published_or_final_version / Electrical and Electronic Engineering / Doctoral / Doctor of Philosophy

Ce travail comprend deux volets. Un premier volet plus « stratégique » concernant l’importance du stockage pour les énergies renouvelables. Un deuxième volet de plus en plus technique et de plus en plus précis concernant le positionnement du stockage électrochimique, la place qu’y tient la batterie Plomb Acide, les variantes technologiques, pour arriver à une modélisation électrochimique détaillée du type de batterie retenu. Dans le premier volet, le chapitre 1 de la thèse met en évidence le bon positionnement du stockage électrochimique pour les besoins des énergies renouvelables. Vis-à-vis des fluctuations aléatoires de la ressource, le temps est un élément important de la discussion : temps de stockage d’une part, temps de mobilisation de l’énergie stocké d’autre part. A cet égard, le cahier des charges pour le lissage de production d’une unité connectée au réseau est bien différent des applications de stockage pour un système de production autonome. Le deuxième chapitre devient plus technique, à l’occasion de la comparaison de la batterie au plomb avec les autres systèmes de stockage. L’idée directrice est d’appuyer cette discussion sur des arguments liés au bases physiques de fonctionnement des composants étudiés : c’est en même temps un prétexte pour commencer l’introduction de principes de bases d’électrochimie qui seront développés et utilisés par la suite. On a raisonné sur trois grandes familles : accumulateurs (exemples batterie au plomb, NiMH, Lithium ion), systèmes de type redox ou plus généralement combustible externe (exemple pile à combustible) et super capacités. Comparaison globalement peu flatteuse pour les performances moyennes de la batterie au plomb, sauvée par son bon rapport performances/prix. Le troisième chapitre entre dans le détail des variantes technologiques, qui démontre une grande flexibilité permettant des compromis pour s’adapter à des besoins spécifiques très variés. On s’est attaché à chercher les aspects spécifiques peu explorés pouvant mener à des améliorations, notamment au niveau de mécanismes réactionnels mis en évidence récemment, 2 En particulier au niveau de l’électrode positive (en liaison notamment avec la mise en évidence par Pavlov d’une phase intermédiaire entre PbO2 et l’électrolyte, de gel Pb(OH)2, aux propriétés mal élucidées). Nous avons placé dans ce chapitre une analyse détaillée de l’hydrolyse, prenant en compte la recombinaison directe de O2 et H2 à l’électrode négative citée également par Pavlov. Ces éléments seront directement repris et complétés au chapitre 4 en modélisation. Le chapitre 4, consacrée à la modélisation et l’expérimentation est l’aboutissement du travail progressif d’introduction de bases d’électrochimie appliquées à la batterie. Il va souligner le rôle central des mécanismes de diffusion/migration dans le fonctionnement. Un premier volet « mathématique » concerne une approximation des équations de diffusion par un réseau de composants discret, optimale du point de vue du nombre de composants. Le modèle global de la batterie peu schématiquement être décomposées en trois grandes fonctions : diffusion, activation, hydrolyse. Ces fonctions sont interconnectées, mais on s’efforcera de les introduire successivement sous forme découplée (au moins de façon approchée). Une première étape est d’obtenir, en grande partie à partir d’expérimentations spécifiques, des valeurs réalistes des paramètres du modèle. Les simulations effectuées démontrent la capacité du modèle à décrire correctement le comportement de la batterie dans les situations les plus variées. / This work has two parts. A first more "strategic" part concerning the importance of storage for renewable energies. An increasingly technical and increasingly precise part concerning the positioning of the electrochemical storage, the position of the Lead Acid battery, the technological variants, to arrive at a detailed electrochemical modeling of the type of battery retained.In the first section, Chapter 1 of the thesis highlights the good positioning of electrochemical storage for the needs of renewable energies. With respect to the random fluctuations of the resource, time is an important element of the discussion: storage time on the one hand, time of mobilization of stored energy on the other hand. In this respect, the specification for the production smoothing of a unit connected to the network is quite different from the storage applications for a stand-alone production system.The second chapter becomes more technical, when comparing the lead-acid battery with the other storage systems. The guiding idea is to support this discussion on arguments related to the physical basis of functioning of the components studied. At the same time, it is a pretext to begin the introduction of basic principles of electrochemistry that will be developed and used by the after. There are three main families: accumulators (examples lead acid battery, NiMH, Lithium ion), redox systems or more generally external fuel (example fuel cell) and super capacitors. Overall comparison unflattering for the average performance of the lead battery, saved by its good performance / price ratio.The third chapter explains the technological variants, which shows a great flexibility that allows compromises to adapt to a wide variety of specific needs. Attention has been given to identifying specific aspects which have not been explored and which can lead to improvements, in particular in the context of recent reaction mechanisms, 2In particular, at the positive electrode (linked in particular with the Pavlov demonstration of an intermediate phase between PbO 2 and the electrolyte, of Pb (OH) 2 gel, with poorly elucidated properties). In this chapter we have placed a detailed analysis of the hydrolysis, taking into account the direct recombination of O2 and H2 at the negative electrode also cited by Pavlov. These elements will be taken up and completed in Chapter 4 in modeling.Chapter 4, devoted to modeling and experimentation, is the culmination of the progressive work of introducing electrochemical bases applied to the battery. It will underline the central role of dissemination / migration mechanisms in the functioning.A first "mathematical" aspect concerns an approximation of the diffusion equations by a discrete component network, optimal in terms of the number of components. The overall model of the battery schematically be broken down into three main functions: diffusion, activation, hydrolysis. These functions are interconnected, but efforts will be made to introduce them successively in decoupled form (at least in an approximate manner). A first step is to obtain, largely from specific experiments, realistic values of the parameters of the model.

Uninterruptable Power Supply (UPS) systems have become essential to modern industries that require continuous power supply to manage critical operations. Since a failure of a single battery will affect the entire backup system, UPS systems providers must replace any battery before it runs dead. In this regard, automated monitoring tools are required to determine when a battery needs replacement. Nowadays, a primitive method for monitoring the battery backup system is being used for this task. This thesis presents a classification model that uses data mining cleansing and processing techniques to remove useless information from the data obtained from the sensors installed in the batteries in order to improve the quality of the data and determine at a given moment in time if a battery should be replaced or not. This prediction model will help UPS systems providers increase the efficiency of battery monitoring procedures. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2013.

Made available in DSpace on 2014-06-11T19:31:04Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-11-06Bitstream added on 2014-06-13T19:01:17Z : No. of bitstreams: 1 chaconsanhueza_ae_dr_bauru_prot.pdf: 7689915 bytes, checksum: 8ebb39720ca5e37b27ba08b395d4278d (MD5) / Este trabalho apresenta o desenvolvimento de dois métodos alternativos para recuperar chumbo. Fusão Alcalina e Eletrohidrometalúrgico. Ambos oferencem a possibilidade de recuperação de outros elementos químicos normalmente perdidos nas escórias. Partindo-se de matérias primas como sucata de baterias chumbo-ácido, resíduos e outras fontes contendo chumbo, a taxa de recuperação foi de 92% a 99% em chumbo com pureza de 99,74%, quando utilizado o método da Fusão Alkalina. Esta taxa foi de 94% em chumbo de 99,99% de pureza, quando empregado o processo Eletrohidrometalúrgico. Cumpre ressaltar que os resíduos gerados por estes métodos são da ordem de 6% a 10% e estão em uma forma química que permite a recuperação de outros metais. Pelo processo convencional (pirometalúrgico), a taxa de recuperação foi de 90% em chumbo com pureza de 98,5% com quantidade de resíduo que chega a 25% do chumbo total produzido e cuja composição obriga o descarte em aterros classe 1. Este trabalho também desenvolve um método para a obtenção de um aditivo que assegura a formação de massas ativas eficientes para placas de baterias chumbo-ácido. O aditivo, à base de sulfato tetrabásico de chumbo (4BS), proporcionou maior reversibilidade ao longo dos dois ciclos, sendo que o tempo de vida útil da bateria dobrou e a quantidade de baterias rejeitadas diminuiu 10% para menos do que 0,5%. Estes índices vêm sendo mantidos durante dois anos em uma empresa do estado de São Paulo, que produz 1000 baterias por mês. Além disso, foi desenvolvido um lacre à base de chumbo que ao ser utilizado nos vasos das baterias durante a sua formação, suprimiu em 97,5% o arraste do ácido sulfúrico para a atmosfera. Finalmente, foi elaborado um processo para tratamento de efluentes liquidos que gera gesso como subproduto e possibilita a reutilização... / This work presents the development of two alternative methods to recycle lead. Alkaline Fuson and Electrohydrometallurgic. Both also offer the possibility to recover other chemical elements that normally are lost as waste. From raw materials such as scrap lead-acid batteries, waste and other sources containing lead, the Alkaline Fusion method yields 92% to 99% of recovering of lead having a purity of 99.74%. Using the Electrohydrometallurgic process, the recovery is 94% of lead of 99.99% purity. It must be emphasized that the generated wastes by these methods are around 6% to 10% and they are in a chemical form, which allows further recycling of other metals. By the conventional process, the pirometallurgic one, it was obtained 90% of recovering of lead of 98.5% purity. Furthermore, the waste amount is around 25% of the total produced lead, whose composition requires an expensive discarding system (Type 1 system). This work also develops a method for obtaining an additive that ensures the efficient active mass formation for lead-acid batteries plates. The additive, constituted by tetrabasic lead sulphate (4BS), provid higher reversibility for charging/discharging cycles being that the battery lifetine increased two folds and the amount of rejected batteries diminished from 10% to less than 0.5%. Such indices are being held for two years in a company of the São Paulo State, Which produces one thousand batteries in a month. In addition, it was developed a lead based sealing device that, when utilized in battery vessel during its formation suppresses the sulfuric acid released to the atmosphere in 97.5%. Finally, it was advanced a process for liquid effluent treatment that produces plaster, a by-product, and allows the reuse of water, since it contains a low metal content. The utilization of the developed methods by a company in... (Complete abstract click electronic access below)

<p>Modern heavy trucks tend to get more and more equipment demanding electric power. As a result, the electric power left for startingbecome more and more limited. If a complete view of the entire starting system-battery, starter and the combustion engine - is used, the total system can be investigated and optimized. This thesis is a study of the starting system and its components. Theories for each component are presented and models are derived for a complete starting system. Focus lies on the battery and starter motor. The purpose of the modelling work is to gain knowledge of the starting system. Some results can also be obtained from the simulations - it is very important to keep the electrical resistance as low as possible and the differences between battery types are surprisingly big.</p>

Modern heavy trucks tend to get more and more equipment demanding electric power. As a result, the electric power left for startingbecome more and more limited. If a complete view of the entire starting system-battery, starter and the combustion engine - is used, the total system can be investigated and optimized. This thesis is a study of the starting system and its components. Theories for each component are presented and models are derived for a complete starting system. Focus lies on the battery and starter motor. The purpose of the modelling work is to gain knowledge of the starting system. Some results can also be obtained from the simulations - it is very important to keep the electrical resistance as low as possible and the differences between battery types are surprisingly big.

This thesis proposes an enhanced ampere-hour counting method based on the depth-of-discharge (DOD) to estimate the state-of-charge (SOC) and state-of-health (SOH) for lead-acid batteries. Not only the losses at different discharging currents, but also the releasable capacity at the exhausted state caused by the larger discharging current are considered and compensated. Furthermore, the SOH is revaluated at the exhausted state by the maximum releasable capacity, consequently leading to more accurate SOC estimation. Through the experiments that emulate practical operations, the experimental results reveal that the maximum error is less than 6 %.

Η εμπειρία έχει δείξει ότι στα αυτόνομα φωτοβολταϊκά συστήματα, η μπαταρία είναι το πιο αδύναμο στοιχείο αφού το προσδόκιμο ζωής της είναι συνήθως αρκετά μικρότερο από ότι όλων των άλλων στοιχείων του συστήματος και για το λόγο αυτό είναι και το πιο ακριβό στοιχείο με το 30% ή και περισσότερο του κόστους ενός αυτόνομου φωτοβολταϊκού συστήματος καθ’όλη τη διάρκεια της ζωής του να οφείλεται στο σύστημα αποθήκευσης. Αντικείμενο αυτής της εργασίας είναι η μελέτη των προβλημάτων που αντιμετωπίζουν οι μπαταρίες μολύβδου οξέος (που είναι ο βασικός τύπος μπαταριών που χρησιμοποιείται για την αποθήκευση στα φωτοβολταϊκά συστήματα) και οι τρόποι αντιμετώπισής τους με σκοπό αφενός την επέκταση της διάρκειας της χρήσιμης ζωής των μπαταριών αυτών και αφετέρου τη μείωση του κόστους συντήρησης και αντικατάστασής τους. Ιδιαίτερη βαρύτητα δίνεται στο πρόβλημα της θειίκωσης, το οποίο έχει αποδειχθεί ο σημαντικότερος παράγοντας γήρανσης και τελικά καταστροφής της πλειοψηφίας των μπαταριών μολύβδου οξέος που χρησιμοποιούνται στα φωτοβολταϊκά συστήματα και παρουσιάζονται τεχνικές που μπορούν να χρησιμοποιηθούν για την πρόληψη και την αντιμετώπιση του πολύ σοβαρού αυτού προβλήματος. / Experience has shown that in stand alone photovoltaic systems, battery is the weakest element since its expected lifetime is usually considerably smaller than those of other elements. Thus its cost is the most expensive with 30% or above of the total cost of stand alone photovoltaic system throughout its whole lifespan. Subject of this dissertation is the study of problems that lead acid batteries face and the way to treat them. The aim is to extend their useful lifetime and the reduction of the cost of maintenance and replacement. The problem of sulphation is given special importance, since it has been proved that it constitutes the main aging factor for the majority of lead acid batteries used in photovoltaic systems. Suggestions for treatment are given.

Made available in DSpace on 2014-06-11T19:23:29Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-08-12Bitstream added on 2014-06-13T19:09:18Z : No. of bitstreams: 1 alessio_p_me_bauru.pdf: 1843758 bytes, checksum: c580a47f245b1c196058f87dfb7ddb59 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Na presente dissertação de mestrado apresentam-se estudos de um material polimérico do tipo poli(azo)uretana, chamada aqui de PAzoU, obtida a partir da reação de azocorante com o bis-carbonato cíclico de di-glicidiléter-bis-fenol A. A reação do azocorante possuindo dois agrupamentos 'NH IND. 2' livres com o bis-carbonato conduz à formação da PAzoU, a qual foi caracterizada por ressonância magnética nuclear de carbono 13 ('INTPOT. 13 C' RMN) em solução e na forma de pó e cromatografia de permeação por gel (GPC). Vale ressaltar a importância ecológica e industrial deste processo, uma vez que a poliuretana resultante é livre de isocianato (NIPU, do inglês non-isocyanate polyurethane) e foi obtida a partir da captura e ativação do 'CO IND. 2'. Uma vez caracterizado o polímero, filmes nanoestruturados foram fabricados com o objetivo principal de se investigar a estruturação em nível molecular do polímero nos filmes finos. Tal estruturação, além das características físicas e químicas do material em si, é um fator fundamental nas propriedades óticas e elétricas do filme. A importância do estudo destes materiais na forma de filmes finos justifica-se porque a maioria dos dispositivos eletrônicos de materiais orgânicos é fabricada tendo o filme fino como elemento transdutor de sinal. Três diferentes tipos de filmes finos foram estudados: filmes de Langmuir, filmes de Langmuir-Blodgett (LB) e filmes evaporados (ou PVD, do inglês physical vapor deposition). Os filmes de Langmuir, estudados na forma de monocamadas na interface ar/água, foram caracterizados por isotermas de pressão de superfície vs área molecular média (isotermas 'pi'-A) variando-se diferentes parâmetros: solventes para a dissolução do polímero, testes de estabilidade, curvas de histereses, velocidade de compressão das moléculas... / This work is related to the results of the study of a polymeric material in a form of ultrathin films. The studied polymer is a poly(azo)urethane, named PAzoU, obtained by the copolymerization of a diazo(4-aminomethyl-benzylamine) with the cyclic bis-carbonate of diglicidilether- bis-phenol A. The final polyurethane is a NIPU, non-isocyanate polyurethane material being remarkable the ecological and industrial role of materials obtained from 'CO IND. 2' capture and activation. The PAzoU was characterized by carbon 13 nuclear magnetic resonance ('INTPOT. 13 C' RMN) in solution and in solid state, and by gel permeation chromatography (GPC). Once the polymer was characterized, nanostructured films were fabricated for investigating the polymer structuration at molecular level. Such structuration, in addition to the physical and chemical characteristics of the material itself, plays an important role on the film optical and electrical properties. In fact, most of the organic electronic devices are fabricated with the signal transducer element as a thin film. This justifies the importance of the study of the polymeric materials in the thin film form. The films have been studied in the monomolecular form by the langmuir technique on the air/water interface. The PAzoU has been characterized by isotherms of surface pressure vs mean molecular area ('pi'-A isotherm). The influence of the solvent has been investigated and N,N-dimethylformamide (DMF) was chosen as the most appropriate for 'pi'-A isotherm experiments. Hence, other experiments were carried out using DMF as solvent: stability tests, hysteresis curves, compression speed of the molecules, and mixed films produced using stearic acid (SA). Afterwards the Langmuir films were transferred onto solid substrate forming Langmuir-Blodgett (LB) films, which were... (Complete abstract click electronic access below)

Resumo: Este trabalho apresenta o desenvolvimento de dois métodos alternativos para recuperar chumbo. Fusão Alcalina e Eletrohidrometalúrgico. Ambos oferencem a possibilidade de recuperação de outros elementos químicos normalmente perdidos nas escórias. Partindo-se de matérias primas como sucata de baterias chumbo-ácido, resíduos e outras fontes contendo chumbo, a taxa de recuperação foi de 92% a 99% em chumbo com pureza de 99,74%, quando utilizado o método da Fusão Alkalina. Esta taxa foi de 94% em chumbo de 99,99% de pureza, quando empregado o processo Eletrohidrometalúrgico. Cumpre ressaltar que os resíduos gerados por estes métodos são da ordem de 6% a 10% e estão em uma forma química que permite a recuperação de outros metais. Pelo processo convencional (pirometalúrgico), a taxa de recuperação foi de 90% em chumbo com pureza de 98,5% com quantidade de resíduo que chega a 25% do chumbo total produzido e cuja composição obriga o descarte em aterros classe 1. Este trabalho também desenvolve um método para a obtenção de um aditivo que assegura a formação de massas ativas eficientes para placas de baterias chumbo-ácido. O aditivo, à base de sulfato tetrabásico de chumbo (4BS), proporcionou maior reversibilidade ao longo dos dois ciclos, sendo que o tempo de vida útil da bateria dobrou e a quantidade de baterias rejeitadas diminuiu 10% para menos do que 0,5%. Estes índices vêm sendo mantidos durante dois anos em uma empresa do estado de São Paulo, que produz 1000 baterias por mês. Além disso, foi desenvolvido um lacre à base de chumbo que ao ser utilizado nos vasos das baterias durante a sua formação, suprimiu em 97,5% o arraste do ácido sulfúrico para a atmosfera. Finalmente, foi elaborado um processo para tratamento de efluentes liquidos que gera gesso como subproduto e possibilita a reutilização... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This work presents the development of two alternative methods to recycle lead. Alkaline Fuson and Electrohydrometallurgic. Both also offer the possibility to recover other chemical elements that normally are lost as waste. From raw materials such as scrap lead-acid batteries, waste and other sources containing lead, the Alkaline Fusion method yields 92% to 99% of recovering of lead having a purity of 99.74%. Using the Electrohydrometallurgic process, the recovery is 94% of lead of 99.99% purity. It must be emphasized that the generated wastes by these methods are around 6% to 10% and they are in a chemical form, which allows further recycling of other metals. By the conventional process, the pirometallurgic one, it was obtained 90% of recovering of lead of 98.5% purity. Furthermore, the waste amount is around 25% of the total produced lead, whose composition requires an expensive discarding system (Type 1 system). This work also develops a method for obtaining an additive that ensures the efficient active mass formation for lead-acid batteries plates. The additive, constituted by tetrabasic lead sulphate (4BS), provid higher reversibility for charging/discharging cycles being that the battery lifetine increased two folds and the amount of rejected batteries diminished from 10% to less than 0.5%. Such indices are being held for two years in a company of the São Paulo State, Which produces one thousand batteries in a month. In addition, it was developed a lead based sealing device that, when utilized in battery vessel during its formation suppresses the sulfuric acid released to the atmosphere in 97.5%. Finally, it was advanced a process for liquid effluent treatment that produces plaster, a by-product, and allows the reuse of water, since it contains a low metal content. The utilization of the developed methods by a company in... (Complete abstract click electronic access below) / Orientador: Margarida Juri Saeki / Coorientador: Nerilso Bocchi / Banca: Adhemar Colla Ruvolo Filho / Banca: Aguinaldo Robinson de Souza / Banca: Patrício Rodolfo Impinisse / Banca: José Humberto Dias da Silva / O Programa de Pós-Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi da Unesp / Doutor