This thesis deals with the problematic of lead acid batteries for HEVs. It starts with classification of electrochemical cells then proceeds to focus on lead acid batteries, mainly because they are the most used source of electrical power in automotive industry. The practical part of the work describes the process of manufacturing the electrode system used in the later parts. The experimental part is focused on the behaviour of the cells under conditions that appear in hybrid electric vehicles. The effect of aditives in active matter of the negative electrode on the parameters of the cells is observed, such as voltage, capacity and operating life

This diploma thesis is focused on in-situ analysis of the composition of the negative electrodes of second secondary cells with using X-ray radiation. The first part is dedicated to the theory of lead accumulators, including charging, discharging, battery components and individual degradation mechanisms. The main part of the thesis includes the preparation of electrochemical in situ XRD cells and following measurement of the growth of lead sulphate crystals on the OCV potential. Furthermore, the lead cell was subjected to the measurement of the cyclic voltammetry around the working point of the negative electrodes. From these measurements was evident gradual increase of the lead sulfate crystals. The analysis was supplemented with electron microscopy images. In addition, were evaluated the in-situ particle analysis of the LTO Sigma sample.

La pile à combustible directe à borohydrures (DBFC en anglais), qui est une sous-catégorie des piles à combustible alcalines, bénéficie des avantages de son combustible, le borohydrure de sodium (NaBH4), qui confère à ce système des caractéristiques thermodynamiques et énergétiques très intéressantes. Cependant, la réaction d’électrooxydation de NaBH4 (BOR en anglais) est très complexe et reste à ce jour encore peu étudiée et mal comprise sur la majorité des électrocatalyseurs (la plupart étant sous forme de nanoparticules métalliques supportées sur des noirs de carbone). De plus, de récentes études ont montré l’agressivité du milieu alcalin sur la durabilité des électrocatalyseurs conventionnels, révélant une grande perte de surface catalytique active, due principalement à un détachement des nanoparticules du support carboné. Dans ce contexte, ces travaux de thèse se sont orientés vers trois axes d’étude : (i) l’étude de la BOR sur des électrocatalyseurs à base de palladium dans des conditions proches des conditions réelles de fonctionnement de la DBFC ; (ii) l’étude de l’impact de la structure de l’anode sur les performances globales de la DBFC, et (iii) l’étude du mécanisme de dégradation d’électrocatalyseurs à base de métaux nobles dans un environnement alcalin. Les expérimentations ont été réalisées en étroite collaboration avec le U.S. Naval Research Laboratory (Washington, USA).Les résultats obtenus ont montré qu’une grande concentration en NaBH4 entraine un ralentissement de la cinétique de la réaction, due en partie à un fort empoisonnement de la surface catalytique. Par ailleurs, des marqueurs d’activité pour la BOR ont été proposés. Ensuite, l’utilisation d’électrodes à gradient de catalyseurs s’est avérée être une solution prometteuse pour mieux valoriser l’hydrogène produit via des réactions secondaires à la BOR. Enfin, l’utilisation de la spectroscopie infrarouge à transformée de Fourier couplée à de la microscopie électronique en transmission à localisation identique a permis de détecter la formation de carbonates au cours d’un test de vieillissement accéléré d’électrocatalyseurs à base de métaux nobles en milieu alcalin. Ce mécanisme explique, en partie, le détachement des nanoparticules observé au cours du test. / The direct borohydride fuel cell (DBFC), a subclass of alkaline fuel cells, benefits from the advantages of its fuel, sodium borohydride (NaBH4), which exhibits very interesting thermodynamic and energetic characteristics. However, the NaBH4 electrooxidation reaction (BOR) is very complex; to date it remains poorly studied and understood on many electrocatalysts (most of them are in the form of metal nanoparticles supported on carbon black). In addition, recent studies reported the aggressiveness of the alkaline medium on the durability of conventional carbon-supported electrocatalysts, revealing a large loss of the active catalytic surface, mainly due to the detachment of nanoparticles from the carbon support. In this context, this thesis focused on three main areas of study: (i) the study of the BOR on palladium-based electrocatalysts in conditions close to the real operating conditions of the DBFC; (ii) the study of the impact of the anode structure on the overall performance of the DBFC, and (iii) the study of the degradation mechanism of noble metal electrocatalysts in alkaline environment. The experiments were carried out in close collaboration with the U.S. Naval Research Laboratory (Washington, USA).The results obtained showed that a high concentration of NaBH4 leads to a decrease of the reaction kinetics, due in part to poisoning of the catalytic surface. In addition, activity markers for the BOR have been proposed. Then, the use of catalysts-gradient electrodes proved to be a promising solution to better valorize the hydrogen produced via side reactions of the BOR. Finally, the use of Fourier transform infrared spectroscopy coupled with identical-location transmission electron microscopy enabled to detect the formation of carbonates during the accelerated stress test of carbon-supported noble metal electrocatalysts in alkaline medium, explaining, in part, the detachment of nanoparticles observed during the test.

De nombreux exemples de matériaux composites obtenus par l’association de fibres végétales et de polymères ont permis des allègements conséquents de structures dans divers domaines d’application. Cependant, la question demeure quant de la durabilité de ces pièces en service, essentiellement par manque de connaissances sur le vieillissement des fibres végétales, sur leurs interactions avec la matrice polymère et sur le comportement hydrothermique des composites biosourcés au cours du temps. Dans cette étude, nous avons étudié les cinétiques et mécanismes de sorption du matériau composite afin d’appréhender son comportement hydrique lors des vieillissements hydrothermiques par immersion dans l’eau à 23°C et 70°C. Cette étude a mis en évidence l’influence des fibres végétales sur les grandeurs caractéristiques de l’absorption en eau du matériau composite : forte prise en eau, gonflement anisotrope. Elle a également permis l’identification des mécanismes de dégradation des fibres de lin ; le rôle très nocif des résidus d’écorce rappelle l’importance du rouissage et du défibrage sur les performances de ces fibres. L’étude du comportement des constituants et du composite confrontés à des vieillissements hydrothermiques a ensuite été entreprise afin d’identifier et quantifier l’influence de chacun des matériaux constitutifs, ainsi que leur synergie. Il en ressort que la détérioration des fibres de lin est la principale cause de l’abattement des propriétés mécaniques du matériau composite. Si une immersion à 23°C pendant 70 jours n’a que peu d’effet sur les propriétés mécaniques, l’élévation de la température à 70°C induit des endommagements importants dès 14 jours d’immersion. La destruction des parois cellulaires et la dégradation des interfaces fibre/matrice sous l’effet de la présence d’eau détériorent le transfert de charge matrice/fibre. La corrélation entre les vieillissements accélérés et naturel a fait ressortir une similitude entre le maintien pendant 70 jours dans l’eau à 23°C et l’exposition aux conditions naturelles pendant 24 mois ; l’immersion à 70°C s’avère trop sévère. Une solution d’amélioration serait d’accentuer le rouissage des fibres afin de supprimer davantage les composés pectiques de la lamelle mitoyenne et de la paroi primaire. L’élimination de ces composés facilement hydrolysables par l’eau permettrait de prétendre à une meilleure qualité de l’interface fibres/matrice tout au long du vieillissement. / A great number of plant fiber – reinforced polymer composites allowed substantial lightening of structures in various fields of application. However, the question remains about the durability of these parts in service, mainly for lack of knowledge about the aging of plant fibers, their interactions with the polymer matrix and the hydrothermal behavior of biosourced composites over time. In this work, water absorption mechanisms and kinetics by the composite material are studied in order to understand the hydric behavior during hydrothermal aging by immersion in deionized water at 23°C or 70°C. The results show that water absorption by the composite is characterized by a high water uptake and an anisotropic swelling. It also allowed the identification of the degradation mechanisms of flax fibers; the very harmful role of bark residues recalls the importance of retting and decortication on the performance of these fibers.The investigation of the behaviors of the constituents and the composite under hydrothermal aging was then undertaken with the aim to identify and quantify the influence of each on the constituent materials, as well as their synergy. It shows that the deterioration of the flax fibers is the main cause of the reduction of the mechanical properties of the composite. If immersion at 23 ° C for 70 days has little effect on the mechanical properties, raising the temperature to 70 ° C induces significant damage from 14 days of immersion. The destruction of the cell walls and the degradation of the fiber/matrix interfaces due to water deteriorate the load transfer efficiency by the fiber/matrix interface. The correlation between accelerated and natural aging showed a similarity between holding for 70 days in water at 23 ° C and exposure to natural conditions for 24 months; immersion at 70 ° C is too severe. An improvement solution would be to increase the retting of the fibers in order to further remove the pectic compounds from the middle lamella and the primary wall. The elimination of these compounds easily hydrolysable by water would claim to a better quality of the fiber / matrix interface throughout aging.

Un objectif important des études de la compatibilité électromagnétique (CEM) est de rendre les produits conformes aux exigences CEM des clients ou les normes. Cependant, toutes les vérifications de la conformité CEM sont appliquées avant la livraison des produits finis. Donc nous pourrions avoir de nouvelles questions sur les performances CEM des systèmes électroniques au cours de leur vie. Les comportements CEM de ces produits seront-ils toujours conformes dans plusieurs années ? Un produit peut-il garder les mêmes performances CEM pendant toute sa durée de vie ? Si non, combien de temps la conformité CEM peut-elle être maintenue ?L'étude à long terme de l'évolution des niveaux CEM, appelée "robustesse électromagnétique», est apparue ces dernières années. Les travaux précédents ont montré que la dégradation causée par le vieillissement pourrait induire des défaillances de système électronique, y compris une évolution de la compatibilité électromagnétique. Dans cette étude, l'évolution à long terme des niveaux CEM de deux groupes de composants électroniques a été étudiée. Le premier type de composant électronique est le circuit intégré. Les courants de hautes fréquences et les tensions induites au cours des activités de commutation de circuits intégrés sont responsables des émissions électromagnétiques non intentionnelles. En outre, les circuits intégrés sont aussi très souvent les victimes d'interférences électromagnétiques. Un autre groupe de composants est formé par les composants passifs. Dans un système électronique, les circuits intégrés fonctionnent souvent avec les composants passifs sur un même circuit imprimé. Les fonctions des composants passifs dans un système électronique, telles que le filtrage et le découplage, ont également une influence importante sur les niveaux de CEM.Afin d'analyser l'évolution à long terme des niveaux CEM des composants électroniques, les travaux présentés dans cette thèse ont pour objectif de proposer des méthodes générales pour prédire l'évolution dans les temps des niveaux de compatibilité électromagnétique des composants électroniques. / One important objective of the electromagnetic compatibility (EMC) studies is to make the products compliant with the EMC requirement of the customers or the standards. However, all the EMC compliance verifications are applied before the delivery of final products. So we might have some new questions about the EMC performance during their lifetime. Will the product still be EMC compliant in several years? Can a product keep the same EMC performance during its whole lifetime? If not, how long the EMC compliance can be maintained? The study of the long-term EMC level, which is called “electromagnetic robustness”, appeared in the recent years. Past works showed that the degradation caused by aging could induce failures of electronic system, including a harmful evolution of electromagnetic compatibility. In this study, the long-term evolution of the EMC levels of two electronic component groups has been studied. The first electronic component type is the integrated circuit. The high-frequency currents and voltages during the switching activities of ICs are responsible for unintentional emissions or coupling. Besides, ICs are also very often the victim of electromagnetic interference. Another group of components is the passive component. In an electronic system, the IC components usually work together with the passive components at PCB level. The functions of passive components in an electronic system, such as filtering and decoupling, also have an important influence on the EMC levels.In order to analyze the long-term evolution of the EMC level of the electronic components, the study in this thesis tends to propose general predictive methods for the electromagnetic compatibility levels of electronic components which evolve with time.

Fuel cells are known for their high efficiency and have the potential to become a major technology for producing clean energy, especially when the fuel, e.g. hydrogen, is produced from renewable energy sources such as wind or solar. Currently, the two main obstacles to wide-spread commercialization are their high cost and the short operational lifetime of certain components. Polymer electrolyte membrane (PEM) fuel cells have been a focus of attention in recent years, due to their use of hydrogen as a fuel, their comparatively low operating temperature and flexibility for use in both stationary and portable (automotive) applications. Perfluorosulfonic acid membranes are the leading ionomers for use in PEM hydrogen fuel cells. They combine essential qualities, such as high mechanical and thermal stability, with high proton conductivity. However, they are expensive and currently show insufficient chemical stability towards radicals formed during fuel cell operation, resulting in degradation that leads to premature failure. The incorporation of durability improving additives into perfluorosulfonic acid membranes is discussed in this work. iv Cerium oxide (ceria) is a well-known radical scavenger that has been used in the biological and medical field. It is able to quench radicals by facilely switching between its Ce(III) and Ce(IV) oxidation states. In this work, cerium oxide nanoparticles were added to perfluorosulfonic acid membranes and subjected to ex-situ and in-situ accelerated durability tests. The two ceria formulations, an in-house synthesized and commercially available material, were found to consist of crystalline particles of 2 – 5 nm and 20 – 150 nm size, respectively, that did not change size or shape when incorporated into the membranes. At higher temperature and relative humidity in gas flowing conditions, ceria in membranes is found to be reduced to its ionic form by virtue of the acidic environment. In ex-situ Fenton testing, the inclusion of ceria into membranes reduced the emission of fluoride, a strong indicator of degradation, by an order of magnitude with both liquid and gaseous hydrogen peroxide. In open-circuit voltage (OCV) hold fuel cell testing, ceria improved durability, as measured by several parameters such as OCV decay rate, fluoride emission and cell performance, over several hundred hours and influenced the formation of the platinum band typically found after durability testing.

L’oxydation photocatalytique des Composés Organiques Volatils (COVs) apparaît comme un procédé très prometteur pour la réduction de la pollution atmosphérique. Ce travail avait pour objectif d’étudier l’oxydation photocatalytique de plusieurs COVs au sein d’un réacteur annulaire: méthyléthylcétone (MEK), acétone, 1-propanol ou encore triéthylamine (TEA). Dans une première partie, l’influence de plusieurs paramètres cinétiques tels que la concentration en polluant, l’intensité lumineuse, le temps de contact et le taux d’humidité a été étudiée. Un mécanisme de dégradation photocatalytique a été établi pour chaque polluant en fonction des sous-produits détectés par GC/MS. Dans une seconde partie, la diffusion de radicaux hydroxyles OH• dans la phase gazeuse, après activation photonique du TiO2, a été mise en évidence par Fluorescence Induite par Laser (LIF). Pour la première fois, ces radicaux OH• ont été détectés à des pressions proches des conditions atmosphériques. Dans ce cas, nous pouvons en conclure que la dégradation photocatalytique des COVs pourrait être partiellement due à une réaction en phase gazeuse entre les COVs et les radicaux OH• / Photocatalytic oxidation of airborne contaminants appears to be a promising process for remediation of air polluted by Volatile Organic Compounds (VOCs). The aim of our study is the photocatalytic oxidation of several VOCs using an annular reactor: methylethylketone (MEK), acetone, 1-propanol and triethylamine (TEA). First, the influence of different kinetic parameters such as pollutant concentration, incident light irradiance, contact time and humidity has been studied. A mechanistic pathway has been indeed proposed for each pollutant according to the produced intermediates species detected by GC/MS. Second, the diffusion of hydroxyls radicals OH• in gas phase, after photonic activation of TiO2, has been highlighted using Laser-Induced Fluorescence (LIF). For the first time, OH• radicals have been detected at atmospheric pressures, close to the major photocatalytic oxidation conditions, leading to the assumption that the photocatalytic degradation of VOCs might be at least partially occurs between pollutants and OH• radicals in gas-phase

Chromatography and extraction techniques, and also chemiluminescence have been utilized to develop new rapid and informative tools in the evaluation of long-term properties and environmental effects of polymeric materials. Methods were developed for classification of materials and for early and rapid degradation detection. Degradable polyethylene films were classified on the basis of their incorporated prooxidant systems using chromatographic fingerprinting of carboxylic acids, the dominating type of degradation product. The fingerprints were also shown to be useful for prediction of the degradation states and evaluation of the degradation mechanisms. Classification and prediction models were obtained by Multivariate Data Analysis, where the diacids were grouped according to both their type of prooxidant system and their state of degradation. The use of total luminescence intensity (TLI) measurements was also investigated as a means of classifying films and for the early detection of degradation. Comparisons were carried out with common techniques, e.g. FTIR and DSC, after both thermal and UV oxidation. TLI gave an earlier detection of degradation and was more sensitive than carbonyl index and crystallinity measurements to relative differences in degradation between the materials. It furthermore offered complementary information regarding changes in activation energies during the course of the degradation. The results were compared with the chromatographic fingerprints. A new way to evaluate the low temperature long-term stabilisation efficiency of antioxidants was investigated. A prooxidant was used to obtain catalytic oxidation, instead of using thermal acceleration, to evaluate the stabilisation efficiency of antioxidants at low temperatures but still during reasonably short aging times. Comparisons were made between polypropylene films stabilised with primary antioxidants (Irganox 1076, Irganox 1010 and α-tocopherol) with and without the prooxidant manganese stearate at different temperatures. The relative efficiencies of the antioxidants obtained under prooxidant acceleration test correlated better than thermal acceleration test with the results of a long-term low temperature test. Additives in plastic packaging materials may affect the environment after migration from the packaging to e.g. their contents, especially if they consist of organic aqueous solutions or oils. The use of Solid-Phase Microextraction (SPME) for the specific task of extraction from an organic aqueous solution such as a simulated food or pharmaceutical solution consisting of 10 vol-% ethanol in water was investigated. Methods were developed and evaluated for extraction both with direct sampling and with headspace sampling. If the extraction method and temperature were selected to suit the concentration levels of the analytes, it was possible to quantify several degradation products simultaneously. Comparisons made with Solid Phase Extraction showed the advantage of SPME for this purpose. / QC 20100929

Les travaux de cette thèse portent sur la simulation de la dégradation des paramètres électriques des transistors MOS et bipolaires sous stress statiques et dynamiques. Cette étude a été menée à l’aide d’un outil de simulation de fiabilité développé en interne. Selon la technologie MOS ou bipolaire, les mécanismes étudiés ont été successivement : Hot Carrier Injection, Bias Temperature instability, Mixed Mode et Reverse base emitter bias. L’investigation a été aussi étendue au niveau circuit. Nous nous sommes ainsi intéressés à l’effet de la dégradation des transistors sur la fréquence d’un oscillateur en anneau et les performances RF d’un amplificateur faible bruit. Les circuits ont été soumis à des contraintes DC , AC et RF. La prédictibilité, établie de ces dégradations, a été validée par des essais de vieillissement expérimentaux sur des démonstrateurs encapsulés et montés sur PCB. Les résultats de ces études ont permis de valider la précision du simulateur et la méthode de calcul quasi-statique utilisée pour calculer les dégradations sous stress dynamiques. Ces travaux de recherche ont pour but d’inscrire cette approche prédictive dans un flot de conception de circuits afin d’assurer leur fiabilité. / The work of this thesis focuses on the simulation of the electrical parameters degradation of MOS and bipolar transistors under static and dynamic stresses. This study was conducted using an in-house reliability simulation tool. According to the MOS or bipolar technology, the studied mechanisms were successively: Hot Carrier Injection, Bias Temperature instability, Mixed Mode and Reverse base emitter bias. The investigation was then extended to circuit-level. The effect of transistors degradation on a ring oscillator frequency and the RF performances of a low noise amplifier were investigated. The circuits were subjected to DC, AC and RF constraints. Predictability of these degradations has been validated by experimental aging tests on encapsulated and PCB-mounted demonstrators. The results of these studies proved the accuracy of the simulator and validated the quasi-static calculation method used to predict the degradation under dynamic stress. The goal of this research is to embed this predictive approach into a circuit design flow to ensure its reliability.

The growing urgency of climate change has led to growth in the electrification technology field, where batteries have emerged as an essential role in the renewable energy transition, supporting the implementation of environmentally friendly technologies such as smart grids, energy storage systems, and electric vehicles. Battery cell degradation is a common occurrence indicating battery usage. Optimizing lithium-ion battery degradation during operation benefits the prediction of future degradation, minimizing the degradation mechanisms that result in power fade and capacity fade. This degree project aims to investigate battery degradation prediction based on capacity using deep learning methods. Through analysis of battery degradation and health prediction for lithium-ion cells using non-destructive techniques. Such as electrochemical impedance spectroscopy obtaining ECM and three different deep learning models using multi-channel data. Additionally, the AI models were designed and developed using multi-channel data and evaluated performance within MATLAB. The results reveal an increased resistance from EIS measurements as an indicator of ongoing battery aging processes such as loss o active materials, solid-electrolyte interphase thickening, and lithium plating. The AI models demonstrate accurate capacity estimation, with the LSTM model revealing exceptional performance based on the model evaluation with RMSE. These findings highlight the importance of carefully managing battery charging processes and considering factors contributing to degradation. Understanding degradation mechanisms enables the development of strategies to mitigate aging processes and extend battery lifespan, ultimately leading to improved performance.