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Preparation and characterization of iron oxide electrode materials for lithium-ion batteries by electrochemical and spectroscopic (XPS, ToF-SIMS) methods / Préparation et caractérisation des matériaux d'électrode en oxyde de fer pour les batteries lithium-ion par méthodes électrochimiques et spectroscopiques (XPS, ToF-SIMS)Tian, Bingbing 10 July 2014 (has links)
Les batteries lithium-ion sont largement utilisées comme source d'énergie pour les appareils électroniques portables. L'oxyde de fer (principalement α-Fe2O3), l'un des oxydes de métal de transition les plus important, a suscité l’intérêt scientifique depuis qu'il a été reporté comme matériau d'anode pour les batteries lithium-ion en raison de sa capacité théorique élevée (1007 mAh g-1), de son respect de l'environnement, de son abondance et de son faible coût. Dans cette thèse, une électrode modèle en couche mince d'oxyde de fer a été préparée par simple oxydation thermique à 300 °C dans l'air d'un substrat de fer métallique pur, utilisé aussi comme collecteur de courant. Une variété de techniques d'analyse, électrochimiques (CV, EIS et cyclage galvanostatique), spectroscopiques (XPS, ToF-SIMS) et microscopiques (MEB et AFM), ont été mises en oeuvre pour étudier les mécanismes réactionnels et la chimie de surface de l'oxyde de fer à différents stades de lithiation/délithiation et cyclage. / Lithium-ion batteries (LIBs) are widely used as power sources for portable electronic devices. Iron oxide (mainly α-Fe2O3), as one of the most important transition metal oxide, has attracted attention due to its high theoretical capacity (1007 mAh g-1), environmental friendliness, abundance and low cost since reported as anode material for LIBs. In this thesis, an iron oxide thin film model electrode was prepared by simple thermal oxidation of pure metallic iron substrate at 300 oC in air, also used as a current collector. Electrochemical methods (CV, EIS and galvanostatic cycling) were combined with surface (XPS, ToF-SIMS) and microscopic (SEM, AFM) analytical techniques to investigate the reaction mechanisms and the surface chemistry of the iron oxide thin film at different stages of lithiation/delithiation and upon cycling.
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Exploration of new sulfate-based cathode materials for lithium ion batteries / Exploration de nouveaux matériaux à base de sulfates pour des batteries lithium ionLander, Laura 04 November 2016 (has links)
Ces vingt dernières années, les batteries lithium-ion sont devenues dominantes parmi les technologies de stockage d’énergie électrique. Selon les applications, ces batteries (ou les matériaux qui la constituent) doivent présenter différentes spécificités: notamment une grande densité d’énergie, un bas coût, des contraintes de sécurité et de durabilité. Dans ce but, le développement de nouveaux matériaux d’électrode est indispensable. Nous nous sommes engagés, dans cette thèse, dans la synthèse des nouveaux composés polyanioniques à base de sulfates et fluorosulfates comme matériaux d’électrodes positives. Au cours de notre étude, nous avons synthétisé un nouveau polymorphe de KFeSO4F, de symétrie monoclinique, dont nous avons déterminé la structure en combinant la diffraction des rayons X et des neutrons sur poudre. Il est possible d’extraire électrochimiquement K+ de KFeSO4F et de réinsérer Li+ dans cette nouvelle matrice «FeSO4F» à un potentiel moyen de 3.7 V vs. Li+/Li0. Ensuite, nous nous sommes penchés vers des matériaux dépourvus de fluor et nous avons découvert une nouvelle phase Li2Fe(SO4)2 orthorhombique, qui présente des propriétés électrochimiques intéressantes avec un potentiel de 3.73 et 3.85 V vs. Li+/Li0 et une bonne cyclabilité. Nous avons également étudié le composé langbeinite K2Fe2(SO4)3 pour son aptitude à intercaler Li+ une fois le K+ extrait, avec cependant peu de succès. Néanmoins, en examinant d’autres phases langbeinites K2M2(SO4)3 avec M=métaux de transition 3d, nous avons découvert un nouveau composé K2Cu2(SO4)3, qui cristallise dans une structure différente de celle des langbeinites. Enfin, nous n’avons pas seulement étudié ces nouveaux matériaux pour leurs propriétés électrochimiques mais nous avons été également capables de révéler d’autres caractéristiques physiques intéressantes, notamment magnétiques. Les composés Li2Fe(SO4)2 orthorhombique et KFeSO4F monoclinique s’ordonnent antiferromagnétiquement à longue distance et leur structure magnétique autorise un couplage magnéto-électrique. / Lithium-ion batteries (LIBs) have become the dominating electrical energy storage technology in the last two decades. However, depending on their applications, LIBs need to fulfill several requirements such as high energy density, low-cost, safety and sustainability. This calls for the development of new electrode materials. Focusing on the cathode side, we embarked on the synthesis of novel sulfate- and fluorosulfate-based polyanionic compounds. During the course of our study, we discovered a monoclinic KFeSO4F polymorph, whose structure was determined via combined X-ray and neutron powder diffraction. We could electrochemically extract K+ and reinsert Li+ into this new polymorphic “FeSO4F” matrix at an average potential of 3.7 V vs. Li+/Li0. We then turned towards fluorine-free materials and synthesized a new orthorhombic Li2Fe(SO4)2 phase, which presents appealing electrochemical properties in terms of working potential (3.73 and 3.85 V vs. Li+/Li0) and cycling stability. In a next step, we tested langbeinite K2Fe2(SO4)3 for its aptitude to intercalate Li+ once K+ is extracted, with however little success. Nevertheless, exploring other langbeinite K2M2(SO4)3 phases (M=3d transition metal), we discovered a new K2Cu2(SO4)3 compound, which crystallizes in an orthorhombic structure distinct from the langbeinite one. Finally, we investigated these compounds not only for their electrochemistry, but we were also able to demonstrate other interesting physical properties, namely magnetic features. Orthorhombic Li2Fe(SO4)2 and monoclinic KFeSO4F both present a long-range antiferromagnetic spin ordering whose symmetry allows a magnetoelectric effect.
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UNDERSTANDING AND IMPROVING MANUFACTURING PROCESSES FOR MAKING LITHIUM-ION BATTERY ELECTRODESAL-Shroofy, Mohanad N. 01 January 2017 (has links)
Lithium-ion batteries (LIBs) have been widely used as the most popular rechargeable energy storage and power sources in today’s portable electronics, electric vehicles, and plug-in hybrid electric vehicles. LIBs have gained much interest worldwide in the last three decades because of their high energy density, voltage, rate of charge and discharge, reliability, and design flexibility. I am exploring the possibility of developing battery manufacturing technologies that would lower the cost, reduce the environmental impact, and increase cell performance and durability.
This dissertation is focused firstly on understanding the effect of mixing sequence (the order of introducing materials) and optimizing the electrode fabrication for the best electrochemical performance, durability, lower cost, and improve the existing manufacturing processes. The electrode system consists of active material, polymer binder, conductive agent, and solvent. I have investigated four different mixing sequences to prepare the slurries for making the positive electrode. The key sequence-related factor appears to be whether the active material and conductive agent are mixed in the presence of or prior to the introduction of the binder solution. The mixing sequences 1, 2, 3, and 4 were optimized, and the rheological behavior of the slurries, morphology, conductivity, and mechanical and electrochemical properties of electrodes were investigated. Slurries from sequences 1 and 4 show different rheological properties from 2 and 3. The amount of NMP required to achieve a comparable final slurry viscosity differed significantly for the sequences under study. The sequence 1 shows better long-term cycling behavior than sequences 2, 3 and 4. This study quantifies the link between electrode slurry mix parameters and electrode quality.
Secondly, a new method of making lithium-ion battery electrodes by adapting an immersion precipitation (IP) technology commonly used in membrane manufacturing was developed and demonstrated. The composition, structure, and electrochemical performance of the electrode made by the IP method were compared favorably with that made by the conventional method. The toxic and expensive organic solvent (NMP) was captured in coagulation bath instead of being released to the atmosphere. The IP electrodes show an excellent performance and durability at potentially lower cost and less environmental impact.
Thirdly, I have developed and demonstrated a solvent-free dry-powder coating process for making LiNi1/3Mn1/3Co1/3O2 (NMC) positive electrodes in lithium-ion batteries, and compared the performance and durability of electrodes made by the dry-powder coating processes with that by wet-slurry coating processes. The technology that has been used is the electrostatic spray deposition (ESD) process. This process eliminates volatile organic compound emission, reduces thermal curing time from hours to minutes, and offers high deposition rates onto large surfaces. The long-term cycling shows that the dry-powder coated electrodes have similar performance and durability as the conventional wet-slurry made electrodes.
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Determining the Power and Energy Capacity of a Battery Energy Storage System Utilizing a Smoothing Feeder Profile to Accommodate High Photovoltaic Penetration on a Distribution FeederMansour, Osama Mohammed Abbas Aly 25 July 2016 (has links)
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.
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Computational modelling studies of lithiated TiO2 nano-architectured structures at different temperatures, for energy storage applicationsRikhotso, Blessing Nkateko January 2019 (has links)
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)
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Computer simulation studies of MnO2 and LiMn2O4 nanotubeTshwane, David Magolego January 2016 (has links)
Thesis (MSc. (Physics)) -- University of Limpopo, 2016 / Nanostructured materials are attractive candidates for efficient electrochemical energy storage devices because of their unique physicochemical properties. Introducing nanotube systems as electrode materials represents one of the most attractive strategies that could dramatically enhance the battery performance. Nanostructured manganese based oxides are considered as ideal electrode materials for energy storage devices such as high energy and high power lithium-ion batteries. In this study, computer simulation strategies were used to generate various structures of MnO2 and spinel LiMn2O4 nanotubes; where Miller index, diameter and symmetry are considered as variables. The effect of these variables on nanotube generation was investigated. MnO2 and spinel LiMn2O4 nanotubes were generated using MedeA® software. Lower Miller indices, namely; {001}, {100}, {110} and {111} with diameter ranging from 5Å30Å were investigated for both systems. There are two ways that a nanotube structures could be wrapped along different directions, i.e., a_around_b or b_around_a. It was observed that wrapping direction has an effect on the geometrical structure of the nanotube. MnO2 nanotube generated from {110} revealed that nanotube wrapped along b_around_a gave a close-packed structure compared to its counterpart nanotube wrapped a_around_b. Diameter represents an important structural parameter of nanotubes; however, precise control of nanotube diameter over a wide range of materials is yet to be demonstrated. In this study, it was found that as the diameter of the nanotube is changed, parameters such as cross-sectional area and bond length change as well. The average bond distance of the nanotubes is less than that of MnO2 and LiMn2O4 bulk structure. Molecular dynamics simulation is further used to investigate the structure of MnO2 and LiMn2O4 nanotubes and the effect of temperature on the generated systems. Molecular graphical images used for the atomic positions for the nanotubes were investigated. The nanotube structures are described using radial distribution functions and XRD patterns. The calculated XRD patterns are in good agreement with the experiments, thus validating the generated structural models for the nanotubes. The resulting models conform to pyrolusite polymorph of MnO2 and LiMn2O4, featuring octahedrally coordinated manganese atoms. It was established that the variables have a direct control on nanotube morphology and the stability of generated nanotube model depends on surface morphology and termination. / National Research Foundation (NRF) and
Centre for High Performance Computing (CHPC) of CSIR
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Silicon-nanographite aerogel-based anodes for high performance lithium ion batteriesPatil, Rohan January 2020 (has links)
No description available.
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Electrochemical Analysis on Reaction Sites of Graphite Electrodes with Surface Film in Lithium-ion Batteries / 表面被膜存在下における黒鉛電極の反応場に関する研究Inoo, Akane 23 March 2020 (has links)
京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22456号 / 工博第4717号 / 新制||工||1737(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 作花 哲夫, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM
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Srovnání různých typů komerčních lithium-iontových baterií / Comparison of different types of commercial lithium-ion batteriesŠindelářová, Anna January 2021 (has links)
The master's thesis is devoted to the comparison of different types of lithium-ion batteries. Primarily, an introduction to electrochemical power sources and their division is described. Furthermore, the thesis deals only with lithium-ion batteries. In the theoretical part, the chapters discuss the history, the principle of operation and a detailed description of the main battery parts, including used materials. A comparison of commercially available lithium-ion cells with each other as well as with other types of batteries is also included in the theoretical part. The practical part deals with the cyclinf of lithium-ion cells and subsequent evaluation of the effect of temperature on the capacitance and current characteristics of these lithium-ion batteries.
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Příprava a charakterizace elektrodových materiálů z elementární síry pro Li-ion akumulátory / Preparation and characterisation of electrode materials based on elementar sulphur for Li-ion cellsJankulár, Tomáš January 2013 (has links)
This thesis deals with the preparation and characterization of electrode materials for Li-ion batteries based on elemental sulfur. The theoretical part is focused on the characteristics of Li-ion batteries, electrochemical reactions, the process of electrochemical lithiation of sulfur and solubility properties of intermediate polysulfides. The practical part of the thesis deals with the preparation of cathode materials for Li-ion cells with an active substance in the form of elemental sulfur. The prepared electrodes were investigated using cyclic voltammetry and galvanostatic cycling. Physical characterization by SEM and XRD was provided.
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