Lithium-ion batteries are most commonly employed as power sources for portable electronic devices. Limited capacity, high cost, and safety problems associated with the commercially used graphite anode materials are hampering the use of lithium-ion batteries in larger-scale applications such as the electric vehicle. Nanocomposite alloys have shown promise as new anode materials because of their better safety due to higher operating potential, increased energy density, low cost, and straightforward synthesis as compared to graphite. The purpose of this dissertation is to investigate and understand the electrochemical properties of several types of nanocomposite alloys and to assess their viability as replacement anode materials for lithium-ion batteries. Tin and antimony are two elements that are active toward lithium. Accordingly, this dissertation is focused on tin-based and antimony-based nanocomposite alloy materials. Tin and antimony each have larger theoretical capacities than commercially available anodes, but the capacity fades dramatically in the first few cycles when metallic tin or antimony is used as the anode in a lithium-ion battery. This capacity fade is largely due to the agglomeration of particles in the anode material and the formation of a barrier layer between the surface of the anode and the electrolyte. In order to suppress agglomeration, the active anode material can be constrained by an inactive matrix of material that makes up the nanocomposite. By controlling the surface of the particles in the nanocomposite via methods such as the addition of additives to the electrolyte, the detrimental effects of the solid-electrolyte interphase layer (SEI) can be minimized, and the capacity of the material can be maintained. Moreover, the nanocomposite alloys described in this dissertation can be used above the voltage where lithium plating occurs, thereby enhancing the safety of lithium-ion batteries. The alloy anodes in this study are synthesized by high-energy mechanical milling and furnace heating. The materials are characterized by X-ray diffraction, scanning and transmission electron microscopies, and X-ray photoelectron spectroscopy. Electrochemical performances are assessed at various temperatures, potential ranges, and charge rates. The lithiation/delithiation reaction mechanisms for these nanocomposite materials are explored with ex-situ X-ray diffraction. Specifically, three different nanocomposite alloy anode materials have been developed: Mo3Sb7-C, Cu2Sb-Al2O3-C, and Cu6Sn5-TiC-C. Mo3Sb7-C has high gravimetric capacity and involves a reaction mechanism whereby crystalline Mo3Sb7 disappears and is reformed during each cycle. Cu2Sb-Al2O3-C with small particles (2 - 10 nm) of Cu2Sb dispersed in the Al2O3-C matrix is made by a single-step ball milling process. It exhibits long cycle life (+ 500 cycles), and the reversibility of the reaction of Cu2Sb-Al2O3-C with lithium is improved when longer milling times are used for synthesis. The reaction mechanism for Cu2Sb-Al2O3-C appears to be dependent upon the size of the crystalline Cu2Sb particles. The coulombic efficiency of Cu2Sb-Al2O3-C is improved through the addition of 2 % vinylethylene carbonate to the electrolyte. With a high tap density of 2.2 g/cm3, Cu6Sn5-TiC-C exhibits high volumetric capacity. The reversibility of the reaction of Cu6Sn5-TiC-C with lithium is improved when the material is cycled above 0.2 V vs. Li/Li+. / text

<p>Surface film formation at the electrode/electrolyte interface in lithium-ion batteries has a crucial impact on battery performance and safety. This thesis describes the characterisation and treatment of electrode interfaces in lithium-ion batteries. The focus is on interface modification to improve battery safety, in particular to enhance the onset temperature for thermally activated reactions, which also can have a negative influence on battery performance. </p><p>Photoelectron Spectroscopy (PES) and Differential Scanning Calorimetry (DSC) are used to investigate the surface chemistry of electrodes in relation to their electrochemical performance. Surface film formation and decomposition reactions are discussed.</p><p>The upper temperature limit for lithium-ion battery operation is restricted by exothermic reactions at the graphite anode; the onset temperature is shown to be governed by the composition of the surface film on the anode. Several electrolyte salts, additives and an anion receptor have been exploited to modify the surface film composition. The most promising thermal behaviour is found for graphite anodes cycled with the anion receptor, tris(pentafluorophenyl)borane, which reduces salt reactions and increases the onset temperature from ~80 °C to ~150 °C.</p><p>The electrochemical performance and surface chemistry of Swedish natural graphite, carbon-treated LiFePO₄ and anodes from high-power lithium-ion batteries are also investigated. Jet-milled Swedish natural graphite exhibits a high capacity and rate capability, together with a decreased susceptibility to solvent co-intercalation. Carbon-treated LiFePO₄ shows promising results: no solvent reaction products are detected. The amount of salt compounds increases, with power fade occurring for anodes from high-power lithium-ion batteries; the solvent reduction products comprise mainly Li-carboxylate type compounds.</p>

Surface film formation at the electrode/electrolyte interface in lithium-ion batteries has a crucial impact on battery performance and safety. This thesis describes the characterisation and treatment of electrode interfaces in lithium-ion batteries. The focus is on interface modification to improve battery safety, in particular to enhance the onset temperature for thermally activated reactions, which also can have a negative influence on battery performance. Photoelectron Spectroscopy (PES) and Differential Scanning Calorimetry (DSC) are used to investigate the surface chemistry of electrodes in relation to their electrochemical performance. Surface film formation and decomposition reactions are discussed. The upper temperature limit for lithium-ion battery operation is restricted by exothermic reactions at the graphite anode; the onset temperature is shown to be governed by the composition of the surface film on the anode. Several electrolyte salts, additives and an anion receptor have been exploited to modify the surface film composition. The most promising thermal behaviour is found for graphite anodes cycled with the anion receptor, tris(pentafluorophenyl)borane, which reduces salt reactions and increases the onset temperature from ~80 °C to ~150 °C. The electrochemical performance and surface chemistry of Swedish natural graphite, carbon-treated LiFePO4 and anodes from high-power lithium-ion batteries are also investigated. Jet-milled Swedish natural graphite exhibits a high capacity and rate capability, together with a decreased susceptibility to solvent co-intercalation. Carbon-treated LiFePO4 shows promising results: no solvent reaction products are detected. The amount of salt compounds increases, with power fade occurring for anodes from high-power lithium-ion batteries; the solvent reduction products comprise mainly Li-carboxylate type compounds.

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Les matériaux dits de conversion à base de Sb et Sn, utilisés comme électrodes, apparaissent comme des composés particulièrement intéressants compte tenu de leur forte capacité théorique. Le matériau TiSnSb a été récemment développé en tant qu’électrode négative pour batteries lithium-ion. Ce matériau est capable d’accueilir, de façon réversible, 6,5 Li par unité formulaire, ce qui correspond à une capacité spécifique de 580 mAh/g. Dans le domaine des batteries lithium-ion, les propriétés de l’interface électrode/électrolyte (« solid electrolyte interphase », SEI), formant une couche de passivation protectrice à la surface des électrodes sont considérées comme essentielles pour les performances au sens large des batteries. Cet aspect représente le sujet majeur traité dans ce travail de thèse. Dans cet optique, nous avons tout d'abord étudié les propriétés électrochimiques de l'électrode TiSnSb sous divers aspects, dont les effets du régime de cyclage, l’influence de la nature des additifs au sein de l’électrolyte ainsi que l’utilisation de liquides ioniques à température ambiante (RTILs). En particulier, un système d'électrolyte à base de RTILs a été développé et optimisé vis-à-vis des performances électrochimiques. Afin de caractériser l’interface électrode-électrolyte, deux techniques de caractérisation majeures ont été utilisées : la Spectroscopie Photoélectronique à Rayonnement X (XPS) et la Spectroscopie d'Impédance électrochimique (EIS). Cette étude a permis de cibler certains paramètres essentiels liant les aspects performances électrochimiques à la nature de l’interface électrode-électrolyte. / In the past decades, the need for portable power has accelerated due to the miniaturization of electronic appliances. It continues to drive research and development of advanced energy systems, especially for lithium ion battery systems. As a consequence, conversion materials for lithium-ion batteries, including Sb and Sn-based compounds, have attracted much intense attention for their high storage capacities. Among conversion materials, TiSnSb has been recently developed as a negative electrode for lithium-ion batteries. This material is able to reversibly take up 6.5 Li per formula unit which corresponds to a specific capacity of 580 mAh/g. In the field of lithium-ion battery research, the solid electrolyte interphase (SEI) as a protective passivation film formed at electrode surface owing to the reduction of the electrolyte components, has been considered as a determinant factor on the performances of lithium-ion battery. Thus it has been a focused topic of many researches. However, little information can be found about the formation and composition of the SEI layer formed on TiSnSb conversion electrode at this time. With the aim to investigate the influences of the SEI layer on the performances of composite TiSnSb electrode, we first studied the electrochemical properties of the electrode from various aspects, including the effects of cycling rates, electrolyte additives, as well as room temperature ionic liquids (RTILs). Especially, a RTILs-based electrolyte system was developed and optimized by evaluating its physicochemical properties to be able to further improve the performances of TiSnSb electrode. In order to characterize the SEI layer formed at electrode surface, we performed X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). This study allowed to target some essential parameters concerning electrochemical performances linked with the nature of the solid electrolyte interphase.*