SOVLENT REACTIVITY AND INTERFACE EVOLUTION AT MODEL ELECTRODES FOR ENERGY APPLICATIONS

The Li-ion rechargeable battery (LIB) is widely used as an energy storage device, but has significant limitations in battery cycle life and safety. During initial charging, decomposition of the ethylene carbonate (EC)-based electrolytes of the LIB leads to the formation of a passivating layer on the anode known as the solid electrolyte interphase (SEI). The formation of an SEI has great impact on the cycle life and safety of LIB, yet mechanistic aspects of SEI formation are not fully understood. In this dissertation, two surface science model systems have been created under ultra-high vacuum (UHV) to probe the very initial stage of SEI formation at the model carbon anode surfaces of LIB. The first model system, Model System I, is an lithium-carbonate electrolyte/graphite C(0001) system. I have developed a temperature programmed desorption/temperature programmed reaction spectroscopy (TPD/TPRS) instrument as part of my dissertation to study Model System I in quantitative detail. The binding strengths and film growth mechanisms of key electrolyte molecules on model carbon anode surfaces with varying extents of lithiation were measured by TPD. TPRS was further used to track the gases evolved from different reduction products in the early-stage SEI formation. The branching ratio of multiple reaction pathways was quantified for the first time and determined to be 70.% organolithium products vs. 30% inorganic lithium product. The obtained branching ratio provides important information on the distribution of lithium salts that form at the very onset of SEI formation. One of the key reduction products formed from EC in early-stage SEI formation is lithium ethylene dicarbonate (LEDC). Despite intensive studies, the LEDC structure in either the bulk or thin-film (SEI) form is unknown. To enable structural study, pure LEDC was synthesized and subject to synchrotron X-ray diffraction measurements (bulk material) and STM measurements (deposited films). To enable studies of LEDC thin films, Model System II, a lithium ethylene dicarbonate (LEDC)-dimethylformamide (DMF)/Ag(111) system was created by a solution microaerosol deposition technique. Produced films were then imaged by ultra-high vacuum scanning tunneling microscopy (UHV-STM). As a control, the dimethylformamide (DMF)-Ag(111) system was first prepared and its complex 2D phase behavior was mapped out as a function of coverage. The evolution of three distinct monolayer phases of DMF was observed with increasing surface pressure — a 2D gas phase, an ordered DMF phase, and an ordered Ag(DMF)2 complex phase. The addition of LEDC to this mixture, seeded the nucleation of the ordered DMF islands at lower surface pressures (DMF coverages), and was interpreted through nucleation theory. A structural model of the nucleation seed was proposed, and the implication of ionic SEI products, such as LEDC, in early-stage SEI formation was discussed.

Using landscape metrics to predict hydrologic connectivity patterns between forested wetlands and streams in a coastal plain watershed

Geographically isolated wetlands, those entirely surrounded by uplands, provide numerous ecological functions, some of which are dependent on the degree to which they are hydrologically connected to nearby waters. There is a growing need for field-validated, landscape-scale approaches for classifying wetlands based on their expected degree of connectivity with stream networks. During the 2015 water year, flow duration was recorded in non-perennial streams (n = 23) connecting forested wetlands and nearby perennial streams on the Delmarva Peninsula (Maryland, USA). Field and GIS-derived landscape metrics (indicators of catchment, wetland, non-perennial stream, and soil characteristics) were assessed as predictors of wetland-stream connectivity (duration, seasonal onset and offset dates). Connection duration was most strongly correlated with non-perennial stream geomorphology and wetland characteristics. A final GIS-based stepwise regression model (adj-R2 = 0.74, p < 0.0001) described wetland-stream connection duration as a function of catchment area, wetland area and number, and soil available water storage.

Landscape and Architecture: A Balance for Fellowship and Contemplation at Dumbarton Oaks

This thesis will explore ideas relating to the engagement of man and nature by promoting the experiences of contemplation and fellowship. The focus will be an urban academic retreat facility to provide an escape from distraction of typical modern urban life. Set within the historic Washington D.C. neighborhood of Georgetown, Dumbarton Oaks is an active academic research institution The Institute is holistically designed; architecture integrated with its surrounding landscape The Institute selects diverse scholars to think, live, and commune within the facility and landscape for up to two years. This thesis will use the existing site, themes, and history of Dumbarton Oaks as a launching point to explore the relationship between architecture, man, and landscape. A proposal to relocate the Fellow’s residences and reorganize the western edge of the site will help reactivate this forgotten piece of the site realize its potential.

TIMESCAPES: an architectural process of memory and adaptation

What if the architectural process of making could incorporate time? All designers who impact the physical environment- consciously and unconsciously are gatekeepers of the past, commentators of the present, and speculators of the future. This project proposes the creation of architecture and adaptive public space that looks to historical memories, foster present day cultural formation, and new alternative visions for the city of the future. The thesis asks what it means to design for stasis and change in a variety of scales- urban, architectural, and detail and arrives at a speculated new neighborhood, institutional buildings, and landscape. Central to this project is the idea of the architect as archeologist, anthropologist, and artist. The project focuses on a rapidly changing part of the city of Fort Worth, Texas and assigns a multipurpose institutional buildings and public space as a method of investigation. The thesis hopes to further architectural discourse about into the role of architecture in the preservation of memory, adaptive potential of public spaces, and the role of time in architecture.

Assessing the influence of abiotic factors and leaf-level properties on the stability of growing-season canopy greenness in a deciduous forest

Maps depicting spatial pattern in the stability of summer greenness could advance understanding of how forest ecosystems will respond to global changes such as a longer growing season. Declining summer greenness, or “greendown”, is spectrally related to declining near-infrared reflectance and is observed in most remote sensing time series to begin shortly after peak greenness at the end of spring and extend until the beginning of leaf coloration in autumn,. Understanding spatial patterns in the strength of greendown has recently become possible with the advancement of Landsat phenology products, which show that greendown patterns vary at scales appropriate for linking these patterns to proposed environmental forcing factors. This study tested two non-mutually exclusive hypotheses for how leaf measurements and environmental factors correlate with greendown and decreasing NIR reflectance across sites. At the landscape scale, we used linear regression to test the effects of maximum greenness, elevation, slope, aspect, solar irradiance and canopy rugosity on greendown. Secondly, we used leaf chemical traits and reflectance observations to test the effect of nitrogen availability and intrinsic water use efficiency on leaf-level greendown, and landscape-level greendown measured from Landsat. The study was conducted using Quercus alba canopies across 21 sites of an eastern deciduous forest in North America between June and August 2014. Our linear model explained greendown variance with an R2=0.47 with maximum greenness as the greatest model effect. Subsequent models excluding one model effect revealed elevation and aspect were the two topographic factors that explained the greatest amount of greendown variance. Regression results also demonstrated important interactions between all three variables, with the greatest interaction showing that aspect had greater influence on greendown at sites with steeper slopes. Leaf-level reflectance was correlated with foliar δ13C (proxy for intrinsic water use efficiency), but foliar δ13C did not translate into correlations with landscape-level variation in greendown from Landsat. Therefore, we conclude that Landsat greendown is primarily indicative of landscape position, with a small effect of canopy structure, and no measureable effect of leaf reflectance. With this understanding of Landsat greendown we can better explain the effects of landscape factors on vegetation reflectance and perhaps on phenology, which would be very useful for studying phenology in the context of global climate change

DISPATCHING AND RELOCATION OF EMERGENCY VEHICLES ON FREEWAYS: THEORIES AND APPLICATIONS

Resource allocation decisions are made to serve the current emergency without knowing which future emergency will be occurring. Different ordered combinations of emergencies result in different performance outcomes. Even though future decisions can be anticipated with scenarios, previous models follow an assumption that events over a time interval are independent. This dissertation follows an assumption that events are interdependent, because speed reduction and rubbernecking due to an initial incident provoke secondary incidents. The misconception that secondary incidents are not common has resulted in overlooking a look-ahead concept. This dissertation is a pioneer in relaxing the structural assumptions of independency during the assignment of emergency vehicles. When an emergency is detected and a request arrives, an appropriate emergency vehicle is immediately dispatched. We provide tools for quantifying impacts based on fundamentals of incident occurrences through identification, prediction, and interpretation of secondary incidents. A proposed online dispatching model minimizes the cost of moving the next emergency unit, while making the response as close to optimal as possible. Using the look-ahead concept, the online model flexibly re-computes the solution, basing future decisions on present requests. We introduce various online dispatching strategies with visualization of the algorithms, and provide insights on their differences in behavior and solution quality. The experimental evidence indicates that the algorithm works well in practice. After having served a designated request, the available and/or remaining vehicles are relocated to a new base for the next emergency. System costs will be excessive if delay regarding dispatching decisions is ignored when relocating response units. This dissertation presents an integrated method with a principle of beginning with a location phase to manage initial incidents and progressing through a dispatching phase to manage the stochastic occurrence of next incidents. Previous studies used the frequency of independent incidents and ignored scenarios in which two incidents occurred within proximal regions and intervals. The proposed analytical model relaxes the structural assumptions of Poisson process (independent increments) and incorporates evolution of primary and secondary incident probabilities over time. The mathematical model overcomes several limiting assumptions of the previous models, such as no waiting-time, returning rule to original depot, and fixed depot. The temporal locations flexible with look-ahead are compared with current practice that locates units in depots based on Poisson theory. A linearization of the formulation is presented and an efficient heuristic algorithm is implemented to deal with a large-scale problem in real-time.