Silicon is a promising negative electrode material for lithium-ion (Li-ion) batteries, with volumetric and gravimetric capacities much higher than those in current commercial batteries. Implementation of Si as a negative electrode is halted, however, by a large irreversible capacity and declining reversible capacity over cycle life. These problems are linked to the large volume expansion that Si undergoes when reacted with lithium, and overcoming them is the focus of this thesis. To overcome this expansion, in the first part titanium silicides were proposed to buffer the volume expansion problem as Ti does not react with Li and is robust. A pure phase of the targeted TiSi and TiSi2 was not achieved, however one product mixture containing TiSi2 and Ti5Si3 was cycled against Li at C/20. A capacity of 715 mAh g-1 was achieved, however rapid capacity fade occurred over the first 10 cycles. The second part of the thesis focused on heterostructured Si-Ge and Ge-Si core- shell nanowires. The morphology of the nanowires allows for better accommodation of strain due to lithiation, and Ge functions as an active matrix, as it can store Li in a similar manner as Si. The specific capacities of the nanowires were good at 1346 mAh g-1 and 1276 mAh g-1, however after 50 cycles the Si-Ge nanowires had a capacity retention of 72.4 % and the Ge-Si retained 62.4 %. The diffusion coefficient of Li was determined from GITT and EIS to be within the range of 10-16 to 10-13 cm2s-1 and was slightly lower than other reported values, attributed to the dense structure of the nanowires slowing diffusion.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第25302号 / 工博第5261号 / 新制||工||2001(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 阿部 竜, 教授 陰山 洋 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

Carbon-based materials are currently used for anodes in commercial lithium ion secondary batteries. The theoretical capacity for carbon is only 372mAh/g, and new materials are being developed for anodes to raise the electrical capacity and cycling times. One of the most promising materials is tin oxide that has 50% more electrical capacity and has been studied extensively in the industrial and academic institutions. While most studies have been concentrated on the electrochemical behavior in the charge-discharge process, microstructure evolution along with phase transformation have been emphasized in this work. Tin oxide films are deposited on stainless steel substrate by sputtering and spray. A cell consists of a pure lithium foil as anode and tin oxide film as cathode along with 1M LiClO4 in DMC/EC mixture as electrolyte is fabricated and employed in the charge-discharge test and Cyclic Voltammetry. In the charge-discharge test, we use a constant current of 0.09mA to charge or discharge to the voltage that we need. In the Cyclic Voltammetry test, we change the scanning rate and scanning range. Microstructures developed and phase transformation in different stages of the charge-discharge or CV test process are examined by XRD, SEM and TEM.

The layered transition metal oxide composition series of Li1+xV1-xO2 was synthesized using the solid state synthesis technique. X-ray diffraction was used to determine the dependence of structure on composition and clearly indicated a structural anomaly at x = 0 caused by the unusual magnetic ordering on the triangular lattice of the V3+ layer. To prevent magnetic frustration V3+ cations undergo orbital ordering and subsequent periodic displacent to form “trimers”. The periodicity of this phenomena results in a superlattice structure that can be observed as a faint peak in XRD spectra. The relationship between composition, superlattice peak intensity and lattice parameters was clearly documented for the first time. Li/Li1+xV1-xO2 cells were made and tested. Recent literature has shown that the transformation to 1T Li2VO2 upon lithiation is dependant on a nonzero x (ideally x = 0.07 for maximum capacity) to make a small number of tetrahedrally coordinated Li sites accessible. These sites then act as a trigger for shearing into the 1T phase. The cells described within this work intercalated significant amounts of lithium at a higher potential than the to 1T transition, possibly signifying occupation of a large number of the tetrahedral sites. LiVO2 is known to undergo delithiation even in ambient conditons and this can lead to cationic disorder. Cationic disorder is an inhibitor of anion sheet shearing and this suggests that sample handling could be a cause of the observed electrochemical behaviour. The effects of air and water exposure were investigated.

Les batteries lithium-ion sont aujourd’hui très utilisées pour alimenter l’électronique portable telle que les ordinateurs, les smartphones et les caméras. Cependant, de nouvelles applications telles que les véhicules électriques et les systèmes stationnaires de stockage d'énergie nécessitent des batteries à performances améliorées. En particulier, de nouveaux matériaux d'électrode avec des densités d'énergie plus élevées sont requis. Les hydrures de MgH2 et TiH2 et leurs mélanges possèdent de très fortes capacités électrochimiques (>1 Ah/g). Ils ont été étudiés comme matériaux d’électrode négative dans les batteries Li-ion. La réaction de conversion de ces hydrures avec du lithium et les changements structuraux induits ont été étudiés en détails pour mieux comprendre les mécanismes réactionnels et leur réversibilité. Les propriétés électrochimiques de couches minces de MgH2 et des poudres composites de MgH2+TiH2 ont été étudiées en utilisant à la fois des électrolytes organiques liquides et un électrolyte solide LiBH4. La capacité réversible et la tenue au cyclage dépendent fortement du rapport molaire entre les deux hydrures et des conditions de cyclage. Le transport de masse et la densité d’interfaces à l'intérieur de l'électrode sont identifiés comme les principaux facteurs affectant la réversibilité de la réaction de conversion / Today, lithium-ion batteries are widely used as power supplies in portable electronics such as laptops, smartphones and cameras. However, new applications such as full electric vehicles and energy storage stationary systems require enhanced battery performances. In particular, novel electrode materials with higher energy density are needed.MgH2 and TiH2 hydrides and mixtures of them have high electrochemical capacity (> 1 Ah/g). They have been studied as negative electrode materials in Li-ion batteries. The conversion reaction of lithium with these hydrides and the related microstructural changes have been deeply investigated to gain a better understanding of reaction mechanisms and their reversibility. The electrochemical properties of MgH2 thin films and MgH2+TiH2 composite powders have been evaluated using both liquid organic and solid (LiBH4) electrolytes. Reversible capacity and cycle-life are found to strongly depend on both molar ratio between the hydrides and cycling conditions. Mass transport and density of interfaces within the electrode are identified as the main factors affecting the reversibility of the conversion reaction

京都大学 / 新制・論文博士 / 博士(工学) / 乙第13407号 / 論工博第4193号 / 新制||工||1762(附属図書館) / (主査)教授 安部 武志, 教授 作花 哲夫, 教授 阿部 竜 / 学位規則第4条第2項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

.Tato diplomová práce se zabývá elektrochemickými procesy v lítium-iontových bateriích. Pro charakterizaci různých elektrochemických procesů se používá metoda nazývaná elektrochemická impedanční spektroskopie (EIS). V prvních kapitolách jsou popsány různé typy baterií a jejich rozdíly. Práce také obsahuje popis experimentálního zařízení používaného pro EIS. Součástí práce je také porovnání experimentálního zařízení a zařízení od společnosti BioLogic Science Instruments.

This doctoral dissertation deals with the study of the effect of additives on the properties of the negative electrode of a lead-acid battery. The work focuses on the investigation of the additive/base material interface for the negative electrode (so-called active mass) using atomic force microscopy (AFM). A lead sheet was used as the base material, on which the given additive was applied. The effects of carbon, TiO2, glass fibers and Indulin AT were specifically investigated. The negative electrode was cycled by a potentiostat in a defined manner and the morphology of the electrode surface was continuously scanned by AFM. This created a time sequence of images on which events on the surface of the electrode during its charging/discharging were captured. These records serve to better understand the effect of additives on the resulting properties of constructed lead-acid cells, specifically on the ability to form or dissolve PbSO4 crystals, which are formed during cell discharge and are responsible for the decrease in total capacity - gradual surface sulfation.

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第22795号 / エネ博第409号 / 新制||エネ||78(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 萩原 理加, 教授 佐川 尚, 教授 野平 俊之 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

The thesis is focused on remitting lead-acid segments of partial charge mode which simulates the conditions in HEV. The experimental cells were submitted to different pressures on the electrode system. The main aim of the thesis was to minimize the irreversible sulphating of the negative electrodes, which are in the PSoC regime limiting in the overall life of lead-acid accumulators. All cells were submitted to measurement of the negative electrode potentials, resistance of active materials, contact resistance of the grid – the active material and measurements of pressure changes during three PSoC cycles.