Li+ ion batteries have been the mainstay of high energy storage devices that have revolutionized the operating life time of consumer electronic devices for the past two decades. However, there is a steady increase in demand for energy storage devices with the ability to store more energy and deliver them at high power at low cost, without comprising safety and lifetime. Li-ion batteries have had significant challenges in increasing the amount of stored energy without affecting the overall lifetime and the ability to deliver stored energy. In order to store and deliver more energy, more lithium ions need to be inserted and extracted from a given electrode (cathode or anode). Upon inserting a large number of Li ions, the crystal lattice of the materials undergo severe mechanical distortions, leading to un-desirable structural changes. This results in underutilization of theoretical energy storage capacities of the electrodes and early failure of the batteries owing to instabilities in the electrode materials. Unlike monovalent Li+ ions, multivalent rechargeable batteries offer a potential solution to the above problems. Multivalent cations, such as Ca2+, are doubly-ionized as opposed to Li+ which is a monovalent cation. The advantages of using Ca2+ ions instead of Li+ ions are multifold. Due to the doubly-ionized nature, only half the number of Ca2+ ions need to be inserted and extracted from a given electrode to store and deliver energy from a high capacity cathode as compared to Li+ ions. This reduces the probability of lattice distortion and un-desirable structural changes, further leading to increased utilization of high theoretical energy storage capacities of the electrodes (cathode and anode). The use of Ca2+ ions also helps in delivering twice the amount of current density as compared to Li+ ions due to its doubly ionized nature. In this work, a set of eight metal hexacyanoferrate compounds were synthesized using the following metal ions: Ba2+, Mn2+, Zn2+, Co2+, Fe3+, Al3+, Sn4+, Mo5+. The resulting metal hexacyanoferrate compounds were subjected to physical characterization using scanning electron microscope (SEM) and powder x-ray diffraction (XRD), to determine physical properties such as size, morphology, unit cell symmetry and unit cell parameters. This was followed by electrochemical characterization utilizing cyclic voltammetry and galvanic cycling, to determine the specific capacity and kinetics involved in the transport of Ca2+ ions to store charge. Optical characterization of the metal hexacyanoferrates using Fourier transform infrared (FTIR) spectroscopy, allowed for the identification of metal-nitrogen stretching frequency, which was used as a measure of the strength of the metal-nitrogen bond to understand the role of the above mentioned metal ions in electron density distribution across the unit cell of the metal hexacyanoferrates. The specific capacity utilization of the metal hexacyanoferrates, when compared to the electronegativity values (Xi) of the above mentioned metal ions, the σ- parameter, and the metal-nitrogen stretching frequency (v), revealed an empirical trend suggesting that the materials (FeHCF, CaCoHCF and CaZnHCF) that possessed intermediates values for the above mentioned parameters demonstrated high capacity utilization (≥50%). Based on these empirical trends, it is hypothesized that a uniform distribution of electron density around a unit cell, as reflected by intermediate values of the electronegativity (Xi) of the above mentioned metal ions, the σ-parameter and the metal-nitrogen stretching frequency (v), results in minimal electrostatic interactions between the intercalating cation and the host unit cell lattice. This results in relatively easy diffusion of the cations, leading to high specific capacity utilization for metal hexacyanoferrate cathodes. These parameters may be used to select high efficiency cathode materials for multivalent batteries.

Thesis (M.S.)--Mississippi State University. Department of Chemistry. / Title from title screen. Includes bibliographical references.

Thesis (M.S.)--Mississippi State University. Department of Chemistry. / Title from title screen. Includes bibliographical references.

The primary objective of this research was to investigate and develop an electrostatic energy-harvesting voltage-constrained CMOS/BiCMOS integrated circuit (IC) that harnesses ambient kinetic energy from vibrations with a vibration-sensitive variable capacitor and channels the extracted energy to charge an energy-storage device (e.g., battery). The proposed harvester charges and holds the voltage across the vibration-sensitive variable capacitor so that vibrations can induce it to generate current into the battery when capacitance decreases (as its plates separate). To that end, the research developed an energy-harvesting system that synchronizes to variable capacitor's state as it cycles between maximum and minimum capacitance by controlling each functional phase of the harvester and adjusting to different voltages of the on-board battery. One of the major challenges of the system was performing all of these duties without dissipating the energy harnessed and gained from the environment. Consequently, the system reduces losses by time-managing and biasing its circuits to operate only when needed and with just enough energy while charging the capacitor through an efficient inductor-based precharger. As result, the proposed energy harvester stores a net energy gain in the battery during each vibration cycle.

Eine der drei Säulen der Krebsbehandlung ist die Strahlentherapie. Einer der neuesten Ansätze hierbei ist die Bestrahlung mit Ionen, zurzeit insbesondere Protonen und Kohlenstoffionen. Diese Hochpräzisionstherapie erfordert ein hohes Maß an Kontrolle, da die applizierte Dosisverteilung sehr empfindlich von Dichteveränderungen im durchstrahlten Gewebe abhängt. Das bisher einzige klinisch eingesetzte Verfahren zur in vivo Überwachung der Dosisapplikation bei Ionenbestrahlungen ist die Positronen-Emissions-Tomographie (PET). Sie ermöglicht eine Verifikation der Teilchenreichweite sowie der Lage des Bestrahlungsfeldes. Die mit der PET-Methode gemessene Aktivitätsverteilung lässt sich jedoch nicht direkt mit der geplanten Dosisverteilung vergleichen. Daher ist eine Vorherberechnung der erwarteten Aktivitätsverteilung auf der Grundlage des Bestrahlungsplanes notwendig, welche dann mit der Messung verglichen wird und eine qualitative Beurteilung der Bestrahlung ermöglicht. Die Vorherberechnung der erwarteten Aktivitätsverteilung erfordert bislang die Kenntnis einer Vielzahl von Wirkungsquerschnitten. Nur für wenige dieser Wirkungsquerschnitte liegen jedoch Messdaten im benötigten Energiebereich und mit ausreichender Genauigkeit vor. Daher verwenden viele Monte-Carlo-Simulationen intrinsische Kernmodelle oder semi-empirische Modellierungen, die häufig eine unzureichende Genauigkeit aufweisen. In Fachkreisen ist bisher noch nicht geklärt, welches die optimale Ionensorte für die Tumortherapie ist. Insbesondere Lithiumionen weisen aufgrund ihrer physikalischen und radiobiologischen Eigenschaften ein großes Potenzial auf. Auch für Bestrahlungen mit diesen Ionen ist ein PET-Monitoring der Therapie erstrebenswert. In der vorliegenden Arbeit wird zunächst die Anwendbarkeit der Reichweite-Verifikation mittels PET bei Bestrahlung mit Lithiumionen gezeigt. Des Weiteren wird ein Konzept zur Modellierung der Positronenemitter-Verteilung ohne Kenntnis der Wirkungsquerschnitte entwickelt. Diese Vorhersage beruht auf in Referenzmaterialien (Wasser, Graphit und Polyethylen) gemessenen tiefenabhängigen Positronenemitter-Yields, mit welchen durch geeignete Linearkombination die Verteilung der Positronenemitter in beliebigen Materialien bekannter Stöchiometrie vorausberechnet werden kann. Die Anwendbarkeit des Yield-Konzeptes wird gezeigt für Lithium- und Kohlenstoffbestrahlungen homogener Polymethylmethacrylat (PMMA) Targets sowie verschiedener inhomogener Targets. / One of the three main tumour treatment forms is radiation therapy. Here, the application of ion beams, in particular protons and carbon ions, is of growing importance. This high precision therapy requires a consequent monitoring of the dose delivery since the induced dose deposition is very sensitive to density changes in the irradiated tissue. Up to now, positron emission tomography (PET) is the only in vivo method in clinical use for monitoring the dose deposition in ion beam therapy. It allows for the verification of the particle range as well as the position of the irradiation field. The distribution of activity measured by means of PET cannot be compared directly to the planned dose distribution. Thus, a calculation of the expected activity distribution is required which then can be compared to the measurement. Simulation of the expected activity distribution requires the exact knowledge of various cross sections. Only a few of them have been measured in the required energy range so far. Therefore, in Monte Carlo simulations often intrinsic nuclear models or semi-empirical parametrization are used which often exhibit insufficient accuray. Among experts the question on the optimum ion species for tumour therapy is still open. Especially lithium ions exhibit a great potential due to their favourable physical and radiobiological properties. Also for these ions a PET monitoring is highly desirable. The presented work shows the feasibility of range verification by means of PET for lithium irradiation. Furthermore, a concept for modeling positron emitter distributions without the knowledge of cross sections is developed. This prediction is based on depth-dependent positron emitter yields measured in reference materials (water, graphite and polyethylene). With these data the positron emitter distribution in any material of known stoichiometry can be calculated by means of an appropriate linear combination. The feasibility of the yield concept is shown for lithium and carbon irradiation, respectively, of homogeneous polymethyl methacrylate (PMMA) as well as various inhomogeneous targets.

Eine der drei Säulen der Krebsbehandlung ist die Strahlentherapie. Einer der neuesten Ansätze hierbei ist die Bestrahlung mit Ionen, zurzeit insbesondere Protonen und Kohlenstoffionen. Diese Hochpräzisionstherapie erfordert ein hohes Maß an Kontrolle, da die applizierte Dosisverteilung sehr empfindlich von Dichteveränderungen im durchstrahlten Gewebe abhängt. Das bisher einzige klinisch eingesetzte Verfahren zur in vivo Überwachung der Dosisapplikation bei Ionenbestrahlungen ist die Positronen-Emissions-Tomographie (PET). Sie ermöglicht eine Verifikation der Teilchenreichweite sowie der Lage des Bestrahlungsfeldes. Die mit der PET-Methode gemessene Aktivitätsverteilung lässt sich jedoch nicht direkt mit der geplanten Dosisverteilung vergleichen. Daher ist eine Vorherberechnung der erwarteten Aktivitätsverteilung auf der Grundlage des Bestrahlungsplanes notwendig, welche dann mit der Messung verglichen wird und eine qualitative Beurteilung der Bestrahlung ermöglicht. Die Vorherberechnung der erwarteten Aktivitätsverteilung erfordert bislang die Kenntnis einer Vielzahl von Wirkungsquerschnitten. Nur für wenige dieser Wirkungsquerschnitte liegen jedoch Messdaten im benötigten Energiebereich und mit ausreichender Genauigkeit vor. Daher verwenden viele Monte-Carlo-Simulationen intrinsische Kernmodelle oder semi-empirische Modellierungen, die häufig eine unzureichende Genauigkeit aufweisen. In Fachkreisen ist bisher noch nicht geklärt, welches die optimale Ionensorte für die Tumortherapie ist. Insbesondere Lithiumionen weisen aufgrund ihrer physikalischen und radiobiologischen Eigenschaften ein großes Potenzial auf. Auch für Bestrahlungen mit diesen Ionen ist ein PET-Monitoring der Therapie erstrebenswert. In der vorliegenden Arbeit wird zunächst die Anwendbarkeit der Reichweite-Verifikation mittels PET bei Bestrahlung mit Lithiumionen gezeigt. Des Weiteren wird ein Konzept zur Modellierung der Positronenemitter-Verteilung ohne Kenntnis der Wirkungsquerschnitte entwickelt. Diese Vorhersage beruht auf in Referenzmaterialien (Wasser, Graphit und Polyethylen) gemessenen tiefenabhängigen Positronenemitter-Yields, mit welchen durch geeignete Linearkombination die Verteilung der Positronenemitter in beliebigen Materialien bekannter Stöchiometrie vorausberechnet werden kann. Die Anwendbarkeit des Yield-Konzeptes wird gezeigt für Lithium- und Kohlenstoffbestrahlungen homogener Polymethylmethacrylat (PMMA) Targets sowie verschiedener inhomogener Targets. / One of the three main tumour treatment forms is radiation therapy. Here, the application of ion beams, in particular protons and carbon ions, is of growing importance. This high precision therapy requires a consequent monitoring of the dose delivery since the induced dose deposition is very sensitive to density changes in the irradiated tissue. Up to now, positron emission tomography (PET) is the only in vivo method in clinical use for monitoring the dose deposition in ion beam therapy. It allows for the verification of the particle range as well as the position of the irradiation field. The distribution of activity measured by means of PET cannot be compared directly to the planned dose distribution. Thus, a calculation of the expected activity distribution is required which then can be compared to the measurement. Simulation of the expected activity distribution requires the exact knowledge of various cross sections. Only a few of them have been measured in the required energy range so far. Therefore, in Monte Carlo simulations often intrinsic nuclear models or semi-empirical parametrization are used which often exhibit insufficient accuray. Among experts the question on the optimum ion species for tumour therapy is still open. Especially lithium ions exhibit a great potential due to their favourable physical and radiobiological properties. Also for these ions a PET monitoring is highly desirable. The presented work shows the feasibility of range verification by means of PET for lithium irradiation. Furthermore, a concept for modeling positron emitter distributions without the knowledge of cross sections is developed. This prediction is based on depth-dependent positron emitter yields measured in reference materials (water, graphite and polyethylene). With these data the positron emitter distribution in any material of known stoichiometry can be calculated by means of an appropriate linear combination. The feasibility of the yield concept is shown for lithium and carbon irradiation, respectively, of homogeneous polymethyl methacrylate (PMMA) as well as various inhomogeneous targets.

Les travaux de cette thèse ont été consacrés à la synthèse de nanoparticules magnétiques d'oxyde de fer et d'oxyde de cobalt et de nanoparticules coeur-coquille constituées d'un coeur d'oxyde de fer recouvert d'oxyde de cobalt et à l'élaboration de nanomatériaux - composites nanostructures carbonées/nanoparticules d'oxyde métallique - pour des applications dans le domaine biomédical et celui de l'énergie. Pour la synthèse des NPs, la forme et la taille des NPs sont fortement dépendantes des conditions de réaction (nature des ligands, des solvants, température de réaction ... ) , ce qui affecte leurs propriétés magnétiques. De plus, des simulations ont montré que les chaînes de stéarate peuvent désorber plus facilement les atomes de fer que les atomes de cobalt et se libérer pour former des germes, ce qui pourrait expliquer le comportement distinctif entre les deux complexes. Ces nanoparticules magnétiques ont été synthétisées à l'intérieur de nanotubes de carbone en deux étapes aboutissant à des taux de remplissage très importants. Après fonctionnalisation, ces nanocomposites ont été introduits dans de cellules tumorales et ont été magnétiquement manipulées. Ils se sont révélés être très efficaces en tant qu'agents de contraste en IRM mais également dans le domaine de l'hyperthermie (activation sous éclairage dans le domaine de !'Infrarouge proche). Enfin, de nouveaux composites à partir de nanoparticules de Nb20 5 et de graphène (ou NTCs) ont été synthétisés et des résultat~prometteurs ont été obtenus dans des tests de batterie lithium-ion : leur utilisation en tant qu'anode a permis d'obtenir des capacités réversibles de 260 mAh/g. / This thesis was focused on the synthesis of magnetic nanoparticles of iron oxide and cobalt oxide and core-shell nanoparticles, consisting of a cobalt oxide coated iron oxide and on the development of composite nanomaterials - nanostructures carbon /metal oxide nanoparticles - for applications in the biomedical field and the energy. For the synthesis of NPs, the shape and size of NPs are dependent of the reaction conditions, which further affect their magnetic properties. Meanwhile, simulation showed that stearate chains can desorb more easily from iron atoms and release to form seeds than from cobalt atoms, which might explain distinctive behavior between the bath complexes. Regarding nanostructures carbon/metal oxide nanoparticles hybrid materials, the properties of the filled magnetic CNTs as heat mediator for photothermal ablation and as contrast agent for MRI were then evaluated and promising results have been obtained. Last, new composite materials (Nb205 nanoparticles/graphene or NTCs) were synthesized and promising results were obtaines in lithium battery tests : their use as anode allowed obtaining reversible capacities of 260 mAh/g.

This master‘s thesis concerns gel polymer electrolytes formed on a methyl methacrylate base with selected types of nanoparticles. In the thesis are also analyzed the methods for measuring electrochemical properties. The practical portion deals with sample preparations of gel polymer electrolytes with different contents of alkaline salt in a solvent, creating gels with different nanoparticle content and comparing gel polymer electrolytes polymerized with heat and UV radiation. The thesis deals with the evaluation of these samples from the viewpoint of electrical conductivity and potential windows as well as thermal analysis of selected samples.

Indiana University-Purdue University Indianapolis (IUPUI) / A gradient free function optimization technique, namely particle swarm optimization (PSO) algorithm, is utilized in parameter identification of the electrochemical model of a Lithium-Ion battery having a LiCoO2 chemistry. Battery electrochemical model parameters are subject to change under severe or abusive operating conditions resulting in, for example, Navy over-discharged battery, 24-hr over-discharged battery, and over-charged battery. It is important for a battery management system to have these parameters changes fully captured in a bank of battery models that can be used to monitor battery conditions in real time. In this work, PSO methodology has been used to identify four electrochemical model parameters that exhibit significant variations under severe operating conditions. The identified battery models were validated by comparing the model output voltage with the experimental output voltage for the stated operating conditions. These identified conditions of the battery were then used to monitor condition of the battery that can aid the battery management system (BMS) in improving overall performance. An adaptive estimation technique, namely multiple model adaptive estimation (MMAE) method, was implemented for this purpose. In this estimation algorithm, all the identified models were simulated for a battery current input profile extracted from the hybrid pulse power characterization (HPPC) cycle simulation of a hybrid electric vehicle (HEV). A partial differential algebraic equation (PDAE) observer was utilized to obtain the estimated voltage, which was used to generate the residuals. Analysis of these residuals through MMAE provided the probability of matching the current battery operating condition to that of one of the identified models. Simulation results show that the proposed model based method offered an accurate and effective fault diagnosis of the battery conditions. This type of fault diagnosis, which is based on the models capturing true physics of the battery electrochemistry, can lead to a more accurate and robust battery fault diagnosis and help BMS take appropriate steps to prevent battery operation in any of the stated severe or abusive conditions.

The research discussed is divided into two parts. The first part discusses the background work involved in preparation of the Li-ion cell testing stage. This includes the preparation of anodes using the doctor blade and a calendar mill, electrolyte preparation, test cell assembly, the Li-ion test cell design, and experiments performed to troubleshoot the cell. The second part deals with the cell testing experiments. Li-ion batteries are amongst the most promising rechargeable battery technology because of their high capacity and low weight. Current research aims at improving the anode quality to increase the capacity. The experiments discussed evaluate the traditional anode materials like SFG44 graphite and conducting grade graphite against the novel ones– and tin oxide (SnO2) based and carbon encapsulated tin based anodes. The solid electrolyte interphase formed on each anode was analyzed to understand the initial capacity fade leading to conditioning of the cell thus stabilizing its performance.