Nos efforts se sont portés sur des fluorophosphates de structure TAVORITE de formule LiMPO4F (M = V, Fe, Ti) et LiVPO4O qui, comparés à d’autres familles structurales de phosphates tels que Li3M2(PO4)3 (NASICON) ou LiFePO4(OH) (Tavorite) possèdent d’excellentes densités d’énergie théorique comme matériaux d’électrodes dans des accumulateurs au Li. Des méthodes de synthèse reproductibles, par voie céramique en tubes scellés et/ou ionothermale (synthèse à basse température), ont été mises au point dans ce travail. Les matériaux ainsi préparés ont été caractérisés en détail par magnétométrie, par RMN et surtout par diffraction des rayons X et des neutrons. Les structures cristallines ont ainsi pu être déterminées ainsi que les mécanismes d’insertion/extraction du Li+, via de nombreuses études par diffraction X insitu lors de la charge/décharge des accumulateurs. / This work focused on TAVORITE-based fluorophosphates LiMPO4F (M = V, Fe, Ti) and LiVPO4O which, when compared with other phosphate structural families such as Li3V2(PO4)3 (NASICON) or LiFePO4(OH) (Tavorite), possess superior energy density as electrode materials for Li batteries. Reproducible synthesis procedures were developed through “classical” ceramic routes in sealed containers and/or low temperature ionothermal reaction. The obtained materials were characterized by magnetometry, solid state NMR and heavily by X-Ray and Neutron diffraction. The crystal structures of all the materials were determined, as well as the mechanisms of Li+ insertion/extraction through insitu X-Ray diffraction during electrochemical charge/discharge of the batteries.

La mesure d'impédance électrique en embarqué sur véhicule est un sujet clé pour améliorer les fonctions de diagnostic d'un pack batterie. On cherche en particulier à fournir ainsi des mesures supplémentaires à celles du courant pack et des tensions cellules, afin d'enrichir les indicateurs de vieillissement dans un premier temps, et d'état de santé et de charge dans un second temps. Une méthode classique de laboratoire pour obtenir des mesures d'impédance d'une batterie est la spectroscopie d'impédance électrochimique (ou EIS). Elle consiste à envoyer un signal sinusoïdal en courant (ou tension) de fréquence variable balayant une gamme de fréquences d'intérêt et mesurer ensuite la réponse en tension (ou courant) pour chaque fréquence. Une technique d'identification active basée sur l'utilisation des signaux large bande à motifs carrés est proposée. En particulier, des simulations ont permis de comparer les performances d'identification de différents signaux d'excitation fréquemment utilisés dans le domaine de l'identification et de vérifier les conditions correspondant à un comportement linéaire et invariant dans le temps de l'élément électrochimique. L'évaluation de la qualité d'estimation est effectuée en utilisant une grandeur spécifique : la cohérence. Cette grandeur statistique permet de déterminer un intervalle de confiance sur le module et la phase de l'impédance estimée. Elle permet de sélectionner la gamme de fréquence où la batterie respecte les hypothèses imposées par la méthode d'identification large bande. Afin de valider les résultats, une électronique de test a été conçue. Les résultats expérimentaux permettent de mettre en valeur l'intérêt de cette approche par motifs carrés. Un circuit de référence est utilisé afin d'évaluer les performances en métrologie des méthodes. L'étude expérimentale est ensuite poursuivie sur une batterie Li-ion soumise à un courant de polarisation et à différents états de charge. Des essais comparatifs avec l'EIS sont réalisés. Le cahier de charge établi à l'aide d'un simulateur de batterie Li-ion a permis d'évaluer les performances de la technique large bande proposée et de structurer son utilité pour l'estimation des états de vieillissement et de charge. / Embedded electrical impedance measurement is a key issue to enhance battery monitoring and diagnostic in a vehicle. It provides additional measures to those of the pack's current and cell's voltage to enrich the aging's indicators in a first time, and the battery states in a second time. A classical method for battery impedance measurements is the electrochemical impedance spectroscopy (EIS). At each frequency, a sinusoidal signal current (or voltage) of a variable frequency sweeping a range of frequencies of interest is at the input of the battery and the output is the measured voltage response (or current). An active identification technique based on the use of wideband signals composed of square patterns is proposed. Particularly, simulations were used to compare the performance of different excitation signals commonly used for system identification in several domains and to verify the linear and time invariant behavior for the electrochemical element. The evaluation of the estimation performance is performed using a specific quantity: the spectral coherence. This statistical value is used to give a confidence interval for the module and the phase of the estimated impedance. It allows the selection of the frequency range where the battery respects the assumptions imposed by the non-parametric identification method. To experimentally validate the previous results, an electronic test bench was designed. Experimental results are used to evaluate the wideband frequency impedance identification. A reference circuit is first used to evaluate the performance of the used methodology. Experimentations are then done on a Li–ion battery. Comparative tests with EIS are realized. The specifications are established using a simulator of Li-ion battery. They are used to evaluate the performance of the proposed wide band identification method and fix its usefulness for the battery states estimation: the state of charge and the state of health.

Les travaux de thèse présentés dans ce manuscrit portent sur l’étude d’électrodes de silicium, matériau prometteur pour remplacer le graphite en tant que matériau actif d’électrode négative pour accumulateur Li-ion. Les mécanismes de (dé)lithiation du silicium sont d’abord étudiés, par Spectroscopie des Electrons Auger (AES). En utilisant cette technique de caractérisation de surface, qui permet d’analyser les particules individuellement dans leur environnement d’électrode, nos résultats montrent que la première lithiation du silicium s’effectue selon un mécanisme biphasé cr-Si / a-Li3,1Si tandis que les processus de (dé)lithiation suivants apparaissent complètement différents et sont du type solution solide. Ces mécanismes d’insertion / désinsertion du lithium conduisent à des variations volumiques importantes des particules de matériau actif lors du cyclage, à l’origine d’une détérioration rapide des performances électrochimiques. En combinant plusieurs techniques de caractérisation, les mécanismes de dégradation d’une électrode de silicium sont étudiés au cours du vieillissement. En utilisant en particulier la spectroscopie d’impédance électrochimique et des analyses par porosimétrie mercure, une véritable dynamique de la porosité de l’électrode est mise en évidence lors du cyclage. Un modèle de dégradation, mettant en cause principalement l’instabilité de la Solid Electrolyte Interphase (SEI) à la surface des particules de silicium, est proposé. Pour tenter de stabiliser cette couche de passivation et ainsi améliorer les performances électrochimiques des électrodes de silicium, l’influence de deux paramètres est étudiée : l’électrolyte et le « domaine de lithiation » du silicium, ce dernier paramètre étant associé à l’évolution de la composition du matériau actif lors du cyclage. A l’issue de ces travaux, des performances prometteuses sont obtenues pour des accumulateurs Li-ion comprenant une électrode de silicium. / The work presented here focuses on electrodes made of silicon, a promising material to replace graphite as an anode active material for Li-ion Batteries (LIBs). The first part of the manuscript is dedicated to the study of silicon (de)lithiation mechanisms by Auger Electron Spectroscopy (AES). By using this technique of surface characterization, which allows investigating individual particles in their electrode environment, our results show that the first silicon lithiation occurs through a two-phase region mechanism cr-Si / a-Li3,1Si, whereas the following (de)lithiation steps are solid solution type process. Upon (de)alloying with lithium, silicon particles undergo huge volume variations leading to a quick capacity fading. By combining several techniques of characterization, the failure mechanisms of a silicon electrode are studied during aging. In particular, by using electrochemical impedance spectroscopy and mercury porosimetry analyses, an impressive dynamic upon cycling of the electrode porosity is shown. A model, which mainly attributes the capacity fading to the Solid Electrolyte Interphase instability at the silicon particles surface, is proposed. To try to stabilize this passivation layer and thus improve silicon electrodes electrochemical performances, the influence of two parameters is studied: the electrolyte and the “lithiation domain” of silicon; the latter is associated with the evolution of the active material composition upon cycling. Finally, by using these last results, promising performances are obtained for silicon electrode containing LIBs.

Afin d'approfondir la compréhension des mécanismes de vieillissement des batteries Li-ion, des analyses post-mortem ont été effectuées sur des cellules commerciales Li-ion C/NMC. Ces autopsies ont révélé des dégradations inattendues qui remettent en question les connaissances actuelles sur les mécanismes de vieillissement de ces cellules. Ainsi, il semble que la réaction parasite des dépôts de Li métallique sur l'électrode en graphite, actuellement associée dans la littérature à des charges à basses températures et / ou à courants élevés, aurait diverses origines selon la chimie et les conditions d'utilisation de la batterie. Dans ce travail de thèse, des dépôts locaux de Li métallique ont été observés sur des cellules vieillies en calendaire à haute température. Paradoxalement, dans des conditions de cyclage à basse température, ce dépôt de Li métallique a résulté de la perte de porosité au niveau de l’électrode négative. Par ailleurs, un modèle de vieillissement semi-empirique, prenant compte les pertes en cyclage ainsi que celles causées par la croissance de la SEI et la polymérisation du biphényl, est proposé. Pour finir, une méthode d'identification des modes de dégradation grâce à des mesures de capacité incrémentale a été entreprise, sur la base du décalage des potentiels de chacune des électrodes. / In order to deepen the understanding of the aging mechanisms of Li-ion batteries, post-mortem investigations were performed on C/NMC Li-ion commercial cells. These autopsies revealed unexpected degradations that question current knowledge about the aging mechanisms of these cells. Thus, it appears that the parasitic reaction of Li metal depositions on the graphite electrode, nowadays associated in the literature with charging at low temperature and / or high C-rates, would have various origins depending on the chemistry and conditions of use of the battery. In this thesis work, local Li deposits were observed on cells aged in calendar at high temperatures, due to the apparition of dry areas. Paradoxically, under low temperature cycling conditions, this Li resulted from anode porosity hindrance. Besides, a semi-empirical aging model, taking into account cycling losses as well as those caused by the SEI growth and the biphenyl polymerization, is proposed. Finally, a method of identifying degradation modes using incremental capacity measurements has been undertaken, based on the potential shifts of each of the electrodes.

In this work we prove two theorems that characterize the hypersurfaces in the unitary sphere of dimension n+1. The first result, obtained by H. Alencar and M. do Carmo, classifies hypersurfaces with constant mean curvature in the sphere. This result was published in April 1994 in Proceedings of The American Mathematical Society, volume 120, number 4 with the title Hypersurfaces with Constant Mean Curvature. The second result was obtained by Li Haizhong in the article Hypersurfaces with Constant Scalar Curvature in Space Forms, published in 1996 in the journal Mathematisch Annalen, volume 305. The theorem of Li Haizhong characterizes hypersurfaces with constant scalar curvature in the sphere. We prove the theorem of Li Haizhong using the results obtained by H. Alencar and M. do Carmo. / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Nesta dissertação apresentamos dois teoremas que caracterizam as hipersuperfícies na esfera unitária de dimensão n+1. O primeiro resultado, obtido por H. Alencar e M. do Carmo, classifica as hipersuperfícies com curvatura média constante na esfera. Este resultado foi publicado em abril de 1994 no Proceedings of The American Mathematical Society, volume 120, número 4 com o título Hypersurfaces With Constant Mean Curvature.O segundo resultado provado nesta dissertação foi obtido por Li Haizhong no artigo Hypersurfaces With Constant Scalar Curvature in Spaces Forms, publicado em 1996 no Mathematische Annalen, volume 305. O Teorema de Li Haizhong caracteriza as hipersuperfícies com curvatura escalar constante na esfera. Demonstraremos o Teorema de Li Haizhong utilizando os resultados obtidos por H. Alencar e M. do Carmo.

A galvanic cell converts chemical energy into electrical energy. Devices that carry out these conversions are called batteries. In batteries, generally the chemical components are contained within the device itself. If the reactants are supplied from an external source as they are consumed, the device is called a fuel cell. A fuel cell converts chemical energy into electrical energy as long as the chemicals are supplied from external reserves. The working principle of a metal-air battery involves the principles of both batteries and fuel cells. The anode of a metal-air cell is stored inside the cell, whereas O2 for the air-electrode is supplied from either atmosphere or a tank. There are several metal-air batteries available academically, which include Zn-air, Alair, Fe-air, Mg-air, Ca-air, Li-air and Na-air batteries. So far, only Zn-air battery is successfully commercialized. Li-air battery is attractive compared to other metal-air batteries because of its high theoretical energy density (11140 Wh kg-1). The energy density of Li-air battery is 3 - 5 times greater than state-of-art Li-ion battery. Li-air (or Li-O2) battery comprises Li-metal as the anode and a porous cathode. The cathode and the anode are separated by a suitable separator soaked in an organic electrolyte. Atmospheric air can enter the battery through the porous cathode. Out of the mixture of gases present in the air, only O2 is electrochemically active. For optimization purpose, most of researchers use pure O2 gas instead of air. Li-air battery is not commercialized till now because of several issues associated with it. The issues include: (i) sluggish kinetics of O2 electrode reaction, (ii) decomposition of the electrolyte during charge-discharge cycling, (iii) formation of Li dendrites, (iv) contamination by moisture, etc. Among these scientific and technical problems related to Li-O2 cell system, studies on rechargeable O2 electrode with fast kinetics of oxygen reduction reaction (ORR) during the cell discharge and oxygen evolution reaction (OER) during charge in non-aqueous electrolytes are important. In non-aqueous electrolytes, the 1-electron reduction of O2 to form superoxide (O2 -) is known to occur as the first step. (ii) Subsequently, superoxide undergoes reduction to peroxide (O2 2-) and then to oxide (O2-). The kinetics of ORR is slow in non-aqueous electrolytes. Furthermore, the reaction needs to be reversible for rechargeable Li-air batteries. In order to realize fast kinetics, a suitable catalyst is essential. The catalyst should be bifunctional for both of ORR and OER in rechargeable battery applications. Noble metal particles have been rarely investigated as catalysts for O2 electrode of Li-O2 cells. Graphene has two-dimensional planar structure with sp2 bonded carbon atoms. It has become an important electrode material owing to its high electronic conductivity and large surface area. It has been investigated for applications such as supercapacitors, Li-ion batteries, and fuel cells. Catalyst nanoparticles prepared and anchored to graphene sheets are expected to sustain discrete existence without undergoing agglomeration and therefore they possess a high catalytic stability for long term experiments as well as applications. In this context, it is intended to explore the catalytic activity of noble metal nanoparticles dispersed on reduced graphene oxide (RGO) for O2 electrode of Li-O2 cells. While a majority of the investigations reported in the thesis involves noble metal and alloy particles dispersed on RGO sheets, results on polypyrrole-RGO composite and also magnesium cobalt silicate for Li-O2 system are included. A chapter on electrochemical impedance analysis of LiMn2O4, a cathode material of Li-ion batteries, is also presented in the thesis. Introduction on electrochemical energy storage systems, in particular on Li-O2 system is provided in the 1st Chapter of the thesis. Synthesis of Ag nanoparticles anchored to RGO and catalytic activity are presented in the 2nd Chapter. Ag-RGO is prepared by insitu reduction of Ag+ ions and graphene oxide in aqueous phase by ethylene glycol as the reducing agent. The product is characterized by powder XRD, UV-VIS, IR, Raman, AFM, XPS, SEM and TEM studies. The SEM images show the layered morphology of graphene and TEM images confirm the presence of Ag nanoparticles of average diameter less than 5 nm anchored to RGO (Fig. 1a). Ag-RGO is investigated for ORR in alkaline (1 M KOH), neutral (1 M K2SO4) and non-aqueous 0.1 M tetrabutyl ammonium perchlorate in dimethyl sulphoxide (TBAP-DMSO) electrolytes. The ORR follows 4e- reduction in aqueous and 1e- reduction pathway in non-aqueous electrolytes. Li-O2 cells are assembled with Ag-RGO as (iii) Fig. 1. (a) TEM image of Ag-RGO and (b) charge-discharge voltage profiles of Li-O2 (Ag-RGO) cells. oxygen electrode catalyst in non-aqueous electrolyte (1 M LiPF6-DMSO) and subjected to charge-discharge cycling at several current densities. The discharge capacity values obtained are 11950 (11.29), 9340 (5.00), and 2780 mAh g-1 (2.47 mAh cm-2) when discharged at 0.2, 0.5, 0.8 mA cm-2, respectively (Fig. 1b). Powder XRD studies of discharged electrodes indicate the formation of Li2O2 and Li2O during the cell discharge. In addition to these studies, Na-O2 cells are also assembled with Ag-RGO in non-aqueous electrolyte. It is concluded that the chemistry Li-O2 and Na-O2 cells are similar except for the capacity values. Metal nanoparticles of Au, Pd and Ir are decorated on RGO sheets by reduction of metal ions on graphene oxide by NaBH4. Au-RGO, Pd-RGO and Ir-RGO are characterized by various physicochemical techniques. Particle size of metal nanoparticles ranges from 2 to Fig.2. Charge-discharge voltage profiles Li-O2(RGO) (i) and Li-O2(Au-RGO) (ii) cells at current density 0.3 mA cm-2. 0 2500 5000 7500 10000 12500 15000 10 nm on graphene sheets. All samples are studied for ORR in aqueous and non-aqueous electrolytes by cyclic voltammetry and rotating disk electrode experiments. Li-O2 cells are assembled in 1 M LiPF6-DMSO and discharge capacity values obtained are 3344, 8192 and 11449 mAh g-1 with Au-RGO, Pd-RGO and Ir-RGO, respectively, at 0.2 mA cm-2 current density. The results of these studies are described in Chapter 3. Synthesis and electrochemical activity of Pt-based alloy nanoparticles (Pt3Ni, Pt3Co and Pt3Fe) on RGO are presented in Chapter 4. The Pt3Ni alloy particles are prepared by simultaneous reduction of Pt4+, Ni2+ and graphene oxide by hydrazine in ethylene glycol medium. Pt3Co-RGO and Pt3Fe-RGO are also prepared similar to Pt3Ni-RGO. Formation of alloys is confirmed with XRD studies. O2 reduction reaction on Pt-alloys in non-aqueous electrolyte follows 1e- reduction to O2 -. RDE results show that Pt3Ni-RGO is a better catalyst than Pt for O2 reduction (Fig. 3). Li-O2 cells are assembled with all samples and subjected to Fig. 3. Linear sweep voltammograms of Pt3Ni-RGO, Pt3Co-RGO and Pt3Fe-RGO in 0.1 M TBAPDMSO with 1600 rpm at 10 mV s-1 scan rate. The area of GC electrode was 0.0314 cm2 with a catalyst mass of 200 μg. charge-discharge cycling at several current densities. The initial discharge capacity values obtained are 14128, 5000 and 10500 mAh g-1 with Pt3Ni-RGO, Pt3Co-RGO and Pt3Fe-RGO, respectively, as the air electrode catalysts. Polypyrrole (PPY) is an attractive conducting polymer with advantages such as high electronic conductivity and electrochemical stability. A combination of advantages of graphene and PPY composite are explained in the Chapter 5. PPY is grown on already synthesized RGO sheets by oxidative polymerization of pyrrole in an acidic PY composite is characterized by XRD and Raman spectroscopy studies. Li-O2 cells are assembled in non-aqueous electrolyte and subjected for charge-discharge cycling at different current densities. The discharge capacity value of Li-O2(PPY-RGO) cell is 3358 mAh g-1 Fig. 4. (a) Discharge-charge performance of Li-O2(PPY-RGO) cell with a current density of 0.2 mA cm-2 limiting to a capacity of 1000 mAh g-1 and (b) variation of cut-off voltages on cycling. (3.94 mAh cm-2) in the first cycle. Li-O2(PPY-RGO) cell delivers 3.7 times greater discharge capacity than Li-O2(RGO) cell. Cycling stability of Li-O2 (PPY-RGO) cell is investigated by charge-discharge cycling by limiting the capacity to 1000 mAh g-1, and the cell voltage at the end of discharge and at the end of charge are found constant at 2.75 and 4.10 V, respectively (Fig. 4 a, b). This study shows that PPY-RGO is stable in Li-O2 cells. Electrochemical impedance study shows that charge-transfer resistant is 500 Ω for freshly assembled Li- O2(PPY-RGO) cell and it decreases to 200 Ω after 1st discharge. Synthesis of magnesium cobalt silicate and its electrochemical activity are presented in Chapter 6. MgCoSiO4 is synthesized by mixed solvothermal approach and characterized by various physicochemical techniques. Cubic shaped MgCoSiO4 is investigated for oxygen evolution reaction (OER) activity in alkaline and neutral media. The current values at 0.95 versus SHE are 43, 0.18, 16 mA cm-2 on MgCoSiO4, bare carbon paper and Pt foil electrodes, respectively (Fig. 5), indicating that MgCoSiO4 is a good catalyst for OER. The onset potential for OER is 0.68 V versus SHE on MgCoSiO4 in 1 M KOH. OER activity on MgCoSiO4 is also studied in K2SO4 and phosphate buffer electrolytes. The results indicate good catalytic activity of MgCoSiO4 in neutral electrolytes also. The catalytic activity of Fig. 5. Cyclic voltammograms of bare carbon paper (i), Pt foil (ii), MgCoSiO4 coated carbon (iii) electrodes in 1 M KOH (sweep rate = 5 mV s-1, loading level = 1.15 mg, area = 0.5 cm-2). MgCoSiO4 towards ORR in aqueous and non-aqueous electrolytes is studied by RDE experiments. Li-O2 cells are assembled with bifunctional MgCoSiO4 catalyst in 1 M LiPF6- DMSO electrolyte and the discharge capacity values obtained are 7721 (8.27), 2510 (1.66) and 1053 mAh g-1 (0.92 mAh cm-2) when discharged at 0.3, 0.5 and 0.8 mA cm-2 current densities, respectively. Electrochemical impedance spectroscopy (EIS) measurements of LiMn2O4 electrode are carried out at different temperatures from -10 to 50 0C and in the potential range from 3.50 to 4.30 V, and the data are analysed in Chapter 7. In the EIS spectra recorded over the frequency range from 100 kHz to 0.01 Hz at different temperatures, there are two semicircles present in the Nyquist plot (Fig. 6a). But in 3.90 to 4.10 V versus Li/Li+(1M) potential range at low temperatures (-10 to 15 oC) range, another semicircle also appears (Fig. 6b). Impedance parameters such as solution resistant (Rs), charge-transfer resistance (Rct), doublelayer capacitance (Cdl), electronic resistance (Re) and Warburg impedance (WR), etc., are obtained by analysis of the EIS data. The variations of resistances with temperature are analysed by Arrhenius-like relationships and the apparent activation energies of the corresponding transport properties are evaluated. The values of activation energy for chargetransfer process are 0.37, 0.30 and 0.42 eV, at 3.50, 3.90 and 4.10 V versus Li/Li+(1M), respectively. The chemical diffusion coefficient of Li+ ions into LiMn2O4 calculated from EIS data. The values of diffusion coefficient calculated are in the range of 2.50 x 10-12 - 4.10 Fig. 6. Nyquist plot of impedance study of Li/LiMn2O4 cell at 3.50 V (a) and 3.90 V (b) at -10 0C. Details of the above studies are described in the thesis.

As novas ligas de alumínio que contém lítio são atraentes devido à sua baixa densidade, alto módulo elástico, elevada resistência mecânica e por terem boa resistência à corrosão em comparação com ligas similares que não contém lítio. A degradação do material devido à fadiga e corrosão são os dois principais fatores que contribuem para o envelhecimento de uma aeronave. O objetivo deste trabalho é estudar a resistência à fadiga de uma nova liga de Al-Li, denominada de AA 2050-T84, considerando os estágios de nucleação e de propagação. No primeiro caso são avaliados o efeito da variação do concentrador de tensão (kt) e o efeito da razão de tensões (R), enquanto que no segundo caso são estudados os efeitos da direção de laminação e da razão de tensões (R) na taxa de propagação da trinca por fadiga. Para o estágio de iniciação é possível observar que quanto maior o valor de R, menor é a vida em fadiga. Para um R constante, o concentrador de tensão reduz significantemente a vida em fadiga. Considerando a vida de propagação de trinca por fadiga, observa-se que, independente da direção de laminação, quanto maior o valor de R, para um mesmo ΔK, maior foi a taxa de propagação de trinca. Para um mesmo R, o expoente m da equação de Paris é maior na direção TL indicando maior velocidade de crescimento de trinca. Independentemente da direção tomada, quanto maior o valor de R maior o valor de m. O modelo matemático utilizado previu muito bem o efeito de R na taxa de propagação de trinca. A liga AA 2050 apresenta resistência à fadiga similar ligas das famílias 2XXX e 7XXX e similar a da liga Al-Li AA 2198 T8. / The new Al-Li alloys are very attractive due to its low density, high elastic modulus, increased mechanical strength, as well as good corrosion resistance in comparison with similar alloys that don\'t contain lithium. The material\'s degradation due to fatigue and corrosion are the main factors of aircrafts aging, and it is quite important to take them in account to guarantee the aircraft structural integrity. The aim of this work is to study the fatigue strength of a new Al-Li alloy, denominated as AA 2050 T84, considering both nucleation and propagation fatigue lives. In the first case were evaluated the effect of the variation of the stress concentrator (kt) and the effect of the stress ratio (R), while in the propagation life were considered the effect of the rolling direction and the stress ratio (R). From the initiation life results, it is possible to observe that as higher was R, lower is fatigue life and that the intensity of the stress concentrator reduces fatigue life significantly, independent of the R value. The results from the propagation life shows that in both LT e TL directions and for a constant ΔK, higher R induces larger fatigue crack propagation rates. Considering a constant R, the TL direction presents a larger exponent m of Paris equation, which is an indicative of higher larger crack propagation rate. Also, larger R causes larger m, independently of the rolling direction. The mathematical model used was able to take in account the R effect on the crack propagation rate. Considering the more traditional Al alloys from 2XXX and 7XXX families, and the Ali-Li alloys AA 2198 T8, the AA 2050 presented a quite similar fatigue behavior.

Ces travaux ont permis d’approfondir les connaissances du mécanisme de déchargepeu conventionnel de l’accumulateur Li/S et de ses limitations. L’ensemble desrésultats a convergé vers une unique conclusion, à savoir que le système Li/S estprincipalement limité par le phénomène de passivation de l’électrode positive en finde décharge. Les polysulfures de lithium à chaines courtes précipitent à la surface del’électrode positive de soufre. Isolants électroniques, ils sont responsables de la perteprogressive de surface active de l’électrode et de la fin prématurée de la décharge.Ainsi, les performances électrochimiques ont pu être significativement améliorées entravaillant sur la morphologie de l’électrode positive, et sur la composition del’électrolyte. En augmentant la surface spécifique de l’électrode, la quantité depolysulfures de lithium qui peut précipiter en fin de décharge est augmentée, et lapassivation totale de l’électrode est retardée. En augmentant la solubilité despolysulfures de lithium dans l’électrolyte, la précipitation des espèces est retardée etla décharge prolongée. Dans cette optique, les solvants de type PEGDME semblentêtre les plus prometteurs à ce jour. Enfin, un mécanisme possible de réduction dusoufre en électrolyte de type éther a pu être proposé. / This work aimed at better understanding the Li/S cell discharge mechanism and itslimiting parameters. A general conclusion was following from these data: the Li/Ssystem is mainly limited by the passivation process of the sulfur positive electrode,occurring at the end of discharge. Insulating lithium polysulfides precipitate on thepositive electrode surface, thus leading to a gradual loss of the electrode activesurface and to the early end of discharge. As a consequence, the electrochemicalperformances can be significantly improved by working either on the positiveelectrode morphology or on the organic electrolyte composition. Increasing thespecific surface of the positive electrode enables to increase the amount ofpolysulfide compounds that can precipitate on the electrode, thus delaying the fullpassivation of the sulfur electrode and the end of discharge. Working on the organicelectrolyte composition enables to increase the polysulfide solubility and to preventthem from quickly precipitating, thus delaying the end of discharge too. To thispurpose, PEGDME solvents seem to be quite promising. Finally, a possiblemechanism for sulfur reduction in ether-based electrolytes could be proposed.

Les travaux présentés dans cette thèse concernent l'étude thermique des batteries Li-ion en vue d'une application de gestion thermique pour l'automobile. La compréhension des phénomènes thermiques à l'échelle accumulateur est indispensable avant de réaliser une approche de type module ou pack batterie. Ces phénomènes thermiques sont mis en évidence à partir d'une modélisation thermique globale de deux accumulateurs de différentes chimies, en décharge à courant constant. La complexité du caractère résistif de l'accumulateur Li-ion a mené au développement d'un modèle prenant en compte l'interaction entre les phénomènes électrochimiques et thermiques, permettant une approche prédictive de son comportement. Enfin la réalisation de deux boucles expérimentales, de simulation de systèmes de gestion thermique d'un module de batterie, montre les limites d'un refroidissement classique par air à respecter les critères de management thermique. En comparaison, le second système basé sur l'intégration innovante d'un matériau à changement de phase (MCP) se montre performant lors de situations usuelles, de défauts ou encore lors du besoin d'une charge rapide de la batterie. / This work relates to the thermal study of Li-ion batteries in order to develop an optimized battery thermal management system. The understanding of thermal phenomena at cell scale is essential before to undertake an approach of the battery module or pack. Galvanostatic discharges of two kind of Li ion cells are modeled to highlight thermal phenomena. The complexity of the resistive behavior of Li-ion cell led to the development of an electrochemical-thermal coupled model to get a predictive approach. Then, two experimental tests benches were designed so as to compare two battery thermal management systems (BTMS). Restrictions of air cooling highlight its disability to achieve thermal management criteria. Innovative integration of a phase change material (PCM) was then tested under several uses of the battery module. This new BTMS showed really promising performances during intensive driving cycles, failure tests, and when a fast charge is needed.

Submitted by Juliane Andrade (juliane.a.andrade@gmail.com) on 2018-09-25T12:53:53Z No. of bitstreams: 1 DissertacaoFinalJulianeAndrade.pdf: 2648304 bytes, checksum: 0feea2eb88019ffdafb37180bd261f3b (MD5) / Approved for entry into archive by Joana Martorini (joana.martorini@fgv.br) on 2018-09-25T15:17:07Z (GMT) No. of bitstreams: 1 DissertacaoFinalJulianeAndrade.pdf: 2648304 bytes, checksum: 0feea2eb88019ffdafb37180bd261f3b (MD5) / Approved for entry into archive by Suzane Guimarães (suzane.guimaraes@fgv.br) on 2018-09-25T16:40:46Z (GMT) No. of bitstreams: 1 DissertacaoFinalJulianeAndrade.pdf: 2648304 bytes, checksum: 0feea2eb88019ffdafb37180bd261f3b (MD5) / Made available in DSpace on 2018-09-25T16:40:46Z (GMT). No. of bitstreams: 1 DissertacaoFinalJulianeAndrade.pdf: 2648304 bytes, checksum: 0feea2eb88019ffdafb37180bd261f3b (MD5) Previous issue date: 2018-08-16 / Esse trabalho apresenta análise combinada entre a macroeconomia e a estrutura a termo das taxas de juros, através de duas modelagens distintas. Primeiramente, utiliza-se o modelo Novo Keynesiano de pequeno porte, que é combinado com o modelo dinâmico de Nelson-Siegel. Em seguida estima-se o modelo dinâmico de Nelson-Siegel integrado com variáveis macroeconômicas. São empregados dados mensais referentes aos contratos futuros de DI, de Setembro de 2002 a Dezembro de 2017. A comparação das modelagens mostra que o modelo combinado apresenta resultados mais consistentes do que o modelo integrado. / This paper aims to present a combined analysis between macroeconomics and the term structure of interest rates, through two different models. Firstly, a small New Keynesian model is used, which is combined with the dynamic Nelson-Siegel model. Then the NelsonSiegel dynamic model integrated with macroeconomic variables is estimated. Monthly data on DI futures contracts are used from September 2002 to December 2017. Comparison of modeling shows that the combined model presents more consistent results than the integrated model.