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.

High energy density batteries have garnered much attention in recent years due to their demand in electric vehicles. Lithium-oxygen (Li-O2) batteries are becoming some of the most promising energy storage and conversion technologies due to their ultra-high energy density. They are still in the infancy stage of development and there are many challenges needing to be overcome before their practical commercial application. Some of these challenges include low round-trip efficiency, lower than theoretical capacity, and poor rechargeability. Most of these issued stem from the poor catalytic performance of the cathode that leads to a high overpotential of the battery. In this doctoral work, Li-O2 cathodes containing nanoparticles of palladium were used to alleviate this problem. Cathodes composed of palladium-coated and palladium-filled carbon nanotubes (CNTs) were prepared and investigated for their battery performance. The full discharge of batteries showed 6-fold increase in the first discharge of the Pdfilled over the pristine CNTs and 35% increase over their Pd-coated counterparts. The Pd-filled CNTs also exhibited improved cyclability with 58 full cycles of 500 mAh·g-1 at current density of 250 mA·g-1 versus 35 and 43 cycles for pristine and Pd-coated CNTs, respectively. The effect of encapsulating the Pd catalysts inside the CNTs proved to increase the stability of the electrolyte during both discharging and charging. Voltammetry, Raman spectroscopy, XRD, UV/Vis spectroscopy, and visual inspection of the discharge products using scanning electron microscopy confirmed the increased stability of the electrolyte due catalyst shielding. The electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on carbon nanotubes (CNT) cathodes with palladium (Pd) catalyst, Pd-coated CNT and Pd-filled CNT, have been evaluated in an ether-based electrolyte solution to develop a lithium oxygen (Li−O2) battery with a high specific energy. The electrochemical properties of CNT cathodes were studied using electrochemical impedance spectroscopy (EIS). The infrared spectroscopy and SEM are employed to analyze the reaction products adsorbed on the electrode surface of the Li-O2 battery developed using Pd-coated and Pd-filled CNTs as cathode and an ether based electrolyte. vii Studies in this dissertation conclude that the use of nanocatalysts composed of palladium improved the overall performance of the Li-O2 batteries, while shielding these catalysts from direct contact with the electrolyte prolonged the life of the battery by stabilizing the electrolyte.

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.

Non-aqueous metal-air (Li-O2 and Na-O2) batteries have been emerging as one of the most promising high-energy storage systems to meet the requirements for demanding applications due to their high theoretical specific energy. In the present thesis work, advanced characterization techniques are demonstrated for the exploration of metal-O2 batteries. Prominently, the electrochemical reactions occurring within the Li-O2 and Na-O2 batteries upon cycling are studied by in operando powder X-ray diffraction (XRD). In the first part, a new in operando cell with a combined form of coin cell and pouch cell is designed. In operando synchrotron radiation powder X-ray diffraction (SR-PXD) is applied to investigate the evolution of Li2O2 inside the Li-O2 cells with carbon and Ru-TiC cathodes. By quantitatively tracking the Li2O2 evolution, a two-step process during growth and oxidation is observed. This newly developed analysis technique is further applied to the Na-O2 battery system. The formation of NaO2 and the influence of the electrolyte salt are followed quantitatively by in operando SR-PXD. The results indicate that the discharge capacity of Na-O2 cells containing a weak solvating ether solvent depends heavily on the choice of the conducting salt anion, which also has impact on the growth of NaO2 particles. In addition, the stability of the discharge product in Na-O2 cells is studied. Using both ex situ and in operando XRD, the influence of sodium anode, solvent, salt and oxygen on the stability of NaO2 are quantitatively identified. These findings bring new insights into the understanding of conflicting observations of different discharge products in previous studies. In the last part, a binder-free graphene based cathode concept is developed for Li-O2 cells. The formation of discharge products and their decomposition upon charge, as well as different morphologies of the discharge products on the electrode, are demonstrated. Moreover, considering the instability of carbon based cathode materials, a new type of titanium carbide on carbon cloth cathode is designed and fabricated. With a surface modification by loading Ru nanoparticles, the titanium carbide shows enhanced oxygen reduction/evolution activity and stability. Compared with the carbon based cathode materials, titanium carbide demonstrated a higher discharge and charge efficiency.

Lithium-oxygen batteries, also known as Lithium-air batteries, could possibly revolutionize energy storage as we know. By letting lithium react with ambient oxygen gas very large theoretical energy densities are possible. However, there are several challenges remaining to be solved, such as finding suitable materials and understanding the reaction, before the lithium-oxygen battery could be commercialized. The scope of this thesis is focusing on the latter of these challenges. Efficient ion transport between the electrodes is imperative for all batteries that need high power density and energy efficiency. Here the mass transport properties of lithium ions in several different solvents was evaluated. The results showed that the lithium  mass transport in electrolytes based on the commonly used lithium-oxygen battery solvent dimethyl sulfoxide (DMSO) was very similar to that of conventional lithium-ion battery electrolytes. However, when room temperature ionic liquids were used the performance severely decreased. Addition of Li salt will effect the oxygen concentration in DMSO-based electrolytes. The choice of lithium salt influenced whether the oxygen concentration increased or decreased. At one molar salt concentration the highest oxygen solubility was 68 % larger than the lowest one. Two model systems was used to study the electrochemical reaction: A quartz crystal microbalance and a cylindrical ultramicroelectrode. The combined usage of these systems showed that during discharge soluble lithium superoxide was produced. A consequence of this was that not all discharge product ended up on the electrode surface. During discharge the cylindrical ultramicroelectrodes displayed signs of passivation that previous theory could not adequately describe. Here the passivation was explained in terms of depletion of active sites. A mechanism was also proposed. The O2 and Li+ concentration dependencies of the discharge process were evaluated by determining the reactant reaction order under kinetic and mass transport control. Under kinetic control the system showed non-integer reaction orders with that of oxygen close to 0.5 suggesting that the current determining step involves adsorption of oxygen. At higher overpotentials, at mass transport control, the reaction order of lithium and oxygen was zero and one, respectively. These results suggest that changes in oxygen concentration will influence the current more than that of lithium. During charging not all of the reaction product was removed. This caused an accumulation when several cycles was examined. The charge reaction pathway involved de-lithiation and bulk oxidation, it also showed an oxygen concentration dependence. / Litiumsyrebatteriet, även känt som litiumluftbatteriet, kan potentiellt revolutionera vårt förhållande till energilagring. Genom att låta litium reagera med syrgas från luften kan teoretiskt höga energitätheter uppnås. Dock så behöver många problem lösas, så som att hitta lämpliga elektrod- och elektrolytmaterial samt att få en ökad förståelse för reaktionsmekanismen, innan litiumsyrebatteriet kan kommersialiseras. Den här avhandlingen behandlar de sistnämnda av dessa problem. För att ett batteri ska kunna leverera hög effekttäthet och energieffektivitet krävs en effektiv jontransport mellan elektroderna. Här utvärderades masstransporten hos flera olika elektrolyter. Resultatet visade att masstransporten av litium i en litiumsyrebatterielektrolyt (baserad på dimetylsulfoxid (DMSO)) är likvärdig med en konventionell litiumjonbatterielektrolyt. När elektrolyter baserade på jonvätskor användes uppvisades väldigt stora energiförluster. När litiumsalt tillsattes påverkades lösligheten av syre i DMSO-baserade elektrolyter. Vilken sorts litiumsalt som användes påverkade om lösligheten av syre ökade eller minskade. Vid en saltkoncentration på en molar var den högsta syrelösligheten 68 \% större än den lägsta. Två olika modellsystem används för att studera den elektrokemiska reaktionen: En elektrokemisk kvartskristallmikrovåg och en cylindrisk ultramikroelektrod. Vid kombinerad användning av dessa system påvisades att löslig litiumsuperoxid bildades vid urladdningen. Följden av detta blev att endast delar av urladdningsprodukten hamnade på elektroden. Vid urladdning visade ultramikroelektroderna tecken på passivering som inte kunde beskrivas av tidigare teori. Här föreslås att passiveringen uppstår på grund av en blockering av de aktiva säten där reaktionen fortskrider. För denna process föreslås även en detaljerad mekanism. Urladdningsprocessens koncentrationsberoende utvärderades genom att bestämma reaktionsordningen för syre och litium under kinetisk- och masstransport kontroll. Under kinetisk kontroll fanns inga heltalsreaktionsordningar, för syre var reaktionsordningen nära 0.5 vilket föreslår att det reaktionssteg som bestämmer strömstorleken innefattar en adsorption av syre. Vid högre överpotentialer, då systemet var under masstransportkontroll, var reaktionsordningarna för litium och syre noll respektive ett. Detta föreslår att ändringar i syrekoncentration påverkar strömmen betydligt mer än vad det gör för litium. Under uppladdning kunde inte all reaktionsprodukt avlägsnas från elektroden. Detta ledde till en ackumulation då flera cykler studerades. Uppladdningens delsteg innefattade en delitiering följt av en oxidation av reaktionsproduktbulken. Denna process uppvisade även ett syrekoncentrationsberoende. / <p>QC 20171114</p>

The purpose of this diploma thesis is to describe the impact of compaction pressure on the electrochemical parameters of lithium-sulfur batteries. Theoretical part of this thesis contains briefly described terminology and general issues of batteries and their division. Every kind of battery is provided with a closer description of a specific battery type. A separate chapter is dedicated to lithium cells, mainly lithium-ion batteries. Considering various composition of lithium-ion batteries, this chapter deeply analyzes mostly used active materials of electrodes, used electrolytes and separators. Considering that the electrochemical principle of Li-S and Li-O batteries is different to Li-ion batteries, these accumulators of new generation are included in individual subhead. In the experimental part of this thesis are described methods used to measure electrochemical parameters of Li-S batteries. Next chapter contains description of preparing individual electrodes and their composition. Rest of the experimental part of my thesis is dedicated to the description of individual experiments and achieved results.