<p>The formation of surface films on electrodes in contact with non-aqueous electrolytes in lithium-ion batteries has a vital impact on battery performance. A basic understanding of such films is essential to the development of next-generation power sources. The surface chemistry, morphology and thermal stability of two typical anode and cathode materials, graphite and LiNi_0.8Co_0.2O₂, have here been evaluated by X-ray photoelectron spectroscopy (XPS), X-ray diffraction, scanning electron microscopy and differential scanning calorimetry, and placed in relation to the electrochemical performance of the electrodes. </p><p>Chemical and morphological information on electrochemically formed graphite surface films has been obtained accurately by combining XPS measurements with Ar⁺ ion etching. An improved picture of the spatial organisation, including thickness determination of the surface film and characterisation of individual component species, has been established by a novel sputtering calibration procedure. The stability of the surface films has been shown to depend strongly on temperature and choice of lithium salt. Decomposition products from elevated-temperature storage in different electrolyte systems were identified and coupled to effects such as capacity loss and increase in electrode resistance. Different decomposition mechanisms are proposed for surface films formed in electrolytes containing LiBF₄, LiPF₆, LiN(SO₂CF₃)₂ and LiCF₃SO₃ salts.</p><p>Surface film formation due to electrolyte decomposition has been confirmed on LiNi_0.8Co_0.2O₂ positive electrodes. An overall surface-layer increase with temperature has been identified and provides an explanation for the impedance increase the material experiences on elevated-temperature storage. </p><p>Surface phenomena are clearly major factors to consider in selecting materials for practical Li-ion batteries.</p>

We have investigated the use of aluminum based amorphous metallic glass as the anode in lithium ion rechargeable batteries. Amorphous metallic glasses have no long-range ordered microstructure; the atoms are less closely packed compared to the crystalline alloys of the same compositions; they usually have higher ionic conductivity than crystalline materials, which make rapid lithium diffusion possible. Many metallic systems have higher theoretical capacity for lithium than graphite/carbon; in addition irreversible capacity loss can be avoided in metallic systems. With careful processing, we are able to obtain nano-crystalline phases dispersed in the amorphous metallic glass matrix. These crystalline regions may form the active centers with which lithium reacts. The surrounding matrix can respond very well to the volume changes as these nano-size regions take up lithium. A comparison study of various kinds of anode materials for lithium rechargeable batteries is carried out. / Singapore-MIT Alliance (SMA)

The formation of surface films on electrodes in contact with non-aqueous electrolytes in lithium-ion batteries has a vital impact on battery performance. A basic understanding of such films is essential to the development of next-generation power sources. The surface chemistry, morphology and thermal stability of two typical anode and cathode materials, graphite and LiNi0.8Co0.2O2, have here been evaluated by X-ray photoelectron spectroscopy (XPS), X-ray diffraction, scanning electron microscopy and differential scanning calorimetry, and placed in relation to the electrochemical performance of the electrodes. Chemical and morphological information on electrochemically formed graphite surface films has been obtained accurately by combining XPS measurements with Ar+ ion etching. An improved picture of the spatial organisation, including thickness determination of the surface film and characterisation of individual component species, has been established by a novel sputtering calibration procedure. The stability of the surface films has been shown to depend strongly on temperature and choice of lithium salt. Decomposition products from elevated-temperature storage in different electrolyte systems were identified and coupled to effects such as capacity loss and increase in electrode resistance. Different decomposition mechanisms are proposed for surface films formed in electrolytes containing LiBF4, LiPF6, LiN(SO2CF3)2 and LiCF3SO3 salts. Surface film formation due to electrolyte decomposition has been confirmed on LiNi0.8Co0.2O2 positive electrodes. An overall surface-layer increase with temperature has been identified and provides an explanation for the impedance increase the material experiences on elevated-temperature storage. Surface phenomena are clearly major factors to consider in selecting materials for practical Li-ion batteries.

Ni - MH batteries have superior properties which are long cycle life, low maintenance, high power, light weight, good thermal performance and configurable design. Hydrogen storage alloys play a dominant role in power service life of a Ni - MH battery and determining the electrochemical properties of the battery. LaNi5, belonging to the CaCu5 crystal structure type, satisfy many of the properties. The most important property of LaNi5 is fast hydrogen kinetics. Recently, CaNi5, belonging to same crystal type, has taken some attention due to its low cost, higher hydrogen storage capacity, good kinetic properties. However, the main restriction of its use is its very low cycle life. The aim of the study is to obtain a more stable structure providing higher cycle life by the addition of different alloying elements. In this study, the effect of sixteen alloying elements (Mn, Sm, Sn, Al, Y, Cu, Si, Zn, Cr, Mg, Fe, Dy, V, Ti, Hf and Er) on cycle life was investigated. Sm, Y, Dy, Ti, Hf and Er were added for replacement of Ca and Mn, Sn, Al, Cu, Si, Zn, Cr, Mg, Fe and V were added for replacement of Ni. Alloys were produced by vacuum casting and heat treating followed by ball milling. The cells assembled, using the produced active materials as anode, which were cycled for charging and discharging. As a result, replacement of Ca with Hf, Ti, Dy and Er, and replacement of Ni with Si and Mn were observed to show better cycle durability rather than pure CaNi5.

Demands for high energy-density batteries have sharpened with the increased use of portable electronic devices, as has the focus global warming is now placing on the need for electric and electric-hybrid vehicles. Li-ion battery technology is superior to other rechargeable battery technologies in both energy- and power-density. A remaining challenge, however, is to find an alternative candidate to graphite as the commercial anode. Several metals can store more lithium than graphite, e.g., Al, Sn, Si and Sb. The main problem is the large volume changes that these metals undergo during the lithiation process, leading to degradation and pulverization of the anode with resulting limitations in cycle-life. The Li-ion battery is studied in this thesis with the goal of better understanding the critical parameters determining high and stable electrochemical performance when using a metal or a metal-alloy anode. Various antimony-containing systems will be presented. These represent different routes to circumvent the problems caused by volume change. Sb-compounds exhibit a high lithium storage capability. At most, three Li-ions can be stored per Sb atom, leading to a theoretical gravimetric capacity of 660 mAh/g. Model systems with stepwise increasing complexity have been designed to better understand the factors influencing lithium insertion/extraction. It is demonstrated that the microstructure of the anode material is crucial to stable cycling performance and high reversibility. The relative importance of the various factors controlling stability, such as particle-size, oxide content and morphology, varies strongly with the type of system studied. The cycling performance of pure Sb is improved dramatically by incorporating a second component, Sb2O3. With a critical oxide concentration of ~25%, a stable capacity close to the theoretical value of 770 mAh/g is obtained for over 50 cycles. Cu2Sb shows stable cycling performance in the absence of oxide. Cu9Sb2 has been presented for the first time as an anode material in a Li-ion battery context. Studies of the Solid Electrolyte Interphase (SEI) formed on AlSb composite electrodes show an SEI layer thinner than graphite, and with a clearly dynamic character.

La précipitation en milieu aqueux d'(oxyhydr)oxydes de manganèse nano-structurés et électroactifs vis-à-vis du lithium a été étudiée. L'influence de différents paramètres expérimentaux (acidité, conditions rédox, contre-cation, température et durée d'évolution) a pu être rationalisée afin de proposer des mécanismes de transformation de phase ainsi que des diagrammes de spéciation pour la synthèse sélective de différents allotropes. Dans le cadre de l'étude des phénomènes de croissance des nanoparticules, des mécanismes d'agrégation ont été mis en évidence et des protocoles ont été développés afin de contrôler ces processus ainsi que la taille des particules. Différentes voies de synthèse de matériaux " hiérarchiques " ont alors été abordées. Les phénomènes de nucléation hétérogène, d'hétéroépitaxie en solution, et d'attachement orienté permettent ainsi d'élaborer des architectures complexes. Enfin, l'influence de la structure des composés, de la taille des nanoparticules, et de la texture du matériau sur le comportement électrochimiques au sein d'électrodes positives de batteries au lithium a été étudiée.

Porous carbons are versatile materials with applications in different fields. They are used in filtration, separation and sequestration of fluids and gases, as conductive additives in many energy storage materials, as coloring agents, as pharmaceutical and food additives, and in many other vital technologies. Porous carbons produced by pyrolysis and activation of organic precursors commonly suffer from poorly controlled morphology, microstructure, chemistry, and pore structure. In addition, the poorly controlled parameters of porous carbons make it challenging to elucidate the underlying key physical parameters controlling their performance in energy storage devices, including electrochemical capacitors (ECs) and lead-acid batteries (LABs). Zeolite-templated carbons (ZTCs) are a novel class of porous carbon materials with uniform and controllable pore size, microstructure, morphology, and chemistry. In spite of their attractive properties, they have never been explored for use in LABs and their studies for ECs have been very limited. Here I report a systematic study of ZTCs applications in ECs operating at temperatures as low as - 70 C and in LABs. Greatly improved power and energy performance, compared to state of the art devices, has been demonstrated in the investigated ECs. Moreover, the application of ZTCs in LABs has resulted in a dramatic enhancement of their cycle life and power and energy densities.

Compounds forming alloys with lithium, such as silicon or tin, are promising negative electrode materials for the next generation of Li-ion batteries due to their higher theoretical capacity compared to the current commercial electrode materials. An important issue is to better understand the phenomena occurring at the electrode/electrolyte interfaces of these new materials. The stability of the passivation layer (SEI) is crucial for good battery performance and its nature, formation and evolution have to be investigated. It is important to follow upon cycling alloying/dealloying processes, the evolution of surface oxides with battery cycling and the change in surface chemistry when storing electrodes in the electrolyte. The aim of this thesis is to improve the knowledge of these surface reactions through a non-destructive depth-resolved PES (Photoelectron spectroscopy) analysis of the surface of new negative electrodes. A unique combination utilizing hard and soft-ray photoelectron spectroscopy allows by variation of the photon energy an analysis from the extreme surface (soft X-ray) to the bulk (hard X-ray) of the particles. This experimental approach was used to access the interfacial phase transitions at the surface of silicon or tin particles as well as the composition and thickness/covering of the SEI. Interfacial mechanisms occurring upon the first electrochemical cycle of Si-based electrodes cycled with the classical salt LiPF6 were investigated. The mechanisms of Li insertion (LixSi formation) have been illustrated as well as the formation of a new irreversible compound, Li4SiO4, at the outermost surface of the particles. Upon long cycling, the formation of SiOxFy was shown at the extreme surface of the particles by reaction of SiO2 with HF contributing to battery capacity fading. The LiFSI salt, more stable than LiPF6, improved the electrochemical performances. This behaviour is correlated to the absence of SiOxFy upon long-term cycling. Some degradation of LiFSI was shown by PES and supported by calculations. Finally, interfacial reactions occurring upon the first cycle of an intermetallic compound MnSn2 were studied. Compared to Si based electrodes, the SEI chemical composition is similar but the alloying process and the role played by the surface metal oxide are different.

The reversible electrochemistry and the superior gravimetric and volumetric energy storage capacities of lithium ion batteries (LIBs) have propelled them as the dominant power source for a range of portable electronic devices. Thin film LIBs are a class of LIBs that have been extensively used for powering Microelectromechanical systems devices, Radio-frequency Identification tags, biomedical sensors and several other low power electronic systems. Thin film electrodes and electrolytes are characteristic of short lithium ion diffusion paths and hence show fast charge/discharge rates. But the thin film battery technology has the major drawback of possessing low energy per footprint area. The three dimensional design for thin film LIBs has been proposed to improve electrode mass loading per footprint area thereby improving the energy delivered by the device. Hence there is interest in assembling the entire battery (current collectors, anode, electrolyte, and cathode) in a three dimensional (3D) nanostructured architecture. This thesis deals with the development and assembly of nanostructured three dimensional designs for Li ion battery components. Several template-based techniques have been used to fabricate nanostructured materials which serve as building blocks for the 3D energy storage devices. Firstly we have addressed the challenging task of fabricating conformal nanostructured polymer electrolytes around nanowire electrode material. The polymer coatings helped in controlling the secondary electrolyte interphase formation and hence in the improvement of cycling characteristics of the nanowire electrode material. We have also fabricated 3D current collectors with both ordered and disordered pore structure. Electrodes coated on 3D nanostructured current collectors showed improved rate capability and energy per footprint area. Finally, we have used a bottom up approach to assemble all essential components (anode, electrolyte, and cathode) of an electrochemical energy storage device onto a single nanowire, and have tested a parallel array of such nanowire devices for its electrochemical performance, hence demonstrating the ultimate miniaturization possible for energy storage devices.

In this thesis information received from a hybrid vehicle battery test equipment wasstructured and analyzed. This test equipment is currently placed on a fleet of Scaniatrucks with the purpose of emulating hybrid vehicle environment on battery cell level.A Microsoft Access database structure was set up in order to make it possible to savetest data in a structured way. In addition, Matlab scripts were made with the purposeof calculating cell aging from pulse- and capacity tests. Furthermore, drive cycleanalysis was performed looking at statistics for selected parameters. Data collectedfrom late October 2010 until beginning of July does not yet show any aging of the fieldtested battery cells regarding capacity loss or resistance increase. The internalresistance of the batteries was calculated to 2 to 4 milli ohm and the capacity wasfrom the tests found to be around 3 ampere hours. The energy efficiency, which wascalculated from pulse test data, shows an efficiency between 95 to 97%.