Les estimations précises des états de charge (« State of Charge » - SoC) et de santé (« State of Health » - SoH) des batteries au lithium sont un point crucial lors d’une utilisation industrielle de celles-ci. Ces estimations permettent d’améliorer la fiabilité et la robustesse des équipements embarquant ces batteries. Cette thèse CIFRE est consacrée à la recherche d’algorithmes de détermination de l’état de santé de batteries lithium-ion, en particulier de chimie Lithium Fer Phosphate (LFP) et Lithium Manganèse Oxyde (LMO).Les recherches ont été orientées vers des solutions de détermination du SoH directement embarquables dans les calculateurs des véhicules électriques. Des contraintes fortes de coût et de robustesse constituent ainsi le fil directeur des travaux.Or, si la littérature actuelle propose différentes solutions de détermination du SoH, celles embarquées ou embarquables sont encore peu étudiées. Cette thèse présente donc une importante revue bibliographique des différentes méthodes d’estimation du SoH existantes, qu’elles soient embarquables ou non. Le fonctionnement détaillé ainsi que les mécanismes de vieillissement d’une batterie lithium-ion sont également explicités.Une partie majoritaire des travaux est consacrée à l’utilisation de l’analyse incrémentale de la capacité (« Incremental Capacity Analysis » - ICA) en conditions réelles, c’est-à-dire avec les niveaux de courant présents lors d’un profil de mission classique d’un véhicule électrique, avec les mesures disponibles sur un BMS (« Battery Management System ») industriel et avec les contraintes de robustesses associées, notamment une gamme étendue de température de fonctionnement. L’utilisation de l’ICA pour déterminer la capacité résiduelle de la batterie est mise en œuvre de façon totalement innovante et permet d’obtenir une grande robustesse aux variations des conditions d’utilisation de la batterie.Une seconde méthode est, elle, dédiée à la chimie LMO et exploite le fait que le potentiel aux bornes de la batterie soit représentatif de son état de charge. Un compteur coulométrique partiel est ainsi proposé, intégrant une gestion dynamique des bornes d’intégration en fonction de l’état de la batterie.A l’issue des travaux, une méthode complète et précise de détermination du SoH est disponible pour chacune des chimies LFP et LMO. La détermination de la capacité résiduelle de ces deux familles de batteries est ainsi possible à 4 % près. / Accurate lithium-ion battery State of Charge (SoC) and State of Health (SoH) estimations are nowadays a crucial point, especially when considering an industrial use. These estimations enable to improve robustness and reliability of hardware using such batteries. This thesis focuses on researching lithium-ion batteries state of health estimators, in particular considering Lithium Iron Phosphate (LFP) and Lithium Manganese Oxide (LMO) chemistries.Researches have been targeted towards SoH estimators straight embeddable into electric vehicles (EV) computers. Cost and reliability constraints are thus the main guideline for this work.Although existing literature offers various SoH estimators, those who are embedded or embeddable are still little studied. A complete literature review about SoH estimators, embedded or not, is therefore proposed. Lithium-ion batteries detailed operation and ageing mechanisms are also presented.The main part of this work is dedicated to Incremental Capacity Analysis (ICA) use with electric vehicle constraints, such as current levels available with a typical EV mission profile or existing measurements on the Battery Management System (BMS). Incremental Capacity Analysis is implemented in an innovative way and leads to a remaining capacity estimator with a high robustness to conditions of use variations, including an extended temperature range.A second method, dedicated to LMO chemistry, take advantage of the fact that the battery potential is representative of its state of charge. Partial Coulomb counting is thus performed, with a dynamic management of integration limits, depending on the battery state.Outcomes of this work are two complete and accurate SoH estimators, one for each chemistry, leading to a remaining capacity estimation accurate within 4 %.

Le développement futur des véhicules électriques est lié à l’amélioration des performances des batteries qu’ils contiennent. Parallèlement aux recherches sur les nouveaux matériaux ayant des performances supérieures en termes d'énergie, de puissance, de durabilité et de coût, il est nécessaire développer des outils de modélisation pour : (i) simuler l'intégration de la batterie dans la chaine de traction et (ii) pour le système de gestion de la batterie, afin d'améliorer la sécurité et la durabilité. Soit de façon directe (par exemple, la prévention de surcharge ou de l’emballement thermique) soit de façon indirecte (par exemple, les indicateurs de l’état de charge). Les modèles de batterie pourraient aussi être utilisés pour comprendre les phénomènes physiques et les réactions chimiques afin d'améliorer la conception des batteries en fonction des besoins de l’utilisateur et de réduire la durée des phases de test. Dans ce manuscrit, un des modèles les plus communs décrivant les électrodes poreuses des batteries au lithium-ion est revisité. De nombreuses variantes dans la littérature s’inspirent directement du travail mené par le professeur J. Newman et son équipe de chercheurs à l’UC Berkeley. Pourtant relativement peu d’études analysent en détail les capacités prédictives de ce modèle. Dans ce travail, pour étudier ce modèle, toutes les grandeurs physiques sont définies sous une forme adimensionnelle, comme on l'utilise couramment dans la mécanique des fluides : les paramètres qui agissent de manière identique ou opposée sont regroupés et le nombre total de paramètres du modèle est considérablement réduit. Cette étude contient une description critique de la littérature incluant le référencement des paramètres du modèle développé par le groupe de Newman et les techniques utilisées pour les mesurer, ainsi que l’écriture du modèle dans un format adimensionnel pour réduire le nombre de paramètres. Une partie expérimentale décrit les modifications de protocoles mis en œuvre pour améliorer la reproductibilité des essais. Les études effectuées sur le modèle concernent d’une part l’identification des états de lithiation dans la cellule avec un attention particulière sur la précision obtenue, et enfin une prospection numérique pour examiner l’influence de chaque paramètre sur les réponses de la batterie en décharge galvanostatique puis en mode impulsion et relaxation. / The future development of electric vehicles is mostly dependent of improvements in battery performances. In support of the actual research of new materials having higher performances in terms of energy, power, durability and cost, it is necessary to develop modeling tools. The models are helpful to simulate integration of the battery in the powertrain and crucial for the battery management system, to improve either direct (e.g. preventing overcharges and thermal runaway) and indirect (e.g. state of charge indicators) safety. However, the battery models could be used to understand its physical phenomena and chemical reactions to improve the battery design according with vehicles requirements and reduce the testing phases. One of the most common model describing the porous electrodes of lithium-ion batteries is revisited. Many variants available in the literature are inspired by the works of prof. J Newman and his research group from UC Berkeley. Yet, relatively few works, to the best of our knowledge, analyze in detail its predictive capability. In the present work, to investigate this model, all the physical quantities are set in a dimensionless form, as commonly used in fluid mechanics: the parameters that act in the same or the opposite ways are regrouped and the total number of simulation parameter is greatly reduced. In a second phase, the influence of the parameter is discussed, and interpreted with the support of the limit cases. The analysis of the discharge voltage and concentration gradients is based on galvanostatic and pulse/relaxation current profiles and compared with tested commercial LGC cells. The simulations are performed with the software Comsol® and the post-processing with Matlab®. Moreover, in this research, the parameters from the literatures are discussed to understand how accurate are the techniques used to parametrize and feed the inputs of the model. Then, our work shows that the electrode isotherms shapes have a significant influence on the accuracy of the evaluation of the states of charges in a complete cell. Finally, the protocols to characterizes the performance of commercial cells at different C-rates are improved to guarantee the reproducibility.

L’utilisation de sulfure de lithium (Li2S), homologue lithié du soufre, en tant que matériau actif d’électrode positive permet le développement de systèmes à haute densité d’énergie plus sûrs, sans lithium métallique en tant qu’électrode négative. Appelés accumulateurs Lithium-ion/Soufre, leur mécanisme de fonctionnement, complexe et mal compris, reste semblable à celui des accumulateurs Li/S à l’exception de la 1ère charge. Cette 1ère charge présente une forte polarisation et très peu reproductible. L’objectif principal de ces travaux de thèse a donc été dédié à la compréhension des mécanismes mis en jeu lors de la charge initiale d’un accumulateur Li-ion/Soufre et en particulier l’étude de l’influence de la taille des cristallites du matériau pristine Li2S sur le mécanisme électrochimique. Il a été mis en évidence, dans un premier temps, la forte réactivité du Li2S nanométrique avec le liant polymère conventionnel PVdF (Polyfluorure de Vinylidène) conduisant au développement d’une nouvelle formulation d’électrode à base de PEO (Polyoxyde d’éthylène). Les résultats électrochimiques ont montré que la diminution de la taille des cristallites couplée à l’augmentation de la surface BET permet d’abaisser drastiquement la polarisation de la 1ère charge. Des caractérisations operando, de Diffraction des Rayons X (DRX) et Diffusion Inélastique Résonante des rayons X (RIXS), ont permis d’interpréter le rôle de la taille des cristallites et de la surface BET. Les résultats DRX ont montré une coexistence du Li2S et du β-S8 tout au long de la charge du Li2S micrométrique, tandis qu’aucun intermédiaire polysulfure soluble n’a été détecté par RIXS. Ces résultats sous-entendent donc une possible conversion solide/solide directe (Li2S micrométrique-->S8). A l’inverse, un comportement classique (Li2S-->Polysulfure solubles-->S8) a été observé à partir d’un matériau Li2S nanométrique avec l’existence successive des deux phases solides et la présence de polysulfures en solution. / Using Li2S instead of S8 as active material allows metallic lithium free batteries, also called Lithium-ion/Sulfur batteries, to be developed and safer systems with high energy density to be designed. The main difference between S8 and Li2S-based systems lies in the first charge. Indeed, during this first charge, a high polarization occurs with lack of reproducibility. Then, the main goal of this work is to focus on the analysis and understanding of the Li2S particle size impact on the electrochemical mechanism during the first charge of a Li-ion/Sulfur battery. Three Li2S types have been studied in this work: two nanometric Li2S and a micrometric one. Firstly, classical PVdF (polyvinylidenefluoride) binder was demonstrated to be highly reactive with nanometric Li2S leading to a new formulation based on PEO (polyethylene oxide) to be developed. Electrochemical investigations confirmed that starting with Li2S nanoparticles can effectively suppress the overall charge polarization. To go deeper, operando characterizations such as X-Ray Diffraction (XRD) and Resonant Inelastic X-ray Scattering (RIXS) have been carried out in order to correlate the particle size and the BET surface area effects. XRD results show that Li2S and β-sulfur phases coexist almost all along the first charge when starting with micrometric Li2S, while no polysulfides are detected by RIXS analysis. Therefore, a solid/solid (micrometric Li2S-->S8) reaction is suggested when using micrometric Li2S. On the opposite, when starting with nanometric Li2S particles, a very classical behavior (Li2S-->Polysulfides in solution-->S8) is obtained with the successive existence of the two solid phases with polysulfides in solution.

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.

Ce travail vise à identifier l’impact potentiel des impulsions périodiques de courant sur laperformance et la durée de vie des accumulateurs graphite/LiFePO4. Il apparait que,contrairement aux résultats connus pour les accumulateurs Plomb-acide et à ceux annoncéspar certains auteurs de la littérature pour les accumulateurs Li-ion, l’application d’impulsionspériodiques de courant ne présente pas d’intérêt dans une logique d’amélioration de laperformance et/ou de la durée de vie des accumulateurs Li-ion. De surcroit, certains typesd’impulsions ont été identifiés pour entrainer des effets préjudiciables à ces derniers. En seréférant à une application de véhicule industriel hybride électrique, nous avons évalué sur descritères techniques et économiques l’intérêt d’implémenter un système de stockage d’énergiecombiné, c'est-à-dire mutualisant l’usage d’une batterie Li-ion et desupercondensateurs/condensateurs. Il apparait que les stratégies consistant à agir sur lescomposantes hautes fréquences du signal pour ajouter/retirer des impulsions du profil vu parla batterie ne permettent pas d’accéder à des allongements de durée de vie qui pourraientcompenser le surcoût actuel lié à l’implémentation de ces systèmes. En outre, il apparait quele meilleur levier d’optimisation du bilan technique et économique associé au système destockage d’énergie est son dimensionnement. En effet, même si les systèmes de stockaged’énergie combinés utilisant les supercondensateurs permettent d’atteindre des réductions duratio coût/durée de vie considérables, la prise en compte globale des critères de coût, de duréede vie, de masse et d’encombrement s’avère plus favorable à la solution constituée d’unebatterie seule, de taille optimisée vis-à-vis de son application. / This work aims to identify the possible impact of periodic current pulses on both performanceand lifetime of graphite/LiFePO4 secondary batteries. Contrary to the well-known results onlead-acid batteries and to results announced in previously published works, periodic pulses donot bring any benefit to the performance and the lifetime of Li-ion batteries. Moreover,certain pulse types have been identified to be detrimental to Li-ion batteries. Using the hybridelectric vehicle application as a reference, we evaluated both the technical and economicalaspects of implementing combined energy storage systems composed with Li-ion batteriesand supercapacitors/capacitors. We found that the control strategies acting on high frequencyharmonics of the current signal to adding/retrieving pulses to the Li-ion battery profile doesnot prolong its life enough to compensate the extra cost of such system implementation.Furthermore, it seems that the best way to optimize the technico-economic balance of theenergy storage system is the sizing. Even if combined energy storage systems using Li-ionbatteries and supercapacitors enable to considerably increase the lifetime/cost ratio, a generalconsideration of the criteria cost, life, mass and volume is more favorable to a solution whereone single Li-ion battery is optimally sized for its application.

De nouvelles architectures de traction (hybride, électrique) entrent en concurrence avec les motorisations thermiques conventionnelles. Des batteries Lithium-ion équipent ces véhicules innovants. La durabilité de ces batteries constitue un enjeu majeur mais dépend de nombreux paramètres environnementaux externes. Les outils de prédiction de durée de vie actuellement utilisés sont souvent trop simplificateurs dans leur approche. L’objet de ces travaux consiste à caractériser les conditions d’usage de ces batteries (température, tension, courant, SOC et DOD) afin d’étudier avec précision la durée de vie que l’on peut en attendre en fonction de l’application visée. Différents types de véhicules électrifiés (vélos à assistance électrique, voitures électriques, voitures hybrides, et trolleybus) ont été instrumentés afin de documenter les conditions d’usage réel des batteries. De larges volumes de données ont été recueillis puis analysés au moyen d’une méthode innovante qui s’appuie sur la classification d’impulsions de courant par l’algorithme des K-means et la génération de cycles synthétiques par modélisation par chaine de Markov. Les cycles synthétiques ainsi obtenus présentent des caractéristiques très proches de l’échantillon complet de données récoltées et permettent donc de représenter fidèlement l’usage réel. Utilisés lors de campagnes de vieillissement de batteries, ils sont susceptibles de permettre l’obtention d’une juste prédiction de la durée de vie des batteries pour l’application considérée. Plusieurs résultats expérimentaux sont présentés afin d’étayer la pertinence de cette approche / Lithium-ion batteries are being used as energy storage systems in recent electric and hybrid electric vehicles coming to market. Current cycle-life estimation techniques show evidence of discrepancy between laboratory results and real-world results. This work is aimed at characterizing actual battery usage in electrified transportation applications. Factors such as temperature, State Of Charge, Depth Of Discharge, current and voltage have to be carefully considered for accurate cycle-life prediction within a given application. Five electrified vehicles have been studied (two electric bicycles, one light EV, one mainstream HEV and one Heavy-Duty trolleybus). These vehicles have been equipped with sensors and data-logger and then test-driven on open roads under real-world conditions. Large amounts of data have been stored and later processed through an innovative method for analysis of actual usage. This method relies on data mining based on K-means clustering and synthetic duty cycle generation based on Markov chain modeling. Resulting synthetic cycles exhibit features similar to those observed on the large original datasets. This enables accurate prediction of cycle-life through realistic ageing trials of Lithium-ion batteries. Several experimental results are presented in order to assess the fitness of this method

Transition metals (TMs) are ‘elements whose atoms have partially filled d-shell, or which can give rise to cations with an incomplete d-shell’. In TMs, the d-shell overlaps with next higher s-shell. Most of the TMs exhibit more than one (multiple) oxidation states. Some TMs, such as silver and gold, occur naturally in their metallic state but, most of the TM minerals are generally oxides. Most of the minerals on the planet earth are metal oxides, because of large free energies of formation for the oxides. The thermodynamic stability of the oxides is determined from the Ellingham diagram. Ellingham diagram shows the temperature dependence of the stability (free energy) for binaries such as metal oxides. Ellingham diagram also shows the ease of reducibility of metal oxides. TM oxides of general formulas MO, M2O3, MO2, M2O5, MO3 are known to exist, many of them being the ultimate products of oxidation in air in their highest oxidation states. In addition, TM oxides also exist in lower oxidation states which are prepared under controlled conditions. The nature of bonding in these oxides varies from mainly ionic (e.g. NiO, CoO) to mainly covalent (e.g. OsO4). Simple binary oxides of the compositions, MO, generally possess the rock salt structure (e.g. NiO), while the dioxides, MO2, possess the rutile structure (e.g. TiO2); many sesquioxides, M2O3, possess the corundum structure (e.g. Cr2O3). TMs form important ternary oxides like perovskites (e.g. CaTiO3), spinels (e.g. MgFe2O4) and so on. In TM oxides, the valence (outer) d-shell could be empty, d0 (e. g. TiO2), partially filled, dn (1≤ n≤ 9) (e.g. TiO, VO, NiO etc.) or completely filled, d10 (e.g. ZnO, CdO, Cu2O etc.). The outer d electrons in TM oxides could be localized or delocalized. Localized outer d electrons give insulators/semiconductors, while delocalized/itinerant d electrons make the TM oxide ‘metallic’ (e.g. ReO3, RuO2). Partially filled dn states are normally expected to give rise to itinerant (metallic) electron behaviour. But most of TM oxides with partially filled d shell are insulators because of special electronic energy (correlation energy) involved in d electron transfer to adjacent sites. Such insulating TM oxides are known as Mott insulators (e. g. NiO, CoO etc.). Certain TM oxides are known to exhibit both localized (insulating) and itinerant (metallic) behaviour as a function of temperature or pressure. For example, VO2 shows a insulator–metal transition at ~340K. Similar transitions are also known for V2O3, metal-rich EuO and so on. The chemical composition and bonding of TM oxides, which determine the crystal and electronic structures, give rise to functional properties. Table 1 gives representative examples. Properties like ionic conductivity and diffusion are governed by both the crystal structure and the defect structure (point defects), whereas properties such as magnetism and electron transport mainly arise from the electronic structures of the materials. Accordingly, TM oxides provide a platform for exploring functional materials properties. Among the various functional materials properties exhibited by transition metal oxides, the present thesis is devoted to investigations of lithium ion battery cathodes, inorganic pigments and magnetic perovskites. Over the years, most of the lithium containing first row transition metal oxides of rock salt derived structure have been investigated for possible application as cathode materials in lithium ion batteries (LIBs). First major breakthrough in LIBs research was achieved by electrochemically deinserting and inserting lithium in LiCoO2. A new series of cathode materials for LIBs were prepared by incorporating excess lithium into the transition metal containing layered lithium oxides through solid solution formation between Li2MnO3–LiMO2 (M = Cr, Mn, Fe, Co, Ni), known as lithium-rich layered oxides (LLOs). LLOs exhibit improved electrochemical performance as compared to the corresponding end members and hence received significant attention as a potential next generation cathode materials for LIBs in recent times. LiCoO2 (R-3m) crystallizes in the layered α-NaFeO2 structure with the oxygens in a ccp arrangement. Li+ and Co3+ ions almost perfectly order in the octahedral sites (3a and 3b) to give alternating (111) planes of LiO6 and CoO6 octahedra. Table 1. Materials properties exhibited by representative TM oxides. Property Example(s) Ferroelectricity BaTiO3, PbTiO3, Bi4Ti3O12 Nonlinear Optical Response LiNbO3 Multiferroic response BiFeO3, TbMnO3 Microwave dielectric properties Ba3ZnTa2O9 Relaxor Dielectric Properties Pb3MgNb2O9, Colossal Magnetoresistance Tl2Mn2O7 Metallic ‘Ferroelectricity’ Cd2Re2O7 Superconductivity AOs2O6(A = K, Rb, Cs) Redox deinsertion/insertion of LiCoO2 lithium Photocatalysis/water splitting TiO2 Pigment Ca(1-x)LaxTaO(2-x)N1+x (yellow-red), YIn1-xMnxO3 (blue) Metallic Ferromagnetism CrO2 Antiferromagnetism NiO, LaFeO3 Zero thermal expansion ZrW2O8 The reversible capacity of LiCoO2 in common LIBs is relatively low at around 140 mA h g-1 (half of theoretical capacity), corresponding to: LiCo3+O2 → Li0.5Co3+0.5Co4+0.5O2 + 0.5Li+ + 0.5e– . Substitution of one or more transition metal ions in LiCOO2 has been explored to improve the electrochemical performance. The structure of LLOs is described as a solid solution or nano composite of Li2MnO3 (C2/m) and LiMO2 (R-3m). The electrochemical deinsertion/insertion behaviour of LLOs is complex and also not yet understood completely. The present thesis consists of four parts. After a brief introduction (Part 1), Part 2 is devoted to materials for Li-ion battery cathode, consisting of three Chapters 2.1, 2.2 and 2.3. In Chapter 2.1, we describe the synthesis, crystal structure, magnetic and electrochemical characterization of new LiCoO2 type rock salt oxides of formula, Li3M2RuO6 (M = Co, Ni). The M =Co oxide adopts the LiCoO2 (R-3m) structure, whereas the M = Ni oxide also adopts a similar layered structure related to Li2TiO3. Magnetic susceptibility measurements reveal that in Li3Co2RuO6, the oxidation states of transition metal ions are Co3+, Co2+ and Ru4+, whereas in Li3Ni2RuO6, the oxidation states are Ni2+ and Ru5+. Li3Co2RuO6 orders antiferromagnetically at ~10K. On the other hand, Li3Ni2RuO6 presents a ferrimagnetic behaviour with a Curie temperature of ~100K. Electrochemical Li-deinsertion/insertion studies show that high first charge capacities (between ca.160 and 180 mA h g−1) corresponding to ca.2/3 of theoretical capacity are reached albeit, in both cases, capacity retention and cyclability are not satisfactory. Chapter 2.2 presents a study of new ruthenium containing LLOs, Li3MRuO5 (M = Co and Ni). Both the oxides crystallize in the layered LLO type LiCoO2 (α-NaFeO2) structure consisting of Li[Li0.2M0.4Ru0.4]O2 layers. Magnetic susceptibility data suggest that the oxidation states of transition metals are Li3Co3+Ru4+O5 for the M = Co compound and Li3Ni2+Ru5+O5 for the M = Ni compound. Electrochemical investigations of lithium deintercalation–intercalation behaviour reveal that both Co and Ni phases exhibit attractive specific capacities of ca. 200 mA h g-1 at an average voltage of 4 V, that has been interpreted as due to the oxidation of Co3+ and Ru4+ in Li3CoRuO5 and Ni2+ to Ni4+ in the case of Li3NiRuO5. Thus, we find that ruthenium plays a favourable role in LLOs than in non-LLOs in stabilizing higher reversible electrochemical capacities. In Chapter 2.3, we describe the synthesis, crystal structure and lithium deinsertion–insertion electrochemistry of two new LLOs, Li3MRuO5 (M=Mn, Fe) which are analogs of the oxides described in Chapter 2.2. The Li3MnRuO5 oxide adopts a structure related to Li2MnO3 (C2/m), while the Li3FeRuO5 oxide adopts a near-perfect LiCoO2 (R-3m) structure. Lithium electrochemistry shows typical behaviour of LLOs for both oxides, where participation of oxide ions in the electrochemical processes is observed. A long first charge process with capacities of 240 mA h g-1 (2.3 Li per f.u.) and 144 mA h g-1 (1.38 Li per f.u.) is observed for Li3MnRuO5 and Li3FeRuO5, respectively. Further discharge–charge cycling points to partial reversibility. X-ray photoelectron spectroscopy (XPS) characterisation of both pristine and electrochemically oxidized Li3MRuO5 reveals that in the Li3MnRuO5 oxide, Mn3+ and Ru4+ are partially oxidized to Mn4+ and Ru5+ in the sloping region at low voltage, while in the long plateau, O2- is also oxidized. In the Li3FeRuO5 oxide, the oxidation process appears to affect only Ru (4+ to 5+ in the sloping region) and O2- (plateau), while Fe seems to retain its 3+ state. Another characteristic feature of TMs is formation of several coloured solid materials where d–d transitions, band gap transitions and charge transfer transitions are involved in the colouration mechanism. Coloured TM oxides absorbing visible light find important applications as visible light photocatalyst (for example, yellow BiVO4 for solar water splitting and red Sr1-xNbO3 for oxidation of methylene blue) and inorganic pigments [for example, Egyptian blue (CaCuSi4O10), Malachite green (Cu2CO3(OH)2), Ochre red (Fe2O3)]. Pigments are applied as colouring materials in inks, dyes, paints, plastics, ceramic glazers, enamels and textiles. In this thesis, we have focused on the coloured TM oxides for possible application as inorganic pigments. Generally, colours arise from electronic transitions that absorb visible light. Colours of the inorganic pigments arise mainly from electronic transitions involving TM ions in various ligand fields and charge transfer transitions governed by different selection rules. The ligand field d–d transitions are parity forbidden but are relaxed due to various reasons, such as distortion (absence of center of inversion) and vibronic coupling. The d-electrons can be excited by light absorption in the visible region of the spectrum imparting colour to the material. Charge transfer transitions in the visible region are not restricted by the parity selection rules and therefore give intense colours. Here we have investigated the colours of manganese in unusual oxidation state (Mn5+) as well as the colours of different 3d-TM ions in distorted octahedral and trigonal prismatic sites in appropriate colourless crystalline host oxides. These results are discussed in Part 3 of the thesis. In Chapter 3.1, we describe a blue/green inorganic material, Ba3(P1−xMnxO4)2 (I) based on tetrahedral Mn5+O4 :3d2 chromophore. The solid solutions (I) which are sky-blue and turquoise-blue for x ≤ 0•25 and dark green for x ≥ 0•50, are readily synthesized in air from commonly available starting materials, stabilizing the Mn5+O4 chromophore in an isostructural phosphate host. We suggest that the covalency/ionicity of P–O/Mn–O bonds in the solid solutions tunes the crystal field strength around Mn(V) such that a blue colour results for materials with small values of x. The material could serve as a nontoxic blue/green inorganic pigment. In Chapter 3.2, an experimental investigation of the stabilization of the turquoise-coloured Mn5+O4 chromophore in various oxide hosts, viz., A3(VO4)2 (A = Ba, Sr, Ca), YVO4, and Ba2MO4 (M = Ti, Si), has been carried out. The results reveal that substitution of Mn5+O4 occurs in Ba3(VO4)2 forming the entire solid solution series Ba3(V1−xMnxO4)2 (0 < x ≤ 1.0), while, with the corresponding strontium derivative, only up to about 10% of Mn5+O4 substitution is possible. Ca3(VO4)2 and YVO4 do not stabilize Mn5+O4 at all. With Ba2MO4 (M = Ti, Si), we could prepare only partially substituted materials, Ba2M1−xMn5+xO4+x/2 for x up to 0.15, that are turquoise-coloured. We rationalize the results that a large stabilization of the O 2p-valence band states occurs in the presence of the electropositive barium that renders the Mn5+ oxidation state accessible in oxoanion compounds containing PO43−, VO43−, etc. By way of proof-of-concept, we synthesized new turquoise-coloured Mn5+O4 materials, Ba5(BO3)(MnO4)2Cl and Ba5(BO3)(PO4)(MnO4)Cl, based on the apatite – Ba5(PO4)3Cl – structure. Chapter 3.3 discusses crystal structures, and optical absorption spectra/colours of 3d-transition metal substituted lyonsite type oxides, Li3Al1-xMIIIx(MoO4)3 (0< x ≤1.0) (MIII = Cr, Fe) and Li3-xAl1-xMII2x(MoO4)3 (0< x ≤1.0) (MII = Co, Ni, Cu). Crystal structures determined from Rietveld refinement of PXRD data reveal that in the smaller trivalent metal substituted lyonsite oxides, MIII ions occupy the octahedral (8d, 4c) sites and the lithium ions exclusively occur at the trigonal prismatic (4c) site in the orthorhombic (Pnma) structure; on the other hand, larger divalent cations (CoII/CuII) substituted derivatives show occupancy of CoII/CuII ions at both the octahedral and trigonal prismatic sites. We have investigated the colours and optical absorption spectra of Li3Al1-xMIIIx(MoO4)3 (MIII = Cr, Fe) and Li3-xAl1-xMII2x(MoO4)3 (MII = Co, Ni, Cu) and interpreted the results in terms of average crystal field strengths experienced by MIII/MII ions at multiple coordination geometries. We have also identified the role of metal-to-metal charge transfer (MMCT) from the partially filled transition metal 3d orbitals to the empty Mo – 4d orbitals in the resulting colours of these oxides. B The ABO3 perovskite structure consists of a three dimensional framework of corner shared BO6 octahedra in which large A cation occupies dodecahedral site, surrounded by twelve oxide ions. The ideal cubic structure occurs when the Goldschmidt’s tolerance factor, t = (rA + rO)/{√2(rB + rO)}, adopts a value of unity and the A–O and B–O bond distances are perfectly matched. The BO6 octahedra tilt and bend the B – O – B bridges co-operatively to adjust for the non-ideal size of A cations, resulting deviation from ideal cubic structure to lower symmetries. Ordering of cations at the A and B sites of perovskite structure is an important phenomenon. Ordering of site cations in double (A2BB'O6) and multiple (A3BB'2O9) perovskites give rise to newer and interesting materials properties. Depending upon the constituent transition metals and ordering, double perovskite oxides exhibit a variety of magnetic behaviour such as ferromagnetism, ferrimagnetism, antiferromagnetism, spin-glass magnetism and so on. We also have coupled magnetic properties such as magnetoresistance (Sr2FeMoO6), magnetodielectric (La2NiMnO6) and magnetooptic (Sr2CrWO6) behaviour. Here we have investigated new magnetically frustrated double perovskite oxides of the formula Ln3B2RuO9(B = Co, Ni and Ln = La, Nd). The Chapter 4.1 describes Ln3B2RuO9 (B = Co, Ni and Ln = La, Nd) oxides (prepared by a solid state metathesis route) which adopt a monoclinic (P21/n) A2BB'O6 double perovskite structure, wherein the two independent octahedral 2c and 2d sites are occupied by B2+ and (B2+1/3Ru5+2/3) atoms, respectively. Temperature dependence of the molar magnetic susceptibility plots obtained under zero field cooled (ZFC) condition exhibit maxima in the temperature range 25–35K, suggesting an antiferromagnetic interaction in all these oxides. Ln3B2RuO9 oxides show spin-glass behavior and no long-range magnetic order is found down to 2 K. The results reveal the importance of competing nearest neighbour (NN), next nearest neighbor (NNN) and third nearest neighbour (third NN) interactions between the magnetic Ni2+/Co2+ and Ru5+ atoms in the partially ordered double perovskite structure that conspire to thwart the expected ferromagnetic order in these materials.

L'utilisation de systèmes de stockage de l'énergie électrique tels que les batteries nécessite l'assemblage de plusieurs cellules. Comme chacune de ces dernières peut avoir des caractéristiques légèrement différentes ainsi que des conditions d'environnement thermique ou de vieillissement distinctes, l'utilisation d'un système d'équilibrage permettant une bonne gestion de la répartition de l'énergie au sein des éléments qui composent le pack est nécessaire. Les travaux de recherche présentés se rapportent à l'étude et à la conception d'un tel circuit d'équilibrage à base de convertisseurs d'énergie intégrables ainsi qu'aux sollicitations électriques engendrées dans les cellules lors de son utilisation. / To store electrical energy in batteries, the use of multiple cells is needed. Since each of these cells can have slightly different characteristics and also different thermal or aging environmental conditions, a balancing system is required to manage the energy inside the battery pack. The researches described in this document show the study and the design of such a balancing system based on power electronics converters and also the impact of these systems on the electrochemical cells.

Ces travaux de thèse se focalisent sur la modélisation électrothermique des batteries Lithium-ion de grande puissance, appliquée pour les véhicules électriques et pour le stockage d’énergie intégré au réseau. Une approche plus particulière est donnée sur la modélisation thermique de la batterie et de ses connectiques dans le but d’anticiper les comportements thermiques sous des sollicitations dynamiques de courant. De nombreuses investigations ont été réalisées dans le but de déterminer les différents paramètres électriques et thermiques de l’accumulateur, nous avons également cherché à comparer plusieurs méthodes de caractérisation différentes.La première partie du manuscrit est consacrée à la caractérisation et à la modélisation électrique.La seconde partie présente la caractérisation thermique et le modèle thermique de la batterie. Nous proposons une approche couplée de différents modèles thermiques, dans le but de prédire les comportements thermiques au niveau de la surface et du cœur de la cellule, mais également au niveau des connectiques et des câbles.Enfin, la dernière partie présente la modélisation électrothermique d’un module assemblé de trois cellules en séries. Les résultats de simulations ont été validés sur des régimes à courant constant, ainsi que sur des régimes de courant dynamique.Le travail accompagne l’intégration des modèles thermiques dans une plateforme de simulation de systèmes énergétique et ouvre des pistes vers des outils d’aide à la conception de packs de batteries, sur l’aide au dimensionnement de systèmes de refroidissement et sur le développement d’outil de diagnostic thermique des batteries. / This thesis work focuses on the electrothermal modeling of high-power Lithium-ion batteries, applied for electric vehicles and the energy storage connected to the the grid. A particular approach is given on the thermal modeling of the battery and its connectors in order to anticipate the thermal behaviors under dynamic charge and discharge current, which is very useful for the thermal management systems of the batteries. Numerous investigations have been carried out in order to determine the different electrical and thermal parameters of the accumulator, we have also tried to compare several different methods.The first part of the manuscript is dedicated to characterization and electrical modeling.The second part presents the thermal characterization and the thermal model of the battery. We propose a coupled approach of different thermal models, with the aim of predicting the thermal behaviors at the level of the surface and the core of the cell, but also at the level of the connectors and the wire.Finally, the last part presents the electrothermal modeling of a small assembled module of three cells in series. The results of simulations have been validated on constant current regimes, as well as on dynamic current regimes.The work aims to integrate the thermal models in a simulation platform of energy systems and opens up paths towards tools to help in the design of battery packs, assistance with the dimensioning of cooling systems and the development of thermal diagnostic tool for batteries.

Les canaux HCN (cycliques nucléotidiques) activés par hyperpolarisation appartiennent à la superfamille des canaux cationiques voltage-dépendants et sont responsables de la génération de courant drôle (If) dans les cellules cardiaques et neuronales. Malgré la similitude structurelle globale avec le potassium voltage-dépendant (Kv) et les canaux ioniques cycliques nucléotidiques (CNG), ils montrent un modèle de sélectivité distinctif pour les ions K+ et Na+. Plus précisément, leur perméabilité accrue aux ions Na+ est essentielle à son rôle dans la dépolarisation des membranes cellulaires. Ils sont également l'une des seules protéines connues à sélectionner entre les ions Na+ et Li+, faisant des HCN des canaux semi-sélectifs. Ici, nous étudions les propriétés de sélectivité uniques des canaux HCN à l'aide de simulations de dynamique moléculaire. Nos simulations suggèrent que le pore HCN1 est très flexible et dilaté par rapport aux canaux Kv et qu'il n'y a qu'un seul site de liaison ionique stable dans le filtre de sélectivité qui les distingue des canaux Kv et CNG. Nous observons également que la coordination et l'hydratation des ions diffèrent dans le filtre de sélectivité de HCN1 par rapport aux canaux Kv et CNG. De plus, la coordination des ions K+ par les groupes carbonyle du filtre de sélectivité est plus stable par rapport aux ions Na+ et Li+, ce qui peut expliquer les propriétés de sélectivité distinctes du canal. / Hyperpolarization-activated cyclic nucleotide-gated (HCN) channels belong to the voltage-gated cation channel superfamily and are responsible for the generation of funny current (If) in cardiac and neuronal cells. Despite the overall structural similarity to voltage-gated potassium (Kv) and cyclic nucleotide-gated (CNG) ion channels, they show distinctive selectivity pattern for K+ and Na+ ions. Specifically, their increased permeability to Na+ ions is critical to its role in depolarizing cellular membranes. They are also one of the only known proteins to select between Na+ and Li+ ions, making HCNs semi-selective channels. Here we investigate the unique selectivity properties of HCN channels using molecular dynamics simulations. Our simulations suggest that the HCN1 pore is very flexible and dilatated compared to Kv channels and that there is only one stable ion binding site within the selectivity filter which discriminates them from both Kv and CNG channels. We also observe that ion co-ordination and hydration differ within the selectivity filter of HCN1 compared to Kv and CNG channels. Additionally, the co-ordination of K+ ions by the carbonyl groups of the selectivity filter is more stable compared to Na+ and Li+ ions, which may explain the channel's distinct selectivity properties.