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.

THE DEVELOPMENT EFFECTIVENESS OF INTERNATIONAL WATER AND SANITATION INFRASTRUCTURE PROJECTS: DEFINING “QUALITY AT ENTRY” OF WORLD BANK PROJECTS.

Over the past 15 years, the number of international development projects aimed at combating global poverty has increased significantly. Within the water and sanitation sector however, and despite heightened global attention and an increase in the number of infrastructure projects, over 800 million people remain without access to appropriate water and sanitation facilities. The majority of donor aid in the water supply and sanitation sector of developing countries is delivered through standalone projects. The quality of projects at the design and preparation stage is a critical determinant in meeting project objectives. The quality of projects at early stage of design, widely referred to as quality at entry (QAE), however remains unquantified and largely subjective. This research argues that water and sanitation infrastructure projects in the developing world tend to be designed in the absence of a specific set of actions that ensure high QAE, and consequently have relatively high rates of failure. This research analyzes 32 cases of water and sanitation infrastructure projects implemented with partial or full World Bank financing globally from 2000 – 2010. The research uses categorical data analysis, regression analysis and descriptive analysis to examine perceived linkages between project QAE and project development outcomes and determines which upstream project design factors are likely to impact the QAE of international development projects in water supply and sanitation. The research proposes a number of specific design stage actions that can be incorporated into the formal review process of water and sanitation projects financed by the World Bank or other international development partners.