The Mechanistic Description of the Open Circuit Potential for the Lithiation of Magnetite Nanoparticles

Batteries are ubiquitous in modern society, from the portable devices we use daily to the yet-to-be realized integration of batteries into the electrical grid and electrical vehicle markets. One of the primary roles of batteries to date has been to enable portability of devices, and as chemical energy storage becomes more affordable, batteries will play a larger role in how society cares for the environment by enabling technologies that are poised to decrease greenhouse gas emissions. Low cost and environmentally conscious materials are pivotal for the economic feasibility and widespread integration of batteries into new markets. Batteries operate far from equilibrium and may operate under extreme stress and varying loads, therefore, for a material to be successful in an operational battery it must meet multiple design criteria. Here, an in-depth analysis of magnetite, a low cost and abundant iron oxide studied for use as an electrode material in lithium-ion batteries, is presented. In the second Chapter, an in-depth analysis into how magnetite accepts lithium into the solid state at low depths of discharge is examined with density functional theory and a mechanistic understanding of a phase change from the parent spinel to a rocksalt-like material is presented. When magnetite is used as an electrode material in a lithium-ion battery, lithium must enter into and eject from the solid state of the host material, where the direction of lithium movement is a function of the current in the battery. In many electrode materials, magnetite included, large structural rearrangements can occur in the host material as lithium moves into and out of the lattice. These structural rearrangements can be irreversible and can contribute to overpotentials, decreasing efficiency and lifecycle for the battery. The structural rearrangements in bulk magnetite occurring due to lithium insertion are found to be driven primarily by Coulombic interactions. Additionally, the energetics and structural rearrangements for lithium insertion into defective magnetite and maghemite are examined, as these derivative structures commonly co-exist with magnetite, especially when the material is nanostructured. It is found that defective magnetite and maghemite accept lithium by a different mechanism, one that does not initially result in substantial structural rearrangement, as is the case in magnetite. In Chapter three, the effects of nanostructuring magnetite on the reversible potential are examined as a function of nanoparticle size. Due to solid-state mass-transport resistances, active electrode materials in batteries are commonly nanostructured. When a material is nanostructured, the bulk properties are often replaced due to interesting phenomena that can occur as a result of stark differences between the nanostructured material and the bulk counterpart. These differences are often attributed to surface area to volume ratios, the exaggerated role of surface energies, lattice defects, and the variation in electronic behavior, all properties which change between a bulk and nanostructured material. The reversible potential is found to be particle size dependent, and this dependence is explained, in part, by the cationic defective surfaces in the particles and the differences in surface area to volume ratio between varying particle sizes. Evidence for these defects is presented with materials characterization techniques such as XRD and EELS studies. Finally, the reversible potential at low lithiation states is predicted theoretically and found to match well to the experimentally measured potential. A study of the DFT predicted potentials and XRD characterization for multiple metastable pathways is examined in the fourth Chapter. Room temperature and long-time scale persistence of metastable phases is a pervasive phenomenon in nature. Magnetite is known to undergo both phase change and conversion reactions upon lithiation. Due to large mass transport and kinetic resistances, multiple phase changes are often observed in parallel during discharge, resulting in heterogenous phase formation in particles which can have large local lithium concentration variations. Phases which form during discharge can become kinetically trapped and the equilibrium state can therefore follow a metastable pathway. Theoretical potentials and XRD patterns are compared to the experimental patterns taken following 600 hours of relaxation following discharge at the slow rate of C/600. The evidence presented supports a metastable pathway occurring on the first voltage plateau. In the fifth Chapter, the methodologies for the density functional theory calculations are presented in full detail. This includes various studies on the more subtle electronic properties of magnetite and its lithiated derivates studied herein. These studies include examination of the charge and orbital ordering problem related to the Verwey transition in magnetite, the charge and magnetic order in the rocksalt-like lithiated magnetite, and a full theoretical description of the various phases in the Li-Fe-O ternary phase diagram that were calculated to make the relevant conclusions in Chapters 2-4. Finally, corrections to DFT predicted formation energy and volume are presented. The aim of this thesis is to use theoretical techniques to examine the lithiation of magnetite on the atomic scale and make meaningful connections to the experimentally observed electrochemical behavior of the material. To accomplish this, magnetite and the structural derivatives of magnetite that co-exist with the material under physically realistic conditions must be treated theoretically. In this thesis, ties between phenomena occurring on the atomic scale and the measurable properties of the macroscopic system, such as voltage, will be related. It will be illustrated that as a function of nanoparticle size, the magnetite system can vary in its atomic structure and the resultant electrochemistry and phase change characteristics are both affected. The findings indicate the relevance of the atomic properties and nanostructure for magnetite to the observed and measured electrochemical properties of the material

Electronic Structure of Transition Metal Dichalcogenides and Molecular Semiconductors

Zweidimensionale (2D) Übergangsmetalldichalcogenide (TMDCs) gehören zu den attraktivsten neuen Materialien für optoelektronische Bauelemente der nächsten Generation. Um die überlegene Funktionalität der mit TMDCs verbundenen Bauelemente zu realisieren, ist ein umfassendes Verständnis ihrer elektronischen Struktur, einschließlich, aber nicht beschränkt auf die Auswirkungen von Defekten auf die elektronischen Eigenschaften und die Ausrichtung der Energieniveaus (ELA) an den TMDCs-Grenzflächen, unerlässlich, aber derzeit nicht ausreichend. Um einen tieferen Einblick in die elektronischen Eigenschaften von TMDCs und den damit verbundenen Grenzflächen in Kombination mit molekularen Halbleitern (MSCs) zu erhalten, untersuchen wir i) die fundamentale Bandstruktur von Monolagen (ML) TMDCs und die durch Schwefelfehlstellen (SVs) induzierte Renormierung der Bandstruktur, um eine solide Grundlage für ein besseres Verständnis der elektronischen Eigenschaften von polykristallinen dünnen Filmen zu schaffen, und ii) die optoelektronischen Eigenschaften ausgewählter MSC/ML-TMDCs-Grenzflächen. Darüber hinaus wird iii) der Einfluss des Substrats auf die elektronischen Eigenschaften einer MSC/ML-TMDC-Grenzfläche untersucht, um das Bauelementedesign zu steuern. Die Charakterisierung erfolgt hauptsächlich durch winkelaufgelöste Photoelektronenspektroskopie (ARPES), ergänzt durch Photolumineszenz (PL), Raman-Spektroskopie, UV-Vis-Absorption, Rastertransmissionselektronenmikroskopie (TEM) und Rasterkraftmikroskopie (AFM). Unsere Ergebnisse tragen zu einem besseren Verständnis der Auswirkungen von Defekten auf ML-TMDC und verwandte Grenzflächen mit MSCs bei, wobei auch die Auswirkungen der Substrate berücksichtigt werden, und sollten dazu beitragen, unser Verständnis des elektronischen Verhaltens in TMDC-verwandten Geräten zu verbessern.Two-dimensional (2D) transition metal dichalcogenides (TMDCs) are amongst the most attractive emerging materials for next-generation optoelectronic devices. To realize the superior functionality of the TMDCs related devices, a comprehensive understanding of their electronic structure, including but not limited to the impact of defects on the electronic properties and energy level alignment (ELA) at TMDCs interfaces, is essential but presently not sufficient. In an attempt to get a deep insight into the electronic properties of TMDCs and the related interfaces combined with molecular semiconductors (MSCs), we investigate i) the fundamental band structure of monolayer (ML) TMDCs and band structure renormalization induced by sulfur vacancies (SVs), in order to provide a solid foundation for a better understanding the electronic properties of polycrystalline thin films and ii) the optoelectronic properties of selected MSC/ML-TMDC interface. In addition, iii) the impact of the substrate on the electronic properties of the MSC/ML-TMDC interface is investigated for guiding device design. The characterization is mainly performed by using angle-resolved photoelectron spectroscopy (ARPES), with complementary techniques including photoluminescence (PL), Raman spectroscopies, UV-vis absorption, scanning transmission electron microscopy (TEM), and atomic force microscopy (AFM) measurements. Our findings contribute to achieving a better understanding of the impact of defects on ML-TMDC and related interfaces with MSCs considering the substrates’ effect and should help refine our understanding of the electronic behavior in TMDC-related devices

Payload specialist station study: Volume 2, part 3: Program analysis and planning for phase C/D

The controls and displays (C&D) required at the Orbiter aft-flight deck (AFD) and the core C&D required at the Payload Specialist Station (PSS) are identified in this document. The AFD C&D Concept consists of a multifunction display system (MFDS) and elements of multiuse mission support equipment (MMSE). The MFDS consists of two CRTs, a display electronics unit (DEU), and a keyboard. The MMSE consists of a manual pointing controller (MPC), five digit numeric displays, 10 character alphanumeric legends, event timers, analog meters, rotary and toggle switches. The MMSE may be hardwired to the experiment, or interface with a data bus at the PSS for signal processing. The MFDS has video capability, with alphanumeric and graphic overlay features, on one CRT and alphanumeric and graphic (tricolor) capability on a second CRT. The DEU will have the capability to communicate, via redundant data buses, with both the spacelab experiment and subsystem computers

Synthesis and Transport Properties of Topological Crystalline Insulator SnTe Nanowires

Over the last decade, significant progress has been made in studying topological materials whose wavefunctions possess a distinct topological invariant signature barring adiabatic deformation from a trivial phase to a non-trivial phase. There has been mounting experimental evidence for the presence of topological nature in nanomaterials due to their favorable surface-to-volume ratio and phase-coherent confinement. Considering that the material synthesis and transport measurement challenges must be overcome before topological nanomaterials can be used in next-generation electronic devices, in my dissertation, I focus on improving crystal quality and controlling dimensions of topological crystalline insulator SnTe in nanoscale as it provides a rich playground to examine interactions of correlated electronic states, such as ferroelectricity, topological surface states, and superconductivity. To develop facile strategies to suppress surface defects during chemical vapor deposition growth of SnTe nanostructures, we systematically investigate the origin and evolution of three-dimensional surface defects commonly observed on SnTe microcrystals and nanostructures. By employing alloy nanoparticles as growth catalyst, SnTe nanowires are synthesized with reduced diameters and high crystalline quality, such that one-dimensional confinement and phase coherence of the topological surface electrons can be ensured to probe the topological surface states. To further alleviate the high carrier density inside the bulk of SnTe nanowires and surface degradation, surface passivation of SnTe nanowires using in situ Te deposition during growth process is investigated. The material improvement approach in this dissertation aims to facilitate future research on understanding the extent of scattering of topological surface states due to crystalline defects, impurities, and coupling to bulk electron states

Airborne Advanced Reconfigurable Computer System (ARCS)

A digital computer subsystem fault-tolerant concept was defined, and the potential benefits and costs of such a subsystem were assessed when used as the central element of a new transport's flight control system. The derived advanced reconfigurable computer system (ARCS) is a triple-redundant computer subsystem that automatically reconfigures, under multiple fault conditions, from triplex to duplex to simplex operation, with redundancy recovery if the fault condition is transient. The study included criteria development covering factors at the aircraft's operation level that would influence the design of a fault-tolerant system for commercial airline use. A new reliability analysis tool was developed for evaluating redundant, fault-tolerant system availability and survivability; and a stringent digital system software design methodology was used to achieve design/implementation visibility