Many material properties depend on specific details of microstructure and both optimal material performance and material reliability often correlate directly to microstructure. In nano- and micro-systems, the material's microstructure has a characteristic length scale that approaches that of the device in which it is used. Fundamental understanding and prediction of material behavior in nano- and micro-systems depend critically on methods for computing the effect of microstructure. Methods for including the physics and spatial attributes of microstructures are presented for a number of materials applications in devices. The research in our group includes applications of computation of macroscopic response of material microstructures, the development of methods for calculating microstructural evolution, and the morphological stability of structures. In this review, research highlights are presented for particular methods for computing the response in: 1) rechargeable lithium ion battery microstructures, 2) photonic composites with anisotropic particulate morphologies, 3) crack deflection in partially devitrified metallic glasses. / Singapore-MIT Alliance (SMA)

The role of nanohybrid materials in the fields of polymer composites and electrochemical energy systems is significant since they affect the enhanced physical properties and improved electrochemical performance, respectively. As basic nanomaterials, carbon nanotubes and graphene were utilized due to their outstanding physical properties. With these materials, hybrid nanostructures were generated through a novel synthesis method, modified sol-gel process; namely, carbon nanotubes (CNTs)-maghemite and reduced graphene oxide (rGO)-maghemite nanohybrid materials were developed. In the study on polymer composities, developed CNTs-maghemite (magnetic carbon nanotbues (m-CNTs)) were readily aligned under an externally applied magnetic field, and due to the aligned features of m-CNTs in polymer matrices, it showed much enhanced anisotropic electrical and mechanical properties. In the study on electrochemical energy system (Li-ion batteries), rGO-maghemite were used as anode materials; as a result, they showed improved electrochemical performance for Li-ion batteries due to their specific morphology and characteristics.

Electric vehicles (EVs) offer an exciting opportunity in China both in terms of the potential to build a domestic manufacturing base and the potential to create a strong domestic market for the product. The Chinese nation stands to benefit from both supply-side and demand-side promotion due to the economic stimulus from EV manufacturing and export, the environmental benefits of reduced air pollution and reduced greenhouse gas emissions, and the energy security benefits of transitioning away from foreign oil dependence. The Chinese have several advantages when it comes to stimulating EV industry development and EV deployment, including: leadership in battery technology, great potential for cost competitiveness, an enormous and emerging number of new car buyers, and high level government support. Yet a number of challenges must be taken into account as well, including: shortfalls in overall automobile R&D spending, consumer concerns about Chinese cars’ safety and reliability, enhancing the appeal of the Chinese brand, and heavy national infrastructure demands. This paper will seek to examine the opportunities and challenges associated with EV deployment in China and identify industry actions and policy measures to facilitate the process.

Die wachsende Weltbevölkerung und die stetigen Entwicklungen in der Industrie benötigen einerseits immer größere Mengen an Grundchemikalien und führen andererseits zu einem ständig steigenden Energiebedarf. Die Dissertation behandelt daher die Themen Zeolithe und Kathodenmaterialien, welche zwei aktuelle Forschungsschwerpunkte der chemischen Industrie darstellen. Der Fokus der Arbeit lag in der Steuerung der Partikelgröße durch die hydrothermale und mikrowellenunterstützte Kristallisation.

Electrochemical copolymerizations of thiophene (Th) and 3,4-ethylenedioxythiophene (EDOT) was performed in this study. Incorporation of Th with EDOT units have accelerated deposition rate in relative to the simple polymerization behavior of EDOT. The electrochemical properties of poly(thiophene-co-3,4-ethylenedioxythiophene) (PTh-EDOT) are different from the homopolymers of polythiophene (PTh) and poly(3,4-ethylenedioxythiophene) (PEDOT). PTh-EDOT were then served as cathode materials of lithium-ion (Li-ion) batteries to test their capability to transfer lithium ion in 1.0 M LiPF6/ethylene carbonate/dimethyl carbonate solution. PTh-EDOT copolymer prepared from the monomer ratio of 1/1 (Th/EDOT) shows better stability than PEDOT and PTh homopolymers, polymer property enhancement by copolymerization is thus demonstrated. A composite electrode material PEDOT/LiCoO2 was prepared from the electrochemical polymerization of EDOT on LiCoO2 electrode was primarily prepared to inspect the influence of PEDOT on the electrochemical features of LiCoO2. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) show the successful deposition of PEDOT over LiCoO2 particles. Compared to the simple LiCoO2 electrode, PEDOT/LiCoO2 composite cathode shows enhanced properties including rate capability and cycle stability for potential Li-ion battery application. Nevertheless, differential scanning calorimetry (DSC) scans on the fully charged cathodes imply that PEDOT may reduce the thermal stability of LiCoO2. Two carbon materials, vapor grown carbon fibers (VGCF) and nano-scaled Ketjen black EC (KB), were implemented into LiCoO2 electrode. The influence of different carbon additive and their content on the performance of LiCoO2 such as rate capability and cycle ability has been evaluated. KB shows more positive effects than VGCF even in the case of a low 1 wt% content. Furthermore, incorporation of PEDOT was made by electrochemical deposition of EDOT on the preformed LiCoO2-VGCF and LiCoO2-KB composite electrodes. The influence of the carbon additives and the conductive PEDOT polymer on LiCoO2 was then investigated. Compared to the electrodes without PEDOT coating, PEDOT-incorporated composite electrodes show larger capacity, better transfer rate of lithium ions in electrolytes, and enhanced cycle ability. The electrochemical deposition of PEDOT on the LiCoO2/nano-carbon cathodes provides a new approach to implement the conducting polymers in Li-ion batteries.

This thesis studies State-of-Charge (SOC) method for widely used lead-acid batteries and the most prospective lithium-ion batteries. First, the relationship between the battery capacity and the open-circuit-voltage under different charging/discharging currents is investigated based on the equivalent circuit. Experimental results indicate that the open-circuit-voltage of the lead-acid battery varies regularly with the charging/discharging current and the duration of time for the battery disconnected from the load. Accordingly, a dynamic open-circuit-voltage method in considerations the open-circuit-time and the previous operating current is capable of precisely estimating the battery capacity in a shorter time. As for the lithium-ion batteries, their charging/discharging characteristics reveal that the Coulomb/Ampere-Hour Counting method is capable of yielding accurate estimations. Finally, through the experiments that emulate practical operations, the SOC estimations of batteries are verified to demonstrate the effectiveness and accuracy of the proposed methods.

The rechargeable lithium ion batteries (LIB) are playing increasingly important roles in powering portal commercial electronic devices. They are also the potential power sources of electric mobile vehicles. The first kind of the cathode materials, LiXCoO2, was commercialized by Sony Company in 1980s, and it is still widely used today in LIB. However, the high cost of cobalt source, its environmental unfriendliness and the safety issue of LiXCoO2 have hindered its widespread usage today. Searching for alternative cathode materials with low cost of the precursors, being environmentally benign and more stable in usage has become a hot topic in LIB research and development. In the first part of this study, lithium nickel manganese cobalt oxide (LiNi0.6Mn0.35Co0.05O2) is studied as the electrode. The materials are synthesized at high temperatures by solid state reaction method. The effect of synthesis temperature on the electrochemical performance is investigated, where characterizations by, for example, X-ray diffraction (XRD) and scanning electron microscopy (SEM), for particle size distribution, specific surface area, and charge-discharge property, are done over samples prepared at different conditions for comparison. The electrochemical tests of the rechargeable Li ion batteries using LiNi0.6Mn0.35Co0.05 cathode prepared at optimum conditions are carried out in various voltage ranges, at different discharge rates and at high temperature. In another set of experiments, the material is adopted as anode with lithium foil as the cathode, and its capacitance is tested. In the second part of this study, the iron based cathode material is investigated. Lithium iron orthosilicate with carbon coating is synthesized at 700℃ by solid state reaction, which is assisted by high energy ball milling. Characterizations are done for discharge capacities of the samples with different carbon weight ratio coatings. / published_or_final_version / Physics / Master / Master of Philosophy

This thesis describes the development of an electrical system for a solar powered racing vehicle with en emphasis on the Battery Protection System (BPS). This battery protection system was designed for the UTSVT’s (University of Texas Solar Vehicles Team) solar powered vehicle, the Samsung Solorean. The system is required due to the dangers of the lithium-ion cobalt battery chemistry. The system monitors the voltage, temperature, and current of each battery module in the 22 module battery pack and will physically isolate the pack from the rest of the vehicle with a high-current electromechanical contactor if any parameter is outside of the safe range. The system can be expanded to monitor any number of series battery cells. The system uses a master-slave microcontroller architecture with a single master microcontroller that interrogates several slave microcontroller boards for readings over a common serial bus. The system uses a new voltage sensing ASIC to monitor cell voltages, along with an analog current output device to measure temperature and a hall-effect device to measure current. The system was a complete success and has allowed the UT solar car to finish the American Solar Challenge cross-country “Rayce.” / text

In the current context of rapidly depleting petroleum resources and growing environmental concerns, it is important to develop materials to harvest and store energy from renewable and sustainable sources. Hydrogen has the potential to be an alternative energy source, since it has higher energy content than petroleum. However, since hydrogen has very low volumetric energy density, hence it is important to design nano porous materials which can efficiently store large volumes of hydrogen gas by adsorption. In this regard carbon nanotube and Metal Organic Framework (MOFs) based materials are worth studying. Ionic liquids (IL) are potential electrolytes that can improve energy storage capacity and safety in Li ion batteries. Therefore it is important to understand IL's thermodynamic and transport properties, especially when it is in contact with electrode surface and mixed with Li salt, as happens in the battery application. This dissertation presents computation and simulation based studies on: 1. Hydrogen storage in carbon nanotube scaffold. 2. Mechanical property and stability of various nanoporous Metal Organic Frameworks. 3. Thermodynamic and transport properties of [BMIM][BF4] ionic liquid in bulk, in Li Salt mixture, on graphite surface and under nanoconfinement. In the first study, we report the effects of carbon nanotube diameter, tube chirality, tube spacer distance, tube functionalization and presence of Li on hydrogen sorption capacity and thermodynamics at different temperature and pressure. In the second one, we observe high pressure induced structural transformation of 6 isoreticular MOFs: IRMOF-1. IRMOF-3, IRMOF-6, IRMOF-8, IRMOF-10 and IRMOF-14, explore the deformation mechanism and effect of Hydrogen inside crystal lattice. In the third study, we observe the equilibrium thermodynamic and transport properties of [BMIM][BF4] ionic liquid. The temperature dependence of ion diffusion, conductivity, dielectric constant, dipole relaxation time and viscosity have been observed and found similar behavior to those of supercooled liquid. The ion diffusion on graphite surfaces and under nanoconfinement was found to be higher compared to those in bulk.

Vertically aligned multi walled carbon nanotube (MWCNT) arrays fabricated by xylene pyrolysis in anodized aluminum oxide (AAO) templates without the use of a catalyst, were integrated into a resistive sensor design. The steady state sensitivities as high as 5% and 10% for 100 ppm of NH3 and NO2 respectively at a flow rate of 750 sccm were observed. A study was undertaken to elucidate (i) the dependence of sensitivity on the thickness of amorphous carbon layers, (ii) the effect of UV light on gas desorption characteristics and (iii) the dependence of room temperature sensitivity on different NH3 and NO2 flow rates. An equivalent circuit model was developed to understand the operation and propose design changes for increased sensitivity. Multi Walled Carbon NanoTubes (MWCNTs) – Polymer composite based hybrid sensors were fabricated and integrated into a resistive sensor design for gas sensing applications. Thin films of MWCNTs were grown onto Si/SiO2 substrates via xylene pyrolysis using chemical vapor deposition technique. Polymers like PEDOT:PSS and Polyaniline (PANI) mixed with various solvents like DMSO, DMF, 2-Propanol and Ethylene Glycol were used to synthesize the composite films. These sensors exhibited excellent response and selectivity at room temperature when exposed to low concentrations (100ppm) of gases like NH3 and NO2. Effect of various solvents on the sensor response imparting selectivity to CNT – Polymer nanocomposites was investigated extensively. Sensitivities as high as 28% was observed for a MWCNT – PEDOT:PSS composite sensor when exposed to 100ppm of NH3 and -29.8% sensitivity for a MWCNT-PANI composite sensor to 100ppm of NO2. A novel nanostructured electrode design for Li based batteries and electrochemical capacitor applications was developed and tested. High density and highly aligned metal oxide nanowire arrays were fabricated via template assisted electrochemical deposition. Nickel and Molybdenum nanowires fabricated via cathodic deposition process were converted into respective oxides via thermal treatments and were evaluated as electrodes for batteries and capacitor applications via Cyclic Voltammetery (CV). Several chemical baths were formulated for the deposition of pristine molybdenum nanowires. Superior electrochemical performance of metal (Ni and Mo) oxide nanowires was observed in comparison to the previously reported nano-particle based electrodes.