First principles computation can be used to investigate an design materials in ways that can not be achieved with experimental means. We show how computations can be used to rapidly capture the essential physics that determines the useful properties in different applications. Some applications for predicting crystal structure, thermodynamic and kinetic properties, and phase stability are discussed. This first principles tool set will be demonstrated with applications from rechargeable batteries and hydrogen storage materials. / Singapore-MIT Alliance (SMA)

Thesis advisor: Udayan Mohanty / Rechargeable batteries, especially lithium ion batteries, have greatly transformed mobile electronic devices nowadays. Due to the ever-depletion of fossil fuel and the need to reduce CO2 emissions, the development of batteries needs to extend the success in small electronic devices to other fields such as electric vehicles and large-scale renewable energy storage. Li-ion batteries, however, even when fully developed, may not meet the requirements for future electric vehicles and grid-scale energy storage due to the inherent limitations related with intercalation chemistry. As such, alternative battery systems should be developed in order to meet these important future applications. This dissertation presents our successes in improving Li-O2 battery performance for electric vehicle application and integrating a redox flow battery into a photoelectrochemical cell for direct solar energy storage application. Li-O2 batteries have attracted much attention in recent years for electric vehicle application since it offers much higher gravimetric energy density than Li-ion ones. However, the development of this technology has been greatly hindered by the poor cycling performance. The key reason is the instability of carbon cathode under operation conditions. Our strategy is to protect the carbon cathode from reactive intermediates by a thin uniform layer grown by atomic layer depostion. The protected electrode significantly minimized parasitic reactions and enhanced cycling performance. Furthermore, the well-defined pore structures in our carbon electrode also enabled the fundamental studies of cathode reactions. Redox flow batteries (RFB), on the other hand, are well-suited for large-scale stationary energy storage in general, and for intermittent, renewable energy storage in particular. The efficient capture, storage and dispatch of renewable solar energy are major challenges to expand solar energy utilization. Solar rechargeable redox flow batteries (SRFBs) offer a highly promising solution by directly converting and storing solar energy in a RFB with the integration of a photoelectrochemical cell. One major challenge in this field is the low cell open-circuit potential, mainly due to the insufficient photovoltages of the photoelectrode systems. By combining two highly efficient photoelectrodes, Ta3N5 and Si (coated with GaN), we show that a high-voltage SRFB could be unassistedly photocharged and discharged with a high solar-to-chemical efficiency. / Thesis (PhD) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis (Ph.D. (Engineering mechanics)) --University of Limpopo, 2004 / This thesis explores the important issues associated with the insertion of Mg2+ and Li+ into the solid materials: molybdenum sulphide and titanium disulphide. This process, which is also known as intercalation, is driven by charge transfer and is the basic cell reaction of advanced batteries. We perform a systematic computational investigation of the new Chevrel phase, MgxMo6S8 for 0 ≤ x ≤ 2, a candidate for high energy density cathode in prototype rechargeable magnesium (Mg) battery systems. Mg2+ intercalation property of the Mo6S8 Chevrel phase compound and accompanied structural changes were evaluated. We conduct our study within the framework of both the local-density functional theory and the generalised gradient approximation techniques. Analysis of the calculated energetics for different magnesium positions and composition suggest a triclinic structure of MgxMo6S8 (x = 1 and 2). The results compare favourably with experimental data. Band-structure calculations imply the existence of an energy gap located ~1 eV above the Fermi level, which is a characteristic feature of the electronic structure of the Chevrel compounds. Calculations of electronic charge density suggest a charge transfer from Mg to the Mo6S8 cluster, which has a significant effect on the Mo-Mo bond length. There is relatively no theoretical work, in particular ab initio pseudopotential calculations, reported in literature on structural stability, cations "site energy" calculations, and pressure work. Structures obtained on the basis from experimental studies of other ternary molybdenum sulphides are examined with respect to pressure-induced structural transformation. We report the first bulk and linear moduli of the new Chevrel phase structures. This thesis also studies the reaction between lithium and titanium disulfide, which is the perfect intercalation reaction, with the product having the same structure over the range of reaction 0  x  1 in LixTiS2. Calculated lattice parameters, bulk moduli, linear moduli, elastic constants, density of states, and Mulliken populations are reported. Our calculations confirm that there is a single phase present with an expansion of the crystalline lattice as is typical for a solid solution, about 10% perpendicular to the basal plane layers. A slight expansion of the lattice in the basal plane is also observed due to the electron density increasing on the sulfur ions. Details on the correlation between the electronic structure and the energetic (i.e. the thermodynamics) of intercalation are obtained by establishing the connection between the charge transfer and lithium intercalation into TiS2. The theoretical determination of the densities of states for the pure TiS2 and Li1TiS2 confirms a charge transfer. Lithium charge is donated to the S (3p) and Ti (3d) orbitals. Comparison with experiment shows that the calculated optical properties for energies below 12 eV agrees well with reflectivity spectra. The structural and electronic properties of the intercalation compound LixTiS2, for x = 1/4, 3/4, and 1, are also investigated. This study indicates that the following physical changes in LixTiS2 are induced by intercalation: (1) the crystal expands uniaxially in the c-direction, (2) no staging is observed. We also focus on the intercalation voltage where the variation of the cell potential with the degree of discharge for LiTiS2 is calculated. Our results show that it can be predicted with these well-developed total energy methods. The detailed understanding of the electronic structure of the intercalation compounds provided by this method gives an approach to the interpretation of the voltage composition profiles of electrode materials, and may now clearly be used routinely to determine the contributions of the anode and cathode processes to the cell voltage. Hence becoming an important tool in the selection and design of new systems. Keywords Magnesium rechargeable battery; Chevrel, Lithium batteries; Li and Mg-ion insertion; TiS2; Mo6S8; Charge transfer; reflectivity, intercalation, elastic constants, voltage, EOS, Moduli. / the National Research Foundation, the Royal Society(U.K),the Council for Scientific and Industrial Research,and Eskom

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)

Thesis (M. Sc. (Chemistry)) -- University of Limpopo, 2019 / Nano-architecture structures of LixTiO2 are very promising as anode materials for lithium rechargeable batteries due to their ability to accommodate more lithium atoms and its ability to withstand high temperatures at atomistic level through charging and discharging. In these studies, we investigated how nano-architectured structures of LixTiO2 behave at high temperatures through the process of amorphisation and recrystallisation. A computational method of molecular dynamics (MD) simulation was employed to recrystallise the amorphous LixTiO2 nano-architectures of bulk, nanosheet, nanoporous and nanosphere, where x depicts the fraction of lithium ions, i.e. 0.03, 0.04 and 0.07. The main objective of this study was to go beyond the previous inserted lithium atoms on TiO2 and understand the effects of concentrations, temperature, defect chemistry and charge storage properties/capacity on the overall lithium transport to improve lithium ion battery performance. Recrystallisation of all four nanostructures from amorphous precursors were successfully achieved and was followed by the cooling process towards 0 K and finally we heated all four nano-architectures at temperature intervals of 100 K up to 500 K. The variation of configuration energies as a function of time, was used to monitor the crystal growth of all nanostructures. Calculated Ti-O radial distribution function, were used to confirm the stability interaction after cooling. Calculated X-Ray Diffraction (XRD) spectra where used to characterise and compare their patterns at cooled and above high temperatures, using the model nanostructures, and they showed polymorphic nanostructures with LixTiO2 domains of both rutile and brookite in accord with experiment. Amorphisation and recrystallization showed good results in generating complex microstructures. In particular, bulk structures show few zigzag tunnels (indicative of micro twinning) with 0.03 Li but 0.04 Li and 0.07 Li show complex v patterns indicating a highly defected structure. While 0.03 and 0.04Li nanospheres show, zigzag and straight tunnels in accord with experiment, the one with 0.07 Li has melted. Lastly, nanoporous and nanosheet structures have pure straight and zigzag patterns that are well in accord with our XRD patterns at all concentrations of lithium atoms and temperatures. The lithium transport was analysed using diffusion coefficient, calculated as a function of temperature in order to confirm the mobility above the given temperatures. An increase in temperature shows an increase in diffusivity of lithium at all lithium concentrations in nanoporous and nanosheet structures. The same trend was observed in bulk but only with 0.03 and 0.07 Li ion concentrations. / National Research Foundation (NRF)

京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第19817号 / 人博第788号 / 新制||人||189(附属図書館) / 27||人博||788(吉田南総合図書館) / 32853 / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 内本 喜晴, 教授 田部 勢津久, 教授 吉田 寿雄 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第21433号 / 人博第871号 / 2018||人博||871(吉田南総合図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 内本 喜晴, 教授 吉田 寿雄, 准教授 戸﨑 充男 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

Room temperature molten liquids are proposed to be good alternates for volatile and harmful organic compounds. They are useful in varied areas of applications ranging from synthesis, catalysis to energy storage molten electrolytes have certain unique characteristics such as low vapour pressure, reasonably high ionic conductivity, high thermal stability and wide electrochemical window. These molten liquids can be classified in to two types depending on the nature of the species present in the liquids. One, those liquids consists only of ions (e.g) conventional imidazolium based ionic liquids and other that consists of ions and solvents (e g) acetamide eutectics. Acetamide and its eutectics from room temperature molten solvents that is unique with interesting physicochemical properties. The solvent properties of molten acetamide are similar to water, with high dielectric consist of 60 at 353 k. its acid – base properties are also similar to water, and it can solublise variety of organic and inorganic compounds as well. in the present studies room temperature molten liquids consisting of acetamide as one of the components have been prepared and used for various applications. Room temperature molten electrolytes consisting of magnesium perchlorate/magnesium triflate as one of the constituents have been used for rechargeable magnesium batteries where as those consisting of zinc perchlorate /zinc triflate have been used for zinc based rechargeable batteries. Full utilization of cathode material (y-mno2) is achieved using amide-based molten liquid as electrolyte in rechargeable zinc based batteries. Ammonium nitrate/ lithium nitrate containing electrolytes have been used for electrochemical super capacitors. They have been used as solvent cum stabilizers for metallic nanochains that can be used as substrate in surface enchanced Raman scattering studies.

Binder free vertical aligned (VA) CNT/sulfur composite electrodes with high sulfur loadings up to 70 wt% were synthesized delivering discharge capacities higher than 800 mAh g−1 of the total composite electrode mass. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

This thesis deals with novel electrolytes for magnesium batteries. Prepared electrolytes were composed of affordable solvents and chemicals, which can be handled at normal laboratory conditions. Specifically, solutions of tetrahydrofurane and dimethylsulfoxide with magnesium chloride, aluminium chloride, nitrilotriacetic acid and disodium ethylenediaminetetraacetic acid, were prepared. To determine electrolyte ability of magnesium stripping and deposition, the cyclic voltammetry was used. The kinetics of electrochemical reactions in terms of polarization resistance was studied by electrochemical impedance spectroscopy. Based on scanning electron microscopy and EDS analysis, the effect of atmospheric oxygen and humidity on magnesium electrode corrosion during cycling was discussed.