Undesired reactions in Li-ion batteries, which lead to capacity loss, can consume or produce charge at either the positive or negative electrode. For example, the formation and repair of the solid electrolyte interphase consumes Li+ and e- at the negative electrode. Electrolyte oxidation at the positive electrode allows extra electrons (with corresponding electrolyte decomposition products) to be extracted at the electrode compared to the number which could be extracted in the absence of electrolyte oxidation. High purity electrolytes, various electrolyte additives, electrode coatings and special electrode materials are known to improve cycle life and therefore must impact coulombic efficiency. Careful measurements of coulombic efficiency are needed to quantify the impact of different battery materials on cell life time in only a few charge-discharge cycles and in a relatively short time. In order to make an impact on Li-ion cells for automotive and energy storage applications, where thousands of charge-discharge cycles are required, coulombic efficiency must be measured to an accuracy and precision of at least 0.01%. An instrument designed to make high-precision coulombic efficiency measurements on Li ion batteries is described in this thesis. Such measurements can be used to detect the influence of different electrode materials, voltage ranges, cell temperature, etc. on the performance of a cell. The effects of cycle induced and time-related capacity loss can be probed using experiments carried out at different C-rates. Precision differential voltage and capacity measurements can also be used to identify the different failure mechanisms that occur in full cells.

Polymer electrolytes are indispensable in numerous electrochemical systems. Existing polymer electrolytes rarely meet all technical demands by their applications (e.g., high ionic conductivity and good mechanical strength), and new types of polymer electrolytes continue to be developed. In this dissertation, the molecular structure and dynamics of three emerging types of polymer electrolytes featuring Coulombic liquids, i.e., polymerized ionic liquids (polyILs), nanoscale ionic materials (NIMs), and polymeric ion gels, were investigated using molecular dynamics (MD) simulations to help guide their rational design. First, the molecular structure and dynamics of a prototypical polyILs, i.e., poly(1-butyl-3-vinylimidazolium hexafluorophosphate), supported on neutral and charged quartz substrates were investigated. It was found that the structure of the interfacial polyILs is affected by the surface charge on the substrate and deviates greatly from that in bulk. The mobile anions at the polyIL-substrate interfaces diffuse mainly by intra-chain hopping, similar to that in bulk polyILs. However, the diffusion rate of the interfacial mobile anions is much slower than that in bulk due to the slower decay of their association with neighboring polymerized cations. Second, the structure and dynamics of polymeric canopies in the modeling NIMs where the canopy thickness is much smaller than their host nanoparticle were studied. Without added electrolyte ions, the polymeric canopies are strongly adsorbed on the solid substrate but maintain modest in-plane mobility. When electrolyte ion pairs are added, the added counter-ions exchange with the polymeric canopies adsorbed on the charged substrate. However, the number of the adsorbed electrolyte counter-ions exceeds the number of desorbed polymeric canopies, which leads to an overscreening of the substrate's charge. The desorbed polymers can rapidly exchange with the polymers grafted electrostatically on the substrate. Finally, the molecular structure and dynamics of an ion gel consisting of PBDT polyanions and room-temperature ionic liquids (RTIL) were studied. First, a semi-coarse-grained model was developed to investigate the packing and dynamics of the ions in this ion gel. Ions in the interstitial space between polyanions exhibit distinct ordering, which suggests the formation of a long-range electrostatic network in the ion gel. The dynamics of ions slow down compared to that in bulk due to the association of the counter-ions with the polyanions' sulfonate groups. Next, the RTIL-mediated interactions between charged nanorods were studied. It was discovered that effective rod-rod interaction energy oscillates with rod-rod spacing due to the interference between the space charge near each rod as the two rods approach each other. To separate two rods initially positioned at the principal free energy minimum, a significant energy barrier (~several kBT per nanometer of the nanorod) must be overcome, which helps explain the large mechanical modulus of the PBDT ion gel reported experimentally. / Ph. D. / Polymer electrolytes are an indispensable component in numerous electrochemical devices. However, despite decades of research and development, few existing polymer electrolytes can offer the electrochemical, transport, mechanical, and thermal properties demanded by practical devices and new polymer electrolytes are continuously being developed to address this issue. In this dissertation, the molecular structure and dynamics of three emerging novel polymer electrolytes, i.e., polymerized ionic liquids (polyILs), nanoscale ionic materials (NIMs), and polymeric ion gels, are investigated to understand how their transport and mechanical properties are affected by their molecular design. The study of polyILs focused on the interfacial behavior of a prototypical polyILs supported on neutral and charged quartz substrates. It was shown that the structure and diffusion mechanism of the interfacial polyILs are sensitive to the surface charges of the substrate and can deviate strongly from that in bulk polyILs. The study of NIMs focused on how the transport properties of the dynamically grafted polymers are affected by electrolyte ion pairs. It was discovered that the contaminated ions can affect the conformation the polymeric canopies and the exchange between the “free” and “grafted” polymers. The study of polymeric ion gels focused on the molecular and mesoscopic structure of the ionic liquids in the gel and the mechanisms of ion transport in these gels. It was discovered that the ions exhibit distinct structure at the intermolecular and the interrod scales, suggesting the formation of extensive electrostatic networks in the gel. The dynamics of ions captured in simulations is qualitatively consistent with experimental observations.

This dissertation describes two independent studies related to charged aerosols. The first study examines the role of electrical conductivity on the amounts of charge and mass emitted during the break-up of charged droplets via Coulombic fission. The second study examines the hygroscopic behavior of mixed particles. The results from both studies are presented here in detail along with an in-depth discussion of pertinent literature and applications in modern technologies. Charged droplets break-up via a process termed Coulombic fission when their charge density reaches a certain level during which they emit a portion of their charge and mass in the form of progeny microdroplets. Although Rayleigh theory can be used to predict the charge level at which break-ups occur, no equivocal theory exists to predict the amounts of charge or mass emitted or the characteristics of the progenies. Previous investigations have indicated that the electrical conductivity of a charged droplet may determine how much charge and mass are emitted during its break-up via Coulombic fission. To further examine this supposition, charged droplets having known electrical conductivities were observed through multiple break-ups while individually levitated in an electrodynamic balance. The amounts of charge and mass emitted during break-ups were determined using a light scattering technique and changes in the DC null point levitation potentials of the charged droplets. Here, electrical conductivity was found to increase and decrease the amounts of charge and mass emitted, respectively, while having no effect on the charge level at which break-ups occurred. The findings of this investigation have significant bearing in nanoparticle generation and electrospray applications. The hygroscopic behavior of atmospherically relevant inorganic salts is essential to the chemical and radiative processes that occur in Earth’s atmosphere. Furthermore, studies have shown that an immense variety of chemical species exist in the atmosphere which inherently mix to form complex heterogeneous particles with differing morphologies. However, how such materials and particle morphologies affect the hygroscopic behavior of atmospherically relevant inorganic salts remains mostly unknown. Therefore, the effects of water insoluble materials, such as black carbon, on the hygroscopic behavior of inorganic salts were examined. Here, water insoluble solids were found to increase the crystallization relative humidities of atmospherically relevant inorganic salts when internally mixed. Water insoluble liquids however, were found to have no effect on the hygroscopic behavior of atmospherically relevant inorganic salts. The findings of this investigation have significant bearing in atmospheric modeling.

Dust capture for small coal particles (<2.5µm) can be improved if one takes advantage of electrostatic charges that resides on the surface of coal dust particles and on the surface of water spray droplets used to capture coal dust. Traditional dust capture methods that use water sprays are ineffective in capturing small dust particles since the motion of small dust particles is governed by electrostatic forces. If additives such as ionic surfactants could be added to water that would enhance the surface charge on water spray droplets, dust capture with water sprays could be improved. The results presented show that n-sodium octyl sulfate causes the greatest charge enhancement versus the longer chained n-sodium dodecyl sulfate and n-sodium octadecyl sulfate. This can be explained by considering the factors that lead to droplet charge enhancement. Those factors are the mass of surfactant ions at the droplet surface, and the diffusion rate of the surfactant ions from the bulk droplet to the surface of the droplet. Sodium octyl sulfate will have a faster diffusion rate to the droplet surface because of its relatively short length, and will also maximize the mass balance of surfactant ions at the drop surface.

Present day water spray based dust removal technologies do not effectively remove respirable submicron coal and silica dust particles in the underground coal mines causing Coal worker’s pneumoconiosis (CWP). The objective of this research was to study the electrostatic charges present in the airborne coal dust in order to develop efficient water spraying based dust removal technology where water drops charged using ionic compounds and surfactants would be used to capture the oppositely charged coal particles. In an experimental scrubbing column, coal particles dispersed in an air stream by a Fluidized Bed Aerosol Generator were captured by water drops sprayed by an atomizer. Characterization studies performed using an Aerodynamic Particle Sizer and Aerosol Electrometer showed that airborne coal particles have a significant amount of positive charge with an average of 140 elementary units of charge. The capture efficiencies of the water drops evaluated were found to be higher than those predicted by previously determined mathematical models. It was predicted that apart from the effects of Brownian diffusion, interception and impaction, the effect of Coulombic attraction was present and the charge of the water drops was predicted to be between - 2 x 10-6 C and -2 x 10-4 C.

Submitted by Lucienne Costa (lucienneferreira@ufcg.edu.br) on 2018-05-11T22:51:17Z No. of bitstreams: 1 JOSÉ ETIMÓGENES DUARTE SEGUNDO – TESE (PPGEQ) 2017.pdf: 3042948 bytes, checksum: e0c377da642dbbf1ba0a1022f463d9de (MD5) / Made available in DSpace on 2018-05-11T22:51:17Z (GMT). No. of bitstreams: 1 JOSÉ ETIMÓGENES DUARTE SEGUNDO – TESE (PPGEQ) 2017.pdf: 3042948 bytes, checksum: e0c377da642dbbf1ba0a1022f463d9de (MD5) Previous issue date: 2018-08-31 / Para satisfazer aplicações industriais e o crescente consumo de combustíveis fósseis, têm-se realizado várias pesquisas sobre o desenvolvimento de materiais e tecnologias para o armazenamento de energia de forma sustentável e renovável. O grafeno é um material que despertou interesse de estudos recentes devido às suas excelentes propriedades físico-químicas, mecânicas, térmicas, elétricas e ópticas. Em uma bateria de íons de lítio, o grafeno supera as limitações de capacidade do grafite, comumente usado como material anódico. Neste trabalho, estudou-se o uso de monocamada de grafeno como ânodo em uma bateria de íons de lítio para verificar a influência da densidade de corrente e da composição do eletrólito no desempenho eletroquímico do material. A densidade de corrente foi aplicada em três níveis diferentes: 3, 5 e 10 μA/cm2. O eletrólito testado foi LiPF6 1M em etilenocarbonato/dietilcarbonato (50/50v) (EC-DEC), etilmetilcarbonato (EMC) ou propilenocarbonato (PC). As análises de microscopia de força atômica e Raman exibiram uma monocamada de grafeno uniforme sobre a superfície do substrato. Os espectros de impedância eletroquímica da célula descarregada foram analisados para investigar a cinética do processo de eletrodo nos diferentes eletrólitos. Os resultados mostraram um processo controlado pela transferência de carga, mas com grande contribuição da difusão de íons de lítio. Na caracterização eletroquímica, os melhores resultados foram obtidos para o eletrólito EC-DEC. A capacidade irreversível no 1º ciclo variou de 11,39 a 77,47%, em função da densidade de corrente aplicada, e maior capacidade de descarga foi de 21 575 mAh/g, para 3 μA/cm2. Com a aplicação dessa mesma densidade de corrente, a eficiência coulômbica média foi de 67,12% e a capacidade de descarga sofreu redução de 87,90%, ao longo de 20 ciclos. Os resultados obtidos confirmaram o grande potencial do grafeno para aplicação em sistemas de armazenamento de energia. / To satisfy industrial applications and the growing consumption of fossil fuels, researches have been performed on the development of materials and technologies for energy storage in a renewable and sustainable way. Graphene is a material that has interested recent studies due to its excellent physical-chemical, mechanical, thermal, electrical and optical properties. In a lithium-ion battery, graphene overcomes the capacity limitations of graphite, commonly used as anode material. In this work, monolayer graphene using as anode was studied in a lithium-ion battery to verify the influence of current density and electrolyte composition on the electrochemical performance of electrode material. Current density was applied in three different levels: 3, 5 and 10 μA/cm2. The electrolyte tested was LiPF6 1M in ethylene carbonate/diethyl carbonate (50/50v) (EC-DEC), ethyl methyl carbonate (EMC) or propylene carbonate (PC). AFM and Raman microscopy analysis exhibited a uniform monolayer graphene over substrate surface. The EIS spectra of discharged cell were analyzed to investigate the kinetics of electrode process in different electrolytes. Results showed a process controlled by charge transfer but with great contribution of lithium-ion diffusion in case of EC-DEC solvent. Irreversible capacity in the 1st cycle ranged from 11.39 to 77.47%, as function of applied current density, and the highest discharge capacity was 21,575 mAh/g, for 3 μA/cm2. With application of this current density value, the average coulombic efficiency was 67.12% and the discharge capacity was reduced by 87.90% over 20 cycles. Results confirmed the great potential of graphene for application in energy storage systems.

No description available.

Physics / M. Sc. (Physics)

1. There is a crisis in economics. The discipline evolved in nineteenth century Europe and is difficult to adapt to modern conditions, even in the West, and particularly in alien cultures. Application of conventional economic analysis to economic activity in a culture as alien as traditional China highlights the biases in assumptions of the paradigm. 2. The concepts, models and vocabulary evolved over one hundred years ago predate important developments in the natural sciences. It is now necessary for economists to concede no goods can ever be 'produced', and they are not 'consumed' either. In clear terms matter is transformed, but is not created or destroyed (First Law of Thermodynamics). 3. When people transform matter, in lay language we say energy is 'used'. In a simple cottage industry, 'raw material' is transformed into a commodity in front of our eyes by the use of human energy and the release of energy from a 'fuel'. In modem complex economic activity, it is difficult or impossible to keep track of the processes from raw matter to transformed 'product' although the principle is the same. 4. The Second Law of Thermodynamics states that in any transformation, energy is not created or destroyed, but becomes 'less available'. In short, entropy increases. This appears to work well for pure physics and chemistry, but its application to analysis of economic activity has only been notional. 5. There is a reason why economists borrowing terms from hard science experience difficulty. It is because physicists and chemists have addressed specific laboratory and engineering problems, but not the broader economic issues. The hypothesis gradually evolved in this research program that not only economic concepts and terms needed reworking, but those in physics as well. The definitions of energy as 'ability to do works and of entropy as 'unavailable energy' jar the logic of our commonsense. 6. The notion of 'available energy' was traced back to the phenomenon in physical chemistry known as exothermicity, or the release of energy during a chemical reaction. It was reasoned that while scientists had focussed on this phenomenon and measured it carefully they saw no need to ask where the energy came from, or to measure its transformation. From the perspective of analysing economic activity, the question was important. 7. It was hypothesised that the energy released from a fuel as electromagnetic radiation (mainly heat) was the residual of the set of coulombic forces within atoms that maintain the structure of shells of electrons around the protons. This idea in turn came from the presumption that molecular bonding is a residual of vectors of the set of coulombic forces within atoms, and the likelihood that in an exothermic reaction, after the reactants are said (by scientists) to 'seek equilibrium', product molecules have a portion of the coulombic forces 'left over' and not required to maintain their structures. An estimate was made of the coulombic forces extant in various fuels, and compared with the known data for their release of energy. 8. The idea was developed in detail. The concept we call in economics, 'production', and should call 'transformation' can only occur when forces locked within atoms are released as electromagnetic forces. (Gravitational forces exist because matter has been put 'there' by electromagnetic radiation). When 100 grams of dry grass fuel is burnt, about 2 megajoules of electromagnetic radiation are released. It was estimated that the coulombic forces between each electron and proton in that amount dry grass total 150 gigajoules (or giganewtons, since the reference is to forces). 9. Within the boundary of a simple economic activity, the ratio of aggregated coulombic forces locked up within atoms to the electromagnetic forces radiated out was estimated at the beginning of the activity, and then after a duration. The ratio of forces always tends towards 'evening out'. This measurement captures the entropy phenomenon which has been said by Georgescu-Roegen to be the basis of all economic activity. 10. At the roots of the economic paradigm founded by Adam Smith is the premise that the material world, as a set of substances, is a stage on which economic actors 'add value', bid prices up and down, and by their rational perception manage their livelihoods and surroundings well. From the findings of this research program it is contended that the surroundings of economic actors can be classed into two categories: locked up (coulombic) electromagnetic forces, and radiated electromagnetic forces. The former has a tendency to convert to the latter. All action, including all economic activity, and all life can be traced to a point in space and time where this conversion is (naturally) occurring. The phenomenon is analogous to a slope where water cascades, and gravitational potential energy converts to other (either useless or useful) forms of energy. To appreciate the nature of this phenomena, and to attempt to fathom its dimensions, sets our perceptions of ourselves as economic actors in a quite different and very humbling context.

Physics / M. Sc. (Physics)