Lithium-ion (Li-Ion) batteries are widely used in various applications and are viable for automotive applications. The effective management of Li-Ion batteries in battery electric vehicles (BEV) plays a crucial role in performance and range. One can achieve good performance and range by using efficient battery models in battery management systems (BMS). Hence, these battery models play an essential part in the development process of battery electric vehicles. Physics-based battery models are used for design purposes, control, or to predict battery behaviour, and these require much information about materials and reaction and mass transport properties. Model parameterization, i.e., obtaining model parameters from different experimental sets (by fitting the model to experimental data sets), can be challenging depending on model complexity and the type and quality of experimental data. Based on the idea of parameter sensitivity, certain current/voltage data sets could be chosen that theoretically has a more considerable sensitivity for a given model parameter that is of interest to extract. In this thesis work, different methods for extracting model parameters for a Nickel-Manganese-Cobalt (NMC) battery composite electrode are experimentally tested and compared. Specifically, model parameterization using \emph{optimal experiments} based on performed parameter sensitivity analysis has been benchmarked against a 1C discharge test and low rate pulse tests. The different parameter sets obtained have then been validated on a drive cycle and 2C pulse tests. Comparing the methods show some promising results for the optimal experiment design (OED) method, but consideration regarding the state of charge (SOC) dependencies, the number of parameters has to be further evaluated. / Litiumjonbatterier (Li-jon) används i olika applikationer och är ett bra alternativ förfordonsapplikationer. Den effektiva hanteringen av litiumjonbatterier i elbilar har en viktigroll för fordonens prestanda och räckvidd. Man kan nå bra prestanda och räckviddgenom att använda bra batterimodeller i batteriets övervakningssystem (BMS). Därförspelar dessa batterimodeller en viktig roll i utvecklingen av elbilar. Fysikbaseradebatterimodeller används för design, reglering eller för att prediktera beteendet hos batteriet,vilket kräver mycket information om material samt dess reaktion och andra beskaffenheter.Modellparametrisering, dvs. att införskaffa modellparametrar från olika experiment (genom attanpassa modell till experimentella data) kan vara utmanande beroende på modellkomplexitetoch typen samt kvalitén på experimentell data. Baserat på idén om parametersensitivitet kan data om ström och spänning väljas så att de teoretiskt har mer sensitivitet för engiven modellparameter som är av intresse att extrahera. I detta examensarbete testas ochjämförs olika metoder för att extrahera modellparametrar för en Nickelmangankobolt (NMC)batterielektrod. Mer specifikt, modellparametrisering genom optimala experiment baseradepå genomförd parametersesitivitetsanalys jämförts med 1C urladdningstest och låg nivåpulstest. Jämförande av metoderna visar goda resultat för OED metoden men flera parametrarmåste fortsatt utvärderas gällande laddningstatusberoenden (SOC).

Cette thèse se concentre sur la fiabilité des batteries lithium pour des applications véhicules à faible émission en CO2. Pour cela, des méthodologies de caractérisation électriques et thermiques, des protocoles et des tests de vieillissement de batteries lithium sous différents modes (cyclage actif, calendaire simple et cyclage/calendaire) ont été mis en œuvre.Une première partie de ces travaux de thèse s’attache à la modélisation et à l’estimation des états de charge et de santé de la batterie.La deuxième partie est consacrée à l’étude du vieillissement calendaire des batteries lithium utilisant la spectroscopie d’impédance comme méthode de caractérisation. Ensuite, une méthode originale pour l’évaluation de l’état santé de la batterie est proposée. Elle est basée sur l’exploitation de l’étape de charge à tension constante lors d’une recharge complète et est donc bien adaptée à une intégration au sein d’un système de gestion de batterie. L’approche introduite est validée sur des données réelles de vieillissement allant jusqu’à deux ans de test.Enfin, une étude du phénomène de régénération de la capacité suite à un vieillissement des batteries de type combiné cyclage/calendaire est menée. Cette dernière partie constitue une ouverture pour le développement de stratégies d’usage des batteries lithium en incluant leur comportement thermique. / In this thesis, we focus on the reliability of lithium batteries used for automotive applications. For this purpose, electric and thermal characterization methodologies as well as aging tests under several modes (calendar, power cycling, calendar/power cycling) are carried out.In a first part of the work, battery modeling and battery state estimation (state-of-charge and state-of-health) are considered.Then, based on periodic characterization from electrochemical impedance spectroscopy, calendar aging is investigated. Next, we proposed an original process for precise battery state-of-health determination that exploits a full recharge and mainly constant-voltage charge step which allows easily its integration within a battery management system. Our experimental results, up to two years real-life data, confirm effectiveness of our technique.Finally, we study the capacity recovery phenomenon occurring due to combined battery aging (calendar/power cycling). This final part is almost dedicated to introduce strategies for battery use presenting at the same time a thermal behavior study.

<p>An emerging technology in the field of transient thermal management is thermal energy storage, or TES, which enables temporary, on-demand heat rejection via storage as latent heat in a phase-change material.  Latent TES devices have enabled advances in many thermal management applications, including peak load shifting for reducing energy demand and cost of HVAC systems and providing supplemental heat rejection in transient thermal management systems.  However, the design of a transient thermal management system with integrated storage comprises many challenges which are yet to be solved.  For example, design approaches and performance metrics for determining the optimal dimensions of the TES device have only recently been studied.  Another area of active research is estimation of the internal temperature state of the device, which can be difficult to directly measure given the transient nature of the thermal storage process.  Furthermore, in contrast to the three main functions of a thermal-fluid system--heat addition, thermal transport, and heat rejection--thermal storage introduces the need for active, real-time control and automated decision making for managing the operation of the thermal storage device. </p> <p>In this thesis, I present the design process for integrating thermal energy storage into a single-phase thermal management system for rejecting transient heat loads, including design of the TES device, state estimation and control algorithm design, and validation in both simulation and experimental environments. Leveraging a reduced-order finite volume simulation model of a plate-fin TES device, I develop a design approach which involves a transient simulation-based design optimization to determine the required geometric dimensions of the device to meet transient performance objectives while maximizing power density.  The optimized TES device is integrated into a single-phase thermal-fluid testbed for experimental testing.  Using the finite volume model and feedback from thermocouples embedded in the device, I design and experimentally validate a state estimator based on the state-dependent Riccati equation approach for determining the internal temperature distribution to a high degree of accuracy.  Real-time knowledge of the internal temperature state is critical for making control decisions; to manage the operation of the TES device in the context of a transient thermal management system, I design and test, both in simulation and experimentally, a logic-based control strategy that uses fluid temperature measurements and estimates of the TES state to make real-time control decisions to meet critical thermal management objectives. Together, these advances demonstrate the potential of thermal energy storage technology as a component of thermal management systems and the feasibility of logic-based control strategies for real-time control of thermal management objectives.</p>

Redox Flow Batteries are chemical based energy storage systems that accumulate energy in liquid electrolytes. Dissolved redox active substances undergo redox reactions in an electrochemical cell and so charge and discharge a battery. Recently, the introduction of organic materials as electrolytes raised research interest. Electrolytes that operate with the bromine/bromide redox couple are interesting due to their high energy density and fast reversible kinetics. They are used in combination with several anodic chemistries (e.g. Zinc, Hydrogen, Quinone), including organic materials.Due to the corrosive and volatile nature of bromine, practical electrolytes use Bromine Complexing Agents (BCAs) in order to bind bromine in a less volatile form and deal with safety issues. These additives have a strong influence on the battery’s operation by influencing the concentration of redox active species, the cell voltage and the electrolyte conductivity. Nevertheless, very little is known about the real properties of aqueous acidic bromine electrolytes, both in pure dilution and in presence of BCAs, which influence on the electrolyte is not predictable so far. The aim of this PhD project is to provide a comprehensive understanding of the behavior of an electrolyte based on bromine and bromide, with particular reference to the one used in semi-organic flow batteries. Along this work an analysis on the performance of a AQDS-Bromine flow battery cell was executed and an extensive study on the physico-chemical behavior of the positive electrolyte was developed. A review of the flow battery technology and of the metrics and methods available for diagnostics was firstly performed as a basis to define macro characteristics,such as State of Charge (SoC) and State of Health (SoH). The cycling behavior of an AQDS-Bromine flow battery was investigated by cell tests and possible degradation mechanisms have been highlighted and explained by interpretation of electrochemical measurements. Following, a broad characterization of the bromine-based electrolyte was performed, producing extended experimental data on physico-chemical properties and a modeling framework for the prediction of the electrolyte behavior.

[pt] O planejamento da expansão da transmissão (PET) visa identificar novos reforços para a rede, permitindo uma conexão tecnicamente adequada entre demanda e geração de energia elétrica, ambas previstas para um determinado horizonte de planejamento. Um bom plano de expansão deve garantir o equilíbrio entre os custos de investimento e operação, mantendo um nível satisfatório de segurança no fornecimento de energia elétrica. Entretanto, a identificação de bons planos de expansão para o PET tem se tornado uma tarefa cada vez mais difícil. Isso se deve, principalmente, às características e dimensões dos sistemas atuais, a não linearidade e natureza combinatória do problema de otimização e às incertezas presentes nos dados. Os erros de previsão, a indisponibilidade de equipamentos e a disponibilidade dos recursos naturais são parâmetros que variam de forma aleatória e inserem um alto grau de incerteza nos sistemas elétricos, o qual aumenta proporcionalmente com o horizonte de planejamento. Uma das incertezas mais relevantes a ser gerenciada nas próximas décadas será a capacidade de geração oriunda de fontes renováveis, em particular as eólicas, devido à sua grande variabilidade. A utilização de dispositivos de armazenamento permitirá melhor aproveitamento dessas fontes e, portanto, torna-se necessário o desenvolvimento de ferramentas computacionais capazes de considerar tais dispositivos no problema PET. Esta dissertação apresenta uma nova metodologia de apoio ao problema PET inserindo armazenadores de energia elétrica para aumentar o aproveitamento de fontes renováveis no sistema. Isso, respeitando as restrições de segurança da rede, acompanhando à curva de demanda e levando em consideração as variáveis operativas destes dispositivos. A possibilidade de incluir sistemas de armazenamento de energia elétrica é avaliada através de uma análise custo-benefício. A metodologia proposta é aplicada a um sistema teste, submetido a diversas condições operativas, e os resultados obtidos são amplamente discutidos. / [en] The transmission expansion planning (TEP) aims at identifying new reinforcements for the network, allowing a technically adequate connection between demand and generation of electric energy, both foreseen for a given planning horizon. A good expansion plan must ensure a balance between investment and operating costs, while maintaining a satisfactory level of security of the electric energy supply. However, identifying good expansion plans for TEP has become an increasingly difficult task. This is mainly due to the characteristics and dimensions of the current systems, the nonlinearity and combinatorial nature of the optimization problem, and the uncertainties present in the data. Forecasting errors, equipment unavailability, and the availability of natural resources are parameters that vary in a random way and insert a high degree of uncertainty in the electrical system, which proportionally increases with the planning horizon. One of the most relevant uncertainties to be managed in the upcoming decades will be the generation capacity from renewable sources, particularly wind power, due to its great variability. Storage devices will allow better use of these sources and, therefore, it becomes necessary to develop computational tools capable of considering such devices in the TEP problem. This dissertation presents a new methodology to support the TEP problem by inserting electric energy storage to increase the use of renewable energy in the system, while respecting the security restrictions of the network, following the demand curve and taking into account the operational variables of these devices. The possibility of including electric energy storage systems is evaluated through a costbenefit analysis. The proposed methodology is applied to a test system, subject to various operating conditions, and the obtained results are widely discussed.

<p>Co and Ni are two major elements in high temperature structural alloys that include superalloys for turbine engines and hard metals for cutting tools. The recent development of complex concentrated alloys (CCAs), loosely defined as alloys without a single principal element (e.g. CoNiFeMn), offers additional opportunities in designing new alloys through extensive composition and structure modifications. Within CCAs and Co- and Ni-based superalloys, solid-solution strengthening and stacking fault energy engineering are two of the most important strengthening mechanisms. While studied for decades, the potency and quantitative materials properties of these mechanisms remain elusive. </p> <p><br></p> <p>Solid-solution strengthening originates from stress field interactions between dislocations and solute of various species in the alloy. These stress fields can be engineered by composition modification in CCAs, and therefore a wide range of alloys with promising mechanical strength may be designed. This thesis initially reports on experimental and computational validation of newly developed theories for solid-solution strengthening in 3d transition metal (MnFeCoNi) alloys. The strengthening effects of Al, Ti, V, Cr, Cu and Mo as alloying elements are quantified by coupling the Labusch-type strengthening model and experimental measurements. With large atomic misfits with the base alloy, Al, Ti, Mo, and Cr present strong strengthening effects comparable to other Cantor alloys. </p> <p> </p> <p>Stacking fault energy engineering can enable novel deformation mechanisms and exceptional strength in face-centered cubic (FCC) materials such as austenitic TRIP/TWIP steels and CoNi-based superalloys exhibiting local phase transformation strengthening via Suzuki segregation. We employed first-principles calculations to investigate the Suzuki segregation and stacking fault energy of the FCC Co-Ni binary alloys at finite temperatures and concentrations. We quantitatively predicted the Co segregation in the innermost plane of the intrinsic stacking fault (ISF). We further quantified the decrease of stacking fault energy due to segregation.  </p> <p><br></p> <p>We further investigated the driving force of segregation and the origin of the segregation behaviors of 3d, 4d and 5d elements in the Co- and Ni-alloys. Using first-principles calculations, we calculated the ground-state solute-ISF interaction energies and revealed the trends across the periodic table. We discussed the relationships between the interaction energies and the local lattice distortions, charge density redistribution, density of states and local magnetization of the solutes. </p> <p><br></p> <p>Finally, this thesis reports on new methodologies to accelerate first-principles calculations utilizing active learning techniques, such as Bayesian optimization, to efficiently search for the ground-state energy line of the system with limited computational resources. Based on the expected improvement method, new acquisition strategies were developed and will be compared and presented. </p>

In der vorliegenden Arbeit wird erstmals das QQDS-Magnetspektrometer für die höchstauflösende Ionenstrahlanalytik leichter Elemente am Helmholtz-Zentrum Dresden-Rossendorf umfassend vorgestellt. Zusätzlich werden sowohl alle auf die Analytik Einfluss nehmenden Parameter untersucht als auch Methoden und Modelle vorgestellt, wie deren Einfluss vermieden oder rechnerisch kompensiert werden kann. Die Schwerpunkte dieser Arbeit gliedern sich in fünf Bereiche. Der Erste ist der Aufbau und die Inbetriebnahme des QQDS-Magnetspektrometers, der zugehörige Streukammer mit allen Peripheriegeräten und des eigens für die höchstauflösende elastische Rückstoßanalyse entwickelten Detektors. Sowohl das umgebaute Spektrometer als auch der im Rahmen dieser Arbeit gebaute Detektor wurden speziell an experimentelle Bedingungen für die höchstauflösende Ionenstrahlanalytik leichter Elemente angepasst und erstmalig auf einen routinemäßigen Einsatz hin getestet. Der Detektor besteht aus zwei Komponenten. Zum einen befindet sich am hinteren Ende des Detektors eine Bragg-Ionisationskammer, die zur Teilchenidentifikation genutzt wird. Zum anderen dient ein Proportionalzähler, der eine Hochwiderstandsanode besitzt und direkt hinter dem Eintrittsfenster montiert ist, zur Teilchenpositionsbestimmung im Detektor. Die folgenden zwei Schwerpunkte beinhalten grundlegende Untersuchungen zur Ionen-Festkörper-Wechselwirkung. Durch die Verwendung eines Magnetspektrometers ist die Messung der Ladungszustandsverteilung der herausgestreuten Teilchen direkt nach einem binären Stoß sowohl möglich als auch für die Analyse notwendig. Aus diesem Grund werden zum einen die Ladungszustände gemessen und zum anderen mit existierenden Modellen verglichen. Außerdem wird ein eigens entwickeltes Modell vorgestellt und erstmals im Rahmen dieser Arbeit angewendet, welches den ladungszustandsabhängigen Energieverlust bei der Tiefenprofilierung berücksichtigt. Es wird gezeigt, dass ohne die Anwendung dieses Modells die Tiefenprofile nicht mit den quantitativen Messungen mittels konventioneller Ionenstrahlanalytikmethoden und mit der Dickenmessung mittels Transmissionselektronenmikroskopie übereinstimmen, und damit falsche Werte liefern würden. Der zweite für die Thematik wesentliche Aspekt der Ionen-Festkörper-Wechselwirkung, sind die Probenschäden und -modifikationen, die während einer Schwerionen-bestrahlung auftreten. Dabei wird gezeigt, dass bei den hier verwendeten Energien sowohl elektronisches Sputtern als auch elektronisch verursachtes Grenzflächendurchmischen eintreten. Das elektronische Sputtern kann durch geeignete Strahlparameter für die meisten Proben ausreichend minimiert werden. Dagegen ist der Einfluss der Grenzflächendurchmischung meist signifikant, so dass dieser analysiert und in der Auswertung berücksichtigt werden muss. Schlussfolgernd aus diesen Untersuchungen ergibt sich für die höchstauflösende Ionenstrahlanalytik leichter Elemente am Rossendorfer 5-MV Tandembeschleuniger, dass die geeignetsten Primärionen Chlor mit einer Energie von 20 MeV sind. In Einzelfällen, wie zum Beispiel der Analyse von Bor, muss die Energie jedoch auf 6,5 MeV reduziert werden, um das elektronische Sputtern bei der notwendigen Fluenz unterhalb der Nachweisgrenze zu halten. Der vierte Schwerpunkt ist die Untersuchung von sowohl qualitativen als auch quantitativen Einflüssen bestimmter Probeneigenschaften, wie beispielsweise Oberflächenrauheit, auf die Form des gemessenen Energiespektrums beziehungsweise auf das analysierte Tiefenprofil. Die Kenntnis der Rauheit einer Probe an der Oberfläche und an den Grenzflächen ist für die Analytik unabdingbar. Als Resultat der genannten Betrachtungen werden die Einflüsse von Probeneigenschaften und Ionen-Festkörper-Wechselwirkungen auf die Energie- beziehungsweise Tiefenauflösung des Gesamtsystems beschrieben, berechnet und mit der konventionellen Ionenstrahlanalytik verglichen. Die Möglichkeiten der höchstauflösenden Ionenstrahlanalytik werden zudem mit den von anderen Gruppen veröffentlichten Komplementärmethoden gegenübergestellt. Der fünfte und letzte Schwerpunkt ist die Analytik leichter Elemente in ultradünnen Schichten unter Berücksichtigung aller in dieser Arbeit vorgestellten Modelle, wie die Reduzierung des Einflusses von Strahlschäden oder die Quantifizierung der Elemente im dynamischen Ladungszustandsnichtgleichgewicht. Es wird die Tiefenprofilierung von Mehrschichtsystemen, bestehend aus SiO2-Si3N4Ox-SiO2 auf Silizium, von Ultra-Shallow-Junction Bor-Implantationsprofilen und von ultradünnen Oxidschichten, wie zum Beispiel High-k-Materialien, demonstriert. / In this thesis the QQDS magnetic spectrometer that is used for high resolution ion beam analysis (IBA) of light elements at the Helmholtz-Zentrum Dresden-Rossendorf is presented for the first time. In addition all parameters are investigated that influence the analysis. Methods and models are presented with which the effects can be minimised or calculated. There are five focal points of this thesis. The first point is the construction and commissioning of the QQDS magnetic spectrometer, the corresponding scattering chamber with all the peripherals and the detector, which is specially developed for high resolution elastic recoil detection. Both the reconstructed spectrometer and the detector were adapted to the specific experimental conditions needed for high-resolution Ion beam analysis of light elements and tested for routine practice. The detector consists of two compo-nents. At the back end of the detector a Bragg ionization chamber is mounted, which is used for the particle identification. At the front end, directly behind the entrance window a proportional counter is mounted. This proportional counter includes a high-resistance anode. Thus, the position of the particles is determined in the detector. The following two points concern fundamental studies of ion-solid interaction. By using a magnetic spectrometer the charge state distribution of the particles scattered from the sample after a binary collision is both possible and necessary for the analysis. For this reason the charge states are measured and compared with existing models. In addition, a model is developed that takes into account the charge state dependent energy loss. It is shown that without the application of this model the depth profiles do not correspond with the quantitative measurements by conventional IBA methods and with the thickness obtained by transmission electron microscopy. The second fundamental ion-solid interaction is the damage and the modification of the sample that occurs during heavy ion irradiation. It is shown that the used energies occur both electronic sputtering and electronically induced interface mixing. Electronic sputtering is minimised by using optimised beam parameters. For most samples the effect is below the detection limit for a fluence sufficient for the analysis. However, the influence of interface mixing is so strong that it has to be included in the analysis of the layers of the depth profiles. It is concluded from these studies that at the Rossendorf 5 MV tandem accelerator chlorine ions with an energy of 20 MeV deliver the best results. In some cases, such as the analysis of boron, the energy must be reduced to 6.5 MeV in order to retain the electronic sputtering below the detection limit. The fourth focus is the study of the influence of specific sample properties, such as surface roughness, on the shape of a measured energy spectra and respectively on the analysed depth profile. It is shown that knowledge of the roughness of a sample at the surface and at the interfaces for the analysis is needed. In addition, the contribution parameters limiting the depth resolution are calculated and compared with the conventional ion beam analysis. Finally, a comparison is made between the high-resolution ion beam analysis and complementary methods published by other research groups. The fifth and last focus is the analysis of light elements in ultra thin layers. All models presented in this thesis to reduce the influence of beam damage are taken into account. The dynamic non-equilibrium charge state is also included for the quantification of elements. Depth profiling of multilayer systems is demonstrated for systems consisting of SiO2-Si3N4Ox-SiO2 on silicon, boron implantation profiles for ultra shallow junctions and ultra thin oxide layers, such as used as high-k materials.