Electricity is a perishable commodity; once it is generated it needs to be consumed or stored. Electric energy storage provides both power and energy capacity. Power capacity applications reduce the need for generation, while energy capacity allows for energy consumption to be decoupled from generation. Previous research was done to develop an algorithm for determining the power (MW) and energy (MWh) capacities of a battery energy storage system (BESS) to mitigate the adverse impacts of high levels of photovoltaic (PV) generation. The algorithm used a flat feeder profile, and its performance was demonstrated on the equinoxes and solstices. Managing feeder power leads to fewer voltage fluctuations along the length of the feeder, potentially mitigating load management issues caused by variability of renewable generation and load profile. These issues include lighting flicker, compressor seizing, equipment shut-off, loss of motor torque, frequent transformer tap changes and even voltage collapse due to loss of reactive power support. The research described in this thesis builds on this algorithm by incorporating a smoothed feeder profile and testing it over an entire year. Incorporating a smoothing function reduces the requisite BESS energy capacity necessary to provide firming and shaping to accommodate the stochastic nature of PV. Specifically, this method is used to conduct a year-long study on a per second basis, as well as a one-minute basis, for a distribution feeder. Statistical analytical methods were performed to develop recommendations for appropriately sizing the BESS. This method may be used to determine the amount of PV generation that could be installed on a distribution feeder with a minimal investment in the BESS power and energy capacities that would be required to manage the distribution feeder power. Results are presented for PV penetration levels of 10%-50% of the distribution feeder capacity and show that the use of a smooth feeder profile reduces the required energy capacity by a minimum factor of 10 when compared to a flat feeder profile. Results indicated that it is sufficient to have a one-minute sampling rate, as it provides the necessary granularity to model cloud-induced fluctuations. This method can be applied to any distribution feeder where a load profile and a PV profile are available.

Thesis (M. Sc. (Chemistry)) -- University of Limpopo, 2019 / Nano-architecture structures of LixTiO2 are very promising as anode materials for lithium rechargeable batteries due to their ability to accommodate more lithium atoms and its ability to withstand high temperatures at atomistic level through charging and discharging. In these studies, we investigated how nano-architectured structures of LixTiO2 behave at high temperatures through the process of amorphisation and recrystallisation. A computational method of molecular dynamics (MD) simulation was employed to recrystallise the amorphous LixTiO2 nano-architectures of bulk, nanosheet, nanoporous and nanosphere, where x depicts the fraction of lithium ions, i.e. 0.03, 0.04 and 0.07. The main objective of this study was to go beyond the previous inserted lithium atoms on TiO2 and understand the effects of concentrations, temperature, defect chemistry and charge storage properties/capacity on the overall lithium transport to improve lithium ion battery performance. Recrystallisation of all four nanostructures from amorphous precursors were successfully achieved and was followed by the cooling process towards 0 K and finally we heated all four nano-architectures at temperature intervals of 100 K up to 500 K. The variation of configuration energies as a function of time, was used to monitor the crystal growth of all nanostructures. Calculated Ti-O radial distribution function, were used to confirm the stability interaction after cooling. Calculated X-Ray Diffraction (XRD) spectra where used to characterise and compare their patterns at cooled and above high temperatures, using the model nanostructures, and they showed polymorphic nanostructures with LixTiO2 domains of both rutile and brookite in accord with experiment. Amorphisation and recrystallization showed good results in generating complex microstructures. In particular, bulk structures show few zigzag tunnels (indicative of micro twinning) with 0.03 Li but 0.04 Li and 0.07 Li show complex v patterns indicating a highly defected structure. While 0.03 and 0.04Li nanospheres show, zigzag and straight tunnels in accord with experiment, the one with 0.07 Li has melted. Lastly, nanoporous and nanosheet structures have pure straight and zigzag patterns that are well in accord with our XRD patterns at all concentrations of lithium atoms and temperatures. The lithium transport was analysed using diffusion coefficient, calculated as a function of temperature in order to confirm the mobility above the given temperatures. An increase in temperature shows an increase in diffusivity of lithium at all lithium concentrations in nanoporous and nanosheet structures. The same trend was observed in bulk but only with 0.03 and 0.07 Li ion concentrations. / National Research Foundation (NRF)

Le travail de cette thèse s’inscrit dans une thématique qui concerne le dimensionnement optimal et la gestion d’énergie résiliente aux défauts d’un système multi-sources (hybride) pour l’alimentation d’un véhicule électrique. Dans notre cas, le système de stockage est composé d’une pile à combustible comme source principale et une source secondaire à base d’une batterie Li-ion. L’étude réalisée sur le dimensionnement montre l’intérêt de l’hybridation par rapport à un système mono-source batterie seule ou bien pile à combustible seule. L’intérêt de cette hybridation en termes de masse, de volume et de coût devient de plus en plus important en augmentant l’autonomie du véhicule. Après avoir dimensionné la source hybride pour une autonomie de 700 km, on s’est intéressé à l’influence de la technologie de la batterie et les méthodes de gestion sur les performances de la source (le volume, la masse, le cout, les contraintes électriques appliquées sur les composants et la consommation d’hydrogène du système PàC/Batterie). La partie dimensionnement est suivie par le développement d’une stratégie de gestion d’énergie originale basée sur la prise en compte de l’état de charge de la batterie (SOC) pour adapter les limites de fonctionnement de la pile à combustible. Les résultats obtenus avec cette méthode sont comparés avec deux autres stratégies de gestion d’énergie en ligne à savoir, la méthode de découpage fréquentiel et l’utilisation d’un superviseur floue. La stratégie développée a donné des bons résultats expérimentaux en termes de contraintes vues par les cellules et de consommation d’hydrogène. Malgré un bon dimensionnement de la source embarquée et une bonne optimisation de la méthode de gestion d’énergie, le système n’est pas à l’abri du défaut et peut être le siège de plusieurs défauts qui peuvent apparaitre au niveau de capteurs de tension et de courant. Afin d’assurer la continuité de service du système hybride en présence de ces défauts, une stratégie de commande tolérante aux fautes a été développée afin de garantir la stabilité de système hybride PàC/Batterie et assurer des performances acceptables en mode dégradé. / The work of this thesis is part of a theme that concerns the optimal sizing and energy management resilient to the faults of a multi-source system (hybrid) for the power supply of an electric vehicle. In our case, the storage system consists of a fuel cell as the main source and a secondary source based on a Li-ion battery. The study carried out on the sizing shows the interest of the hybridization compared to a mono-source single battery or fuel cell only system. The interest of this hybridization in terms of weight, volume and cost becomes more and more important by increasing the autonomy of the vehicle. After scaling the hybrid source for a 700 km drive range, we investigated the influence of battery technology and management methods on the performance of the source (volume, mass, cost, electrical stress applied to the components and the hydrogen consumption of the Fuel Cell / Battery system).The sizing part is followed by the development of an original energy management strategy based on the state of charge of the battery (SOC) to adapt the operating limits of the fuel cell. The results obtained with this method are compared with two other online energy management strategies namely, the frequency division method and the use of a fuzzy supervisor. The strategy developed gave good experimental results in terms of constraints seen by cells and hydrogen consumption. Despite a good sizing of the on-board source and a good optimization of the energy management method, the system is not immune from the fault and can be the seat of several faults that can appear at voltage sensors. and current. In order to ensure the service continuity of the hybrid system in the presence of these faults, a fault-tolerant control strategy has been developed in order to guarantee the stability of the hybrid Fuel Cell/ Battery system and to ensure acceptable performance in degraded mode.

<p>The single particle model was extended to include electrode and particle volume expansion effects observed in high capacity alloying electrodes. The model was used to predict voltage profiles in sodium ion batteries with tin and tin-phosphide negative electrodes. It was seen that the profiles predicted by the modified model were significantly better than the classical model. A parametric study was done to understand the impact of properties such as particle radius, diffusivity, reaction rate etc on the performance of the electrode. The model was also modified for incorporating particles having a cylindrical morphology. For the same material properties, it was seen that cylindrical particles outperform spherical particles for large L/R values in the cylinder due to the diffusion limitations at low L/R ratios. A lattice spring-based degradation model was used to observe crack formation and creep relaxation within the particle. It was observed that the fraction of broken bonds increases with an increase in strain rate. At low strain rates, it was seen that there was a significant expansion in particle volumes due to creep deformation. This expansion helped release particle stresses subsequently reducing the amount of fracture.</p>

Le contact entre l'électrode et l'électrolyte est primordial pour le bon fonctionnement d'une batterie Lithium-Ion. L'imprégnation de l'électrode positive par un électrolyte liquide a toujours été considérée comme totale, cependant les phénomènes ne sont pas exactement connus. Ainsi, ces travaux s'intéressent à l'influence de la composition de l'électrode positive (matière active et agent conducteur) sur cette imprégnation. Après une première étude des propriétés conductrices, électrochimiques et morphologiques d'électrodes présentant des formulations plus ou moins éloignées des formulations industrielles, une méthode utilisant l'équation de Washburn a été développée afin d'étudier l'imprégnation des pores modélisés par un ensemble de tubes capillaires. L'utilisation de l'hexadecane, considéré comme un liquide parfaitement mouillant, a permis de déterminer la taille effective des pores indépendamment de l'électrolyte, et celle-ci a pu être comparée à des résultats obtenus grâce à la méthode de thermoporosimétrie. Puis, les régimes de Washburn obtenus lors de la diffusion de l'électrolyte ont mis en évidence les cinétiques d'ascension. Par la suite, la méthode de Washburn a été utilisée afin de caractériser les propriétés d'imprégnation d'électrodes élaborées avec un nouveau liant et selon un procédé innovant s'affranchissant de l'utilisation de solvant. L'utilisation d'un additif permettant la création de porosité d'une part, et la réticulation du liant d'autre part permettent d'obtenir une imprégnation de l'électrolyte comparable à celle observée pour les électrodes fabriquées par voie solvant / The contact between the electrode and the electrolyte is essential for a Lithium-Ion battery functioning. The impregnation of a positive electrode by the electrolyte has always been considered as total; however the phenomena are not exactly known. Thus, in this work, the influence of the positive electrode composition (active material, conductive agent and binder) on the impregnation has been investigated. After a first study focusing on the conductive, electrochemical and morphological properties of the electrodes, with different types of formulation, a method using Washburn equation has been developed in order to study the impregnation of the electrode’s pores, which were modeled as capillary tubes. With the use of hexadecane, considered as a perfectly wetting liquid, the effective pore size has been determined and then compared to the results given by the thermoporosimetry method. Then, the kinetics of ascension have been identified with the Washburn regimes obtained with the diffusion of the electrolyte in the cathodes. Afterwards, Washburn method has been used in order to characterize the impregnation properties of electrodes elaborated with an innovative process without solvent. Thanks to the use of an additive allowing the creation of porosity in one hand and the reticulation of the binder in the other hand, an impregnation of these new electrode by the electrolyte has been considered as comparable to the one observed for the cathodes made with solvent

Indiana University-Purdue University Indianapolis (IUPUI) / Lithium based batteries have become ubiquitous with our everyday life. They have propelled a generation of smart personal electronics and electric transport. Their use is now percolating to various fields as a source of energy to facilitate the operation of devices from nanoscale to mega scale. This need for a portable energy source has led to tremendous scientific interest in this field to develop electrochemical devices like batteries with higher capacities, longer cycle life and increased safety at a low cost. To this end, the research presented in this thesis focuses on two emerging and promising technologies called lithium-oxygen (Li-O₂) and lithium-sulfur (Li-S) batteries. These batteries can offer an order of magnitude higher capacities through cheap, environmentally safe and abundant elements, namely oxygen and sulfur. The first work introduces the concept of closed system lithium-oxygen batteries wherein the cell contains the discharge product of Li-O₂ batteries namely, lithium peroxide (Li₂O₂) as the starting active material. The reversibility of this system is analyzed along with its rate performance. The possible use of such a cathode in a full cell is explored. Also, this concept is used to verify if all the lithium can be extracted from the cathode in the first charge. In the following work, lithium peroxide is chemically synthesized and deposited in a carbon nanofiber matrix. This forms a free-standing cathode that shows high reversibility. It can be cycled up to 20 times, and while using capacity control protocol, a cycle life of 50 is obtained. The cause of cell degradation and failure is also analyzed. In the work on full cell lithium-sulfur system, a novel electrolyte is developed that can support reversible lithium insertion and extraction from a graphite anode. A method to deposit solid lithium polysulde is developed for the cathode. Coupling a lithiated graphite anode with the cathode using the new electrolyte yields a full cell whose performance is characterized and its post-mortem analysis yields information on the cell failure mechanism. Although still in their developmental stages, Li-O₂ and Li-S batteries hold great promise to be the next generation of lithium batteries, and these studies make a fundamental contribution towards novel cathode and cell architecture for these batteries.

No description available.

Conversion material electrodes such as FeF2 possess the potential to deliver transformative improvements in lithium ion battery performance because they permit a reversible change of more than one Li-ion per 3d metal cation. They outperform current state of the art intercalation cathodes such as LiCoO2, which have volumetric and gravimetric energy densities that are intrinsically limited by single electron transfer. Current studies focus on composite electrodes that are formed by mixing with carbon (FeF2-C), wherein the carbon is expected to act as a binder to support the matrix and facilitate electronic conduction. These binders complicate the understanding of the electrode-electrolyte interface (SEI) passivation layer growth, of Li agglomeration, of ion and electron transport, and of the basic phase transformation processes under electrochemical cycling. This research uses thin-films as a model platform for obtaining basic understanding to the structural and chemical foundations of the phase conversion processes. Thin film cathodes are free of the binders used in nanocomposite structures and may potentially provide direct basic insight to the evolution of the SEI passivation layer, electron and ion transport, and the electrochemical behavior of true complex phases. The present work consisted of three main tasks (1) Development of optimized processes to deposit FeF2 and LiPON thin-films with the required phase purity and microstructure; (2) Understanding their electron and ion transport properties and; (3) Obtaining insight to the correlation between structure and capacity in thin-film microbatteries with FeF2 thin-film cathode and LiPON thin-film solid electrolyte. Optimized pulsed laser deposition (PLD) growth produced polycrystalline FeF2 films with excellent phase purity and P42/mnm crystallographic symmetry. A schematic band diagram was deduced using a combination of UPS, XPS and UV-Vis spectroscopies. Room temperature Hall measurements reveal that as-deposited FeF2 is n-type with an electron mobility of 0.33 cm2/V.s and a resistivity was 0.255 Ω.cm. The LiPON films were deposited by reactive sputtering in nitrogen, and the results indicate that the ionic conductivity is dependent on the amount of nitrogen incorporated into the film during processing. The highest ionic conductivity obtained was 1.431.9E-6 Scm-1 and corresponded to a chemical composition of Li1.9PO3.3N.21. FeF2/LiPON thin films microbatteries were assembled using a 2032 coin cell configuration and subjected to Galvanostatic cycling. HRTEM and EELS spectroscopy where performed across the FeF2/LiPON interface of samples cycled once 15 times in their lithiated and delithiated states to understand the relationship between microstructural evolution and capacity. The EELS measurements provided evidence of a three-phase conversion reaction over the first discharge described by FeF2 +2e-+2Li+↔Fe +LiF, and of incomplete reconversion back to FeF2 after the 1st cycle resulting in new Fe0 and LiF phases in delithiated samples. This incomplete conversion results in (a) a smaller phase fraction of FeF2 participating in the conversion process subsequently and (b) the formation of LiF which is resistive to both electron and ion transport. This results in the observed drastic drop in capacity after the1st cycle. More study to understand the reconversion reaction pathways is required to fully exploit the potential of FeF2 and other conversion materials as cathodes in Li ion batteries.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24925号 / エネ博第467号 / 新制||エネ||87(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 萩原 理加, 教授 佐川 尚, 教授 野平 俊之 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

In today’s fast adjustment to renewable energy, new battery technologies are needed to meetthe ever-growing demands of energy storage. Cheaper and easier to produce materials areneeded, as well as materials with a lower environmental impact. One new and interestingtechnology is the dual-ion battery, and more specifically the aluminum dual-ion battery. Thisbattery uses cheap and abundant aluminum together with a graphitic cathode to work. However,a lot of research today uses expensive and sophisticated cathode materials to make this type ofbattery work. Therefore, this thesis focuses on creating a cheap and easy to produce graphitecathode material through the phase inversion method for the use in aluminum dual-ionbatteries, that is also freestanding for better energy density. Graphene is also used as anadditive to improve the electrical conductivity of the material, and the material is later tested in afull cell with the typical ionc liquid electrolyte EMImCL/AlCl4.Through phase inversion, a freestanding graphite cathode is produced with 8 wt% PVDF binderand 0.4 wt% graphene. The material has a porous structure and an enhanced electricalconductivity with the graphene added. Through CV cycling and symmetric Al-Al tests the batteryreactions are shown to work. However, when cycling the cell with a constant current there areproblems, probably coming from some sort of soft shorting or side reactions. It is revealed thatapart from the expected reactions, Ni dissolution from the contact tabs also takes place, andmay cause problems. Further tests are needed to validate if this material works. However,because no new active materials have been introduced to the battery chemistry, it is reasonableto believe that the battery will work with some small changes.Tek nisk-naturvetensk apliga fak ulteten, Upps ala universitet. Utgiv nings ort U pps al a/Vis by . H andledare: Anwar Ahniy az , Äm nesgranskar e: D aniel Brandell, Ex aminator: Lena Klintberg