Capacity Fade Analysis and Model Based Optimization of Lithium-ion Batteries

Electrochemical power sources have had significant improvements in design, economy, and operating range and are expected to play a vital role in the future in a wide range of applications. The lithium-ion battery is an ideal candidate for a wide variety of applications due to its high energy/power density and operating voltage. Some limitations of existing lithium-ion battery technology include underutilization, stress-induced material damage, capacity fade, and the potential for thermal runaway. This dissertation contributes to the efforts in the modeling, simulation and optimization of lithium-ion batteries and their use in the design of better batteries for the future. While physics-based models have been widely developed and studied for these systems, the rigorous models have not been employed for parameter estimation or dynamic optimization of operating conditions. The first chapter discusses a systems engineering based approach to illustrate different critical issues possible ways to overcome them using modeling, simulation and optimization of lithium-ion batteries. The chapters 2-5, explain some of these ways to facilitate: i) capacity fade analysis of Li-ion batteries using different approaches for modeling capacity fade in lithium-ion batteries,: ii) model based optimal design in Li-ion batteries and: iii) optimum operating conditions: current profile) for lithium-ion batteries based on dynamic optimization techniques. The major outcomes of this thesis will be,: i) comparison of different types of modeling efforts that will help predict and understand capacity fade in lithium-ion batteries that will help design better batteries for the future,: ii) a methodology for the optimal design of next-generation porous electrodes for lithium-ion batteries, with spatially graded porosity distributions with improved energy efficiency and battery lifetime and: iii) optimized operating conditions of batteries for high energy and utilization efficiency, safer operation without thermal runaway and longer life

Coupling thermodynamic mineralogical models and mantle convection

In this thesis I advance the integration of mineral thermodynamics into convection modeling. I have compiled a thermodynamic model of mantle mineralogy in the five component CFMAS system (CaO-FeO-MgO-Al2O3-SiO2), including mineral phases that occur close to typical chemical models of the mantle and reasonable mantle temperatures. In this system I have performed a system Gibbs free energy minimization, including pure end-member phases and a non-ideal formulation for solid solutions. Solid solutions were subdivided into discrete pseudocompounds and treated as stoichiometric phases during computation of chemical equilibrium by the simplex method. I have complemented the thermodynamic model with a model of shear wave properties [Stixrude and Lithgow-Bertelloni, 2005] to obtain a full description of aggregate elastic properties (density, bulk and shear moduli) that provide a useful basis for the consideration of seismic and geodynamic models of the Earth's mantle. By using this new thermodynamic database for the mantle I have coupled the resulting density dynamically (through the buoyancy term) with mantle convection models. I have linked the database with a high-resolution 2-D convection code (2DTERRA), dynamically coupling the thermodynamic model (density) with the conservation equations of mantle flow. The coupled model is run for different parameterisations of viscosity, initial temperature conditions, and varying internal vs. external heating. A common feature of all the models is that the convecting flow creates a characteristic discontinuity of temperature around 660 km depth in order to compensate for the entropy change due to the phase transitions. I have studied the importance and the possible consequences of such a thermal regime on the excess temperature of plumes and on the transition zone thickness. The thermodynamic mantle mineralogy model provides the conversion of the temperature field into seismic velocities so that predictions from mantle convection can be compared to seismic observations in terms of radial profiles or lateral variations. This approach allows us to predict a number of seismic observables from the convection model, all of which agree remarkably well with observations from seismic tomography

Mini-Workshop: Mathematical Models for Cancer Cell Migration

Tumour cell invasion is an essential hallmark in the progression of malignant cancer. Thereby, cancer cells migrate through the surrounding tissue (normal cells, extracellular matrix, interstitial fluid) towards blood or lymph vessels which they penetrate and thus access the blood flow. They are carried by blood circulation to distant locations where they extravasate and develop new tumours, a phenomenon known as metastasis. The invasive spread of cancer cells is highly complex – it involves several mechanisms, like diffusion, chemotaxis and haptotaxis; these in turn are conditioned by and influence the subcellular dynamics. Mathematical models offer a powerful tool to gain insight into the complicated biological processess connected to tumour invasion and have also stimulated advanced mathematical research. Some of the new developments in the field of biomedical oncology were inspired by such models. A significant challenge arises due to the interactions of cancer cells with a complicated and structured microenvironment of healthy tissue. Many of the models of cancer cell migration are based on partial differential equations (PDEs) including spatial heterogeneity, orientational tissue structure, tissue stiffness and deformability. Specific settings relate to reaction-diffusion equations, transport equations, continuum equations, and to their multi-scale analysis, to local and global existence and uniqueness, to pattern formation, blow-ups and invasions. A further approach involves agent-based models providing a characterisation of cell migration by way of simulating the (inter)actions of autonomous agents (individual cells, collective dynamics) and aiming for assessing their effects on the entire system. In this meeting we covered the full spectrum between macroscopic PDE models and microscopic individual based models with the common goal of modelling cancer cell migration. Of particular interest was the derivation of macroscopic properties from microscopic details. Similar multiscale models have been used in other contexts (such as chemotaxis for example), and we gained some significant insight from the collaborations in this workshop. In this one week meeting we posted nine open ended problems (outlined below), which will form the seed for new collaborations going far beyond this workshop

Numerical Investigation of The Effect of Inlet Turbulence Intensity on a Bluff-Body Stabilized Flame at Near Blow-off Condition

This thesis investigates the effect of a boundary condition on the dynamics of a bluff-body stabilized f lame operating near blow-off condition. Special emphasis is given to the effect of inlet turbulence intensity. This work is motivated by the understanding that more stringent regulations on fossil fuels generated emissions necessitate the design of combustion systems that operate at very fuel-lean conditions. Combustion at very lean conditions, however, induces flame instability that can ultimately lead to flame fluttering and eventual extinction. The dynamics of the flame at lean conditions can therefore be very sensitive to its boundary conditions. To better understand this, a numerical investigation was needed as experimental research used for our model validation ceased to provide this information. The first stage of the numerical research is based on the experiment conducted in the Volvo Flygmotor AB program. The numerical models are validated by comparing the results with the available experimental data. The near blow-off equivalence ratio is then determined using the validated set of models. The effect of ITI on the flame dynamics is subsequently investigated for a lean flame that is near blow-off condition. For the computational analysis Large Eddy Simulation (LES) method was selected for its accuracy and efficiency. Combustion is accounted for through the transport of chemical species and the turbulence-combustion interaction through laminar finite-rate model. The sensitivity to inlet turbulence is assessed by carrying out simulations at near blow-off condition. The inlet turbulence intensity is varied in increments of 5%. It is observed that while the inlet intensity of 5% causes blow-off, further increase to 10% preserves a healthy flame on account of more heat release arising from greater entrainment of combustible mixtures into the f lame zone just behind the bluff-body. This balance is again lost as the inlet turbulence intensity is further increased to 15%. These conclusions are first obtained using 2D LES and selected cases are verified through 3D LES. Further, the importance of chemical kinetics is addressed by comparative analysis using global and detailed chemical kinetics models. The results jointly highlight strategies that can be used to reduce the required computational costs without loss of critical flow features of near blow-off bluff body turbulent flame

Diesel Engine

Diesel engines, also known as CI engines, possess a wide field of applications as energy converters because of their higher efficiency. However, diesel engines are a major source of NOX and particulate matter (PM) emissions. Because of its importance, five chapters in this book have been devoted to the formulation and control of these pollutants. The world is currently experiencing an oil crisis. Gaseous fuels like natural gas, pure hydrogen gas, biomass-based and coke-based syngas can be considered as alternative fuels for diesel engines. Their combustion and exhaust emissions characteristics are described in this book. Reliable early detection of malfunction and failure of any parts in diesel engines can save the engine from failing completely and save high repair cost. Tools are discussed in this book to detect common failure modes of diesel engine that can detect early signs of failure

Quantum shot noise in mesoscopic superconductor-semiconductor heterostructures

Shot noise in a mesoscopic electrical conductor have become one of the most attentiondrawing subject over the last decade. This is because the shot-noise measurements provide a powerful tool to study charge transport in mesoscopic systems [1]. While conventional resistance measurements yield information on the average probability for the transmission of electrons from source to drain, shot-noise provides additional information on the electron transfer process, which can not be obtained from resistance measurements. For example, one can determine the charge ‘q’ of the current carrying quasi-particles in different systems from the Poisson shot noise SI = 2q�I� [2] where �I� is the mean current of the system. For instance, the quasi-particle charge is a fraction of the electron charge ‘e’ in the fractional quantum Hall regime [3, 4, 5]. The multiple charge quanta were observed in an atomic point contact between two superconducting electrodes [6]. Shot-noise also provides information on the statistics of the electron transfer. Shot noise in general is suppressed from its classical value SI = 2e�I�, due to the correlations. In mesoscopic conductors, due to the Pauli principle in fermion statistics, electrons are highly correlated. As a results, the noise is fully suppressed in the limit of a perfect open channel T = 1. For the opposite limit of low transmission T � 1, transmission of electron follows a Poisson process and recovers the Schottky result SI = 2e�I� [2]. For many channel systems, shot-noise is suppressed to 1/2 × 2e�I� for a symmetric double barrier junction [7, 8], to 1/3 in a disordered wire [9, 10, 11, 12, 13, 14] and to 1/4 in an open chaotic cavity [15, 16, 17]. When a superconductor is involved, the shot-noise can be enhanced by virtue of the Andreev reflection process taking place at the interface between a normal metal and a superconductor. In some limiting cases, e.g. in the tunneling and disordered limit, the shot-noise can be doubled with respect to its normal state value [18, 19, 20, 21]. One of the main results of this thesis is an extensive comparison of our experimental data on conductance and shot noise measurements in a S-N junction with various theoretical models. In addition to measure shot-noise in a two-terminal geometry, one can also perform the fluctuation measurements on multi-terminal conductors. Whereas shotnoise corresponds to the autocorrelation of fluctuations from the same leads, crosscorrelation measurements of fluctuations between different leads provide a wealth of new experiments. For example, the exchange-correlations can be measured directly from these geometry [22]. Experimental attempt in mesoscopic electronic device was the correlation measurements [14, 23] on electron beam-splitter geometry [24] which is the analogue to the Hanbury-Brown Twiss (HBT) experiment in optics. In their experiment, Hanbury-Brown and Twiss demonstrated the intensity-intensity correlations of the light of a star in order to determine its diameter [25]. They measured a positive correlations between two different output photon beams as predicted to the particles obeying Bose-Einstein statistics. This behavior is often called ‘bunching’. On the other hand, a stream of the particles obeying Fermi-Dirac statistics is expected to show a anti-bunching behavior, resulting in a negative correlation of the intensity fluctuations. Latter one was confirmed by a Fermionic version of HBT experiments in single-mode, high-mobility semiconductor 2DEG systems [14, 23]. Whereas in a single electron picture, correlations between Fermions are always negative1 (anti-bunching), the correlation signal is expected to become positive if two electrons are injected simultaneously to two arms and leave the device through different leads for the coincident detection in both outputs2. One simple example is the splitting of the cooper pair in a Y-junction geometry in front of the superconductor. Fig.1.1 shows the possible experimental scheme of the correlation measurement as described here and the sample realized in an high-mobility semiconductor heterostructures. Since all three experiments were done3, only one left unfolded, ‘The positive correlations from the Fermionic system’. The main motivation of this thesis work was to find a positive correlations in the device shown in Fig.1.1. In a well defined single channel collision experiment on an electron beam splitter, it has theoretically been shown that the measured correlations are sensitive to the spin entanglement [29, 30]. This is another even more exciting issue and we would like to mention that the experimental quest for positive correlations is important for the new field of quantum computation and communication in the solid state, [31, 32] in which entangled electrons play a crucial role. A natural source of entanglement is found in superconductors in which electrons are paired in a spin-singlet state. A source of entangled electrons may therefore be based on a superconducting injector.[33, 34, 27, 35, 36, 37, 38, 38, 39, 40, 41] Even more so, an electronic beamsplitter is capable of distinguishing entangled electrons from single electrons.[29, 42] However, the positive correlations have not been observed in solid-state mesoscopic devices until today. This thesis is organized as follows. Chapter 2 is devoted to the theoretical background of the electrical transport and the current fluctuations. We introduce the basic concept of electrical transport and the shot noise in normal state and superconductor-normal metal (S-N) junction. We also briefly review the theoretical proposals and arguments about the current-current cross-correlations in threeterminal systems. In Chapter 3, we describe the sample fabrication techniques which have been done in our laboratory such as e-beam lithography, metallization and etching. We present also the characterization of our particular system, niobium (Nb) / InAs-based 2DEG junction. Chapter 4 describes the reliable low-temperature measurement technique for detecting the noise. We characterize our measurement setup using a simple RC-circuit model. In Chapter 5, our main results about the shot noise of S-N junction are presented in detail

Experimental and gyrokinetic studies of impurity transport in the core of Alcator C-Mod Plasmas

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Nuclear Science and Engineering, 2012.Cataloged from PDF version of thesis.Includes bibliographical references (p. 227-238).Using a unique set of diagnostics and modeling tools, a comprehensive study of impurity transport was performed on Alcator C-Mod L-mode discharges. A new, multi-pulse laser blow-off system was designed and constructed to introduce trace amounts of non-recycling, non-intrinsic, impurities in the plasma edge. This system was coupled with an x-ray crystal spectrometer, a single chord x-ray/ultraviolet spectrometer, and measurement of the laser blow-off neutral source at the plasma edge to provide full, time-evolving, radial profiles of a single impurity charge state. An iterative X2 minimization scheme was created to infer the experimental impurity transport coefficients and their uncertainty by minimizing the difference in the measured and STRAHL simulated emission. These measurements and data analysis methodology allowed for determination of impurity transport coefficient profiles with realistic errors from 0.0 </= r/a </= 0.6. The gyrokinetic co(le, GYRO, was use to analyze the same discharges. Motivated by linear stability analysis and a rigorous assessment of simulation sensitivities, nonlinear gyrokinetic simulations were performed such that small modifications of the Ion Temperature Gradient (ITG) drive term, a/LT, were made to match the simulated ion heat flux, Qj. to the experimental value. These simulations demonstrated simultaneous, quantitative agreement with experiment across the simulation domain in the ion heat and impurity particle transport channels, and indicated the possibility of missing electron dynamics from the nonlinear gyrokinetic simulation. A study of Ip scaling used four discharges, constituting a scan of I, from 0.6 to 1.2 MA. These discharges displayed a clear reduction of the experimental impurity diffusion and inward convection, allowing for qualitative and quantitative comparison of experimental with gyrokinetic simulation. Linear stability analysis and high fidelity, global (0.29 </= r/a </= 0.62), nonlinear GYRO simulation of ion scale turbulence (kop, </= 1.15) were performed on these discharges with the result that nonlinear gyrokinetic simulation was generally able to reproduce both quantitative values and trends for the measured decrease in impurity diffusion and inward convection observed experimentally. Initial analysis of three discharges operated at various levels of ICRH input power displayed a reduction of the experimental impurity diffusion coefficient with input power. An in-depth linear stability analysis suggests a transition of the turbulence character (ITG to TEM) with input power which may explain changes in the measured diffusion.by Nathaniel Thomas Howard.Ph.D

Development of Landslide Warning System

Landslides cause approximately 25 to 50 deaths and US$1 - 2 billion worth of damage in the United States annually. They can be triggered by humans or by nature. It has been widely recognized that rainfall is one of the major causes of slope instability and failure. Slope remediation and stabilization efforts can be costly. An early warning system is a suitable alternative and can save human lives. In this project, an early warning system was developed for a 40-foot-high cut slope on the island of Hawaii. To achieve the objective, subsurface investigations were performed and undisturbed samples were collected. For the purpose of unsaturated soil testing, new testing apparatuses were developed by modifying the conventional oedometer and direct shear cells. The unsaturated soil was characterized using two separate approaches and, later, the results were discussed and compared. The slope site was instrumented for the measurement of suction, water content, displacement, and precipitation. The collected climatic data along with the calibrated hydraulic parameters were used to build an infiltration-evapotranspiration numerical model. The model estimations were compared with the field measurements and showed good agreement. The verified model was used to determine the pore-water pressure distribution during and after a 500-years return storm. Later, the pore-water pressure distribution was transferred to a slope stability software and used to study the slope stability during and after the storm. Based on a 2D slope stability analysis, the slope can survive the 500-year storm with a factor of safety of 1.20. Instrument threshold values were established for water content sensors and tensiometers using a traffic-light-based trigger criterion