Electric and hybrid electric vehicles are gaining momentum as a sustainable alternative to conventional combustion based transportation. The operating temperature of the vehicle will vary significantly over the vehicle lifetime and this variance in operating temperature will strongly impact the performance, driving range, and durability of batteries used in the vehicles. In the first part of this thesis, an experimental facility is developed to accurately quantify the effects of battery operating temperature on discharge characteristics through precise control of the battery operating temperatures, utilizing a water-ethylene glycol solution in a constant temperature thermal bath. A prismatic 20Ah LiFEPO4 battery from A123 is tested using the developed method, and temperature measurements on the battery throughout discharge show a maximum variation of 0.3°C temporally and 0.4°C spatially at a 3C discharge rate, in contrast to 13.1°C temperature change temporally and 4.3°C spatially when using the conventional air convection temperature control method under the same test conditions. A comparison of battery discharge curves using the two methods show that the reduction in spatial and temporal temperature change in the battery has a large effect on the battery discharge characteristics. The developed method of battery temperature control yields more accurate battery discharge characterization due to both the elimination of state-of-charge drift caused by spatial variations in battery temperature, and inaccurate discharge characteristics due to battery heat up at various discharge and ambient conditions. Battery discharge characterization performed using the developed method of temperature control exhibits a reduction in battery capacity of 95% when the operating temperature is decreased from 20°C to -10°C at 3C discharge rate. A reduction of 35% in battery capacity is observed when for the same temperature decrease at a 0.2C discharge rate. The observed effect of operating temperature on the capacity of the tested battery highlights the importance of an effective thermal management system, the design of which requires accurate knowledge of the heat generation characteristics of the battery under various discharge rates and operating temperatures. In the second part of this thesis, a calorimeter capable of measuring the heat generation rates of a prismatic battery is developed and verified by using a controllable electric heater. The heat generation rate of a prismatic A123 LiFePO4 battery is measured for discharge rates ranging from 0.25C to 3C and operating temperature ranging from -10°C to 40°C. Results show that the heat generation rates of Lithium ion batteries are greatly affected by both battery operating temperature and discharge rate. At low rates of discharge the heat generation is not significant, even becoming endothermic at the battery operating temperatures of 30°C and 40°C. Heat of mixing is observed to be a non-negligible component of total heat generation at discharge rates as low as 0.25C for all tested battery operating temperatures. A double plateau in battery discharge curve is observed for operating temperatures of 30°C and 40°C. The developed experimental facility can be used for the measurement of heat generation for any prismatic battery, regardless of chemistries. The characterization of heat generated by the battery under various discharge rates and operating temperatures can be used to verify the accuracy of battery heat generation models currently used, and for the design of an effective thermal management system for electric and hybrid electric vehicles in the automotive industry.

Lithium-rich transition metal oxides are candidates for the next-generation lithium-ion battery positive electrode materials. They have a much higher first charge and low-rate cycling capacity compared to non-lithium rich transition metal oxides. In this thesis, the preparation of spherical and dense transition metal oxide was studied. The morphology and tap-density of the hydroxide precursor was found to be dependent on the coprecipitation reaction pH. The coprecipitation reaction in the presence of aqueous ammonia was studied by analyzing the relevant chemical equilibria. The electrochemistry of lithium-rich oxides was studied as a function of particle size. The apparent oxygen diffusion coefficients were estimated using the Atlung graph method and were determined to be several orders of magnitude lower than normal lithium deintercalation. Isothermal mass calorimetry measurements showed evidence of a local Jahn-Teller distortion in the MnO6 units during discharge. Other studies of the lithium-rich oxides were also carried out.

A novel method to detect and quantify the growth of the solid electrolyte interphase (SEI) on battery electrode materials using in-situ spectroscopic ellipsometry (SE) is presented. The effects of additives in 1 M LiPF6/EC:DEC (1:2) electrolyte on the SEI were studied. Thin film electrodes of a-Si, Ni, and TiN were prepared by magnetron sputtering for use with a custom-designed tubular in-situ electrochemical cell. Li/a-Si and Li/Ni in-situ cells in 0.1 M LiPF6/EC:DEC (1:2) were studied by galvanostatic chronopotentiometry. Large changes in the ellipsometric parameters, ? and ?, were observed for both materials. These changes were closely related to the state of charge of the in-situ cell. The formation of an a-LixSi alloy, the formation of an SEI layer, or both contributed to these large changes for a Li/a-Si in-situ cell. For a Li/Ni in-situ cell, a thin transparent surface layer was observed. The surface layer, presumably made from SEI species and species from the displacement reaction between NiO and Li, increased to roughly 17 nm during the first discharge. During the first charge, the surface layer thickness decreased to roughly 5.5 nm and could not be removed, even at high potentials. The effect of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) additives on SEI formation were studied using a Li/TiN in-situ cell in 1 M LiPF6/EC:DEC (1:2) by potentiostatic chronoamperometry. SEI thicknesses for cells containing no additives, VC, and FEC were roughly 18 nm, 25 nm and 30 nm, respectively, after a 10 h hold at 0.1 V. SE is a useful technique for measuring thin film growth in-situ on electrode materials for Li-ion batteries.

Electrolyte additives are generally used in commercial Li-ion cells to improve capacity retention and calendar life. Although it is apparent that electrolyte additives play an important role, the details of how they work are poorly understood. In order to be able to distinguish the effect of an additive on the positive or negative electrodes, an experimental method has been developed based on electrochemical impedance spectroscopy of symmetric cells constructed from electrodes of disassembled full cells similar to the method described by previous workers. This technique proved to be useful and showed that the effects of additives on both electrodes depend strongly on their concentration. It also showed that in some cases, when two additives are introduced in the same cell, both additives contribute to the formation of the surface layer of both electrodes. In other cases, each additive controls the formation of the surface layer of only one electrode.

<p>The current work focuses on the synthesis and characterization of nano-devices with potential application in alkaline electrolysis and secondary polymer lithium ion batteries.</p>

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.

Because of its high theoretical specific capacity (4200mAh/g) and natural abundance (2nd most abundant element on earth), silicon is considered a promising anode candidate for high energy density lithium-ion batteries. However, the dramatic volume changes (up to 400%) that occur during lithiation/delithiation and the relative low electrical conductivity of silicon prevent the implementation of this material. In this work, a nano-silicon/polyaniline/reduced graphene oxide composite was synthesized via a two-step process: in-situ polymerization of polyaniline (PANi) in the presence of nano-silicon followed by combination of the prepared n-Si/PANi binary composite with reduced graphene oxide (RGO), to form a n-Si/PANi/RGO composite. Electron microscopy reveals the unique nano-architecture of the n-Si/PANi/RGO composite: silicon nanoparticles are well dispersed within a PANi matrix, which in turn is anchored to the surface of RGO sheets. The n-Si/PANi/RGO ternary composite delivered an initial capacity of 3259 mAh/g and 83.5% Coulombic efficiency. The new composite displayed better rate performance and capacity recovery than either nano-Si or n-Si/PANi. Structural and morphological studies combined with AC impedance analysis suggest that the n-Si/PANi/RGO composite has higher electrical conductivity than the other two component materials, yielding better performance at high current densities or C rates. The good rate performance, high initial specific capacity and stable Coulombic efficiency of n-Si/PANi/RGO make it a promising anode material for high energy density lithium-ion batteries.

Because of its high theoretical specific capacity (4200mAh/g) and natural abundance (2nd most abundant element on earth), silicon is considered a promising anode candidate for high energy density lithium-ion batteries. However, the dramatic volume changes (up to 400%) that occur during lithiation/delithiation and the relative low electrical conductivity of silicon prevent the implementation of this material. In this work, a nano-silicon/polyaniline/reduced graphene oxide composite was synthesized via a two-step process: in-situ polymerization of polyaniline (PANi) in the presence of nano-silicon followed by combination of the prepared n-Si/PANi binary composite with reduced graphene oxide (RGO), to form a n-Si/PANi/RGO composite. Electron microscopy reveals the unique nano-architecture of the n-Si/PANi/RGO composite: silicon nanoparticles are well dispersed within a PANi matrix, which in turn is anchored to the surface of RGO sheets. The n-Si/PANi/RGO ternary composite delivered an initial capacity of 3259 mAh/g and 83.5% Coulombic efficiency. The new composite displayed better rate performance and capacity recovery than either nano-Si or n-Si/PANi. Structural and morphological studies combined with AC impedance analysis suggest that the n-Si/PANi/RGO composite has higher electrical conductivity than the other two component materials, yielding better performance at high current densities or C rates. The good rate performance, high initial specific capacity and stable Coulombic efficiency of n-Si/PANi/RGO make it a promising anode material for high energy density lithium-ion batteries.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24001号 / エネ博第437号 / 新制||エネ||82(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)准教授 高井 茂臣, 教授 萩原 理加, 教授 佐川 尚 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

Lithium-ion (Li-ion) batteries are the most popular energy storage technology in consumer electronics and electric vehicles and are increasingly applied in stationary storage systems. Yet, concerns about safety and reliability remain major obstacles, which must be addressed in order to improve the acceptance of this technology. The gradual degradation of Li-ion cells over time lies at the heart of this problem. Time, usage and environmental conditions lead to performance deterioration and cell failures, which, in rare cases, can be catastrophic due to res or explosions. The physical and chemical mechanisms responsible for degradation are numerous, complex and interdependent. Our understanding of degradation and failure of Li-ion cells is still very limited and more limited yet are reliable and practical methods for the detection and prediction of these phenomena. This thesis presents a comprehensive approach for the diagnosis and prognosis of degradation in Li-ion cells. The key to this approach is the extraction of information on electrode-speci c degradation through open circuit voltage (OCV) measurements. This is achieved in three stages. Firstly, a parametric OCV model is created, which computes the OCV of each electrode. Secondly, a diagnostic algorithm is devised, through which the OCV model is tted to OCV measurements recorded on Li-ion cells at various stages throughout their cycle life. The algorithm identi es the nature and quanti es the extent of degradation experienced by the cells. Lastly, the outputs of the algorithm are used to identify the likely failure modes of the cells and predict their end-of-life. The presented methods improve safe operation and predictions of remaining useful cycle life for commercial Li-ion cells. Greater certainty about the reliability, safety, required maintenance and depreciation of Li-ion battery systems can signi cantly enhance the competitiveness of battery electric storage in both automotive and stationary applications. The ndings presented in this work are therefore not only of technological but also of commercial interest.