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Novel lithium-ion host materials for electrode applicationsLyness, Christopher January 2011 (has links)
Two novel lithium host materials were investigated using structural and electrochemical analysis; the cathode material Li₂CoSiO₄ and the LiMO₂ class of anodes (where M is a transition metal ion). Li₂CoSiO₄ materials were produced utilising a combination of solid state and hydrothermal synthesis conditions. Three Li₂CoSiO₄ polymorphs were synthesised; β[subscript(I)], β[subscript(II)] and γ₀. The Li₂CoSiO₄ polymorphs formed structures based around a distorted Li₃PO₄ structure. The β[subscript(II)] material was indexed to a Pmn2₁ space group, the β[subscript(I)] polymorph to Pbn2₁ and the γ₀ material was indexed to the P2₁/n space group. A varying degree of cation mixing between lithium and cobalt sites was observed across the polymorphs. The β[subscript(II)] polymorph produced 210mAh/g of capacity on first charge, with a first discharge capacity of 67mAh/g. It was found that the β[subscript(I)] material converted to the β[subscript(II)] polymorph during first charge. The γ₀ polymorph showed almost negligible electrochemical performance. Capacity retention of all polymorphs was poor, diminishing significantly by the tenth cycle. The effect of mechanical milling and carbon coating upon β[subscript(II)], β[subscript(I)] and γ₀ materials was also investigated. Various Li[subscript(1+x)]V[subscript(1-x)]O₂ materials (where 0≤X≤0.2) were produced through solid state synthesis. LiVO₂ was found to convert to Li₂VO₂ on discharge, this process was found to be strongly dependent on the amount of excess lithium in the system. The Li₁.₀₈V₀.₉₂O₂ material had the highest first discharge capacity at 310mAh/g. It was found that the initial discharge consisted of several distinct electrochemical processes, connected by a complicated relationship, with significant irreversible capacity on first discharge. Several other LiMO₂ systems were investigated for their ability to convert to layered Li₂MO₂ structures on low voltage discharge. While LiCoO₂ failed to convert to a Li₂CoO₂ structure, LiMn₀.₅Ni₀.₅O₂ underwent an addition type reaction to form Li₂Mn₀.₅Ni₀.₅O₂. A previously unknown Li₂Ni[subscript(X)]Co[subscript(1-X)]O₂ structure was observed, identified during the discharge of LiNi₀.₃₃Co₀.₆₆O₂.
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Modèle multiphysique et méthodes d'analyse in-situ, non destructives, qualitatives et quantitatives de diverses sources de vieillissement d'accumulateurs lithium-ion / Mutiphysic model and in-situ, non-destructive, qualitative and quantitative analytical methods of different ageing origins for lithium-ion battery concernLegrand, Nathalie 19 November 2013 (has links)
L'optimisation de la durée de vie d'une batterie nécessite la prédiction de son vieillissement et donc l'identification des mécanismes de vieillissement qui en sont à l'origine. Pour pallier les limitations des outils de caractérisation du vieillissement classiquement utilisés (mesures intermittentes de performance au cours du vieillissement et tests de caractérisation post-mortem), des outils d'étude non destructive de l'état des électrodes en cours de vie ont été mis au point et testés. Il s'agit d'un modèle multiphysique de fonctionnement de la batterie lithium-ion et de deux méthodes d'extraction de paramètres in-situ : la première basée sur le traitement de la dérivée du profil de tension et la seconde sur la différence des pentes de profils de tension entre l'état neuf et l'état considéré. Les paramètres non disponibles mais nécessaires à l'établissement du modèle multiphysique d'un élément ont été estimés pour différents états de charge et différentes températures. Ce modèle a été validé par comparaison avec des mesures expérimentales. L'application de ces outils est illustrée dans le cas de trois mécanismes de vieillissement différents. En outre, ces outils ont été plus particulièrement appliqués au vieillissement par dépôt de lithium. L'utilisation du modèle de l'élément commercial VL41M Saft a permis de dresser un abaque de ses courants limites de fonctionnement et a fait l'objet d'une validation expérimentale mettant en oeuvre la méthode dite de la dérivée / Optimisation of a battery life time requires the prediction of its ageing and the identification of the involved ageing mechanisms. In order to avoid the limitations due to standard ageing characterisation methods (performance evaluations conducted regularly along ageing and post-mortem characterisations), other tools allowing assessment of the electrode state without deterioration along the life time, have been tested. It concerns a multiphysic model of lithium-ion battery and two methods for in-situ parameter extraction: the first is based on the study of the derivative of the tension profile and the second one, on the difference between the slope of the tension profiles at the fresh state and at the considered state. The non-available parameters required for set up of the multiphysic model for one battery have been evaluated for different states of charge and various temperatures. This model has been validated by comparison with experimental measurements. The application of these tools is illustrated for three different ageing mechanisms. Moreover these methods have been especially applied for the case of lithium plating ageing. Use of the VL41M Saft model allowed to set up an abacus of the limiting charge currents and an experimental validation has been performed in using the method so-called derivation method
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Apport de la spectrométrie de masse en temps réel à l’étude de la dégradation thermique d’électrolytes de batteries lithium-ion au contact de matériaux d’électrode positive / Contribution of real-time mass spectrometry to the study of the thermal degradation of lithium-ion battery electrolytes in contact with positive electrode materialsGaulupeau, Bertrand 11 July 2017 (has links)
L’utilisation des batteries lithium-ion est dorénavant une technologie de choix pour le secteur automobile notamment pour son utilisation dans les véhicules hybrides et électriques, du fait d’une importante densité d’énergie disponible ainsi que d’une forte densité de puissance nécessaire à la traction d’un véhicule. Cependant, à cause de l’importante énergie embarquée, la sécurité de tels dispositifs doit être renforcée. Il a été rapporté qu’en conditions abusives de température, l’effet cumulé de la dégradation d’un électrolyte utilisant le sel LiPF6 et l’effet catalytique de matériaux d’électrode positive mène à la formation d’espèces organo-fluorées telles que le 2-fluoroéthanol. Ce projet de thèse vise alors à approfondir la compréhension du rôle des matériaux d’électrode positive vis-à-vis de la dégradation d’électrolyte à base de LiPF6, notamment en étudiant la nature des gaz produits en conditions abusives de température. Pour mener à bien ce projet, un dispositif permettant une analyse in situ des gaz formés a été développé. Le rôle de l’eau sur la formation des espèces organo-fluorées fait également l’objet d’une attention toute particulière. L’influence de plusieurs matériaux d’électrode positive sur la nature des produits de dégradation de l’électrolyte a pu être mise en évidence. Ce travail a ainsi permis d’évaluer l’influence de différents paramètres sur la dégradation thermique de l’électrolyte en vue de prédire le choix des différents constituants d’une batterie lithium-ion / The use of lithium-ion batteries is now a technology of choice for the automotive sector especially for its use in hybrid and electric vehicles, due to a high density of energy available as well as a high power density necessary to the traction of a vehicle. However, due to the high on-board energy, the safety of such devices must be enhanced. It has been reported that under abusive thermal conditions the cumulative effect of degradation of a LiPF6-based electrolyte and the catalytic effect of positive electrode materials leads to the formation of fluoro-organic species such as 2-fluoroethanol. This thesis aims to deepen the understanding of the role of positive electrode materials towards the degradation of LiPF6-based electrolyte, in particular by studying the nature of the gases produced under abusive thermal conditions. To carry out this project, a device allowing an in situ analysis of the formed gases has been developed. The role of water on the formation of fluoro-organic species is also the subject of a particular attention. The influence of several positive electrode materials on the nature of the degradation products of the electrolyte has been demonstrated. This work allowed to evaluate the influence of different parameters on the thermal degradation of the electrolyte in order to predict the choice of the various constituents of a lithium-ion battery
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Contribution de l'émission acoustique pour la gestion et la sécurité des batteries Li-ion / Combining methods for improved safety and energy managment of Li-ion batteries application.Kircheva, Nina 16 January 2013 (has links)
L'objectif de cette thèse est de démontrer que l'Emission Acoustique (AE) est une technique appropriée pour devenir un outil de diagnostic de l'état de charge, de santé et de sécurité pour les batteries lithium-ion. Ces questions sont actuellement des points clés important pour l'amélioration des performances et des durées de vie de la technologie. La structure de ce document est organisée en deux principaux chapitres expérimetaux l'un consacré à deséléments lithium-ion composés de composés d'intercalation et l'autre à desalliages de lithium.Dans le premier cas, les résultats présentés concernent le suivi par AE de la formation de la SEI et de la première intercalation des ions lithium dans la structure du graphite pour des éléments LiFePO4/C. Les événements AE provenant de plusieurs sources ont été identifiés et correspondent à la formation de gaz (bulles) et à des phénomènes de craquelures (ouvertures du bord des plans de graphène quand la SEI est formée et l'écartement quand les stades d'insertion du graphite-lithium sont finis). De plus, une étude par spectroscopie d'impédance a été menée durant un vieillissement calendaire en température sur des éléments formés à différents régimes de courant. Dans le second cas, le mécanisme d'insertion/extraction du lithium dans des éléments LiAl/LiMnO2 a été étudié en associant plusieurs techniques incluant des techniques électrochimiques, AE et post-mortem pour évaluer les mécanismes de dégradation. Lors du cyclage, les événements acoustiques sont plus intenses lors du processus de décharge et ils peuvent être attribués principalement à l'alliage avec la transformation de phase de -LiAl en -LiAl accompagnée d'une expansion volumique importante. L'émission acoustique peut ainsi offrir une nouvelle approche pour gérer le fonctionnement des technologies lithium-ion basées non plus seulement sur des paramètres électrochimiques classiques mais aussi sur des paramètres acoustiques. Des nouveaux d'états de santé et de sécurité peuvent ainsi être envisagés. / The aim of this thesis is to demonstrate that the Acoustic Emission (AE) is an appropriate technique for diagnostics of for state of charge, state of health and state of safety for lithium-ion batteries. The availability and optimization of the latter issues are key points for both performance and durability improvements of this technology. The frame of this document is organized in two main result chapters focused on AE study of two different Li-ion technologies. The beginning of the thesis is focused on the monitoring of the SEI formation by AE and the first lithium ion intercalation inside the graphite structure for LiFePO4/C cells. AE events coming from different sources have been analyzed and identified. It was found that they correspond to gas emission (bubbles) and cracking phenomena (opening on the edge of the graphene plane when the SEI is formed and spacing when lithium graphite insertion stages are completed). Further, a study of the calendar aging process supported by electrochemical impedance spectroscopy linked the aging rate with the mechanism of the SEI formation characterized by AE monitoring. The second part of the thesis studied of lithium ion insertion/extraction in LiAl/LiMnO2 cells combining a variety of techniques including electrochemical characterization, AE monitoring and post-mortem analysis in order to evaluate the degradation mechanisms. It was found that during the cycling, the acoustic events are much more intensive during the discharge process and they can be attributed mainly to the alloy were the phase transformation from -LiAl to -LiAl and a huge volume expansion occurs. It was found that battery operation under abusive conditions (overcharge, overdischarge) can be detected by AE providing new rates for battery safety management.
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Électrodes négatives composites à base d'étain ou de silicium pour accumulateur lithium-ion avec accrochage souple et/ou enrobage à mémoire de forme / Tin- or silicon-based negative electrode composites for lithium-ion battery with floppy pinning and/or memory shape coatingLadam, Alix 08 December 2016 (has links)
Ce mémoire est consacré à l’étude de nouveaux composites à base de Ni/Ti/Sn/Si comme matériaux d’électrodes négatives pour accumulateurs rechargeables Li-ion. Ces matériaux se présentent sous la forme d’une matrice active ou inactive électrochimiquement, enrichie avec du silicium pour former un composite nanostructuré. Ils présentent des capacités massiques supérieures à celles du carbone avec de bonnes performances en terme de capacité réversible, stabilité électrochimique, et cinétique de réaction. La mécanosynthèse a été choisie comme méthode d’élaboration de ces composites. Les propriétés physico-chimiques des composites ainsi synthétisés ont été caractérisées par diffraction des Rayons X, spectrométrie Mössbauer de 119Sn et microscopie électronique à balayage. Les caractérisations électrochimiques ont été effectuées par cyclages galvanostatiques. La complémentarité entre ces différentes techniques a permis d’analyser les mécanismes réactionnels. L’étude détaillée de ces nouveaux matériaux composites, nous a permis de mettre en évidence l’influence de la matrice et du taux d’enrichissement en silicium sur les performances électrochimiques (capacité réversible pouvant atteindre 1300 mAh.g¡1 et efficacité coulombique >99,5%). Ces matériaux présentent une grande flexibilité de composition permettant d’adapter leur capacité massique aux applications visées. / This work has been devoted to new Ni/Ti/Sn/Si based composites as negative electrode materials for lithium-ion batteries. Thesematerials are formed by tin based electrochemically active matrix and/or silicon based electrochemically inactive matrix enriched with silicon. They were obtained by ball milling method leading to nanostructured compositeswith strongly improved electrochemical performances compared to commercially used carbon. This includes reversible capacity, electrochemical stability and reaction kinetics.The composites were characterized by X-ray diffraction, 119Sn Mössbauer spectroscopy and scanning electron microscopy while their electrochemical performances were carried out by galvanostatic cycling. Finally, the reaction mechanisms were elucidated from X-ray diffraction and 119Sn Mössbauer spectroscopy used in operando mode. By combining these results with empirical models, it has been possible to optimize the composition and the synthesis conditions of the composite to improve the electrochemical properties and obtain reversible specific capacity up to 1300 mAh.g-1 with Coulombic efficiency higher than 99.5%. In addition, the composition flexibility of these materials allows to adapt their electrochemical properties to specific applications.
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Accumulateur lithium-ion à cathode de fluorures de métaux de transition / Transition metal fluoride for lithium-ion batteries applicationsDelbegue, Diane 25 September 2017 (has links)
Les batteries lithium ions sont la technologie de référence pour le stockage électrochimique de l’énergie. Cependant, les matériaux cathodiques de ces batteries comme LiCoO2, LiMn2O4 ou LiFePO4 présentent une capacité spécifique limitée (<160 mAh/g). De nombreux composés sont à l’étude pour améliorer cette performance dont le fluorure de fer (III) en raison de sa capacité théorique de 711 mAh.g-1. Ce travail présentera la synthèse de FeF3 par différentes méthodes de fluoration. Les matériaux obtenus seront comparés en termes de structures et de liaison (DRX, Mössbauer, spectroscopies IR et Raman) mais aussi de texture (isothermes d’adsorption à l’azote à 77K). Les propriétés électrochimiques des matériaux obtenus seront également comparées et testées. Enfin, l’étude du mécanisme électrochimique de cette famille de composés sera menée via une méthode de caractérisation « in operando » : la spectroscopie d’absorption des rayons X (XAS). / The lithium-ion batteries are the current solution for electrochemical energy storage. However, their performances are limited by the cathode materials, such as LiCoO2, LiMn2O4 or LiFePO4 of specific capacity lower than 160 mAh/g. Many materials are good candidates to improve this capacity such as iron trifluoride of theoretical capacity of 711 mAh.g-1. This work will present the synthesis of FeF3 through different fluorination ways. The resulting materials will be characterized owing to their structure by XRD, Mössbauer, Raman and IR spectroscopies and their texture by nitrogen adsorption isotherms at 77K and SEM. After that, the electrochemical properties will be evaluated and compared. Finally, the study of the electrochemical mechanism of this family of compounds will be led with a method of characterization “in operando” : the X-rays absorption spectroscopy (XAS).
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Modélisation non entière et non linéaire d'un accumulateur lithium-ion en vue de la mise en oeuvre d'observateur pour l'observation de variable interneMerveillaut, Mathieu 20 January 2011 (has links)
Avec l’apparition du véhicule électrique, le besoin électrique est en progression constante. La taille des batteries étant contrainte et leurs performances étant limitées, il est devenu indispensable de disposer d’une Gestion de l’Energie Electrique (GEE) performante. Il est donc nécessaire de maitriser l’énergie et la puissance disponibles de l’accumulateur grâce à des estimateurs d’états internes. Ce travail de thèse présente une étude détaillée de la modélisation des accumulateurs lithium-ion à partir de la théorie des électrodes poreuses ainsi que des méthodes de paramétrisation de ces modèles. Sur la base de cette étude, des structures d’observation de l’état de charge d’un accumulateur lithium-ion ont été créées. Ces structures permettent d’estimer l’état de charge de manière fiable tout en prenant en compte des erreurs de mesures des courants et tensions mises en jeu. / In electric cars, electrical need increases continuously. Since, the battery size is limited and its performances do not improve any more, it is essential to have a high-performance electrical energy management. It is thus necessary to control the battery resources, in terms of available energy and power, thanks to an ageing-integrated state estimator. This thesis work presents a detailed study of the modeling of the lithium-ion battery thanks to the porous electrodes theory and parameterization methods of these models. Following this study, structures of observation of the SOC of lithium-ion batteries has been made. Those structures allow us to estimate the Soc in a reliable way taking into account of currents and voltages errors involved.
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Etude des risques d'arc électrique dans les batteries lithium-ion / Electric arc risks study in lithium-ion batteriesAugeard, Amaury 10 November 2015 (has links)
La sûreté de fonctionnement des batteries est un point clé pour la croissance de ce marché et le déploiement de solutions hybrides afin de réduire la consommation d’énergie. L’électrification croissante de ces systèmes ne fait qu’aggraver l’augmentation de l’occurrence de ce problème qui bien que connu depuis longtemps dans le domaine des applications DC ne fait l’objet de recherches intensives que depuis peu comme en témoigne le développement récent des premiers détecteurs d’arc pour l’aviation. L’arc dans les batteries représente aujourd’hui un risque potentiel pour l’intégrité du matériel et des personnes du fait de l’utilisation des batteries au sein d’applications industrielles de fortes puissances. Afin de caractériser ce risque et d’en évaluer la dangerosité, plusieurs bancs d’essais sont réalisés au niveau élément et système afin de reproduire le phénomène d’arc électrique. Les essais réalisés permettent d’extraire les caractéristiques intrinsèques de l’arc. En complément de cette caractérisation, un modèle d’arc permettant d’évaluer les paramètres et d’améliorer la compréhension de ce phénomène est réalisé. Des solutions de limitation, voire de suppression de l’arc issues de cette étude sont proposées. Parmi ces nombreuses solutions, l’utilisation de capteurs optiques, les méthodes numériques pour le traitement des signaux issus de l’arc, la modification de l’architecture batterie ainsi que l’augmentation du niveau de tension lors de l’amorçage de l’arc ouvrent la voie à la conception de systèmes de batteries innovants et plus sûrs en termes de fiabilité, sécurité et de robustesse. Les nombreuses perspectives de recherches proposées permettront également d’améliorer la couverture de ce risque. / The operational security of batteries is a key element in the growth of this market and the deployment of hybrid solutions to reduce energy consumption.The increasing electrification of these systems can only exacerbate the occurrence ratio increase of this problem. Although known for a number of years in the field of DC applications, electric arcs are the subject of intensive research for a short time as shown by the recent development of the first arc sensors for aviation. Electric arcs in batteries currently represent a potential risk to the integrity of the equipment and people because of the use of these batteries in industrial high power applications. To characterize this risk and assess its dangerousness, several test benches were designed at the cell and system level to reproduce the electric arc phenomenon. The tests carried out allow extracting the intrinsic characteristics of the arc. In addition to this characterization, an arc model to evaluate the parameters and improve the understanding of this phenomenon is realized. Limiting mitigation solutions or suppression of the arc resulting from this study are proposed. Among the many solutions, the use of optical sensors, the numerical methods for digital signal processing from the arc, the modification of the architecture as well as the increase of the arc ignition voltage pave the way for the design of innovative and safer batteries systems in terms of reliability, security and robustness. The numerous proposed research perspectives will also improve the coverage of this risk.
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Influence Of Nanostructuring On Electrochemical Performance Of Titania-Based Electrodes And Liquid Electrolytes For Rechargeable Lithium-Ion BatteriesDas, Shyamal Kumar 10 1900 (has links) (PDF)
The present thesis deals with the beneficial influence of nanostructuring on electrochemical performance of certain promising electrode and electrolyte materials for lithium-ion batteries (LIBs). Electrochemical performances of chosen electrodes and electrolytes have been presented in a systematic and detailed manner via studies related to both transport and lithium storage. Titanium dioxide (TiO2) or titania, a promising non-carbonaceous anode material for LIBs was chosen for the study. As part of the study, variety of nanostructured titania were synthesized. In general, all materials exhibited high lithium storage ( theoretical value for lithium storage in titania) and some of them showed exemplary rate capability, typically desired for modern lithium-ion batteries. Studies related to performance of these materials and mechanistics of lithium storage and kinetics are presented in Chapters 2-5. “Soggy sand” electrolyte, a promising soft matter electrolyte for LIBs was studied on the electrolyte side. Ion transport, mechanical strength and electrochemical properties of “soggy sand” electrolytes synthesized via dispersion of various surface chemically functionalized silica particles dispersed in model as well as LIB relevant electrolytes were studied in this thesis. Extensive physico-chemical and battery performance studies of “soggy sand” electrolytes are discussed in Chapters 6-8. A brief discussion of the contents and highlights of the individual chapters are described below:
Chapter 1 briefly discusses the importance of electrochemical power sources as a viable green alternative to the combustion engine. Various facets of rechargeable LIBs, one of the most important electrochemical storage devices, are presented following the general discussion on electrochemical power devices. The importance of nanostructuring of electrodes with special emphasis on anodes for high lithium storage capacities and rate capabilities are also discussed in the opening chapter. The various advantages and disadvantages of the most commonly used electrolytes in LIB i.e. the liquid electrolytes are also discussed in Chapter 1. Suggestions for improvement of the physico-chemical properties of liquid electrolytes especially via nanostructuring (demonstrated via dispersions of fine oxide particles in liquid electrolytes in Chapters 6-8) using the concept of Heterogeneous doping are discussed in detail. A brief description on the importance of rheology for comprehension of soft matter microstructure is also provided in this chapter.
Chapter 2 discusses composite of anatase titania (TiO2) nanospheres and carbon grown and self-assembled into micron-sized mesoporous spheres via a solvothermal synthesis route as prospective anode for rechargeable lithium-ion battery. The morphology and carbon content and hence the electrochemical performance are observed to be significantly influenced by the synthesis parameters. Synthesis conditions resulting in a mesoporous arrangement of an optimized amount of carbon and TiO2 exhibited the best lithium battery performance. The first discharge cycle capacity of carbon-titania mesoporous spheres (solvothermal reaction at 150 oC at 6 h, calcination at 500 oC under air, BET surface area 80 m2g-1) was 334 mAhg-1 (approximately 1 Li) at current rate of 66 mAg-1. High storage capacity and good cyclability is attributed to the nanostructuring (i.e. mesoporosity) of TiO2 as well as due to formation of a percolation network of carbon around the TiO2 nanoparticles. The micron-sized mesoporous spheres of carbon-titania composite nanoparticles also show good rate cyclability in the range (0.066-6.67) Ag-1. The electrochemical performance of the mesoporous carbon-TiO2 spheres has been compared with nonporous TiO2 spheres, normal mesoporous TiO2 and bulk TiO2.
Implications of nanostructuring and conductive carbon interface on lithium insertion/removal capacity and insertion kinetics in nanoparticles of anatase polymorph of titania is discussed in Chapter 3. Sol-gel synthesized nanoparticles of titania (particle size ~ 6 nm) were hydrothermally coated ex situ with a thin layer of amorphous carbon (layer thickness: 2-5 nm) and calcined at a temperature much higher than the sol-gel synthesis temperature. The carbon-titania composite particles (resulting size 10 nm) displayed immensely superior cyclability and rate capability (higher current rates 4 Ag-1) compared to unmodified calcined anatase titania. The conductive carbon interface around titania nanocrystals enhances the electronic conductivity and inhibits crystallite growth during electrochemical insertion/removal thus preventing detrimental kinetic effects observed in case of un-modified anatase titania. The carbon coating of the nanoparticles also stabilized the titania crystallographic structure via reduction in the accessibility of lithium ions to the
trapping sites. This resulted in decrease in the irreversible capacity observed in case of nanoparticles without any carbon coating.
Chapter 4 discusses the morphology and electrochemical performance of mixed crystallographic phase titania nanotubes and nanosheets for prospective application as anode in rechargeable lithium-ion batteries. Hydrothermally grown nanotubes/nanosheets of titania (TiO2) and carbon/silver-titania (C/Ag-TiO2) comprise a mixture of both anatase and TiO2(B) crystallographic phases. The first cycle capacity (at current rate = 10 mAg-1) for bare TiO2 nanotubes was 355 mAhg-1 (approximately 1.06 Li), which is higher than both the theoretical capacity (335 mAhg-1) as well as reported values for pure anatase and TiO2(B) nanotubes. Higher capacity is attributed to a combination of presence of mixed crystallographic phases of titania as well as trivial size effects. The surface area of bare TiO2 nanotubes was very high being equal to 340 m2g-1. Surface modification of the TiO2 nanotubes via amorphous carbon and Ag nanoparticles resulted in significant improvement in battery performance. The first cycle irreversible capacity loss can be minimized via effective coating of the surface. Carbon coated TiO2 nanotubes showed superior performance than Ag nanoparticle coated TiO2 nanotubes in terms of long term cyclability. Unlike Ag nanoparticles which are randomly distributed over the TiO2 nanotubes, the effective homogeneous carbon coating forms an efficient percolation network for the conducting species thus exhibiting better battery performance. The C-TiO2 and Ag-TiO2 nanotubes showed a better rate capability i.e. higher capacities compared to bare TiO2 nanotubes in the current range 0.055-2 Ag-1. Although titania nanosheets retains mixed crystallographic phases, the lithium battery performance (first cycle capacity = 225 mAhg-1) is poor compared to TiO2 nanotubes. It is attributed to lower surface area (22 m2g-1) which resulted in lesser electrode/electrolyte contact area and inefficient transport pathways for Li+ and e-.
Implications of iron on electrochemical lithium insertion/removal capacity of iron (Fe3+) doped anatase TiO2 is discussed in Chapter 5. Iron doped anatase TiO2 nanoparticles with different doping concentrations were synthesized by simple sol-gel method. The electrochemistry of anatase TiO2 is observed to be a strong function of concentration of iron (Fe3+). A high 1st cycle discharge capacity of 704 mAhg−1 (2.1 mol of Li) and 272 mAhg−1 (0.81 mol of Li) at the 30th discharge cycle with Coulombic efficiency greater than 96% has been observed for 5% iron (Fe3+) doped TiO2 at a current density of 75 mAg−1. Additional increase in the iron (Fe3+) concentrations deteriorates the lithium storage of TiO2. An improvement in lithium storage of more than 50% is noticed for 5% iron (Fe3+) doped TiO2 compared to pure anatase TiO2 which shows an initial discharge capacity of 279 mAhg−1. The anomalous lithium storage behavior in all the iron (Fe3+) doped TiO2 has been accounted, in addition to homogeneous Li insertion in the octahedral sites, on the basis of formation of metallic Fe and Li2O during initial lithiation process and subsequent heterogeneous interfacial storage between Fe and Li2O interface.
Chapter 6 discusses in a systematic manner the crucial role of oxide surface chemical composition on ion transport in “soggy sand” electrolytes. A “soggy sand” electrolytic system comprising of aerosil silica functionalized with various hydrophilic and hydrophobic moeities dispersed in lithium perchlorate ethylene glycol solution ( = 37.7) was used for the study. Detailed rheology studies show that the attractive particle network in case of the composite with unmodified aerosil silica (with surface silanol groups) is most favorable for percolation in ionic conductivity as well as rendering the composite with beneficial elastic mechanical properties. Though weaker in strength compared to the composite with unmodified aerosil particles, attractive particle networks are also observed in composites of aerosil particles with surfaces partially substituted with hydrophobic groups. However, ionic conductivity is observed to be dependent on the size of the hydrophobic moiety. No spanning attractive particle network was formed for aerosil particles with surfaces modified with stronger hydrophilic groups (than silanol) and as a result no percolation in ionic conductivity was observed. The composite with hydrophilic particles was a sol contrary to gels obtained in case of unmodified aerosil and partially substituted with hydrophobic groups.
Chapter 7 also discusses the influence of oxide surface chemical composition but additionally the role of solvent on ion solvation and ion transport of “soggy sand” electrolytes. Compared to the liquid electrolyte in Chapter 6, a lower dielectric constant
liquid electrolyte was employed for the study in this chapter. A “soggy sand” electrolyte system comprising of dispersions of hydrophilic/hydrophobic functionalized aerosil silica in lithium perchlorate-methoxy polyethylene glycol solution ( = 10.9) was employed for the study. Static and dynamic rheology measurements again showed formation of an attractive particle network in case of the composite with unmodified aerosil silica (i.e. with surface silanol groups) as well as composites with hydrophobic alkane groups. While particle network in the composite with hydrophilic aerosil silica (unmodified) were due to hydrogen bonding, hydrophobic aerosil silica particles were held together via van der Waals forces. The network strength in the latter case (i.e. for hydrophobic composites) were weaker compared with the composite with unmodified aerosil silica. Both unmodified silica as well as hydrophobic silica composites displayed solid-like mechanical strength. However, this time around no enhancement in ionic conductivity compared to the liquid electrolyte was observed in case of the unmodified silica. This is attributed to the existence of a very strong particle network which leads to the “expulsion” of all conducting entities from the interfacial region between adjacent particles. The ionic conductivity for composites with hydrophobic aerosil particles displayed ionic conductivity as a function of the size of the hydrophobic chemical moiety. No spanning attractive particle network was observed for aerosil particles with surfaces modified with stronger hydrophilic groups (than silanol). The composite resembled a sol and no percolation in ionic conductivity was observed.
Chapter 8 describes the influence of dispersion of uniformly sized mono-functional or bi-functional (“Janus”) particles on ionic conductivity in lithium battery solutions and it’s implications on battery performance. Mono-functionalized (hydrophilic or hydrophobic) and bi-functionalized Janus (hydrophilic and hydrophobic) particles form physical gels of varying strength over a wide range of concentration (0.1 0.4; , oxide volume fraction). While the composites with mono-functionalized particles display shear thinning typical of gels (due to gradual breaking up spanning particle network held together by hydrogen/van der Walls force), the bi-functionalized “Janus” particles exhibit both complementary properties of gel and sol. The latter observation is interpreted in terms of existence of both hydrogen and van der Waals force arising out of the particle
arrangement which get perturbed under the influence of external shear. Composites with homogeneous hydrophilic surface group show the highest ionic conductivity whereas the homogeneous hydrophobic surfaces exhibit superior electrode/electrolyte interface stability and battery cyclability. The Janus particles did not show any enhancement in ionic conductivity however, battery performance is highly satisfactory taking intermediate values between the homogeneously functionalized hydrophilic and hydrophobic particle composites.
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Développement de solutions innovantes d'électrolytes pour sécuriser les accumulateurs lithium-ion / Development of innovative electrolytes for safer lithium-ion batteriesChancelier, Léa 24 October 2014 (has links)
Les batteries lithium-ion dominent le marché des appareils nomades et celui des véhicules électriques. Néanmoins elles posent des problèmes de sécurité liés à leur électrolyte, contenant des carbonates inflammables et volatils. Pour sécuriser ces systèmes, les liquides ioniques (LI) sont étudiés comme électrolytes alternatifs. Ce sont des sels liquides à température ambiante, réputés stables thermiquement et non inflammables. Ce caractère sécuritaire des LI, souvent avancé, est pourtant peu étayé par des expériences probantes. Les travaux de cette thèse visent à comprendre le comportement de ces LI en situations abusives, telles qu'un échauffement de la batterie, un feu ou une surcharge. Les températures de décomposition de LI contenant les cations imidazolium ou pyrrolidinium différemment substitués et l'anion bis(trifluoromethanesulfonyl)imide ont été déterminées par analyse thermogravimétrique (ATG). Une analyse critique des données (de la littérature et de nos mesures) a permis de définir une procédure optimisée, pour obtenir des résultats reproductibles et comparables. Des électrolytes constitués de mélanges de carbonates ou de LI et de sels de lithium ont été analysés par ATG dynamique et isotherme, et leurs produits de décomposition ont été identifiés. Leur comportement au feu a été testé par la mesure des chaleurs de combustion, des délais d'inflammation et l'identification des gaz générés. Des tests de cyclage électrochimique ont été menés avec ces mêmes électrolytes dans des systèmes lithium-ion constitués des électrodes Li4Ti5O12 et LiNi1/3Mn1/3Co1/3O2. L'évolution des électrolytes et des surfaces des électrodes en situation de surcharge a été examinée / Lithium-ion batteries are dominating both the nomad device and electric vehicle markets. However they raise safety concerns related to their electrolyte, which consists of flammable and volatile carbonate mixtures and toxic salts. The replacement of the latter by ionic liquids (IL), liquid salts claimed to be thermally stable and non-flammable, could provide a safer alternative. Yet this often claimed feature has been poorly examined by experiments. The work of this thesis investigates IL behaviour under abuse conditions such as overheating, fire or overcharge. Decomposition temperatures of IL based on differently substituted imidazolium or pyrrolidinium cations and the bis(trifluoromethanesulfonyl)imide anion were determined by thermogravimetric analysis (TGA). A critical study of gathered data (from literature and our work) led to the determination of an optimised procedure to obtain reproducible and comparable results. Electrolytes based on carbonates mixtures or IL and containing lithium salt were studied by dynamic and isothermal TGA, and their decomposition products were identified. Their combustion behaviour was also tested by measuring heats of combustion and ignition delays. Emitted gases were analysed and quantified. Electrochemical cycling tests were carried out with these electrolytes in lithium-ion systems based on Li4Ti5O12 and LiNi1/3Mn1/3Co1/3O2 electrodes. The evolution of the electrolytes and electrodes surface was also examined under overcharge
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