Lightweight metal halide and hydride fast Li ion conductors

This work was motivated by the extensive research on lithium solid state materials, which have attracted increasing interest for potential applications in hydrogen storage and/or lithium ion batteries due to their extraordinary properties. In this thesis, LiBH4-derived materials, LiInBr4 and complex phases based on lithium ammonia borane with potential use as solid state electrolytes were successfully synthesised and characterised.

EXPERIMENTAL DEMONSTRATION OF LIGHT TRAPPING AND INTERNAL LIGHT SCATTERING IN SOLAR CELLS

Renewable energy technologies have long-term economic and environmental advantages over fossil fuels, and solar power is the most abundant renewable resource, supplying 120 PW over earth’s surface. In recent years the cost of photovoltaic modules has reached grid parity in many areas of the world, including much of the USA. A combination of economic and environmental factors has encouraged the adoption of solar technology and led to an annual growth rate in photovoltaic capacity of 76% in the US between 2010 and 2014. Despite the enormous growth of the solar energy industry, commercial unit efficiencies are still far below their theoretical limits. A push for thinner cells may reduce device cost and could potentially increase device performance. Fabricating thinner cells reduces bulk recombination, but at the cost of absorbing less light. This tradeoff generally benefits thinner devices due to reduced recombination. The effect continues up to a maximum efficiency where the benefit of reduced recombination is overwhelmed by the suppressed absorption. Light trapping allows the solar cell to circumvent this limitation and realize further performance gains (as well as continue cost reduction) from decreasing the device thickness. This thesis presents several advances in experimental characterization, theoretical modeling, and device applications for light trapping in thin-film solar cells. We begin by introducing light trapping strategies and discuss theoretical limits of light trapping in solar cells. This is followed by an overview of the equipment developed for light trapping characterization. Next we discuss our recent work measuring internal light scattering and a new model of scattering to predict the effects of dielectric nanoparticle back scatterers on thin-film device absorption. The new model is extended and generalized to arbitrary stacks of stratified media containing scattering structures. Finally, we investigate an application of these techniques using polymer dispersed liquid crystals to produce switchable solar windows. We show that these devices have the potential for self-powering.

Understanding Co-translational Protein Targeting and Lithium Dendrite Formation through Free Energy Simulations and Coarse-Grained Models

We describe the application of alchemical free energy methods and coarse-grained models to study two key problems: (i) co-translational protein targeting and insertion to direct membrane proteins to the endoplasmic reticulum for proper localization and folding, (ii) lithium dendrite formation during recharging of lithium metal batteries. We show that conformational changes in the signal recognition particle, a central component of the protein targeting machinery, confer additional specificity during the the recognition of signal sequences. We then develop a three-dimensional coarse-grained model to study the long-timescale dynamics of membrane protein integration at the translocon and a framework for the calculation of binding free energies between the ribosome and translocon. Finally, we develop a coarse-grained model to capture the dynamics of lithium deposition and dissolution at the electrode interface with time-dependent voltages to show that pulse plating and reverse pulse plating methods can mitigate dendrite growth.

AMPLITUDE-VERSUS-ANGLE ANALYSIS AND WIDE-ANGLE-INVERSION OF CROSSWELL SEISMIC DATA IN A CARBONATE RESERVOIR

Crosswell data set contains a range of angles limited only by the geometry of the source and receiver configuration, the separation of the boreholes and the depth to the target. However, the wide angles reflections present in crosswell imaging result in amplitude-versus-angle (AVA) features not usually observed in surface data. These features include reflections from angles that are near critical and beyond critical for many of the interfaces; some of these reflections are visible only for a small range of angles, presumably near their critical angle. High-resolution crosswell seismic surveys were conducted over a Silurian (Niagaran) reef at two fields in northern Michigan, Springdale and Coldspring. The Springdale wells extended to much greater depths than the reef, and imaging was conducted from above and from beneath the reef. Combining the results from images obtained from above with those from beneath provides additional information, by exhibiting ranges of angles that are different for the two images, especially for reflectors at shallow depths, and second, by providing additional constraints on the solutions for Zoeppritz equations. Inversion of seismic data for impedance has become a standard part of the workflow for quantitative reservoir characterization. Inversion of crosswell data using either deterministic or geostatistical methods can lead to poor results with phase change beyond the critical angle, however, the simultaneous pre-stack inversion of partial angle stacks may be best conducted with restrictions to angles less than critical. Deterministic inversion is designed to yield only a single model of elastic properties (best-fit), while the geostatistical inversion produces multiple models (realizations) of elastic properties, lithology and reservoir properties. Geostatistical inversion produces results with far more detail than deterministic inversion. The magnitude of difference in details between both types of inversion becomes increasingly pronounced for thinner reservoirs, particularly those beyond the vertical resolution of the seismic. For any interface imaged from above and from beneath, the results AVA characters must result from identical contrasts in elastic properties in the two sets of images, albeit in reverse order. An inversion approach to handle both datasets simultaneously, at pre-critical angles, is demonstrated in this work. The main exploration problem for carbonate reefs is determining the porosity distribution. Images of elastic properties, obtained from deterministic and geostatistical simultaneous inversion of a high-resolution crosswell seismic survey were used to obtain the internal structure and reservoir properties (porosity) of Niagaran Michigan reef. The images obtained are the best of any Niagaran pinnacle reef to date.

Tin Oxide Based Composites Derived Using Electrostatic Spray Deposition Technique as Anodes for Li-Ion Batteries

Recent advances in the electric & hybrid electric vehicles and rapid developments in the electronic devices have increased the demand for high power and high energy density lithium ion batteries. Graphite (theoretical specific capacity: 372 mAh/g) used in commercial anodes cannot meet these demands. Amorphous SnO2 anodes (theoretical specific capacity: 781 mAh/g) have been proposed as alternative anode materials. But these materials have poor conductivity, undergo a large volume change during charging and discharging, large irreversible capacity loss leading to poor cycle performances. To solve the issues related to SnO2 anodes, we propose to synthesize porous SnO2 composites using electrostatic spray deposition technique. First, porous SnO2/CNT composites were fabricated and the effects of the deposition temperature (200,250, 300 oC) & CNT content (10, 20, 30, 40 wt %) on the electrochemical performance of the anodes were studied. Compared to pure SnO2 and pure CNT, the composite materials as anodes showed better discharge capacity and cyclability. 30 wt% CNT content and 250 oC deposition temperature were found to be the optimal conditions with regard to energy capacity whereas the sample with 20% CNT deposited at 250 oC exhibited good capacity retention. This can be ascribed to the porous nature of the anodes and the improvement in the conductivity by the addition of CNT. Electrochemical impedance spectroscopy studies were carried out to study in detail the change in the surface film resistance with cycling. By fitting EIS data to an equivalent circuit model, the values of the circuit components, which represent surface film resistance, were obtained. The higher the CNT content in the composite, lower the change in surface film resistance at certain voltage upon cycling. The surface resistance increased with the depth of discharge and decreased slightly at fully lithiated state. Graphene was also added to improve the performance of pure SnO2 anodes. The composites heated at 280 oC showed better energy capacity and energy density. The specific capacities of as deposited and post heat-treated samples were 534 and 737 mAh/g after 70 cycles. At the 70th cycle, the energy density of the composites at 195 °C and 280 °C were 1240 and 1760 Wh/kg, respectively, which are much higher than the commercially used graphite electrodes (37.2-74.4 Wh/kg). Both SnO2/CNTand SnO2/grapheme based composites with improved energy densities and capacities than pure SnO2 can make a significant impact on the development of new batteries for electric vehicles and portable electronics applications.

Hybrid power system intelligent operation and protection involving plug-in electric vehicles

Two key solutions to reduce the greenhouse gas emissions and increase the overall energy efficiency are to maximize the utilization of renewable energy resources (RERs) to generate energy for load consumption and to shift to low or zero emission plug-in electric vehicles (PEVs) for transportation. The present U.S. aging and overburdened power grid infrastructure is under a tremendous pressure to handle the issues involved in penetration of RERS and PEVs. The future power grid should be designed with for the effective utilization of distributed RERs and distributed generations to intelligently respond to varying customer demand including PEVs with high level of security, stability and reliability. This dissertation develops and verifies such a hybrid AC-DC power system. The system will operate in a distributed manner incorporating multiple components in both AC and DC styles and work in both grid-connected and islanding modes. ^ The verification was performed on a laboratory-based hybrid AC-DC power system testbed as hardware/software platform. In this system, RERs emulators together with their maximum power point tracking technology and power electronics converters were designed to test different energy harvesting algorithms. The Energy storage devices including lithium-ion batteries and ultra-capacitors were used to optimize the performance of the hybrid power system. A lithium-ion battery smart energy management system with thermal and state of charge self-balancing was proposed to protect the energy storage system. A grid connected DC PEVs parking garage emulator, with five lithium-ion batteries was also designed with the smart charging functions that can emulate the future vehicle-to-grid (V2G), vehicle-to-vehicle (V2V) and vehicle-to-house (V2H) services. This includes grid voltage and frequency regulations, spinning reserves, micro grid islanding detection and energy resource support. ^ The results show successful integration of the developed techniques for control and energy management of future hybrid AC-DC power systems with high penetration of RERs and PEVs.^

Effect of light-sticks and electralunie attractors on surface-longline catches of swordfish (Xiphias gladius, Linnaeus, 1959) in the southwest equatorial Atlantic

Two experimental fishing trials were carried out off the coast of Pernambuco, Brazil, in 1999 and 2001, using a small artisanal longliner. In experiment 1, six-hook baskets with three chemical light-sticks on alternating hooks had significantly higher catch rates than those with zero or with a light-stick on every hook, with most swordfish accounted for by hooks with light-sticks. Analysis of the data from experiment 2 showed no significant difference between electralume attractors, consisting of AA lithium batteries protected by a solid cover and light-sticks that produce a fluorescent light when two chemical products are mixed. Significant differences were detected in mean CPUE by size class, with most swordfish belonging to class 'b' (125-170 cm lower jaw to fork length (LJFL)). No differences, however, were found for swordfish catches in classes 'a' (< 125 cm LJFL) and V, and no evidence was found of interaction between the two factors (attractor and size class). Although there was no significant difference between the total length-frequency distributions of swordfish caught with light-sticks and electralume attractors, signibcant differences were found for fish smaller than 125 cm LJFL, with electralume catches consisting of smaller swordfish than those of gear using light-sticks. (c) 2004 Elsevier B.V. All rights reserved.

Effect of light-sticks and electralume attractors on surface-longline catches of swordfish (Xiphias gladius, Linnaeus, 1959) in the southwest equatorial Atlantic

Two experimental fishing trials were carried out off the coast of Pernambuco, Brazil, in 1999 and 2001, using a small artisanal longliner. In experiment 1, six-hook baskets with three chemical light-sticks on alternating hooks had significantly higher catch rates than those with zero or with a light-stick on every hook, with most swordfish accounted for by hooks with light-sticks. Analysis of the data from experiment 2 showed no significant difference between electralume attractors, consisting of AA lithium batteries protected by a solid cover and light-sticks that produce a fluorescent light when two chemical products are mixed. Significant differences were detected in mean CPUE by size class, with most swordfish belonging to class ‘b’ (125–170 cm lower jaw to fork length (LJFL)). No differences, however, were found for swordfish catches in classes ‘a’ (<125 cm LJFL) and ‘b’, and no evidence was found of interaction between the two factors (attractor and size class). Although there was no significant difference between the total length-frequency distributions of swordfish caught with light-sticks and electralume attractors, significant differences were found for fish smaller than 125 cm LJFL, with electralume catches consisting of smaller swordfish than those of gear using light-sticks.

Advances in integration of photovoltaic power and energy production in practical systems

This thesis presents advances in integration of photovoltaic (PV) power and energy in practical systems, such as existing power plants in buildings or directly integrated in the public electrical grid. It starts by providing an analyze of the current state of PV power and some of its limitations. The work done in this thesis begins by providing a model to compute mutual shading in large PV plants, and after provides a study of the integration of a PV plant in a biogas power plant. The remainder sections focus on the work done for project PVCROPS, which consisted on the construction and operation of two prototypes composed of a PV system and a novel battery connected to a building and to the public electrical grid. These prototypes were then used to test energy management strategies and validate the suitability of the two advanced batteries (a lithium-ion battery and a vanadium redox ow battery) for households (BIPV) and PV plants. This thesis is divided in 7 chapters: Chapter 1 provides an introduction to explain and develop the main research questions studied for this thesis; Chapter 2 presents the development of a ray-tracing model to compute shading in large PV elds (with or without trackers); Chapter 3 shows the simulation of hybridizing a biogas plant with a PV plant, using biogas as energy storage; Chapters 4 and 5 present the construction, programming, and initial operation of both prototypes (Chapter 4), EMS testing oriented to BIPV systems (Chapter 5). Finally, Chapters 6 provides some future lines of investigation that can follow this thesis, and Chapter 7 shows a synopsis of the main conclusions of this work; Resumo: Avanços na integracão de potência fotovoltaica e producão de energia em sistemas práticos Esta tese apresenta avanços na integração de potência e energia fotovoltaica (PV) em sistemas práticos, tais como centrais existentes ou a rede eléctrica pública. Come ça por analisar o estado corrente do fotovoltaico no mundo e aborda algumas das suas limitações. O trabalho feito para esta tese de doutoramento começou pelo desenvolvimento de um modelo para calcular os sombreamentos que ocorrem em grandes campos fotovoltaicos, e depois apresenta um estudo sobre a integração um sistema fotovoltaico em uma central eléctrica a bióg as. As ultimas secções da tese focam-se no trabalho feito para o projecto PVCROPS, que consistiu na construção e operação de dois demonstratores, cada um formado por um sistema fotovoltaico e bateria conectados a um edíficio e a rede eléctrica pública. Estes protótipos foram posteriormente utilizados para testar estratégias de gestão de energia (EMS) e para validar a operação de duas baterias avançadas (bateria de Iões de Li tio e bateria de Fluxo Redox de Van adio) e a sua utiliza ção para habitações e centrais PV. A tese está dividida em 7 capitulos: O capitulo 1 apresenta uma introdução para explicar e desenvolver as principais questões que foram investigadas nesta tese; O capitulo 2 mostra o desenvolvimento de um modelo baseado em traçados de raios para calcular sombreamentos mútuos em grandes centrais PV (com e sem seguidores); O capitulo 3 mostra a simulação da hibridização de uma central electrica a biogas com uma central PV, e utilizando o biógas como armazenamento de energia. Os capitulos 4 e 5 apresentam a construção, programação e operação inicial dos dois demonstradores (Capitúlo 4), o teste de EMS orientadas para sistemas PV em habitações (Capítulo 5). Finalmente, o capítulo 6 sugere algumas futuras linhas de investigação que poderão seguir esta tese, e o Capítulo 7 faz uma sinopse das principais conclusões deste trabalho.

A staggered approach for the coupling of Cahn–Hilliard type diffusion and finite strain elasticity

We develop an algorithm and computational implementation for simulation of problems that combine Cahn–Hilliard type diffusion with finite strain elasticity. We have in mind applications such as the electro-chemo- mechanics of lithium ion (Li-ion) batteries. We concentrate on basic computational aspects. A staggered algorithm is pro- posed for the coupled multi-field model. For the diffusion problem, the fourth order differential equation is replaced by a system of second order equations to deal with the issue of the regularity required for the approximation spaces. Low order finite elements are used for discretization in space of the involved fields (displacement, concentration, nonlocal concentration). Three (both 2D and 3D) extensively worked numerical examples show the capabilities of our approach for the representation of (i) phase separation, (ii) the effect of concentration in deformation and stress, (iii) the effect of Electronic supplementary material The online version of this article (doi:10.1007/s00466-015-1235-1) contains supplementary material, which is available to authorized users. B P. Areias pmaa@uevora.pt 1 Department of Physics, University of Évora, Colégio Luís António Verney, Rua Romão Ramalho, 59, 7002-554 Évora, Portugal 2 ICIST, Lisbon, Portugal 3 School of Engineering, Universidad de Cuenca, Av. 12 de Abril s/n. 01-01-168, Cuenca, Ecuador 4 Institute of Structural Mechanics, Bauhaus-University Weimar, Marienstraße 15, 99423 Weimar, Germany strain in concentration, and (iv) lithiation. We analyze con- vergence with respect to spatial and time discretization and found that very good results are achievable using both a stag- gered scheme and approximated strain interpolation.