Indiana University-Purdue University Indianapolis (IUPUI) / In recent years Lithium-Ion battery as an alternate energy source has gathered lot of importance in all forms of energy requiring applications. Due to its overwhelming benefits over a few disadvantages Lithium Ion is more sought of than any other Battery types. Any battery pack alone cannot perform or achieve its maximum capacity unless there is some robust, efficient and advanced controls developed around it. This control strategy is called Battery Management System or BMS. Most BMS performs the following activity if not all Battery Health Monitoring, Temperature Monitoring, Regeneration Tactics, Discharge Profiles, History logging, etc. One of the major key contributor in a better BMS design and subsequently maintaining a better battery performance and EUL is Regeneration Tactics. In this work, emphasis is laid on understanding the prevalent methods of regeneration and designing a new strategy that better suits the battery performance. A performance index is chosen which aims at minimizing the effort of regeneration along with a minimum deviation from the rated maximum thresholds for cell temperature and regeneration current. Tuning capability is provided for both temperature deviation and current deviation so that it can be tuned based on requirement and battery chemistry and parameters. To solve the optimization problem, Pontryagin's principle is used which is very effective for constraint optimization with both state and input constraints. Simulation results with different sets of tuning shows that the proposed method has a lot of potential and is capable of introducing a new dynamic regeneration tactic for Lithium Ion cells. With the current optimistic results from this work, it is strongly recommended to bring in more battery constraints into the optimization boundary to better understand and incorporate battery chemistry into the regeneration process.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24108号 / 工博第5030号 / 新制||工||1785(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 作花 哲夫, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

The present thesis demonstrates and discusses polymeric ion and mixed ion-electron conductors for rechargeable batteries based on lithium viz. lithium-ion and lithium-sulphur batteries. The proposed polymer ion conductors in the thesis are discussed primarily as potential alternatives to conventional liquid and solid-crystalline electrolytes in lithium-ion batteries. These discussions are part of Chapters 2-4. On the other hand, the polymer based mixed ion-electron conductor is demonstrated as a novel electrode for lithium-Sulphur battery in Chapter 5. Possibility of application of polymer ion conductors is discussed in the context of Li-S battery in Chapter 6. A distinct correlation between the physical properties and electrochemical performance of the proposed conductors is highlighted in detail in this thesis. Systematic investigation of the ion transport mechanism in the polymeric ion conductors has been carried out using various spectroscopic techniques at different time and length scales. Such detailed investigations demonstrate the key structural and physical parameters for design of alternative polymer conductors for rechargeable batteries. Though the thesis discusses the various polymeric conductors in the context of lithium-based batteries, it is strongly felt that the design strategies are equally likely to be beneficial for different battery chemistries as well as for other electrochemical generation and storage devices. A brief discussion of the contents and highlights of the individual chapters are described below: The thesis comprises of six Chapters. Chapter 1 briefly reviews the important developments and materials of lithium-based batteries, with specific focus on Li-ion and Li-S batteries. It starts with discussions on different types of liquid, solid crystalline and solid-like electrolytes. Their materials characteristics, advantages and disadvantages are discussed in the context of secondary batteries such as lithium-ion and lithium-sulphur batteries. As prospective alternative electrolytes polymer based soft matter electrolytes are discussed in detail. Special emphasis is given to the recent developments in polymer electrolytes and their ion conduction mechanism, which are central themes to this thesis. The importance of investigation of charge transport, typically ion, on electrochemical processes is also briefly discussed in Chapter 1. A brief discussion about the characteristics, materials and non-trivialities of the electrochemical storage process in Li-S battery is also reviewed. Chapter 2A demonstrates a binary polymer physical network based gel (PN-x) electrolyte, comprising of an ionic liquid confined inside a binary polymer system for electrochemical devices such as secondary batteries. The synthesis, physical property and electrochemical performances are studied as a function of content of one of the polymers in this Chapter. A physical network of two polymers with different functional groups leads to multiple interesting consequences. The polymer physical network characteristics determine all physical properties including electrochemical property of the ionic liquid integrated PN based GPE. The conductivities of the proposed gel are nearly an order in magnitude higher than the unconfined ionic liquid electrolyte and displays good dimensional stability and electrochemical performance in a separator-free battery configuration. The ac-impedance spectroscopy, steady shear viscosity measurement, dynamic rheology are employed to study physical properties of the proposed gel polymer electrolyte. Chapter 2B discusses the detailed investigations of the ion transport mechanism of the gel polymer electrolyte, as discussed in Chapter 2A. Ion conduction mechanism is investigated in the light of ion diffusion and solvent dynamics of the entrapped ionic liquid inside the polymer. The studies reveal a heavy influence of network characteristics on the ion conduction mechanism. The influence of solvent dynamics on the ion transport is drastically altered by polymer physical network. Consequently, a drastic change in the ion mobility and nature of predominant charge carrier is observed in the polymer physical network based gel electrolyte. A clear transformation from dual ion conductivity to a predominantly anion conductivity is observed on going from single polymer to a dual polymer network. The spectroscopic tools such as pulsed field gradient nuclear magnetic resonance (PFG–NMR), Brillouin light scattering spectroscopy, ac-impedance spectroscopy, FT-Raman and FTIR spectroscopy were used to elucidate the ion transport mechanism in the Chapter. Chapter 3 demonstrates a simple design strategy of gel polymer electrolyte comprising of a lithium salt (lithium bis(trifluoromethanesulfonyl) imide, LiTFSI) solvated by two plastic crystalline solvents, one a solid (succinonitrile, abbreviated as SN) and another a (room temperature) ionic liquid (1-butyl-1-methyl-pyrrolidinium bis(trifluoromethane sulfonyl) imide, (abbreviated as IL) confined inside a linear network of poly(methyl methacrylate) (PMMA). The concentration of the IL component determines the physical properties of the unconfined electrolyte and when confined inside the polymer network in gel polymer electrolyte. Intrinsic dynamics of one plastic crystal influences the conduction mechanism of gel polymer electrolytes. The enhanced disordering in the plastic phase of succinonitrile by IL doping alters both the local ion environment and viscosity. The proposed plastic crystal electrolytes show predominantly anion conduction (tTFSI ≈ 0.5) however, lithium transference number (tLi ≈ 0.2) is nearly an order higher than the ionic liquid electrolyte (IL-LiTFSI) (tLi ≈ 0.02-0.06), discussed in Chapter 2. The gel polymer electrolyte displayed high mechanical compliability, stable Li-electrode | electrolyte interface, low rate of Al corrosion and stable cyclability. The promising electrochemical performance further justifies simple strategy of employing mixed physical state plasticizers to tune the physical properties of polymer electrolytes requisite for application in rechargeable batteries. Chapter 4A proposes a novel liquid dendrimer–based single ion conducting liquid electrolyte as potential alternative to conventional molecular liquid solvent–salt solutions and conventional solid polymer electrolytes for rechargeable batteries, sensors and actuators. The physical properties are investigated as a function of peripheral functionalities in the first generation poly(propyl ether imine) (G1-PETIM)–lithium salt complexes. The change in peripheral group simultaneously affects the effective physical properties viz. viscosity, ionic conductivity, ion diffusion coefficients, transference numbers and also the electrochemical response. The specific change from ester (–COOR) to cyano (–CN) terminated peripheral group resulted in a remarkable switch over from a high cation (tLi+ = 0.9 for –COOR) to a high anion (tPF6- = 0.8 for –CN) transference number. Chapter 4B presents an analysis of the frequency dependent ionic conductivity of single ion dendrimer conductors by using time temperature scaling principles (TTSPs) and dielectric modeling of the electrode polarization. The TTSP provides information on the salt dissociation and number density of mobile charges and hence provides direct insights into the ion conduction mechanism. Summerfield and Baranovskii–Cordes scaling laws, which are well known TTSPs, have been applied to analyze the ion conductivity. The electrode polarization, which quantifies the number density of mobile charges and ionic mobility, is studied using Macdonald-Coelho model of electrode polarization. The combination of these two theoretical investigations of the experimental data emanating from one technique i.e. ac– impedance spectroscopy, predicts independently the contributions of the effect of mobile ion charges and ionic mobility to ion conduction mechanism. In Chapter 5 focus shifts from polymer ion conductors to polymer mixed ion-electron conductor. The polymer mixed ion-electron conductor is demonstrated as a novel electrode material for Li-S battery. A simple strategy to overcome the challenges towards practical realization of a stable high performance Li–S battery is discussed. A soft mixed conducting polymeric network is utilized to configure sulphur nanoparticle. The soft matter network provides efficient and distinct pathways for lithium and electron conduction simultaneously. A lithiated polyethylene glycol (PEG) based surfactant tethered on ultra-small sulphur nanoparticles and wrapped up with polyaniline (PAni) (abbreviated as S-MIEC) is demonstrated here as an exceptional cathode for Li–S batteries. The S-MIEC is characterized by several methods: powder-X-ray diffraction (PXRD), thermo gravimetric analysis (TGA), fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), ac-impedance spectroscopy and dc current-voltage measurements are performed to evaluate conductivity of S-MIEC cathode. Electrochemical studies such as cyclic voltammetry, galvanostatic charge-discharge cycling, galvanostatic intermittent titration (GITT) are performed to demonstrate feasibility of S-MIEC in the Li–S battery performance. Chapter 6 provides a brief summary of the work carried out as part of this thesis and also demonstrates the future perspective of the present work. Potential of the polymer physical network based gel polymer electrolytes, which are discussed in Chapter 2A-B for lithium-ion batteries, are demonstrated in Li-S battery. The proposed polymer physical network confines higher order lithium polysulfides (typically Li2S8) dissolved in tetraethylene glycol dimethyl ether (TEGDME) based electrolyte (TEGDME-1M LiTFSI). The three dimensional polymer network is proposed to be formed by physical blending of the poly(acrylonitrile) (PAN) with the copolymer of AN and poly(ethylene glycol) methyl ether methacrylate (PEGMA), [ P(AN–co–PEGMA)]. We extend here the similar synthetic approaches as described in Chapter 2A. The approach proposed and demonstrated in this concluding Chapter is expected to mitigate some of the major issues of Li-S chemistry. The proposed Li2S8 confined gel electrolyte exhibits moderately high values of ionic conductivity, 2 × 10-3 Ω-1cm-1 and shows a stable capacity of 350 mAhg-1 over 30 days in a separator free Li-S battery.

Indiana University-Purdue University Indianapolis (IUPUI) / Due to the drastic increase in the cost of fossil fuels and other environmental issues, the demand for energy and its storage has risen globally. Rather than being dependent on intermittent energy sources like wind and solar energy, focus has been on alternative energy sources. To eliminate the need for fossil fuels, advances are being made to provide energy for hybrid electric vehicles (HEV), plug-in hybrid vehicles (PHEV) and pure electric vehicles (EV) thus providing scope for much greener environment. Hence, focus has been on development in lithium ion batteries to provide with materials that have high energy density and voltage. Ortho olivine lithium transitional metals are known to be abundant and inexpensive; these compounds are less noxious than other cathode materials. Advancement in research is being done in finding iron and manganese compounds as cathode materials for advanced technologies. However, Lithium manganese phosphates are known to suffer with poor electrochemical performances due the manganese dissolution in the organic liquid electrolyte due to Jahn-Teller Lattice distortion. This problem was tried to endorse in this thesis. In the second chapter by synthesizing nano sized cathode particles with good electronic conductivity, good performance was achieved. In the third chapter additive olivine cathode was synthesized my modified sol gel process. A wt. % of TMSP was added as an additive in the organic liquid electrolyte. By comparing the properties between the two kinds of electrolytes it was observed that by the addition of the additive in the organic electrolyte good electrochemical properties could be achieved hindering the Mn dissolution in the electrolyte. In the final chapter, a composite solid electrolyte was fabricated by using NASICON-type glass ceramic of Lithium aluminum titanium phosphate (LATP) with organic binder of Polyethylene oxide. The flexible solid electrolyte exhibited good ionic conductivity. An all solid state cell was fabricated using the composite solid electrolyte using LiMn2O4 as the symmetric electrodes. At different pressures, the performance of the solid state cell was studied.

Indiana University-Purdue University Indianapolis (IUPUI) / Heat generation is a major safety concern in the design and development of Li ion batteries (LIBs) for large scale applications, such as electric vehicles. The total heat generation in LIBs includes entropic heat, enthalpy, reaction heat, and heat of mixing. The main objective of this study is to investigate the influence of heat of mixing on the LIBs and to understand whether it is necessary to consider the heat of mixing during the design and development of LIBs. In the previous research, Thomas and Newman derived methods to compute heat of mixing in LIB cells. Their results show that the heat of mixing cannot be neglected in comparison with the other heat sources at 2 C rate. In this study, the heat of mixing in different materials, porosity, particle sizes, and charging/discharging rate was investigated. A COMSOL mathematical model was built to simulate the heat generation of LIBs. The LIB model was based on Newman’s model. LiMn2O4 and LiCoO2 were applied as the cathode materials, and LiC6 was applied as the anode material. The results of heat of mixing were compared with the other heat sources to investigate the weight of heat of mixing in the total heat generation. The heat of mixing in cathode is smaller than the heat of mixing in anode, because of the diffusivity of LiCoO2 is 1 ×10-13 m2/s, which is larger than LiC6's diffusivity 2.52 × 10-14 m2/s. In the comparison, the heat of mixing is not as much as the irreversible heat and reversible heat, but it still cannot be neglected. Finally, a special situation will be discussed, which is the heat of mixing under the relaxation status. For instance, after the drivers turn off their vehicles, the entropy, ix enthalpy and reaction heat in LIBs will stop generating, but the heat will still be generated due to the release of heat of mixing. Therefore, it is meaningful to investigate to see if this process has significant influence on the safety and cycle life of LIBs.

Crystalline polymer/salt complexes can conduct, in contrast to the view held for 30 years. The alpha-phase of the crystalline poly(ethylene oxide)₆:LiPF₆ is composed of tunnels formed from pairs of (CH₂-CH₂-O)ₓ chains, within which the Li⁺ ions reside and along which the latter migrate.¹ When a polydispersed polymer is used, the tunnels are composed of 2 strands, each built from a string of PEO chains of varying length. It has been suggested that the number and the arrangement of the chain ends within the tunnels affects the ionic conductivity.² Using polymers with uniform chain length is important if we are to understand the conduction mechanism since monodispersity results in the chain ends occurring at regular distances along the tunnels and imposes a coincidence of the chain ends between the two strands.² Since each Li⁺ is coordinated by 6 ether oxygens (3 oxygens from each of the two polymeric strands forming a tunnel), monodispersed PEOs with the number of ether oxygen being a multiple of 3 (NO = 3n) can form either “all-ideal” or “all-broken” coordination environments at the end of each tunnel, while for both NO = 3n-1 and NO = 3n+1 complexes, both “ideal” and “broken” coordinations must occur throughout the structure. A synthetic procedure has been developed and a series of 6 consecutive (increment of EO unit) monodispersed molecular weight PEOs have been synthesised. The synthesis involves one end protection of a high purity glycol, functionalisation of the other end, ether coupling reaction (Williamson's type ether synthesis³), deprotection and reiteration of ether coupling. The parameters of the process and purification methods have been strictly controlled to ensure unprecedented level of monodispersity for all synthesised samples. Thus obtained high purity polymers have been used to study the influence of the individual chain length on the structure and conductivity of the crystalline complexes with LiPF₆. The results support the previously suggested model of the chain-ends arrangement in the crystalline complexes prepared with monodispersed PEO² over a range of consecutive chain lengths. The synthesised complexes constitute a series of test samples for establishing detailed mechanism of ionic conductivity. Such series of monodispersed crystalline complexes have been studied and characterised here (PXRD, DSC, AC impedance) for the first time. References: 1. G. S. MacGlashan, Y. G. Andreev, P. G. Bruce, Structure of the polymer electrolyte poly(ethylene oxide)₆:LiAsF₆. Nature, 1999, 398(6730): p. 792-794. 2. E. Staunton, Y. G. Andreev, P. G. Bruce, Factors influencing the conductivity of crystalline polymer electrolytes. Faraday Discussions, 2007, 134: p. 143-156. 3. A. Williamson, Theory of Aetherification. Philosophical Magazine, 1850, 37: p. 350-356.

Solid state lithium ion electrolytes are important to the development of next generation safer and high power density lithium ion batteries. Perovskite-structured LLT is a promising solid electrolyte with high lithium ion conductivity. LLT also serves as a good model system to understand lithium ion diffusion behaviors in solids. In this thesis, molecular dynamics and related atomistic computer simulations were used to study the diffusion behavior and diffusion mechanism in bulk crystal and grain boundary in lithium lanthanum titanate (LLT) solid state electrolytes. The effects of defect concentration on the structure and lithium ion diffusion behaviors in LLT were systematically studied and the lithium ion self-diffusion and diffusion energy barrier were investigated by both dynamic simulations and static calculations using the nudged elastic band (NEB) method. The simulation results show that there exist an optimal vacancy concentration at around x=0.067 at which lithium ions have the highest diffusion coefficient and the lowest diffusion energy barrier. The lowest energy barrier from dynamics simulations was found to be around 0.22 eV, which compared favorably with 0.19 eV from static NEB calculations. It was also found that lithium ions diffuse through bottleneck structures made of oxygen ions, which expand in dimension by 8-10% when lithium ions pass through. By designing perovskite structures with large bottleneck sizes can lead to materials with higher lithium ion conductivities. The structure and diffusion behavior of lithium silicate glasses and their interfaces, due to their importance as a grain boundary phase, with LLT crystals were also investigated by using molecular dynamics simulations. The short and medium range structures of the lithium silicate glasses were characterized and the ceramic/glass interface models were obtained using MD simulations. Lithium ion diffusion behaviors in the glass and across the glass/ceramic interfaces were investigated. It was found that there existed a minor segregation of lithium ions at the glass/crystal interface. Lithium ion diffusion energy barrier at the interface was found to be dominated by the glass phase.

Le travail de thèse, présenté dans ce mémoire, est consacré à l'étude de nouveaux matériaux d'électrode pour batterie lithium-ion pour le stockage d'énergie photovoltaïque. Ce type de production d'énergie impose de nombreuses intermittences de charge, des non synchronisations entre les périodes de production et de consommation, etc. L'objectif est d'évaluer le comportement de différents types de matériau d'électrode dans des batteries soumises à des profils de charge photovoltaïque pour ensuite sélectionner les plus adaptés à ce stockage spécifique d'énergie. Les matériaux choisis, Li4Ti5O12, Li2Ti3O7, NiP3, TiSnSb, présentent tous des mécanismes de réaction vis-à-vis du lithium très différents. Afin d'améliorer la durée de vie de ces matériaux d'électrodes, un travail d'optimisation des performances électrochimiques a été effectué en travaillant sur leur synthèse puis sur la formulation des électrodes. La formulation d'électrode en utilisant la carboxymethylcellulose sodique a notamment donné d'excellents résultats. La caractérisation de leurs propriétés physico-chimiques a été réalisée par diffraction des rayons X, in situ et en température, MEB, ATD, cyclage galvanostatique, etc.). Afin de reproduire des profils représentatifs de la production photovoltaïque à l'échelle des accumulateurs expérimentaux de laboratoire, un banc de simulation a été élaboré et validé avec un accumulateur de référence à base de Li4Ti5O12. Après cette étape de validation, les différents matériaux d'électrode ont été testés en condition photovoltaïque. Cette étude a permis de montrer que les intermittences de courte de durée (passages nuageux) et les régimes variables qu'impose ce type de production n'ont pas que peu d'influence sur les propriétés électrochimiques de l'ensemble de ces matériaux. Cependant, les périodes d'absence de production (nuit, journée pluvieuse, etc.) correspondant à une relaxation pour le matériau peuvent avoir un impact important. Les matériaux de conversion (NiP3, TiSnSb) ont montré de surprenants bons résultats. Enfin, les observations montrent que chaque type de matériau (mécanisme électrochimique différent) pourrait convenir i) à un type de production photovoltaïque, c'est à dire à une zone géographique et ii) à un type d'application particulière. / The thesis work, presented in this manuscript, is devoted to the study of new materials for lithium-ion battery for storing solar energy. This type of energy production imposes intermittent loading, non-synchronization between periods of production and consumption, etc. The objective is to evaluate the behavior of different types of electrode material in batteries under photovoltaic (PV) charge profiles and then to select the most suitable for this specific energy storage. The chosen materials, Li4Ti5O12, Li2Ti3O7, NiP3, TiSnSb, follow all very different reaction mechanisms versus lithium. To improve the cycling life of these electrode materials, a work on electrochemical performance optimization was performed by working on the synthesis and the electrode formulation. The electrode formulation, using in particular carboxymethyl cellulose, presented excellent results. Characterization of their physico-chemical properties was carried out by X-ray diffraction, in situ and as function of temperature, SEM, DTA, galvanostatic cycling, etc.). To reproduce representative profiles of the photovoltaic production at the experimental batteries scale, a test bench has been developed and validated with reference batteries (Li4Ti5O12). After this step of validation, different electrode materials were tested under photovoltaic conditions. This study shows that both intermittences with short duration (clouds) and variable rates of current imposed by this type of production don't strong influence on the electrochemical properties of all these materials. However, periods of no production (night, rainy day, etc.), corresponding to a relaxation for the material, can impact significantly. Materials following conversion mechanism (NiP3, TiSnSb) showed surprising good results. Finally, the observations indicated that each type of material (with different electrochemical mechanism) could be adapted to i) a type of photovoltaic production, ie to a geographical area and ii) a type of application.

Dans ce travail de thèse, la microspectrométrie Raman a été mise à profit pour décrire les changements structuraux induits par la réaction électrochimique d'insertion/désinsertion des ions lithium dans des composés de structure lamellaire LiCoO2 et cubique LiMn2O4 et LiNi0.4Mn1.6O4, utilisés comme électrodes positives dans les batteries Li-ion. L'étude du composé d'électrode LiCoO2 pendant le processus de charge permet de mettre en évidence une région biphasée où la phase initiale coexiste avec une nouvelle phase hexagonale caractérisée par une expansion du paramètre inter-feuillets de l'ordre de 3% et un affaiblissement de la liaison Co-O dans le plan des feuillets. Dans le cas de LiMn2O4, une nouvelle attribution du spectre Raman a pu être proposée. Pendant la charge à 4V, un mécanisme à trois phases (phase initiale LiMn2O4, phase intermédiaire, phase pauvre en lithium) est décrit par spectroscopie Raman alors que la diffraction des RX ne permet pas d'observer la phase intermédiaire dans nos conditions de mesure. L'étude de l'insertion électrochimique du lithium dans LiMn2O4 (région 3V), a permis de montrer pour la première fois par spectroscopie Raman la formation progressive d'une phase tétragonale de composition Li2Mn2O4 qui coexiste avec la phase cubique initiale et qui est pure en fin de décharge. La réversibilité de cette transition structurale a également été démontrée. Dans le cas du composé substitué au nickel, LiNi0.4Mn1.6O4, une attribution complète du spectre Raman est proposée pour la première fois. L'étude par diffraction des RX du matériau en fonction de l'état de charge et de décharge met en évidence une conservation de la structure cubique avec des variations modérées de paramètres de maille. Le spectre Raman présente quant à lui des variations très significatives qui rendent compte de la présence dans des proportions différentes des espèces redox impliquées dans le fonctionnement électrochimique (Mn4+, Mn3+, Ni2+, Ni3+, Ni4+). Une analyse spectrale par décompositions de bandes permet d'identifier et de quantifier les proportions relatives des différents couples redox du nickel. Une réversibilité complète de la signature Raman est observée en décharge. Une application concrète et originale de la spectroscopie Raman a consisté à étudier le mécanisme d'autodécharge qui est observé pour le matériau LiNi0.4Mn1.6O4 complètement chargé. L'évolution des spectres Raman permet de mettre en évidence une réduction rapide et quantitative des ions Ni4+ pendant les premières heures de séjour dans l'électrolyte, puis un processus plus lent de réduction des ions Ni3+. Enfin, pour la première fois également, l'insertion du lithium dans le composé LiNi0.4Mn1.6O4 a été explorée par microspectrométrie Raman et a permis notamment d'identifier l'empreinte Raman de la phase la plus réduite de symétrie tétragonale Li2Ni0.4Mn1.6O4. L'originalité de ce travail a été d'apporter un grand nombre de données Raman expérimentales sur des matériaux d'électrode performants fonctionnant à 4V. De nouvelles attributions ont pu être proposées pour les composés initiaux, et des données vibrationnelles inédites ont été fournies sur les composés formés en charge et en décharge. Dans certains cas, ces données ont permis, sur la base d'une analyse détaillée des spectres Raman par décompositions de bandes, de proposer un raisonnement quantitatif sur l'existence de phases ou d'espèces redox en mélange. Il conviendrait bien sûr de corroborer ces nouvelles données et attributions par des calculs théoriques ab initio capables de simuler les fréquences et les intensités des modes vibrationnels dans les structures hôtes et lithiées / In this work, we show the relevance of Raman spectroscopy as a useful technique to investigate the local changes induced by the electrochemical reaction of intercalation/deintercalation of lithium in positive electrode materials for rechargeable lithium ion batteries.Raman investigations concern three types of high voltage cathode materials (4-5Volts) which are layered LiCoO2 and cubic LiMn2O4 and LiNi0.4Mn1.6O4.During electrochemical deintercalation of LiCoO2, we show the existence of a two phase region where the initial hexagonal phase coexist with a second hexagonal phase with a 3% expansion of the lattice parameter indicating a weakening of the Co-O bond in the Li1-xCoO2 material.On the other hand, a new assignment of LiMn2O4 Raman spectrum was proposed. During the charge in the 4V region, a three region phase (initial LiMn2O4 phase, intermediary phase and poor lithium phase) was described using Raman spectroscopy. RX measurements can not detect this intermediary phase. Lithiated phase Raman signature shows a specific local order: Fd3m for extreme phases and F43m for partially lithiated phase. A rich Raman band spectrum is attributed to this later phase in coherence with literature calculations. Structural changes reversibility is demonstrated. Identification of this intermediary phase as a major component of a cycled electrode, underline the incomplete reduction and explain the important loss of capacity observed during cycling. Raman study of LiMn2O4 electrochemical insertion in the 3V region, has demonstrated for the first time a progressive formation of tetragonal Li2Mn2O4 phase, which is in coexistence with initial cubic phase and is pure at the end of discharge. Structural transition reversibility was also demonstrated.In the case of LiNi0.4Mn1.6O4, the assignment of the Raman spectrum of LiNi0.4Mn1.6O4 is provided for the first time. DRX study in function of the state of charge and discharge, exhibit cubic structure conservation with moderate lattice parameters variations. The Raman spectrum of the spinel oxide exhibits drastic spectral changes during Li extraction. These changes have been directly related to the Mn and Ni oxidation states in the cathode material under operation. It comes out that electrochemical reactions of LiNi0.4Mn1.6O4 are reversible and based on three redox couples of Mn3+/Mn4+, Ni2+/Ni3+, and Ni3+/Ni4+. An original and concrete Raman spectroscopy application is the study of self discharge mechanism of completely charged LiNi0.4Mn1.6O4. Raman spectra evolution exhibits a quantitative Ni4+ reduction during the first hours, and then a slower Ni3+ reduction process. Finally, LiNi0.4Mn1.6O4 lithium insertion has been explored for the first time using Raman spectroscopy, and a tetragonal Li2Ni0.4Mn1.6O4 phase has been identified.The originality of this work is the important number of experimental Raman data of 4V electrode materials. New assignment of initial compound has been proposed and original vibrationnal data of compound during charge/discharge has been presented. These Raman data has permitted to propose a quantitative explanation which must be completed with ab initio calculations to simulate vibrationnal modes frequencies/ intensities

Ce mémoire est consacré à l'étude de nouveaux matériaux composites de type Si/Sn-Ni/Al/C pour former des électrodes négatives de batteries lithium ion. La microstructure de ces matériaux se présente sous la forme de nanoparticules de Si enrobées dans une matrice conductrice constituée de carbone et d'un composé intermétallique Ni3,4Sn4. La nanostructure et la composition du matériau composite lui confèrent de très bonnes performances en termes de capacité réversible, de stabilité électrochimique, et de cinétique de réaction. La mécanosynthèse a été choisie comme méthode d'élaboration. Les propriétés structurales et chimiques du composite ont été déterminées par analyses DRX, par microscopies électroniques MET et MEB, par analyses EDX et EFTEM et par spectroscopie Mössbauer de 119Sn. La caractérisation électrochimique a été réalisée par cyclage galvanostatique et par voltamétrie cyclique. La réactivité de ces matériaux envers le lithium a été étudiée par analyses DRX et spectroscopie Mössbauer de 119Sn in-situ. Ce mémoire détaille les résultats structuraux et électrochimiques obtenus pour différents matériaux composites basés sur Ni3,4Sn4 en ajoutant les éléments C, Al et Si. Une étude des mécanismes réactionnels lors du broyage mécanique ainsi que pendant le cyclage électrochimique a été effectuée et le rôle des différents éléments a été mis en évidence. Enfin, une discussion sur l'influence de la microstructure sur les performances électrochimiques des matériaux composites est donnée. Les meilleures performances électrochimiques sont obtenues pour le composite de composition nominale Ni0,14Sn0,17Si0,32Al0,04C0,35. Il présente une capacité réversible de 920 mAh/g avec une très bonne stabilité sur 280 cycles. Le matériau possède une excellente cinétique de délithiation : 90% de la capacité peut être délivrée en moins de 5 minutes. La capacité irréversible (20%) reste toutefois élevée et doit être encore améliorée en stabilisant l'interface solide/électrolyte (SEI) / This study is devoted to a new Si/Sn-Ni/Al/C composite material usable as negative electrode for lithium-ion batteries. The composite microstructure is made from Si nanoparticles embedded in a matrix, consisting of conductive carbon and Ni3.4Sn4 intermetallic compound. The nanostructure and composition of the composite material give excellent properties regarding reversible capacity, electrochemical stability, and reaction kinetics. Mechanical alloying has been chosen as synthesis method. The material structural and chemical properties have been determined by XRD analysis, by electron microscopy TEM and SEM, by EDX and EFTEM analysis and 119Sn Mössbauer spectroscopy. The electrochemical characterization was carried out by galvanostatic cycling and cyclic voltammetry. Lithium reactivity of these materials was studied by in-situ XRD analysis and 119Sn Mössbauer spectroscopy. This manuscript details the structural and electrochemical results obtained from various composite materials based on Ni3.4Sn4 by adding C, Al and Si elements. Reaction mechanisms during mechanical alloying and during electrochemical cycling have been investigated and the role of the different elements has been demonstrated. Finally, a discussion of the microstructure influence on the electrochemical performance of the composite materials is given. The best electrochemical properties are obtained for the composite material with nominal composition Ni0.14Sn0.17Si0.32Al0.04C0.35, which has a reversible capacity of 920 mAh/g with a very good stability of 280 cycles. Excellent kinetics during délithiation are obtained : 90% of capacity can be delivered in less than 5 minutes. However, the irreversible capacity (20 %) remains high and should be improved by stabilizing the solid/electrolyte interface (SEI)