Nanotubes (inner diameter of 8nm and outer diameter of 10nm with a length of up to several hundred nm) and nanowires (diameter 20 – 50nm and up to several μm in length) of TiO₂-B have been synthesised and characterised for the first time. These exhibit excellent properties as a host for lithium intercalation and are able to accommodate lithium up to a composition of Li₀.₉₈TiO₂-B for the nanotubes and Li₀.₈₉TiO₂-B for the nanowires. Following some irreversible capacity on the first cycle, which could be reduced to 4% for the nanowires, capacity retention for the nanowires is 99.9% and for the nanotubes is 99.5% per cycle. In both cases, the cycling occurs at ~1.6V versus lithium. The cycling performance was compared with other forms of bulk and nano-TiO₂, all of which were able to intercalate less lithium. Nanowires of VO₂-B (50 – 100nm in diameter and up to several μm in length) were synthesised by a hydrothermal reaction and characterised. By reducing the pressure inside the hydrothermal bomb, narrower VO₂-B nanowires with a diameter of 2 – 5nm and length of up to several hundred nm were created - some of the narrowest nanowires ever made by a hydrothermal reaction. These materials are isostructural with TiO₂-B and were also found to perform well in rechargeable lithium ion batteries, being able to intercalate 0.84Li for the ultra-thin nanowires and 0.57Li for the standard nanowires. The standard VO₂-B nanowires have a capacity retention of 99.8% and the ultra-thin nanowires have 98.4% per cycle after some irreversible capacity on the first cycle. This was found to improve markedly when different electrolytes were used. Macroporous Co₃O₄ (pore size 400nm with a surface area of 208m²/g) was prepared and cycled in rechargeable lithium cells with capacities of 1500mAh/g being achieved. The structure was found to break down on the first cycle and after this the material behaved in the manner of Co₃O₄ nanoparticles. Finally a new candidate for next generation rechargeable lithium batteries was examined; Li/O₂ cells. The cathode is composed of porous carbon in which Li⁺, e⁻ and O₂ meet to form Li₂O₂ on discharge. The reaction is reversible on charge. Capacities of 2800mAh/g can be achieved when 5%mole of αMnO₂ nanowires catalyst is used. Fade is high at 3.4% per cycle meaning that there is much work to do to develop these into a commercial prospect.

Currently, automotive batteries use intercalation cathodes such as lithium iron phosphate (LiFePO4) which provide high levels of safety while sacrificing cell voltage and therefore energy density. Lithium transition metal oxide (LiMO2) batteries achieve higher cell voltages at the risk of releasing oxygen gas during charging, which can lead to ignition of the liquid electrolyte. To achieve both safety and high energy density, oxide cathodes must be well characterized under operating conditions. In any intercalation cathode material, the loss of positive lithium ions during charge must be balanced by the loss of negative electrons from the host material. Ideally, the TM ions oxidize to compensate this charge. Alarmingly, the stoichiometry of the latest LiMO2 cathode materials includes more lithium ions than the TM ions can compensate for. Inevitably, peroxide ions or dioxygen gas must form. The former mechanism is vital for lithium-air batteries, while the latter must be avoided. Battery researchers have long sought to completely characterize the intercalation reaction in working batteries. However, the volatile electrolytes employed in batteries are not compatible with vacuum-based characterization techniques, nor are the packaging materials required to contain the liquid. For the first time, a solid state battery (using exposed particles of Li1.17Ni0.25Mn0.58O2) was charged while using soft X-ray absorption spectroscopy to observe the redox trends in nickel, manganese and oxygen. This was combined with innovative hard X-ray absorption spectroscopic studies on the same material to create the most complete picture yet possible of charge compensation.

abstract: This thesis focused on physicochemical and electrochemical projects directed towards two electrolyte types: 1) class of ionic liquids serving as electrolytes in the catholyte for alkali-metal ion conduction in batteries and 2) gel membrane for proton conduction in fuel cells; where overall aims were encouraged by the U.S. Department of Energy. Large-scale, sodium-ion batteries are seen as global solutions to providing undisrupted electricity from sustainable, but power-fluctuating, energy production in the near future. Foreseen ideal advantages are lower cost without sacrifice of desired high-energy densities relative to present lithium-ion and lead-acid battery systems. Na/NiCl2 (ZEBRA) and Na/S battery chemistries, suffer from high operation temperature (>300ºC) and safety concerns following major fires consequent of fuel mixing after cell-separator rupturing. Initial interest was utilizing low-melting organic ionic liquid, [EMI+][AlCl4-], with well-known molten salt, NaAlCl4, to create a low-to-moderate operating temperature version of ZEBRA batteries; which have been subject of prior sodium battery research spanning decades. Isothermal conductivities of these electrolytes revealed a fundamental kinetic problem arisen from "alkali cation-trapping effect" yet relived by heat-ramping >140ºC. Battery testing based on [EMI+][FeCl4-] with NaAlCl4 functioned exceptional (range 150-180ºC) at an impressive energy efficiency >96%. Newly prepared inorganic ionic liquid, [PBr4+][Al2Br7-]:NaAl2Br7, melted at 94ºC. NaAl2Br7 exhibited super-ionic conductivity 10-1.75 Scm-1 at 62ºC ensued by solid-state rotator phase transition. Also improved thermal stability when tested to 265ºC and less expensive chemical synthesis. [PBr4+][Al2Br7-] demonstrated remarkable, ionic decoupling in the liquid-state due to incomplete bromide-ion transfer depicted in NMR measurements. Fuel cells are electrochemical devices generating electrical energy reacting hydrogen/oxygen gases producing water vapor. Principle advantage is high-energy efficiency of up to 70% in contrast to an internal combustion engine <40%. Nafion-based fuel cells are prone to carbon monoxide catalytic poisoning and polymer membrane degradation unless heavily hydrated under cell-pressurization. This novel "SiPOH" solid-electrolytic gel (originally liquid-state) operated in the fuel cell at 121oC yielding current and power densities high as 731mAcm-2 and 345mWcm-2, respectively. Enhanced proton conduction significantly increased H2 fuel efficiency to 89.7% utilizing only 3.1mlmin-1 under dry, unpressurized testing conditions. All these energy devices aforementioned evidently have future promise; therefore in early developmental stages. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2014

The aim of this thesis is to investigate pyroborates, M2B2O5, and orthoborates, M3(BO3)2, where M = Mg, Mn, Co, Ni, as high capacity and high voltage Li- and Mg-ion cathode materials. We explore the layered orthoborates (M3(BO3)2 which, to our knowledge, have not been previously considered as Li- or Mg-ion cathodes, perhaps due to the lack of Li analogues. Structural analysis shows that mixed metal orthoborates form a solid solution, with cation order driven by the presence of directional d orbitals. Electrochemical studies show that Mg can be removed from the structure and replaced with Li in a 1:1 ion ratio. In the compound Mg2Mn(BO3)2 removal of 1 Mg is achieved giving a capacity of 209.9 mAh g 1. The pyroborates (M2B2O5) are an unexplored family of borate polyanions, which offer higher theoretical capacities and voltages than LiMBO3 due to their more condensed frameworks. There are no known Li containing pyroborates, we use electrochemical ion exchange, with the aim of replacing each Mg with 2 Li to form LixMB2O¬5. The stoichiometry can be varied to alter the redox couple utilised and the Mg available for removal. MgxM2-xB2O5 has been synthesised for M = Mn, Co, Fe and Ni and all forms have been shown to form a solid solution with cation ordering over the two M sites. In MgMnB2O5 we have shown that Mg can be fully removed while retaining the pyroborate structure. Subsequently up to 1.1 Li can be inserted giving discharge capacities of 240 mAhg-1 above 1.5 V. After 100’s of cycles 2 Li can be reversibly cycled. The insertion of Li has been confirmed by 7Li NMR and the oxidation state changes in Mn have been investigated by SQUID magnetometry and XANES spectroscopy. Electrochemical studies in materials where M = Fe, Co, and Ni show high voltage plateaus ( > 3.5 V) but limited capacity at room temperature. Increased temperatures improves cycling, with Co and Fe based compounds reaching full theoretical capacities ( > 200 mAhg-1). As Mg can be removed from the structure, the pyroborates could be of interest in Mg-ion batteries, which offer benefits in energy density, cost, and safety. Mg-ion battery research is still in its infancy, therefore here we develop methods to reliably test Mg-ion cathodes and electrolytes. We demonstrate that despite significant side reactions, Mg can be reversibly cycled in the MgMnB2O5 system in a full Mg-ion cell, showing that pyroborates are a promising family of materials for high capacity, high voltage Mg-ion cathodes. This study shows that the pyroborates and orthoborates are a promising family of materials for Li- and Mg-ion cathodes, with the light weight structure leading to high specific capacities. The ability to replace Mg for Li in polyanion materials without disrupting the crystal structure opens a new way to search for novel, high energy density, Li-ion cathodes.

Le domaine du transport aérien est en plein effort de réduction de ses émissions de gaz à effet de serre. Les PEMFC sont sérieusement envisagées afin d'introduire d'avantage d'énergie électrique à bord des avions. On se propose d'étudier la faisabilité de la propulsion d'avions légers alimentés par des systèmes pile à combustible hybridés. On étudie plus spécifiquement un système hybride PEMFC / Batteries Li-Ion produisant un total de 40 kW (20 kW PàC + 20 kW Li-Ion) permettant de propulser un avion léger biplace. Le premier aspect de cette étude est la navigabilité des PEMFC, c'est à dire leur aptitude à fonctionner en milieu aérien. Le second aspect est l'architecture électrique du système hybride, son dimensionnement et son comportement lors de différents profils de vol. Des essais expérimentaux en altitude sont menés et permettent de quantifier la diminution des performances de PàC aérobies liée à la diminution de pression ambiante. Grâce à ces essais et à un modèle numérique de PàC, on compare les technologies aérobies et anaérobies pour différents profils de vol. Un bilan des masses et des volumes associé à chacune de ces deux technologies est dressé. Par ailleurs, des essais en inclinaisons de systèmes PEMFC sont réalisés. L'hybridation directe de PEMFC avec des batteries Lithium est étudiée numériquement et expérimentalement. Un modèle Matlab Simulink de PàC et de batteries Lithium est développé afin de prédire le comportement du système hybride direct et de le dimensionner. Enfin, un banc expérimental d'hybridation directe est réalisé et des essais sont menés, révélant l'intérêt de cette architecture innovante. / The domain of air transport is working at reducing its emissions of greenhouse gases. PEMFC are seriously considered as electrical source for future aircraft. The present study focusses on the feasibility of propulsion of a light aircraft powered by hybridized PEMFC systems. The hybrid PEMFC / Li-Ion batteries system studied here produces 40 kW (20 kW PEMFC + 20 kW Li-Ion) and should be able to power a two-seat light aircraft. The first part of the study is dedicated to PEMFC airworthiness, meaning their capacity to work properly in aeronautical conditions. The second part is dedicated to the hybrid system electrical architecture, its dimensioning and its response to various flight profiles. Aerobic PEMFC performance loss due to drop in ambient pressure is quantified thanks to experiments at various altitude. Thanks to these measurements and to a numerical model, aerobic and anaerobic PEMFC are compared according to various flight profiles. A mass and volume balance of each technology is drawn up. In addition, inclination tests of PEMFC systems are performed. Direct hybridization of PEMFC and Li-Ion batteries is studied numerically and experimentally. A Matlab Simulink model of PEMFC and battery is developed in order to forecast the hybrid system's response and to size it. Finally, an experimental bench is settled up and tests are led, proving the interest of such an innovative architecture.

Orientador: Annete Gorenstein / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-08T01:04:35Z (GMT). No. of bitstreams: 1 FigueroaCadillo_Robinson_D.pdf: 6828830 bytes, checksum: 25774e9d4bb796e5048a90db527b894e (MD5) Previous issue date: 2007 / Resumo: Em dispositivos eletroquímicos como microbaterias ou dispositivos eletrocrômicos o catodo está presente na forma de filme fino. Com o objetivo de otimizar a performance de tais dispositivos, a pesquisa cientifica e tecnológica tem sido orientada na busca de novos materiais para o catodo. Este trabalho, contudo, propõe-se estudar a influencia da morfologia e da microestrutura do catodo no comportamento eletroquímico das microbaterias. O material escolhido foi o WO3. As amostras foram depositadas por sputtering reativo, e diversos parâmetros de deposição foram variados. Explorou-se a variação da potência durante a deposição e, trabalhou-se com o substrato inclinado, em modo estacionário ou rodante. Utilizaram-se diversas técnicas de caracterização. A técnica de Microscopia de Força Atômica (AFM) foi utilizada para analise de área da superfície, rugosidade, e tamanho de grão. A técnica de microscopia eletrônica MEV-FEG foi utilizada na analise da seção transversal dos filmes. O estudo eletroquímico por cronopotenciometria cíclica com limite de potencial permitiu a obtenção da capacidade de carga/descarga durante diversos ciclos. Foram obtidas amostras com e sem estrutura colunar; além disto, morfologias tipo hélice ou pilares foram conseguidas com rotação do substrato. A capacidade de carga depende fortemente do tipo de morfologia. Os melhores resultados foram obtidos com alta potência, para todas as estruturas / Abstract: In electrochemical devices like microbatteries or electrochromic devices, the cathode is present in thin film form. In order to optimize the performance of these devices, the scientific and technological research has been oriented in the search of new cathode materials. The aim of this work, however, is to study the influence of the cathode morphology and microstructure on the electrochemical behavior of microbatteries. WO3 was chosen as the thin film compound. The samples were deposited by reactive sputtering, and several deposition parameters were varied. The power during deposition was fixed in different values, and the samples were deposited with inclined substrates either stationary or rotating. Atomic Force Microscopy was used in order to obtain the surface area, roughness and grain size. Scanning electron microscopy was used in the analysis of the cross sections. The electrochemical study using chronopotentiometry with potential limits allowed the obtention of the charge/discharge capacity during several cycles. Depending on the deposition conditions, samples with or without columnar structures were obtained; also, helicoidal or pillar morphologies were attained with the rotation of the substrate. The charge capacity is strongly dependent on the morphology. The best results were obtained with high power, for all structures / Doutorado / Física / Doutor em Ciências

No description available.

Metal-based high entropy oxides are considered promising electrode materials for use in Li- ion batteries. In this work, the most widely studied high entropy oxide Mg0.2Ni0.2Cu0.2Co0.2Zn0.2O (M-HEO) with rock salt structure was successfully synthesized by Modified Pechini synthesis, characterized by X-ray diffraction analysis, and investigated as anode active material (negative electrode) in a coin cell. M-HEO has the concept of entropy stabilisation of crystal structure in oxide system with the configurational entropy value of 1,6R which confirmed that M-HEO classified as high entropy oxide.  To test the electrochemical performance, full cells comprising M-HEO as anode, lithium manganese oxide (LMO) as cathode together with ionic liquid electrolyte were assembled to explore their potential for practical applications. The electrochemical cycling performance was studied by two electrochemical experiments which are three-electrode cyclic voltammetry and galvanostatic charge/discharge. The cyclic voltammetry measurement was used to determine the behaviour of the system such as potential window and scan rate, while galvanostatic charge/discharge was used to determine the performance of the battery over time by applying constant current.  The results demonstrate that high entropy oxide possess a stable structure. This points out the direction for the preparation of M-HEOs with stable structure and excellent performance and provides a promising candidate for anode materials for LIBs. / Metallbaserade högentropioxider anses vara lämpliga för användning av elektrodmaterial för litium-jon batterier. I detta arbete syntetiserades den första högentropioxiden Mg0.2Ni0.2Cu0.2Co0.2Zn0.2O (M-HEO) som har stensaltstruktur genom Modifierad Pechini- syntesmetod, karakteriserad av röntgendiffraktionsanalys och undersöktes som aktivt material i den negativa elektroden. M-HEO har konceptet av entropistabilisering av kristallstrukturen i oxidsystem som har det konfigurerade entropivärdet av 1,6R. Detta bekräftade att M-HEO klassificerades som högentropioxid.  För att testa den elektrokemiska prestandan, användes fullceller bestående av M-HEO som anod, litiummanganoxid (LMO) som katod tillsammans med jonisk flytande elektrolyt. Detta gjordes för att undersöka M-HEO potentiella praktiska tillämpningar. Den elektrokemiska cyklingsprestandan studerades genom två elektrokemiska experiment, cyklisk voltammetri med tre-elektroder och galvanostatisk laddning/urladdning med knapp-celler. Den cykliska voltammetri mätningen användes för att bestämma vart i systemet sker redox reaktion för att sedan kunna identifiera på vilka potentialintervall samt skanningshastighet, medan galvanostatisk laddning/urladdning användes för att bestämma batteriets prestanda över tid genom att applicera konstant ström. Resultaten visar sig att hög entropi oxider har en stabil stensaltstruktur. Detta bidrar till att M-HEO som har en stabil struktur kan vara ett lämpligt anodmaterial i litium-jon batterier.

Ni-rich layered oxide materials have gained significant attention due to the ongoing advances and demands in energy storage. The energy revolution continues to catapult the need for improved battery materials, especially for applications in portable electronic devices and electric vehicles. Lithium batteries are at the frontier of energy storage. Due to geopolitical concerns, there is a growing need to understand the chemistries of Co-free, Ni-rich layered oxide materials which are cost-efficient and possess increased practical capacity. The challenge to studying this class of materials is their inherent electronic and structural fragility. The fragility of these materials is facilitated by a cooperation of metal cation migration, lattice oxygen loss, and undesirable oxide cathode-electrolyte interfacial reactions. Each of these phenomena contribute to complex electrolyte decomposition pathways and oxide cathode structural distortions. Structural instability leads to poor battery performance metrics including specific capacity fading and decreased Coulombic efficiency. Electrolyte decomposition occurs at the oxide cathode surface, but it can lead to bulk electronic and structural changes, chemomechanical breakdown, and irreversible phase transformations in the material. The work in this dissertation focuses on understanding some of the chemistries associated with degradation of representative Ni-rich layered oxides, specifically LiNiO2 (LNO) and LiNixMnyCozO2 (NMC) (where x+y+z =1) materials. Chapter 1 provides a comprehensive review of the interfacial chemistries of fragile, Ni-rich layered oxide materials with carbonate-based liquid electrolytes. These reactions are key in deducing mechanistic pathways that promote thermal runaway. Uncontrollable oxygen loss and electrolyte oxidation leads to catastrophic battery fires and explosions. The chapter highlights the material properties that become perturbed during high states-of-charge which complicate the materials chemistry associated with Ni-rich layered oxides. Lastly, a few strategies to mitigate undesired, structurally detrimental reactions at the Ni-rich layered oxide cathode surface are provided in Chapter 1. To obtain the technical data detailed in this dissertation, a variety of analytical methods are employed. Chapter 2 introduces the working principles of the X-ray techniques, electron microscopy, and other quantification methods. X-ray techniques including synchrotron X-ray absorption spectroscopy (XAS), and its components XANES and EXAFS are discussed. Other X-ray techniques, including X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) are additionally included. Electron microscopy techniques, including transmission electron microscopy (TEM), scanning electron microscopy (SEM), and scanning transmission electron microscopy (STEM) are provided. Quantification methods, such as gas chromatography – flame ionization detection (GC-FID) and other electrochemical testing methods are also described. Detailed experimental information obtained using the analytical methods is provided in the technical chapters. In understanding the chemistry of Ni-rich layered oxides, exploring surface reconstruction is key. Surface reconstruction, a phenomenon caused by a collaboration between Li/Ni cation intermixing and lattice oxygen loss, is one of the major explanations for structural degradation in Ni-rich layered oxide materials. Chapter 3 explores surface reconstruction and deduces a mechanism by which lattice oxygen is loss in LiNi0.6Mn0.2Co0.2O2 (NMC622). By exploiting Li+ intercalation chemistry, the work emulates various states-of-charge to explore how delithiation impacts small, organic molecule oxidation. Benzyl alcohol serves as a good probing molecule. It is similar to an oxidizable, nonaqueous electrolytic species that undergoes oxidation at the oxide cathode surface. Structure-reactivity trends are defined to correlate electronic and structural changes, lattice oxygen loss, and small molecule oxidation. After studying a proxy molecule, a practical system is required to grasp the complexity of the cathode-electrolyte interfacial reactions that promote Ni-rich layered oxide degradation. In Chapter 4, an electrolyte stirring experiment is described. Stirring experiments provide an accelerated testing method which helps to deduce the influences of chemical electrolyte decomposition on structural degradation of LiNiO2 (LNO). X-ray techniques are used to illustrate electronic perturbations and structural distortions in the material after probing with EC/DMC w/w 3:7 LiPF6. Additionally, this dissertation chapter features a novel voltage oscillation experiment that is employed to quantify Ni-rich oxide cathode degradation at the phase transition regions. LNO has three charging plateaus – H1  M, M  H2, and H2  H3. The latter two plateaus have been largely associated with irreversible structural fragility in Ni-rich layered oxides. Cation intermixing and oxygen loss are two phenomena that are largely associated with decreased Li+ intercalation kinetics and increased undesired side reactions. Although researchers debate the chemical phenomenon that occur at each of the phase transitions, most agree that the H2  H3 transition is highly influenced by irreversible lattice oxygen loss. This dissertation chapter describes the studies used to explore the electronic changes and structural distortions that accompany the voltage oscillation electrochemical testing. While Ni-rich layered oxides are largely employed as lithium battery cathodes, this class of material is unique in that it is a reducible and electronically tunable. Electronically modifiable metal oxide materials provide a unique platform to lend information to other applications, such as catalysis. There is much debate surrounding the role of metal oxides on metal nanocatalyst performance for catalytically reductive pathways. Chapter 5 discusses the method of employing LiNiO2 and other NMC materials as electronically tunable metal oxides to determine the role of the reducible metal oxide support on the gold (Au) nanocatalyst for p-nitrophenol reduction to p-aminophenol. By obtaining a continuum of nickel (Ni) oxidation states using delithiation strategies, structural-activity relationship trends are provided. Conversion rates for each of the delithiated materials was calculated using pseudo first-order kinetics. Lastly, a detailed discussion on metal oxide reducibility and its influences on key mechanistic factors, such as the induction period is included. Chapter 6 in this dissertation provides conclusions for the technical work provided. It bridges the works together and describes the overarching findings associated with the chemistries of Ni-rich layered oxide materials. This dissertation lays the foundation for future experimentation and innovation in understanding the surface chemistry of Ni-rich layered oxides. Chapter 7 provides future perspectives for each of the technical works included herein. Additionally, the final chapter includes insights toward the future of lithium batteries and other cathode chemistries. As the world navigates the energy revolution, it is important to provide global perspectives expected to catapult a sustainable future with batteries towards a greener world. / Doctor of Philosophy / Rechargeable lithium batteries have gained a significant surge of interest due to the ongoing demands for portable electronic devices, as well as the global trend towards electric vehicles to decrease the carbon footprint. Lithium batteries reside at the pinnacle of the energy transition. Layered oxide materials are typically employed as the cathode in Li-ion batteries. Ni-rich layered oxides have gained much interest due to their low cost and good charge/discharge capabilities. As consumers want increased charging rates and longer lifetimes, researchers struggle to optimize the balance between incorporating Ni-rich cathodes and increased safety concerns caused by cathode structural fragility. The lack of structural robustness is largely due to the surface reactivity of Ni-rich layered oxide materials. Bonding arrangements and electron transfer pathways intrinsic to this class of material increases the complexity in understanding the surface chemistry and the associated degradation pathways. Oxygen loss is the major cause of the safety issues in lithium batteries such as battery fires and explosions. To mitigate the safety concerns, it is imperative to understand the chemistries that promote organic, liquid electrolyte decomposition, electronic and structural changes, chemomechanical breakdown, and irreversible phase transformations. Each of these components leads to decreased battery performance. The work in this dissertation describes model and practical platforms to probe and understand the chemistries associated with battery performance degradation. A variety of analytical methods were utilized to determine overall structure-activity relationship trends and are highlighted in Chapter 2. Chapters 3-5 is technical research providing insight on Ni-rich layered oxide degradation pathways and behaviors. The work advances the understanding of battery surface chemistry which will lead to improved cathode design. As batteries continue to grow, it is important to know other applications that benefit from the unique chemistry of Ni-rich layered oxide materials. By exploiting the lithium battery cathode chemistry, this dissertation highlights a method to utilize these materials to understand the role of metal oxides on Au nanocatalysts. Conclusions to the findings in this dissertation are provided in Chapter 6. Future perspectives on the technical research provided herein this dissertation is included in Chapter 7. Additionally, Chapter 7 details future perspectives for lithium batteries and how they can facilitate the global transition toward a sustainable future.

L’électrification des moyens de transport est de plus en plus importante. Sa mise en œuvre nécessite des systèmes de stockage de l’énergie plus performants, moins coûteux, et plus sûrs. Actuellement, les batteries lithium-ion équipent la majorité de ces véhicules innovants. Toutefois, ces systèmes sont complexes, onéreux, et leur performance se dégrade au cours du temps. Leur durabilité constitue donc un enjeu majeur.Son estimation est complexe car elle ne dépend pas que des kilomètres parcourues mais des conditions d’usage. Actuellement, les outils de prédiction de durée de vie des batteries sont simplificateurs ou pas compatible avec l’usage automobile.L’objet de ces travaux consiste à développer un outil de simulation capable de reproduire le comportement électrique, thermique, et de vieillissement d’un pack batteries au cours de sa vie. Cet outil doit permettre l’optimisation de la conception et l’usage des packs afin d’augmenter leur durabilités. Des campagnes d’essais ont permis de calibrer et de valider des modèles électrothermiques au niveau de la cellule puis à l’échelle de l’assemblage. De même, la mise en place et l’analyse de tests de vieillissement accélérés ont permis de développer une loi de vieillissement et de mettre en avant un optimum d’usage.Le comportement du pack a été par la suite testé dans différentes conditions d’usage par l’intermédiaire d’un simulateur de scénario. Des stratégies de conception et de recharges ont été donc proposées et vérifiées par simulation. / Lithium batteries are key solutions as power storage systems for several applications including portable devices, aviation, space, and electrified vehicles. Their success is principally due to their high power and energy density. Therefore, several researchers are attempting to develop more powerful, cheaper, longer-lived and more secure batteries. One drawback of lithium batteries is their durability: lithium batteries’ energy and power capability decrease over time. The degradation rate is sensitive to operating conditions. A crucial step towards the large-scale introduction of electrified vehicles in the market is to reduce the cost of their energy storage devices.The aim of this study is to develop a simulation tool at the pack level able to reproduce its electro-thermal-aging behavior overtime. Thanks to an accelerated aging tests and experimental approach the models are calibrated and coupled with a usage scenario simulator at the vehicle level. The behavior of the pack is thus studied under different conditions and simulations were compared and discussed. Strategies of usage and charging were then proposed and validated by simulation.