est donc nécessaire de déposer la zircone dans la phase quadratique. Cependant, les couches minces de zircone ne sont pas entièrement cristallisées dans la phase quadratique. De plus, elles ne répondent pas aux critères de fiabilité requis par la microélectronique. L'objectif de cette thèse est la stabilisation de la zircone dans la phase quadratique par le dopage. Le tantale et le germanium sont les deux dopants choisis grâce à une étude de sélection de matériaux. Des couches minces d'environ 8 nm de zircone dopée à différentes concentrations ont été réalisées par PEALD (Plasma Enhanced Atomic Layer Deposition). Après les dépôts, des recuits à 400°C pendant 30 min ont été effectués afin de reproduire les traitements thermiques subis par les couches lorsqu'elles sont intégrées dans des puces de microélectronique. Plusieurs types de caractérisations ont été effectuées afin d'étudier l'influence des dopants sur la structure cristalline de la zircone mais aussi sur ses propriétés physico-chimiques. Des tests électriques sur des capacités MIM intégrées ont permis de mesurer les propriétés électriques des couches et la fiabilité de la zircone dopée a été évaluée. Ce travail a pour but la fabrication d'une capacité MIM planaire à base d'oxyde de zirconium dopée dont la densité de capacité sera supérieure à 30 fF/µm² pour des applications de découplage. / For more than ten years Metal-Insulator-Metal capacitors (MIM) have been integrated at the level of copper interconnections. All new technology nodes have led to a decrease of the surface of chips; capacitance density must be thus enhanced. The best solution is to use a material with a high dielectric constant commonly named “high-k”. For the next MIM capacitor generation, capacitance density has to be higher than 30 fF/µm². Tantalum oxide, currently used, has reached its limits and it must be replaced. Zirconium dioxide has a high dielectric constant of 47 in the tetragonal phase with a sufficient band gap for MIM applications. When deposited in thin films, zirconia is not fully crystalized in the tetragonal phase. Moreover, this pure zirconium oxide does not fulfill the reliability criteria. The aim of this work is to stabilize zirconia in its tetragonal phase by alloying it with other elements. Tantalum and Germanium are the two dopants selected thanks to a bibliographic study. Thin layers of zirconia of 8 nm alloyed with Tantalum and Germanium have been deposited by Plasma Enhanced Atomic Layer Deposition (PEALD). Samples were annealed at 400°C during 30 minutes after deposition to reproduce the thermal conditions that microelectronic chips are submitted to. Different characterization technics have been used to study the effect of dopants on zirconia's crystalline structure and its physic-chemical properties. Tests have been made on integrated MIM capacitors with Titanium Nitride electrodes to determine the electrical properties of the layers. Reliability of zirconia doped layers was also evaluated. The purpose of this work is the production of zirconia based planar MIM capacitor with a capacitance density of 30 fF/µm².

Le développement des mémoires dynamiques (DRAM) à haute performance basées sur la structure métal-isolateur-métal (MIM) nécessite de remplacer la couche de dioxyde de silicium par des matériaux diélectriques à haute permittivité diélectrique. L'utilisation de ces isolants dits high-k permet de réduire la taille du dispositif DRAM tout en conservant une densité de capacité élevée et un faible courant de fuite pour diminuer la fréquence de rafraichissement. Parmi les nombreux matériaux high k, le dioxyde de titane (TiO2) est l'un des candidats les plus prometteurs en raison de sa constant diélectrique relativement élevée pouvant atteindre 170 dans le TiO2 cristallisé en phase rutile. De plus, il est possible d’obtenir cette phase à basse température par le procédé ALD (< 250 °C) si le dépôt est réalisé sur un substrat RuO2 (phase rutile) grâce à une très faible différence de paramètres de maille entre les deux matériaux. L'objectif principal de cette thèse est d'étudier les mécanismes des réactions chimiques qui se produisant à l'interface RuO2/TiO2 lors du dépôt et leur influence sur les propriétés structurales et diélectriques du film TiO2, en particulier l'influence des espèces oxydantes, le plasma O2 et le H2O. L’influence des électrodes supérieure et inferieures sur les propriétés électriques et structurales de TiO2 a également été étudiée. Ensuite, la constante diélectrique, la conductivité ac et la tangente de perte des structures MIM à base d’oxyde de titane dopé aluminium ont été étudiés dans une gamme de fréquences large bande, de 1 Hz à 2 GHz. Enfin, la réalisation des MIM tridimensionnelles (3D) utilisant un substrat de silicium structuré en réseaux des trous coniques denses a été démontrée. Les structures MIM 3D réalisées ont permis d’augmenter sensiblement la densité de capacité tout en gardant de bonnes performances en termes de courant de fuite. / The development of high performance dynamic random access memory (DRAM) based on metal-insulator-metal (MIM) structure made it necessary to replace the conventional silicon dioxide layer by dielectric materials with high dielectric constants. The use of these so-called high-k insulators allows aggressive scaling of DRAM devices while keeping high capacitance density and, more importantly, low leakage current. Among the numerous high k dielectrics, titanium dioxide (TiO2) is one of the most attractive candidate due to its rather high dielectric constant (k). Rutile TiO2 is the interesting phase due to its high dielectric constant and the possibility to deposit this phase at low temperature by ALD (< 250 °C) by using RuO2 substrate thanks to a very small lattice mismatch between the two materials. The main objective of this thesis is to investigate the surface chemical reactions mechanisms at the RuO2/TiO2 interface and their influence on the ALD TiO2 film properties, especially the influence of oxidizing species, namely, H2O or O2 plasma. The influence of bottom and top electrode on electrical and structural proprieties of TiO2 MIM structure was also studied. Then, the dielectric constant, the ac conductivity and the loss tangent of aluminum doped titanium oxide are measured through a wide band frequency range, from 1 Hz to 2 GHz. Finally, the feasibility of three-dimensional (3D) MIM structures was studied by using dense array of truncated conical holes etched in a silicon substrate. The 3D MIM capacitors showed a large increase in the capacitance density while retaining very good electrical properties especially a leakage current comparable to planar MIM devices.

Philosophiae Doctor - PhD / To meet a fast-growing market demand for next generation portable electronic devices with higher performance and increased device functionalities, efficient electrical energy devices with substantially higher energy, power densities and faster recharge times such as supercapacitors are needed. The overall aim of this thesis was to synthesize nanostructured sulphonated polyaniline and transition metal single, binary and ternary mixed oxide doped nanocomposites with electro-conductive properties. These nanocomposites were anchored on activated graphitic carbon and used in design of asymmetric supercapacitors. Tantalum(IV)oxide, tantalum(IV)oxide-nickel(II)oxide, tantalum(II)oxide-manganese(III)oxide, tantalum(II)oxide-nickel(II)oxide-manganese(II,III)oxide nanoparticles were synthesised using modified sol-gel methods. These were then dispersed, individually, in acidic media through sonication and incorporated in-situ into the polymeric matrix during the oxidative chemical polymerization of aniline doped with poly(4-styrene sulphonic acid). These novel polymeric nanocomposites were characterised with FTIR, UV-visible, TEM, SEM, EDS, XRD to ascertain successful polymerization, doping, morphology and entrapment of the metal oxide nanoparticles. SECM approach curves and interrogation of CV revealed that these nanocomposites are conductive and electro-active. The cells showed good supercapacitor characteristics with high specific capacitances of 170.5 Fg⁻¹ in TaO₂- PANi-PSSA, 166.1 Fg⁻¹ in TaO₂-NiO-PANi-PSSA, 248.4 Fg-1 in TaO-Mn₂O₃-PANi- PSSA and 119.6 Fg⁻¹ in TaO-NiO-Mn₃O₄-PANi-PSSA. Their corresponding energy densities were calculated as 245.5 Whg⁻¹, 179.4 Whg⁻¹, 357.7 Whg⁻¹ and 172.3 Whg⁻¹ respectively. They also gave respective power densities of 0.50 Whg⁻¹, 0.61 Whg⁻¹, 0.57 Whg⁻¹ and 0.65 Whg⁻¹ and showed good coulombic efficiencies ranging between 77.97% and 83.19%. These materials are found to have a long cycle life and therefore good electrode materials for constructing supercapacitor cells. / National Research Foundation (NRF)

L'objectif de cette thèse est de développer et d'optimiser un électrolyte organique performant et sécuritaire pour supercondensateur. En effet, l'acétonitrile est un solvant couramment employé dans la conception des électrolytes, mais celui-ci étant inflammable, il faut lui trouver une alternative performante. Différentes familles de solvants ont été évaluées. Les solvants stables d'un point de vue électrochimique ont été sélectionnés en vue de leur utilisation dans des électrolytes. Dans le but de trouver un compromis entre mobilité et concentration ionique, des mélanges de solvants ont été réalisés. L'addition de solvants peu visqueux comme des esters ou le méthoxypropionitrile dans l'éthylène carbonate et le sulfolane ont permis d'obtenir des électrolytes performants. L'étude des interactions solvant / solvant et solvant / sel ont été menées par des mesures calorimétriques, viscosimétriques et spectroscopiques. Ces interactions, bien que de très faible amplitude, permettent d'augmenter notablement la température d'évaporation du solvant volatil de l'électrolyte, donc son point éclair. / The aim of this work is to to develop and optimize an efficient and safe organic electrolyte for supercapacitor. Indeed, acetonitrile is the solvent commonly used in supercapacitor electrolytes. Due to its flammable character, innovative solvents have to be developed. Several solvent families have been investigated. Thanks to an electrochemical study, stable solvents have been selected to be used in electrolytes. In order to find a compromise between mobility and ionic concentration, solvent mixtures have been studied. The addition of low viscous solvents, as ester and methoxypropionitrile in ethylene carbonate or sulfolane based electrolytes, permits to develop efficient electrolytes. The study of the interactions solvent / solvent and solvent / salt has been performed by calorimetric, viscosimetric and spectroscopic studies. Even if they are very weak, the interactions lead a neat increase of the boiling temperature of the more volatile solvent, thus the flash point.

abstract: The increased adoption of Internet-of-Things (IoT) for various applications like smart home, industrial automation, connected vehicles, medical instrumentation, etc. has resulted in a large scale distributed network of sensors, accompanied by their power supply regulator modules, control and data transfer circuitry. Depending on the application, the sensor location can be virtually anywhere and therefore they are typically powered by a localized battery. To ensure long battery-life without replacement, the power consumption of the sensor nodes, the supply regulator and, control and data transmission unit, needs to be very low. Reduction in power consumption in the sensor, control and data transmission is typically done by duty-cycled operation such that they are on periodically only for short bursts of time or turn on only based on a trigger event and are otherwise powered down. These approaches reduce their power consumption significantly and therefore the overall system power is dominated by the consumption in the always-on supply regulator. Besides having low power consumption, supply regulators for such IoT systems also need to have fast transient response to load current changes during a duty-cycled operation. Supply regulation using low quiescent current low dropout (LDO) regulators helps in extending the battery life of such power aware always-on applications with very long standby time. To serve as a supply regulator for such applications, a 1.24 µA quiescent current NMOS low dropout (LDO) is presented in this dissertation. This LDO uses a hybrid bias current generator (HBCG) to boost its bias current and improve the transient response. A scalable bias-current error amplifier with an on-demand buffer drives the NMOS pass device. The error amplifier is powered with an integrated dynamic frequency charge pump to ensure low dropout voltage. A low-power relaxation oscillator (LPRO) generates the charge pump clocks. Switched-capacitor pole tracking (SCPT) compensation scheme is proposed to ensure stability up to maximum load current of 150 mA for a low-ESR output capacitor range of 1 - 47µF. Designed in a 0.25 µm CMOS process, the LDO has an output voltage range of 1V – 3V, a dropout voltage of 240 mV, and a core area of 0.11 mm2. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2018

Orientador: Luiz Felipe Mendes de Moura / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-18T04:18:01Z (GMT). No. of bitstreams: 1 Barros_TiagoRodriguesde_M.pdf: 8532346 bytes, checksum: 17a941d128ad1bcad0846f1722bc6270 (MD5) Previous issue date: 2011 / Resumo: Este trabalho tem como objetivo a simulação numérica de um sensor de tomografia capacitiva elétrica, em função da permissividade elétrica relativa das fases presentes dentro da tubulação, com a finalidade de determinar a melhor geometria do sensor para a geração de imagem de escoamentos numa mistura bifásica ar-água, levando em consideração fluidos com efeito da condutividade nula. A simulação numérica do sensor de tomografia capacitiva é de crucial importância para o desenvolvimento de um tomógrafo capacitivo usado em aplicações específicas, como é o caso do monitoramento de escoamentos bifásicos. A tomografia capacitiva elétrica é uma tecnologia recente que vem se desenvolvendo desde o início de 1980, quando começou a ser utilizada para análise de processos industriais, principalmente em escoamentos multifásicos. Ela é utilizada para gerar uma imagem do interior da tubulação de acordo com a permissividade relativa das fases ali presentes, sendo atualmente o tipo de tomografia de processos mais utilizada. Após a determinação de algumas premissas do projeto como, o diâmetro da tubulação que foi simulada na horizontal, o comprimento dos eletrodos que seriam montados do lado externo da tubulação, as simulações bidimensionais foram realizadas para se obter o melhor espaçamento entre os doze eletrodos do sensor e a distância ideal da blindagem externa. Com as simulações tridimensionais, foi investigada a necessidade de utilização dos eletrodos de guarda, assim como, foi realizada a simulação da geometria final do sensor numa mudança dos componentes de ar para água no interior da tubulação. Os resultados obtidos neste trabalho permitiram determinar a geometria mais adequada do sensor para a situação proposta, assim como, obter o valor das capacitâncias para diferentes condições de escoamento. Os resultados das simulações tridimensionais apontaram as principais limitações de uma análise bidimensional / Abstract: This study was aimed to realize numerical simulations of a capacitive electrical tomography sensor, depending on the relative permittivity of the phases inside the pipe, in order to determine the best geometry of the sensor to generate the image of the flow in the air-water two-phase flow, taking into account the effect of conductivity zero in the fluids. Numerical simulation of the ECT sensor is of crucial importance to develop a capacitive tomograph used in specific applications such as monitoring biphasic flow. Electrical capacitance tomography is a new technology that has been developed since early 1980, when it began to be used in industrial processes, mainly in multiphase flows. It is used to generate an image from inside the pipe according to the relative permittivity of the phases present there, and is currently the type of process tomography procedures most commonly used. After the determination of some assumptions of the project as the diameter of the pipe that was simulated in the horizontal, the length of the electrodes that must be assembled outside the pipe, the two-dimensional simulations were performed to obtain the best spacing between the twelve electrodes of the sensor and the ideal distance of the outer shield. With the three-dimensional simulations, we investigated the necessity of use guard electrodes, as well as, it was realized the simulation of the final geometry of the sensor components in a change of air to water inside the pipe. The results of this study allow us to determine the most suitable sensor geometry for the proposed situation, as well as obtaining the value of capacitance for different flow conditions. The results of three-dimensional simulations showed the main limitations of a two dimensional analysis / Mestrado / Termica e Fluidos / Mestre em Engenharia Mecânica

Les moteurs asynchrones diphasés sont largement utilisés dans des applications de moins d’un kW, où le prix est un facteur important de choix, en particulier pour les volets roulants. Ces applications, pour des raisons de sécurité, nécessitent une détection précoce des obstacles et donc l’implantation d’un capteur de vitesse. Dans un souci de réduction de coût, une des pistes intéressantes est l’estimation de la vitesse à partir de la mesure des courants et des tensions, de manière à faire l’économie du capteur de vitesse. La première partie de notre travail a consisté à étudier et réaliser différentes alimentations : sur le secteur avec condensateur de déphasage ou par convertisseur statique. Dans une seconde partie, la modélisation du moteur en régime permanent et transitoire et celle du volet (tablier, frein, réducteur) nous a permis d’établir les caractéristiques électromagnétiques du motoréducteur et le comportement mécanique de la charge. Les paramètres de ces modèles ont été identifiés et les résultats analysés. Dans la troisième partie, à partir de ces modèles, différentes stratégies de détection de fin de course du volet sans capteur, d’arrêt sur obstacles ainsi qu’une commande de limitation de couple ont été mises au point et validées expérimentalement. Une carte électronique économique a été réalisée. / The single-phase induction motor is widely used for capacity of less than the kW in applications where the price is an important consideration, particularly for rolling shutters. For safety reasons, these applications require an early detection of obstacles and thus it is necessary to implement a speed sensor. In a preoccupation of cost saving, one tries to estimate the speed on the basis of voltage and current measurements, in order to economize on the speed sensor. The first part of our work deals with the study and realization of different power supplies : Capacitor-run single-phase induction motor or static converter supply. In a second part, the static and transient modeling of the motor and the rolling shutter (shutter, gears and brake) has provided the electromagnetic characteristics of the geared motor and the mechanical behavior of the load. The parameters of these models have been identified and the results have been discussed. In the third part, from these models, different strategies have been devised and validated for detecting the arrival of a rolling shutter on the abutment, implementing a soft stop on obstacles and limiting the torque. A low cost electronic command board has been realized.