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Fizičko-hemijska karakterizacija binarnih smeša jonskih tečnosti i laktona i njihova primena kao elektrolita za litijum-jonske baterije / Physicochemical characterisation of ionic liquids and lactones binary mixtures and their application as electrolytes for lithium-ion batteriesPapović Snežana 20 July 2018 (has links)
<p>U ovoj doktorskoj disertaciji ispitivani su elektroliti na bazi binarnih smeša imidazolijumovih jonskih tečnosti i laktona koji su pogodni za primenu u litijum-jonskim baterijama. Fizičkohemijska svojstva binarnih smeša jonskih tečnosti na bazi imidazolijum katjona i <em>bis </em>(trifluorometilsulfonil)imidnog anjona i laktona ispitana su u celom opsegu molskih udela i na različitim temperaturama. Na osnovu izmerenih gustina, viskoznosti i električne provodljivosti izračunati su različiti fizičko-hemijski parametri i diskutovane interakcije između komponenata smeša. Ispitana je termička i elektrohemijska stabilnost odabranih elektrolita. Na osnovu dobijenih rezultata, prvo je odabran odgovarajući lakton koji je kasnije kombinovan sa jonskim<br />tečnostima na bazi imidazola, koje se međusobno razlikuju u dužini bočnog niza katjona. Na osnovu fizičko-hemijskih svojstava na različitim temperaturama i pri različitim sastavima binarnih smeša diskutovan je način organizacije njihovih<br />komponenata. U binarne smeše koje su se pokazale kao najperspektivnije sa stanovišta električne provodljivosti, viskoznosti, elektrohemijske stabilnosti i (ne)zapaljivosti dodata je litijumova so. Tako dobijeni ternarni sistemi su okarakterisani<br />u zavisnosti od koncentracije litijumove soli. Odabrani elektroliti upotrebljeni su za ispitivanje performansi litijum-jonske ćelije sa elektrodama na bazi anatas TiO<sub>2</sub> nanocevi. Cikličnom voltametrijom i galvanostatskim cikliranjem ispitane su<br />performanse ćelije u toku 350 ciklusa punjenja i pražnjenja. Na osnovu ciklovoltametrijskih merenja izračunati su koeficijenti difuzije jona Li<sup> + </sup>i energija aktivacije za difuziju. Kombinacijom jonskih tečnosti i laktona moguće je dobiti elektrolite smanjene viskoznosti, povećane električne provodljivosti, povećane<br />termičke stabilnosti usled međusobnog stabilizacionog efekta laktona na imidazolijumove jonske tečnosti.</p> / <p>In this doctoral dissertation, binary mixtures based on imidazolium ionic liquids with lactones were tested for use in lithium-ion batteries. The physicochemical properties of binary mixtures of imidazolium based ionic liquids with <em> bis </em>(trifluoromethylsulfonyl)imide anions and lactones were examined throughout the whole composition range and at different temperatures. Based on the measured densities, viscosity and electrical conductivity, various physical chemical parameters and discrete interactions between the components of the mixture are calculated. Thermal and electrochemical stability of selected binary mixtures were examined. Based on obtained results was selected lactone which is later combined with imidazolium based ionic liquid, differing from each other in the length of the cation. Based on the physico-chemical properties at different temperatures and in the different compositions of binary mixtures, the way of organizing their components is discussed. Lithium salt is added to the binary mixtures that have been shown as the most perspective from the standpoint of electrical conductivity, viscosity, electrochemical stability and (non)flammability. The resulting ternary systems are characterized according to the concentration of lithium salt. The selected electrolytes were used to test the performance of the lithium-ion cell with anatase TiO<sub>2</sub> nanotubular electrodes. Cyclic voltammetry and galvanostatic cycling tested the cell's performance during the 350 charge and discharge cycles. Based on cyclic voltammetric measurements, the Li <sup>+</sup> ion diffusion coefficients and activation energies for diffusion were calculated. Combination ionic liquid and lactone could be obtained electrolytes with lower viscosity, higher electrical conductivity, improved thermal stability due to stabilization effect of lactone on imidazolium based ionic liquids.</p>
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Synthesis and battery application of nanomaterials and the mechanism of O2 reduction in aprotic Li-O2 batteriesLiu, Zheng January 2016 (has links)
Hunting for improved energy storage devices based on rechargeable Li-ion batteries and other advanced rechargeable batteries is one of the hottest topics in today's society. Both Li- ion batteries and Li-O2 batteries have been studied within the thesis. The research work of this thesis contains two different parts. Part 1. The controlled synthesis of the extreme small sized nanoparticles and their application for Li-ion batteries; Part 2. The study of the O2 reduction mechanism in Li-O2 batteries with aprotic electrolytes. In the first part, two different types of extremely small-sized TiO2 nanoparticles with at lease on dimension less than 3 nm was synthesised via solvothermal/hydrothermal reaction, i.e., anatase nanosheets and TiO2(B). These nanoparticles were obtained without any contamination of long chain organic surfactants. A series of systematic characterisation methods were employed to analyse the size, phase purity, and surface condition. These extremely small-sized nanoparticles exhibit improved capacity, rate performance as anode materials for Li-ion batteries. The shapes of load curves of charge and discharge are significantly modified due to the reduced size of TiO2 nanoparticles. In chapter 3, we will see the variation of the capacity and the load curve shape of the anatase nanosheets according to their thickness and surface conditions. The origin of the excessive capacity is analysed based on the electrochemical data. It has been identified that both pseudocapacitive (interfacial) Li+ storage and the excessive Li+ -storage from the bulk contribute to the increased capacity. In chapter 4, the shape and size of the sub-3 nm TiO2(B) nanoparticles are studied, a method based the PXRD data is established. These nanoparticles demonstrate a reversible capacity of 221 mAh/g at a rate of 600 mA/g and remain 135 mAh/g at 18000 mA/g without significant capacity fading during cycling. In the last part, a systematic study of O2 reduction mechanism for aprotic Li-O2 batteries based on the combination of a series of electrochemical and spectroscopic data is presented. The novel mechanism unifies two previous models for the growth of Li2O2 during discharge, i.e., Li2O2 particle formation in the solution phase and Li2O2 film formation on the electrode surface. The new mechanism provides fundamental conceptions for the improvement of Li2O2 batteries and shed light on the future research of Li2O2 batteries.
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DEFECT CHEMISTRY AND TRANSPORT PROPERTIES OF SOLID STATE MATERIALS FOR ENERGY STORAGE APPLICATIONSZhan, Xiaowen 01 January 2018 (has links)
Replacing organic liquid electrolytes with nonflammable solid electrolytes can improve safety, offer higher volumetric and gravimetric energy densities, and lower the cost of lithium-ion batteries. However, today’s all-solid-state batteries suffer from low Li-ion conductivity in the electrolyte, slow Li-ion transport across the electrolyte/electrode interface, and slow solid-state Li-ion diffusion within the electrode. Defect chemistry is critical to understanding ionic conductivity and predicting the charge transport through heterogeneous solid interfaces. The goal of this dissertation is to analyze and improve solid state materials for energy storage applications by understanding their defect structure and transport properties.
I have investigated defect chemistry of cubic Li7La3Zr2O12 (c-LLZO), one of the most promising candidate solid electrolytes for all-solid-state lithium batteries. By combining conductivity measurements with defect modeling, I constructed a defect diagram of c-LLZO featuring the intrinsic formation of lithium vacancy-hole pairs. The findings provided insights into tailoring single-phase mixed lithium-ion/electron conducting materials for emerging ionic devices, i.e., composite cathodes requiring both fast electronic and ionic paths in solid-state batteries. I suggested that oxygen vacancies could increase the Li-ion conductivity by reducing the amount of electron holes bound with lithium vacancies.
Using a simpler but also attractive solid electrolyte Li2ZrO3 (LZO) as an example, I significantly improved Li-ion conductivity by creating extra oxygen vacancies via cation doping. In particular, Fe-doped LZO shows the highest Li-ion conductivity reported for the family of LZO compounds, reaching 3.3 mS/cm at 300 °C. This study brought attentions to the long-neglected oxygen vacancy defects in lithium-ion conductors and revealed their critical role in promoting Li-ion transport. More importantly, it established a novel defect engineering strategy for designing Li-oxide based solid electrolytes for all-solid-state batteries.
I surface-modified LiNi0.6Co0.2Mn0.2O2 cathode material with a LZO coating prepared under dry air and oxygen, and systematically investigated the effect of coating atmosphere on their transport properties and electrochemical behaviors. The LZO coating prepared in oxygen is largely amorphous. It not only provided surface protection against the electrolyte corrosion but also enabled faster lithium-ion transport. Additionally, oxygen atmosphere facilitated Zr diffusion from the surface coating to the bulk of LiNi0.6Co0.2Mn0.2O2, which stabilized the crystal structure and enhanced lithium ion diffusion. Consequently, LiNi0.6Co0.2Mn0.2O2 cathodes coated with Li2ZrO3 in oxygen achieved a significant improvement in high-voltage cycling stability and high-rate performance.
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Insights in Li-ion Battery Interfaces through Photoelectron Spectroscopy Depth ProfilingPhilippe, Bertrand January 2013 (has links)
Compounds forming alloys with lithium, such as silicon or tin, are promising negative electrode materials for the next generation of Li-ion batteries due to their higher theoretical capacity compared to the current commercial electrode materials. An important issue is to better understand the phenomena occurring at the electrode/electrolyte interfaces of these new materials. The stability of the passivation layer (SEI) is crucial for good battery performance and its nature, formation and evolution have to be investigated. It is important to follow upon cycling alloying/dealloying processes, the evolution of surface oxides with battery cycling and the change in surface chemistry when storing electrodes in the electrolyte. The aim of this thesis is to improve the knowledge of these surface reactions through a non-destructive depth-resolved PES (Photoelectron spectroscopy) analysis of the surface of new negative electrodes. A unique combination utilizing hard and soft-ray photoelectron spectroscopy allows by variation of the photon energy an analysis from the extreme surface (soft X-ray) to the bulk (hard X-ray) of the particles. This experimental approach was used to access the interfacial phase transitions at the surface of silicon or tin particles as well as the composition and thickness/covering of the SEI. Interfacial mechanisms occurring upon the first electrochemical cycle of Si-based electrodes cycled with the classical salt LiPF6 were investigated. The mechanisms of Li insertion (LixSi formation) have been illustrated as well as the formation of a new irreversible compound, Li4SiO4, at the outermost surface of the particles. Upon long cycling, the formation of SiOxFy was shown at the extreme surface of the particles by reaction of SiO2 with HF contributing to battery capacity fading. The LiFSI salt, more stable than LiPF6, improved the electrochemical performances. This behaviour is correlated to the absence of SiOxFy upon long-term cycling. Some degradation of LiFSI was shown by PES and supported by calculations. Finally, interfacial reactions occurring upon the first cycle of an intermetallic compound MnSn2 were studied. Compared to Si based electrodes, the SEI chemical composition is similar but the alloying process and the role played by the surface metal oxide are different.
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Database and Modeling of Field Test Data fromLithium Ion Batteries in Hybrid Electrical Vehicles.Höök, Niclas January 2011 (has links)
In this thesis information received from a hybrid vehicle battery test equipment wasstructured and analyzed. This test equipment is currently placed on a fleet of Scaniatrucks with the purpose of emulating hybrid vehicle environment on battery cell level.A Microsoft Access database structure was set up in order to make it possible to savetest data in a structured way. In addition, Matlab scripts were made with the purposeof calculating cell aging from pulse- and capacity tests. Furthermore, drive cycleanalysis was performed looking at statistics for selected parameters. Data collectedfrom late October 2010 until beginning of July does not yet show any aging of the fieldtested battery cells regarding capacity loss or resistance increase. The internalresistance of the batteries was calculated to 2 to 4 milli ohm and the capacity wasfrom the tests found to be around 3 ampere hours. The energy efficiency, which wascalculated from pulse test data, shows an efficiency between 95 to 97%.
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Electrochemical behavior of organic radical polymer cathodes in organic radical batteries with ionic liquid electrolytesCheng, Yen-Yao 09 October 2012 (has links)
The electrochemical behavior of a poly(2,2,6,6-tetramethylpiperidin- 1-oxyl-4-yl methacrylate) (PTMA) cathode in organic radical batteries with lithium bis(trifluoromethylsulfonyl)imide in N-butyl-N-methyl- pyrrolidinium bis(trifluoromethylsulfonyl)imide (LiTFSI/BMPTFSI) ionic liquid electrolytes is investigated. The ionic liquid electrolytes containing a high concentration of the LiTFSI salt have a high polarity, preventing the dissolution of the polyvinylidene fluoride (PVdF) binder and PTMA in the electrolytes. The results of cyclic voltammetry and AC impedance indicate that an increase in the LiTFSI concentration results in a decrease in the impedance of the lithium electrode, which affects the C-rate performance of batteries. The discharge capacity of the PTMA composite electrode in a 0.6 m LiTFSI/BMPTFSI electrolyte is 92.9 mAh g−1 at 1 C; its C-rate performance exhibits a capacity retention, 100 C/1 C, of 88.3%. Moreover, the battery with the 0.6-m LiTFSI/BMPTFSI electrolyte has very good cycle-life performance.
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Modeling of electrochemical energy storage and energy conversion devicesChandrasekaran, Rajeswari 29 July 2010 (has links)
With increasing interest in energy storage and conversion devices for automobile applications, the necessity to understand and predict life behavior of rechargeable batteries, PEM fuel cells and super capacitors is paramount. These electrochemical devices are most beneficial when used in hybrid configurations rather than as individual components because no single device can meet both range and power requirements to effectively replace internal combustion engines for automobile applications. A system model helps us to understand the interactions between components and enables us to determine the response of the system as a whole. However, system models that are available predict just the performance and neglect degradation. In the first part of the thesis, a framework is provided to account for the durability phenomena that are prevalent in fuel cells and batteries in a hybrid system. Toward this end, the methodology for development of surrogate models is provided, and Pt catalyst dissolution in PEMFCs is used as an example to demonstrate the approach. Surrogate models are more easily integrated into higher level system models than the detailed physics-based models. As an illustration, the effects of changes in control strategies and power management approaches in mitigating platinum instability in fuel cells are reported. A system model that includes a fuel cell stack, a storage battery, power-sharing algorithm, and dc/dc converter has been developed; and preliminary results have been presented. These results show that platinum stability can be improved with only a small impact on system efficiency. Thus, this research will elucidate the importance of degradation issues in system design and optimization as opposed to just initial performance metrics.
In the second part of the thesis, modeling of silicon negative electrodes for lithium ion batteries is done at both particle level and cell level. The dependence of the open-circuit potential curve on the state of charge in lithium insertion electrodes is usually measured at equilibrium conditions. Firstly, for modeling of lithium-silicon electrodes at room temperature, the use of a pseudo-thermodynamic potential vs. composition curve based on metastable amorphous phase transitions with path dependence is proposed. Volume changes during lithium insertion/de-insertion in single silicon electrode particle under potentiodynamic control are modeled and compared with experimental data to provide justification for the same. This work stresses the need for experiments for accurate determination of transfer coefficients and the exchange current density before reasoning kinetic hysteresis for the potential gap in Li-Si system. The silicon electrode particle model enables one to analyze the influence of diffusion in the solid phase, particle size, and kinetic parameters without interference from other components in a practical porous electrode. Concentration profiles within the silicon electrode particle under galvanostatic control are investigated. Sluggish kinetics is established from cyclic voltammograms at different scan rates. Need for accurate determination of exchange current density for lithium insertion in silicon nanoparticles is discussed. This model and knowledge thereof can be used in cell-sandwich model for the design of practical lithium ion cells with composite silicon negative electrodes. Secondly, galvanostatic charge and discharge of a silicon composite electrode/separator/ lithium foil is modeled using porous electrode theory and concentrated solution theory. Porosity changes arising due to large volume changes in the silicon electrode with lithium insertion and de-insertion are included and analyzed. The concept of reservoir is introduced for lithium ion cells to accommodate the displaced electrolyte. Influence of initial porosity and thickness of the electrode on utilization at different rates is quantitatively discussed. Knowledge from these studies will guide design of better silicon negative electrodes to be used in dual lithium insertion cells for practical applications.
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Microwave-assisted synthesis and characterization of inorganic materials for energy applicationsHarrison, Katharine Lee 12 November 2013 (has links)
Lithium-ion batteries play a crucial role in portable electronics, but require further innovation for electric vehicle and grid storage applications. To meet this demand, significant emphasis has been placed on developing safe, inexpensive, high energy density cathode materials. LiFePO₄ is a candidate cathode material for electric vehicle and grid storage applications. Vanadium-doped LiFePO₄ cathodes of the form [chemical formula] (0 ≤ x ≤ 0.25) were synthesized here by a facile, low-temperature microwave-assisted solvothermal (MW-ST) method. Such an approach offers manufacturing-energy and cost savings compared to conventional synthesis. Additionally, although [chemical formula] has been synthesized previously by conventional methods, it is shown here that the MW-ST method allows much higher doping levels than can be achieved at conventional temperatures, indicating that metastable phases can be isolated through the low-temperature microwave-assisted synthesis. LiFePO₄ suffers from poor ionic conductivity, but this limitation can be minimized by microwave-assisted synthesis through a tuning of the particle size, allowing for decreased Li⁺ diffusion paths. LiVOPO₄ is another polyanion material with higher energy density than LiFePO₄, but similar ionic conductivity limitations. It has not been previously synthesized by MW-ST. Thus, a MW-ST method was developed here to prepare LiVOPO₄. By varying reaction conditions, three polymorphic modifications of LiVOPO₄ were accessed and the electrochemical performance was optimized. LiVOPO₄ can be further discharged to Li₂VOPO₄, which has been suggested in the literature, but the structural transformation that accompanies this process has not been detailed. To this end, the delithiation process was studied by ex situ XRD measurements to better understand how the second lithium is accommodated. Finally, MW-ST has also been exploited to grow thin films of anatase TiO₂ phase on indium tin oxide (ITO)-coated glass substrates. The microwave field is selectively absorbed by the conductive ITO layer on the glass substrates, leading to ohmic heating. The resulting heated ITO layer acts as a favorable site for nucleation and growth. TiO₂ thin films have widespread applications in the energy and electronics sectors. Such selective microwave-assisted ohmic heating of solid materials within a growth solution represents a promising new avenue for microwave synthesis, which has been minimally explored in the literature. / text
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Low-temperature synthesis and electrochemical properties of aliovalently-doped phosphates and spinel oxidesGutierrez, Arturo, 1978- 01 July 2014 (has links)
Lithium-ion batteries are being intensely pursued as energy storage devices because they provide higher energy and power densities compared to other battery systems such as lead-acid and nickel-metal hydride batteries. This dissertation (i) explores the use of a low-temperature microwave-assisted synthesis process to obtain aliovalently-doped lithium transition-metal phosphates and lower-valent vanadium oxide spinels, some of which are difficult to obtain by conventional high-temperature processes, and (ii) presents an investigation of the electrochemical properties of the aliovantly-doped phosphate cathodes and doped lithium manganese oxide and oxyfluoride spinel cathodes in lithium-ion batteries. Following the introduction and general experimental procedures, respectively, in Chapters 1 and 2, Chapter 3 first focuses on understanding of how the inductive effect and structural features in lithium transition-metal borate, silicate, and phosphate cathodes affect the M²⁺ʹ³⁺redox energies. It is found that the magnitude of the voltages delivered by the polyanion cathodes can be predicted based simply on the coordination of the transition-metal ion. Furthermore, the differences in the voltages delivered by the phosphates and pyrophosphates are explained by considering the resonance structures and their contribution to the covalency of the polyanion. Chapter 4 presents a low-temperature microwave-assisted solvothermal process to substitute 20 atom % V³⁺ for Mn²⁺ in LiMnPO₄. It is shown that the solubility of vanadium in LiMnPO₄ decreases upon heating the doped samples to ≥ 575 °C, demonstrating the importance of employing a low-temperature process to achieve aliovalent doping in LiMnPO₄. It is further demonstrated that by increasing the vanadium content in the material, the discharge capacity in the first cycle could be increased without any additional carbon coating. Subsequent X-ray absorption spectroscopy data reveal that the better performance is facilitated by enhanced Mn-O hybridization upon incorporating vanadium into the lattice. Chapter 5 explores the influence of various factors, such as the oxidation state of Mn, electronegativity of the dopant cation Mn+, and the dissociation energy of M-O bond, on the electrochemical properties of cation-doped oxide and oxyfluoride spinel cathodes. As an extension, Chapter 6 presents the effect of processing conditions on the surface concentration of the dopant cation Mn+. Chapter 7 presents an extension of the low-temperature microwave-assisted synthesis process to obtain AV₂O₄ (Mg, Fe, Mn, and Co) spinel oxides. The method is remarkably effective in reducing the synthesis time and energy use due to the efficiency of dielectric heating compared to conventional heating. The ability to access V³⁺ is facilitated by the relative positions of the energy levels of the cations in solution, which is lower than that in the solid, and the use of a strong reducing solvent like TEG. Finally, Chapter 8 provides a summary of the salient findings in this dissertation. / text
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Charging of lithium-ion batteries with a hydrogen fuel cell for an electrical bicycle.Monjaux, Aurelien. January 2012 (has links)
M. Tech. Electrical Engineering. / Hydrogen is in the middle of many discussions as being a good alternative to petrol for the struggle against pollution and global warming. The fact that hydrogen can be found in infinite quantities such as in water or in space makes it a renewable energy. It is the object of much research works in order to be used in replacement of fossil energy such as in hybrid vehicles. However, the main shed of hydrogen is the difficulties to store it. Indeed, being the first element of the periodic table, it is the lightest, spreads a lot and can burn easily. The aim of this project is to achieve the wiring diagram of an electrical bicycle. The use of a hydrogen fuel cell allows feeding the electrical motor of the vehicle. However, due to a matter of low response time of the fuel cell, lithium-ion batteries are also used. Indeed, at the start state for instance, the fuel cell needs some time to warm and reach the nominal temperature of functioning. Lithium-ion batteries allow feeding the electrical motor during the warm up time but also to respond to peak of load. Hybrid motorization represents the future of car industry and tends to be used as a replacement of petrol engine partly responsible of greenhouse gases emissions. Some of those vehicles are already put in place in some big cities all over the world and allow moving rapidly without polluting. This project concerns a hybrid system for an electrical bicycle but the idea is to extend to bigger kind of vehicles.
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