The recycling of lead-acid batteries (LABs) is currently an energy intensive, inefficient and polluting procedure. An alternative hydrometallurgical recycling process is investigated in this study. PbO, PbO2, and PbSO4 were individually reacted with a mixture of aqueous citric acid and sodium hydroxide solution, with hydrogen peroxide being used as a reducing agent for PbO2. Pure lead citrate of either Pb(C6H6O7)·H2O or Pb3(C6H5O7)2·3H2O was the product crystallized in each leaching experiment depending on the initial conditions. Combined spent electroactive paste materials from industry were leached and processed. 2.5 M H2O2, 3.2 M C6H8O7·H2O and 3.5 M NaOH were used for optimal leaching and were successful in synthesising Pb3(C6H5O7)2·3H2O after less than one hour. These amounts could be reduced by individual leaching of plate materials. The combustion-calcination of Pb3(C6H5O7)2·3H2O was successful in generating PbO containing both forms of the polymorph α and β crystal phases together with metallic Pb. A novel method to generate PbO from lead citrate was found through a self-sustaining combustion route where leached waste materials were preheated to 270 °C for ~15 minutes and were found to self-sustain a smouldering reaction to produce PbO with a predominately β phase containing metallic Pb. Electrochemical analysis of PbO from Pb3(C6H5O7)2·3H2O demonstrated the viability in the by-product to be used in an electroactive paste and therefore reused in new LABs. Pure α-PbO was generated from both forms of lead citrate, Pb(C6H6O7)·H2O and Pb3(C6H5O7)2·3H2O using NaOH. Pure β-PbO was also generated from Pb(C6H6O7)·H2O and Pb3(C6H5O7)2·3H2O using NaOH through dissolution/re-precipitation reactions. PbCO3 was successfully generated from Pb(C6H6O7)·H2O and Pb3(C6H5O7)2·3H2O using NaOH, NaHCO3 and an acid in a series of disassociation and re-precipitation reactions. PbCO3 could be used to thermally generate α and β-PbO as well as Pb3O4 by calcination at 350, 600 and 450 °C respectively. Glycerol was entrained in both PbCO3 and α-PbO as an in-situ reducing agent to generate PbO containing metallic Pb. Acid reactivity and absorption characteristics of PbO derived from Pb3(C6H5O7)2·3H2O heated in CO2 were equal to and greater than those used in industry for both automotive and industrial batteries.

This thesis investigates the performance of pulse charging, which is believed to be superior to constant current charging in some respects, such as charging efficiency and charging speed. The investigation is focused upon the extensively used secondary batteries, lead-acid batteries. The consecutive orthogonal arrays method is applied to search for the optimum operating variables of pulse charging, including pulse amplitude, duty ratio and frequency of the charging current. Unfortunately, the experimental results of consecutive orthogonal arrays reveal that charging efficiency is not obviously affected by pulse amplitude, duty ratio or frequency. Instead, charging rate is dominantly influenced by average charging current. These results indicate that pulse charging scheme is not superior to constant current charging. To compare these two charging schemes further, a series of experiments are carried out to discuss the effects of each operating variables. Unfortunately, no evidence from the experimental results can prove the superiority of pulse charging to constant current charging as formerly documented.

The work in this thesis is focused on the development and validation of an automotive battery monitoring system that estimates the health of a lead-acid battery during engine cranking and provides a low state of health (SOH) warning of potential battery failure. A reliable SOH estimation should assist users in preventing a sudden battery failure and planning for battery replacement in a timely manner. Most commercial battery health estimation systems use the impedance of a battery to estimate the SOH with battery voltage and current; however, using a current sensor increases the installation cost of a system due to parts and labor. The battery SOH estimation method with the battery terminal voltage during engine cranking was previously proposed. The proposed SOH estimation system intends to improve existing methods. The proposed method requires battery voltages and temperature for a reliable SOH estimation. Without the need for a costly current sensor, the proposed SOH monitoring system is cost-effective and useful for automotive applications. Measurement results presented in this thesis show that the proposed SOH monitoring system is more effective in evaluating the health of a lead-acid battery than existing methods. A low power microcontroller equipped prototype implements the proposed SOH algorithm on a high performance ARM Cortex-M4F based MCU, TM4C123GH6PM. The power dissipation of the final prototype is approximately 144 mW during an active state and 36 mW during a sleep state. With the reliability of the proposed method and low power dissipation of the prototype, the proposed system is suitable for an on-board battery monitoring as there is no on-board warning that estimates the health of a battery in modern cars. / Master of Science

This thesis describes the development of a system to continuously monitor the battery in a car and warn the user of an upcoming battery failure. An automotive battery endures enormous strain when it starts the engine, and when it supplies loads without the engine running. Note that the current during a cranking event often exceeds 500 Amperes. Despite the strains, a car battery still typically lasts 4-6 years before requiring replacement. There is often no warning of when a battery should be replaced and there is never a good time for a battery failure. All currently available lead-acid battery monitoring systems use voltage and current sensing to monitor battery impedance and estimate battery health. However, such a system is costly due to the current sensor and typically requires an expert to operate the system. This thesis describes a prototype system to monitor battery state of health and provide advance warning of an upcoming battery failure using only voltage sensing. The prototype measures the voltage during a cranking event and determines if the battery is healthy or not. The voltage of an unhealthy battery will drop lower than a healthy one, and it will not recover as quickly. The major contributions of the proposed research to the field are an algorithm to predict automotive battery state-of-health that is temperature-dependent and a prototype implementation of the algorithm on an ARM processor development board. / Master of Science

This thesis studies the operating characteristics of lead acid batteries with the intermittent discharging current. Rest time is added periodically on purpose during the battery discharging to observe its impact on the releasable capacity. From the experimental results that take the frequency and the duty-ratio as two variables, batteries with the intermittent discharging at high frequencies or low duty ratios can release more capacity. The results also indicate that the depth of discharge (DOD) affects the intermittent discharging. More capacity is released while approaching the end of the discharging, whereas no clear difference is found in the beginning. Last but not least, the average current is proved experimentally to play a significant role in current discharging. With the same average current, the maximum capacity obtained from the intermittent current discharging is close to that from the constant current discharging.

Ecologist Tom Dale and Vernon Gill Carter Published a book ¡mTopsoil and Civilization¡n in 1955, There is a paragraph in the prolog¡G ¡uCivilized human always can temporarily control the environment mostly. Their main problem caused of the misconceiving that the temporary control can be forever. They misconceive that they are the ¡§dominator of the world¡¨, but don¡¦t realize the rule of the nature at all. Human no matter civilized or not, nevertheless, is the son not the master of nature. If they want to sustain and maintain the ecological environment, their behavior must follow the rule of nature. If they try to evade these rules, the consequence usually ruins the surrounding environment what nurture them. When the environment gets worst rapidly, their civilization declines too.¡v It seems to be a fate, like Morrie said in ¡mTuesday with Morrie¡n¡G¡uEvery one knows he will die, but nobody takes it as real.¡vHuman does not only treat his own life like this way, but also the environment what they survive and live in! From 1992, ¡¦Rome Club¡¦ published the book ¡mThe limit of growth¡n, the consciousness of environmental protection started to head up. Some issues like Ecology of commerce, Sustainable development, Land ethics, Deep ecology and Environmental economic came out one after one. Purely economic and efficient considering of design and production can¡¦t satisfy these kinds of demand. For this sake, International Standard Organization issued out the ISO-14000 series and accepted worldwide gradually. ISO-14040¡GLife Cycle Assessment¡Aevaluating the impact to the environment from material input, manufacturing, transportation, using, recycle, disposal, by other words--- ¡¥from the cradle to grave¡¦. LCA try to use quantitative concept to interpret the environmental impact or damage from human made product. It may provide environmental protection user a systematic thinking to distinguish which product is environmental amity product, which is not; also could be a stand for environment strategy. Applied on the production, it can be a good tool for ¡¥Green Design¡¦ thinking, to reduce the impact to the environment from every stage in production. This thesis is going to study the 6V4Ah Lead acid battery that used widely in the market. Quoting LCA¡¦s indications and SimaPro 4.0 software developed by Pre Consultants B.V. as the database and tools to evaluate the impact and damage to our environment. About the basic data bank, we adopt the local databank built by ITRI (Industrial Technology Research Institute) for years and the data included in SimaPro software. Those are Pre4, PreNL, BUWAL250 and IDEMAT96. Following the analysis procedures as Classification, Normalization, Evaluation by both impact orientation method --- Eco-indicator 95 method and damage orientation method --- Eco-indicator 99 method to evaluate this product¡¦s LCA study. Further more, look forward to provide a potential evaluation way to evaluate and compare to other various batteries.

No description available.

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.

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>