Doctor of Philosophy / Department of Mechanical and Nuclear Engineering / Gurpreet Singh / The inevitable depletion of fossil fuels and related environmental issues has led to exploration of alternative energy sources and storage technologies. Among various energy storage technologies, rechargeable metal-ion batteries (MIB) are at the forefront. One dominant factor affecting the performance of MIB is the choice of electrode material. This thesis reports synthesis of paper like electrodes composed for three representative layered materials (van der Waals sheets) namely reduced graphene oxide (rGO), molybdenum disulfide (MoS₂) and hexagonal boron nitride (BN) and their use as a flexible negative electrode for Li and Na-ion batteries. Additionally, layered or sandwiched structures of vdW sheets with precursor-derived ceramics (PDCs) were explored as high C-rate electrode materials. Electrochemical performance of rGO paper electrodes depended upon its reduction temperature, with maximum Li charge capacity of 325 mAh.g⁻¹ observed for specimen annealed at 900°C. However, a sharp decline in Na charge capacity was noted for rGO annealed above 500 °C. More importantly, annealing of GO in NH₃ at 500 °C showed negligible cyclability for Na-ions while there was improvement in electrode's Li-ion cycling performance. This is due to increased level of ordering in graphene sheets and decreased interlayer spacing with increasing annealing temperatures in Ar or reduction at moderate temperatures in NH₃. Further enhancement in rGO electrodes was achieved by interfacing exfoliated MoS₂ with rGO in 8:2 wt. ratios. Such papers showed good Na cycling ability with charge capacity of approx. 225.mAh.g⁻¹ and coulombic efficiency reaching 99%. Composite paper electrode of rGO and silicon oxycarbide SiOC (a type of PDC) was tested as high power-high energy anode material. Owing to this unique structure, the SiOC/rGO composite electrode exhibited stable Li-ion charge capacity of 543.mAh.g⁻¹ at 2400 mA.g⁻¹ with nearly 100% average cycling efficiency. Further, mechanical characterization of composite papers revealed difference in fracture mechanism between rGO and 60SiOC composite freestanding paper. This work demonstrates the first high power density silicon based PDC/rGO composite with high cyclic stability. Composite paper electrodes of exfoliated MoS₂ sheets and silicon carbonitride (another type of PDC material) were prepared by chemical interfacing of MoS₂ with polysilazane followed by pyrolysis . Microscopic and spectroscopic techniques confirmed ceramization of polymer to ceramic phase on surfaces on MoS₂. The electrode showed classical three-phase behavior characteristics of a conversion reaction. Excellent C-rate performance and Li capacity of 530 mAh.g⁻¹ which is approximately 3 times higher than bulk MoS₂ was observed. Composite papers of BN sheets with SiCN (SiCN/BN) showed improved electrical conductivity, high-temperature oxidation resistance (at 1000 °C), and high electrochemical activity (~517 mAh g⁻¹ at 100 mA g⁻¹) toward Li-ions generally not observed in SiCN or B-doped SiCN. Chemical characterization of the composite suggests increased free-carbon content in the SiCN phase, which may have exceeded the percolation limit, leading to the improved conductivity and Li-reversible capacity. The novel approach to synthesis of van der Waals sheets and its PDC composites along with battery cyclic performance testing offers a starting point to further explore the cyclic performance of other van der Waals sheets functionalized with various other PDC chemistries.

abstract: Tin (Sn) has a high-specific capacity (993 mAhg-1) as an anode material for Li-ion batteries. To overcome the poor cycling performance issue caused by its large volume expansion and pulverization during the charging and discharging process, many researchers put efforts into it. Most of the strategies are through nanostructured material design and introducing conductive polymer binders that serve as matrix of the active material in anode. This thesis aims for developing a novel method for preparing the anode to improve the capacity retention rate. This would require the anode to have high electrical conductivity, high ionic conductivity, and good mechanical properties, especially elasticity. Here the incorporation of a conducting polymer and a conductive hydrogel in Sn-based anodes using a one-step electrochemical deposition via a 3-electrode cell method is reported: the Sn particles and conductive component can be electrochemically synthesized and simultaneously deposited into a hybrid thin film onto the working electrode directly forming the anode. A well-defined three dimensional network structure consisting of Sn nanoparticles coated by conducting polymers is achieved. Such a conductive polymer-hydrogel network has multiple advantageous features: meshporous polymeric structure can offer the pathway for lithium ion transfer between the anode and electrolyte; the continuous electrically conductive polypyrrole network, with the electrostatic interaction with elastic, porous hydrogel, poly (2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylonitrile) (PAMPS) as both the crosslinker and doping anion for polypyrrole (PPy) can decrease the volume expansion by creating porous scaffold and softening the system itself. Furthermore, by increasing the amount of PAMPS and creating an interval can improve the cycling performance, resulting in improved capacity retention about 80% after 20 cycles, compared with only 54% of that of the control sample without PAMPS. The cycle is performed under current of 0.1 C. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2015

The research work presented in this thesis comprises a detailed investigation of conductivity mechanism in crystalline polymer electrolytes and development of a new class of ceramic-polymer composite electrolytes for Li-ion batteries. Firstly, a robust methodology for the synthesis of monodispersed poly(ethylene oxides) has been established and a series of dimethyl-protected homologues with 13, 15, 17, 28, 29, 30 ethylene oxide repeat units was prepared. The approach is based on reiterative cycles of chain extension and deprotection, followed by end-capping of the oligomeric chain ends with methyl groups. The poly(ethylene oxide) homologues show a superior level of monodispersity to previous work and were subsequently used to prepare crystalline PEO6:LiPF6 polymer electrolytes. A correlation between the number of ether oxygens in the polymer chain and the ionic conductivity of crystalline polymer electrolytes has been established. The structure and dynamics of the monodispersed complexes were studied using solid-state NMR spectroscopy for the first time. The results are in agreement with the proposed mechanism of ionic conductivity in crystalline polymer electrolytes. A new class of composite solid electrolytes for all-solid-state batteries with a lithium metal anode is reported. The composite material consists of a 3D interpenetrating network of a ceramic electrolyte, Li₁.₄Al₀.₄Ge₁.₆(PO₄)₃, and an inert polymer (polypropylene), providing continuous pathways for the ionic transport and excellent mechanical properties. 3D connectivity of this novel composite was confirmed using X-ray microtomography and AC impedance spectroscopy.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第15672号 / 工博第3330号 / 新制||工||1502(附属図書館) / 28209 / 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 垣内 隆, 教授 井上 正志 / 学位規則第4条第1項該当

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第17587号 / 工博第3746号 / 新制||工||1571(附属図書館) / 30353 / 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 陰山 洋, 教授 阿部 竜 / 学位規則第4条第1項該当

>Magister Scientiae - MSc / Architecturally enhanced electrode materials for lithium ion batteries (LIB) with permeable morphologies have received broad research interests over the past years for their promising properties. However, literature based on modified porous nanoparticles of lithium manganese phosphate (LiMnPO₄) is meagre. The goal of this project is to explore lithium manganese phosphate (LiMnPO₄) nanoparticles and enhance its energy and power density through surface treatment with transition metal nanoparticles. Nanostructured materials offer advantages of a large surface to volume ratio, efficient electron conducting pathways and facile strain relaxation. The material can store lithium ions but have large structure change and volume expansion during charge/discharge processes, which can cause mechanical failure. LiMnPO₄ is a promising, low cost and high energy density (700 Wh/kg) cathode material with high theoretical capacity and high operating voltage of 4.1 V vs. Ag/AgCl which falls within the electrochemical stability window of conventional electrolyte solutions. LiMnPO₄ has safety features due to the presence of a strong P–O covalent bond. The LiMnPO₄ nanoparticles were synthesized via a sol-gel method followed by coating with gold nanoparticles to enhance conductivity. A magnesium oxide (MgO) nanowire was then coated onto the LiMnPO₄/Au, in order to form a support for gold nanoparticles which will then form a thin film on top of LiMnPO₄ nanoparticles crystals. The formed products will be LiMnPO₄/Mg-Au composite. MgO has good electrical and thermal conductivity with improved corrosion resistance. Thus the electronic and optical properties of MgO nanowires were sufficient for the increase in the lithium ion diffusion. The pristine LiMnPO₄ and LiMnPO₄/Mg-Au composite were examined using a combination of spectroscopic and microscopic techniques along with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Microscopic results revealed that the LiMnPO₄/Mg-Au composite contains well crystallized particles and regular morphological structures with narrow size distributions. The composite cathode exhibits better reversibility and kinetics than the pristine LiMnPO₄ due to the presence of the conductive additives in the LiMnPO₄/Mg-Au composite. This is demonstrated in the values of the diffusion coefficient (D) and the values of charge and discharge capacities determined through cyclic voltammetry. For the composite cathode, D= 2.0 x 10⁻⁹ cm²/s while for pristine LiMnPO₄ D = 4.81 x 10⁻¹⁰ cm2/s. The charge capacity and the discharge capacity for LiMnPO₄/Mg-Au composite were 259.9 mAh/g and 157.6 mAh/g, respectively, at 10 mV/s. The corresponding values for pristine LiMnPO₄ were 115 mAh/g and 44.75 mAh/g, respectively. A similar trend was observed in the results obtained from EIS measurements. These results indicate that LiMnPO₄/Mg-Au composite has better conductivity and will facilitate faster electron transfer and therefore better electrochemical performance than pristine LiMnPO₄. The composite cathode material (LiMnPO₄/Mg-Au) with improved electronic conductivity holds great promise for enhancing electrochemical performances, discharge capacity, cycle performance and the suppression of the reductive decomposition of the electrolyte solution on the LiMnPO₄ surface. This study proposes an easy to scale-up and cost-effective technique for producing novel high-performance nanostructured LiMnPO₄ nanopowder cathode material.

Master of Science / Department of Mechanical and Nuclear Engineering / Gurpreet Singh / Polymer-derived ceramics (PDCs) such as silicon oxycarbide (SiOC) have shown promise as an electrode material for rechargeable Li-ion batteries (LIBs) owing to the synergy between its disordered carbon phase and hybrid bonds of silicon with oxygen and carbon. In addition to their unique structure, PDCs are known for their high surface area (~822.7 m² g⁻¹), which makes them potential candidates for supercapacitor applications. However, low electrical conductivity, voltage hysteresis, and first cycle lithium irreversibility have hindered their introduction into commercial devices. One approach to improving charge storage capacity is by interfacing the preceramic polymer with boron or aluminium prior pyrolysis. Recent research has shown that chemical interfacing with elemental boron, bulk boron powders and even exfoliated sheets of boron nitride leads to enhancements in thermal and electronic properties of the ceramic. This thesis reports the synthesis of a new type of PDC composite comprising of SiOC embedded with boron nitride nanotubes (BNNTs). This was achieved through the introduction of BNNT in SiOC pre-ceramic polymer at varying wt.% loading (0.25, 0.5 and 2.0 wt.%) followed by thermolysis at high temperature. Electron microscopy and a range of spectroscopy techniques were employed to confirm the polymer-to-ceramic transformation and presence of disordered carbon phase. Transmission electron microscopy confirmed the tubular morphology of BNNT in the composite. To test the material for electrochemical applications, the powders were then made into free-standing paper-like electrodes with reduced graphene oxide (rGO) acting as support material. The synthesized free-standing electrodes were characterized and tested as electrochemical energy storage materials for LIBs and symmetric supercapacitor applications. Among the SiOC-BNNT composite paper tested as anode materials for LIBs, the 0.25 wt.% BNNT composite paper demonstrated the highest first cycle lithiation capacity corresponding to 812 mAh g⁻¹ (at a current density of 100 mA g⁻¹) with a stable charge capacity of 238 mAh g⁻¹ when asymmetrically cycled after 25 cycles. On the contrary, the 0.5 wt.% BNNT composite paper demonstrated the highest specific capacitance corresponding to 78.93 F g⁻¹ at a current density of 1 A g⁻¹ and a cyclic retention of 86% after 185 cycles. This study shows that the free carbon content of SiOC-BNNT ceramic composite can be rationally modified by varying the wt.% of BNNT. As such, the paper composite can be used as an electrode material for electrochemical energy storage.

Recent advances in the electric & hybrid electric vehicles and rapid developments in the electronic devices have increased the demand for high power and high energy density lithium ion batteries. Graphite (theoretical specific capacity: 372 mAh/g) used in commercial anodes cannot meet these demands. Amorphous SnO2 anodes (theoretical specific capacity: 781 mAh/g) have been proposed as alternative anode materials. But these materials have poor conductivity, undergo a large volume change during charging and discharging, large irreversible capacity loss leading to poor cycle performances. To solve the issues related to SnO2 anodes, we propose to synthesize porous SnO2 composites using electrostatic spray deposition technique. First, porous SnO2/CNT composites were fabricated and the effects of the deposition temperature (200,250, 300 oC) & CNT content (10, 20, 30, 40 wt %) on the electrochemical performance of the anodes were studied. Compared to pure SnO2 and pure CNT, the composite materials as anodes showed better discharge capacity and cyclability. 30 wt% CNT content and 250 oC deposition temperature were found to be the optimal conditions with regard to energy capacity whereas the sample with 20% CNT deposited at 250 oC exhibited good capacity retention. This can be ascribed to the porous nature of the anodes and the improvement in the conductivity by the addition of CNT. Electrochemical impedance spectroscopy studies were carried out to study in detail the change in the surface film resistance with cycling. By fitting EIS data to an equivalent circuit model, the values of the circuit components, which represent surface film resistance, were obtained. The higher the CNT content in the composite, lower the change in surface film resistance at certain voltage upon cycling. The surface resistance increased with the depth of discharge and decreased slightly at fully lithiated state. Graphene was also added to improve the performance of pure SnO2 anodes. The composites heated at 280 oC showed better energy capacity and energy density. The specific capacities of as deposited and post heat-treated samples were 534 and 737 mAh/g after 70 cycles. At the 70th cycle, the energy density of the composites at 195 °C and 280 °C were 1240 and 1760 Wh/kg, respectively, which are much higher than the commercially used graphite electrodes (37.2-74.4 Wh/kg). Both SnO2/CNTand SnO2/grapheme based composites with improved energy densities and capacities than pure SnO2 can make a significant impact on the development of new batteries for electric vehicles and portable electronics applications.

This thesis first uses physical scale models to investigate solid-state phenomena - surface layer formation, solid-state diffusion of lithium, electrochemical reactions at the solid-electrolyte interface, as well as homogeneous chemical phase change reactions. Evidence is provided that surface layer formation on the magnetite, Fe3O4, electrode can accurately be described mathematically as a nucleation and growth process. To emulate the electrochemical results of the LiV3O8 electrode, a novel method is developed to capture the phase change process; this method describes phase change as a nucleation and growth process. The physical parameters of the LiV3O8 electrode: the solid-state diffusion coefficient, phase change saturation concentration, phase reaction rate constant, and exchange current density, are all quantified and the agreement with experimental results is compelling. Electrochemical evidence, corroborated by results from density functional theory, indicate that delithiation is a more facile process than lithiation in the LiV3O8 electrode. Further investigation of the LiV3O8 electrode is undertaken by coupling the crystal scale model to electrode scale phenomena. Characterization of the LiV3O8 electrode by operando EDXRD experiments provides a unique and independent set of observations that validate the previously estimated physical constants for the phase change saturation concentration and phase change reaction rate constant; they are both found to be consistent with their previous estimates. Finally, it is observed that anodic physical phenomena are important during delithiation of the cathode because the kinetics at the anode become mass-transfer limited. Finally, it is illustrated that coupling physical models to data science and algorithmic computing is an effective method to accelerate model development and quantitatively guide the design of experiments.

In this report, which is written for Halmstad University and on behalf of Semcon, a mechanical design process was implemented to evaluate the possibility of executing a low-cost cooling system for one of the battery company’s products. The report started from the background of former studies to clarify the problem and finding existing solutions in the first step and following up with developing concepts based on gathered information from the literature study. The battery company provides a high-performance battery based on customer requirements because of the flexible lithium battery technology. There are two similar conditions in the operating period of the battery. One in the high performance usage of the battery and two in the charging period by adding power to the battery cells. Both of these actions generate heat which is the result of resistance of the material in the cells and the chemical reaction of the cells. The battery company wants to decrease the time of charging period in order to reach the operative condition as fast as possible by enabling fast charging. According to the battery management system (BMS), at high temperatures the efficiency of charging rate decreases and also it has a negative influence on the battery cells performance and lifetime. A cooling system is required in order to fulfil the requirement of having high performance and making fast charging possible for the battery. The goal of this thesis is to develop a cooling system based on literature study with consideration of applying to the lithium battery in order to reduce charging time by decreasing temperature in the modules during the operating period. This report contains the whole developing conceptual design process of the cooling system by starting a wide range of information gathering in the purpose of determining the main variables which have an influence on different cooling techniques. In specific, after deciding about the type of cooling method for the product, the study has been focused on the fluid dynamics and heat transfer by forced convection with airflow. The concept generation executed on the information which was gathered through the information retrieval. The final developed concept has been introduced in this thesis work which has the potential of fulfilling the requirement of designing a cooling system to decrease the temperature of the battery’s modules without making any serious changes in the product. The final concept has been developed by various changes in its components and evaluating those changes by executing simulation for each change. The final concept contains twelve similar heat sinks which have been installed over connectors to provide more surface in the purpose of exchanging heat through the airflow provided by three high-speed fans. In order to force the airflow over the heat sinks, a cover has been designed.