En raison de l'augmentation de la demande d'énergie, ressources écologiques respectueux de l'environnement et durables (solaires, éoliennes) doivent être développées afin de remplacer les combustibles fossiles. Ces sources d'énergie sont discontinues, étant corrélés avec les conditions météorologiques et leur disponibilité est fluctuant dans le temps. En conséquence, les dispositifs de stockage d'énergie à grande échelle sont devenus incontournables, pour stocker l'énergie sur des échelles de temps longues avec une bonne compatibilité environnementale. La conversion d'énergie électrochimique est le mécanisme clé pour les développements technologiques des sources d'énergie alternatives. Parmi ces systèmes, les batteries Lithium-ion (LIB) ont démontré être les plus robustes et efficaces et sont devenus la technologie courante pour les systèmes de stockage d'énergie de haute performance. Ils sont largement utilisés comme sources d'énergie primaire pour des applications populaires (ordinateurs portables, téléphones cellulaires, et autres). La LIB typique est constitué de deux électrodes, séparés par un électrolyte. Celui-ci joue un rôle très important dans le transfert des ions entre les électrodes fournissant la courante électrique. Ce travail de thèse porte sur les matériaux complexes utilisés comme électrolytes dans les LIB, qui ont un impact sur les propriétés de transport du ion Li et les performances électrochimiques. Habituellement l'électrolyte est constitué de sels de Li et de mélanges de solvants organiques, tels que les carbonates cycliques ou linéaires. Il est donc indispensable de clarifier les propriétés structurelles les plus importantes, et leurs implications sur le transport des ions Li+ dans des solvants purs et mixtes. Nous avons effectué une étude théorique basée sur la théorie du fonctionnelle densité (DFT) et la dynamique moléculaire (MD), et nous avons consideré des carbonates cyclique (carbonate d'éthylène, EC, et carbonate de propylène, PC) et le carbonate de diméthyle, DMC, linéaire. Les calculs DFT ont fourni une image détaillée des structures optimisées de molécules de carbonate et le ion Li+, y compris les groupes pures Li+(S)n (S =EC,PC,DMC et n=1-5), groupes mixtes binaires, Li+(S1)m(S2)n (S1,S2=EC,PC,DMC, m+n=4), et ternaires Li+(EC)l(DMC)m(PC)n (l+m+n=4). L'effet de l'anion PF6 a également été étudié. Nous avons aussi étudié la structure de la couche de coordination autour du Li+, dans tous les cas. Nos résultats montrent que les complexes Li+(EC)4, Li+(DMC)4 et Li+(PC)3 sont les plus stables, selon les valeurs de l'énergie libre de Gibbs, en accord avec les études précédentes. Les énergies libres de réactions calculés pour les mélanges binaires suggèrent que l'ajout de molécules EC et PC aux clusters Li+ -DMC sont plus favorables que l'addition de DMC aux amas Li+-EC et Li+-PC. Dans la plupart des cas, la substitution de solvant aux mélanges binaires sont défavorables. Dans le cas de mélanges ternaires, la molécule DMC ne peut pas remplacer EC et PC, tandis que PC peut facilement remplacer EC et DMC. Notre étude montre que PC tend à substituer EC dans la couche de solvation. Nous avons complété nos études ab-initio par des simulations MD d'une ion Li immergé dans les solvants purs et dans des mélanges de solvants d'intérêt pour les batteries, EC:DMC(1: 1) et EC:DMC:PC(1:1:3). MD est un outil très puissant et nous a permis de clarifier la pertinence des structures découvertes par DFT lorsque le ion est entouré par des solvants mélangés. En effet,la DFT fournit des informations sur les structures les plus stables de groupes isolés, mais aucune information sur leur stabilité ou de la multiplicité (entropie) lorsqu'il est immergé dans un environnement solvant infinie. Les données MD, ainsi que les calculs DFT nous ont permis de donner une image très complète de la structure locale de mélanges de solvants autour le ion lithium, sensiblement amélioré par rapport aux travaux précédents. / Due to the increasing global energy demand, eco-friendly and sustainable green resources including solar, or wind energies must be developed, in order to replace fossil fuels. These sources of energy are unfortunately discontinuous, being correlated with weather conditions and their availability is therefore strongly fluctuating in time. As a consequence, large-scale energy storage devices have become fundamental, to store energy on long time scales with a good environmental compatibility. Electrochemical energy conversion is the key mechanism for alternative power sources technological developments. Among these systems, Lithium-ion (Li+) batteries (LIBs) have demonstrated to be the most robust and efficient, and have become the prevalent technology for high-performance energy storage systems. These are widely used as the main energy source for popular applications, including laptops, cell phones and other electronic devices. The typical LIB consists of two (negative and positive) electrodes, separated by an electrolyte. This plays a very important role, transferring ions between the electrodes, therefore providing the electrical current. This thesis work focuses on the complex materials used as electrolytes in LIBs, which impact Li-ion transport properties, power densities and electrochemical performances. Usually, the electrolyte consists of Li-salts and mixtures of organic solvents, such as cyclic or linear carbonates. It is therefore indispensable to shed light on the most important structural (coordination) properties, and their implications on transport behaviour of Li+ ion in pure and mixed solvent compositions. We have performed a theoretical investigation based on combined density Functional Theory (DFT) calculations and Molecular Dynamics (MD) simulations, and have focused on three carbonates, cyclic ethylene carbonate (EC) and propylene carbonate (PC), and linear dimethyl carbonate (DMC). DFT calculations have provided a detailed picture for the optimized structures of isolated carbonate molecules and Li+ ion, including pure clusters Li+(S)n (S=EC, PC, DMC and n=1-5), mixed binary clusters, Li+(S1)m(S2)n (S1, S2 =EC, PC, DMC, with m+n=4), and ternary clusters Li+(EC)l(DMC)m(PC)n with l+m+n=4. Pure solvent clusters were also studied including the effect of PF6- anion. We have investigated in details the structure of the coordination shell around Li+ for all cases. Our results show that clusters such as Li+(EC)4, Li+(DMC)4 and Li+(PC)3 are the most stable, according to Gibbs free energy values, in agreement with previous experimental and theoretical studies. The calculated Gibbs free energies of reactions in binary mixtures suggest that the addition of EC and PC molecules to the Li+-DMC clusters are more favourable than the addition of DMC to Li+-EC and Li+-PC clusters. In most of the cases, the substitution of solvent to binary mixtures are unfavourable. In the case of ternary mixtures, the DMC molecule cannot replace EC and PC, while PC can easily substitute both EC and DMC molecules. Our study shows that PC tends to substitute EC in the solvation shell. We have complemented our ab-initio studies by MD simulations of a Li-ion when immersed in the pure solvents and in particular solvents mixtures of interest for batteries applications, e.g. , EC:DMC (1:1) and EC:DMC:PC(1:1:3). MD is a very powerful tool and has allowed us to clarify the relevance of the cluster structures discovered by DFT when the ion is surrounded by bulk solvents. Indeed, DFT provides information about the most stable structures of isolated clusters but no information about their stability or multiplicity (entropy) when immersed in an infinite solvent environment. The MD data, together the DFT calculations have allowed us to give a very comprehensive picture of the local structure of solvent mixtures around Lithium ion, which substantially improve over previous work.

Doctor of Philosophy / Department of Mechanical and Nuclear Engineering / Gurpreet Singh / The inevitable depletion of fossil fuels and related environmental issues has led to exploration of alternative energy sources and storage technologies. Among various energy storage technologies, rechargeable metal-ion batteries (MIB) are at the forefront. One dominant factor affecting the performance of MIB is the choice of electrode material. This thesis reports synthesis of paper like electrodes composed for three representative layered materials (van der Waals sheets) namely reduced graphene oxide (rGO), molybdenum disulfide (MoS₂) and hexagonal boron nitride (BN) and their use as a flexible negative electrode for Li and Na-ion batteries. Additionally, layered or sandwiched structures of vdW sheets with precursor-derived ceramics (PDCs) were explored as high C-rate electrode materials. Electrochemical performance of rGO paper electrodes depended upon its reduction temperature, with maximum Li charge capacity of 325 mAh.g⁻¹ observed for specimen annealed at 900°C. However, a sharp decline in Na charge capacity was noted for rGO annealed above 500 °C. More importantly, annealing of GO in NH₃ at 500 °C showed negligible cyclability for Na-ions while there was improvement in electrode's Li-ion cycling performance. This is due to increased level of ordering in graphene sheets and decreased interlayer spacing with increasing annealing temperatures in Ar or reduction at moderate temperatures in NH₃. Further enhancement in rGO electrodes was achieved by interfacing exfoliated MoS₂ with rGO in 8:2 wt. ratios. Such papers showed good Na cycling ability with charge capacity of approx. 225.mAh.g⁻¹ and coulombic efficiency reaching 99%. Composite paper electrode of rGO and silicon oxycarbide SiOC (a type of PDC) was tested as high power-high energy anode material. Owing to this unique structure, the SiOC/rGO composite electrode exhibited stable Li-ion charge capacity of 543.mAh.g⁻¹ at 2400 mA.g⁻¹ with nearly 100% average cycling efficiency. Further, mechanical characterization of composite papers revealed difference in fracture mechanism between rGO and 60SiOC composite freestanding paper. This work demonstrates the first high power density silicon based PDC/rGO composite with high cyclic stability. Composite paper electrodes of exfoliated MoS₂ sheets and silicon carbonitride (another type of PDC material) were prepared by chemical interfacing of MoS₂ with polysilazane followed by pyrolysis . Microscopic and spectroscopic techniques confirmed ceramization of polymer to ceramic phase on surfaces on MoS₂. The electrode showed classical three-phase behavior characteristics of a conversion reaction. Excellent C-rate performance and Li capacity of 530 mAh.g⁻¹ which is approximately 3 times higher than bulk MoS₂ was observed. Composite papers of BN sheets with SiCN (SiCN/BN) showed improved electrical conductivity, high-temperature oxidation resistance (at 1000 °C), and high electrochemical activity (~517 mAh g⁻¹ at 100 mA g⁻¹) toward Li-ions generally not observed in SiCN or B-doped SiCN. Chemical characterization of the composite suggests increased free-carbon content in the SiCN phase, which may have exceeded the percolation limit, leading to the improved conductivity and Li-reversible capacity. The novel approach to synthesis of van der Waals sheets and its PDC composites along with battery cyclic performance testing offers a starting point to further explore the cyclic performance of other van der Waals sheets functionalized with various other PDC chemistries.

Thesis (MTech (Chemistry))--Cape Peninsula University of Technology, 2017. / Certain resins used in ion-exchange separation techniques have become very expensive. Although ion-exchange is an economical method to soften water it is important to keep the cost low during the process. Any exorbitant costs will make a process unattractive and eventually obsolete. Bio-Rad AG MP-50 macroporous resin (supplied by Bio-Rad Laboratories, Ltd.) at present costs approximately R20000 (twenty thousand rand) for 500 g compared to Amberlyst 15 R840.00 for 500 mL and Dowex Marathon MSC R312.34 macroporous resin for 500 mL (both supplied by Dow, Rohm and Haas Co). This motivated the research to determine by a comparative study if there is any difference in the efficiency and effectiveness in the quantitative analysis of trace elements when these resins are used. The following elements will be used to determine distribution coefficients for the elements on these resins: Mn, Fe(III), Co, Ni, Cu, Zn, Al, Ag, Cd, In, Ga, Tl, Pb and Bi in 0.1, 0.2, 0.5, 1.0, 2.0, 3.0, 4.0 M nitric acid solutions. Another question is whether there is a difference or a preference when selecting either a microporous or a macroporous resin for the ion-exchange separation. Determination of distribution coefficients for 46 elements had been done by Strelow (Strelow F. W., 1984) in nitric acid on Bio-Rad AG 50W-X8. The results obtained in this study will be compared with the distribution coefficients obtained by Strelow. The Bio-Rad, Amberlyst and Dowex resins were stirred for approximately 30 minutes in deionised water and then packed in a column. Impurities in the resin column were eluted with 5 M HCl and the resin was then rinsed with deionised water to remove the acid. Thereafter the resins was rinsed out of the column with deionised water, filtered off and then dried under vacuum in an oven at 60 0C for approximately 24 hours. Stock solutions of the elements were prepared as 0.1 M solutions and then diluted with deionised water to obtain solutions having the respective concentrations of 0.1, 0.2, 0.5, 1.0, 2.0, 3.0, and 4.0 M. Quadruplicate reference standards of each element were prepared. Distribution coefficients of the elements on each resin were determined as described by Strelow (Strelow F. W., Distribution coefficients and ion exchange behaviour of some chloride complex forming elements with Bio Rad AG50W - X8 cation exchange resin in mixed Nitric-Hydrochloric acid solutions, 1989). From the distribution coefficients, obtained from the ICP-OES data, a selectivity series for the 14 elements, mentioned above, was arranged in the decreasing order for each resin’s affinity for the elements. The distribution coefficients also give an indication whether the elements can be quantitatively separated by the cation exchangers in nitric acid media. Elution curves for some elements were done to establish the experimental conditions for quantitative separations of the elements by column cation exchange chromatography.

M.Sc. (Chemistry) / Please refer to full text to view abstract

Magister Scientiae - MSc / Beams of polarized protons play an important part in the study of the spin dependence of the nuclear force by measuring the analyzing power in nuclear reactions. The source at iThemba LABS produces a beam of polarized protons that is pre-accelerated by an injector cyclotron (SPC2) to a energy of 8 MeV before acceleration by the main separated-sector cyclotron to 200 MeV for physics research. The polarized ion source is one of the two external ion sources of SPC2. Inside the ion source hydrogen molecules are dissociated into atoms in the dissociator and cooled to a temperature of approximately 30 K in the nozzle. The atoms are polarized by a pair of sextupole magnets and the nucleus is polarized by RF transitions between hyperfine levels in hydrogen atoms. The atoms are then ionized by electrons in the ionizer. The source has various sensitive devices, which influence beam intensity and polarization. Nitrogen gas is used to prevent recombination of atoms after dissociation. The amount of nitrogen and the temperature at which it is used plays a very important role in optimizing the beam current. The number of electrons released in the ionizer is influenced by the size and shape of the filament. Optimization of the source will ensure that beams of better quality (a better current and stability) are produced. / South Africa

The potentiometric method is one of the most exact techniques of electrochemistry. Its use is widespread in both routine measurements, such as pH determination, and in applications which demand the highest accuracy. Perhaps its severest limitation is the error due to liquid junction potentials. Although this has been the subject of much study, and although various means of combating it have been proposed, it has defied all attempts at a satisfactory solution. Indeed, so serious is the position that it has become the accepted practice in the more accurate fields to abandon altogether the use of potentiometric techniques in favour of others, usually less convenient and otherwise less accurate, when the presence of liquid junctions cannot be avoided. Intro. p. 1.

AParmi les différentes sources d’énergie, les microaccumulateurs tout solide au lithium sont de bons candidats pour l’alimentation de systèmes miniaturisés. Afin d’outrepasser les limitations actuelles de ces microsources, les films minces de germanium sont prometteurs comme matériau d’électrode négative de par leurs meilleures stabilités chimique et thermique, comparées à celles du lithium métal. Ce travail de thèse a consisté à développer et à optimiser le procédé de synthèse par pulvérisation cathodique magnétron d’électrodes de germanium en couches minces, dont les propriétés physiques ont été mises en relation avec les performances électrochimiques. L’analyse du comportement électrochimique en régime et sur la tenue en cyclage a mis en évidence l’influence de la morphologie et du dopage des films de germanium. Malgré d’importantes variations volumiques de l’électrode, une étude a permis de montrer la faisabilité d’une intégration de ces couches minces dans des microaccumulateurs tout solide Ge pré-lithié/ LiPON/ Li par des procédés basse température (compatibles Above IC). Avec ce type d’empilement, une capacité spécifique élevée de 50 µAh/cm² (» 800 µAh/cm².µm) a été maintenue sur une quarantaine de cycles sous 10 µA/cm². Diverses propositions ont été envisagées afin d’accroître la cyclabilité de ces dispositifs et de permettre la réalisation de microaccumulateurs Li-ion pour des applications en microélectronique. / Among the different energy sources, all solid state lithium microbatteries are the most promising candidates for the alimentation of miniaturised systems. In the aim of overcoming the current limitations of these micro power sources, germanium thin films prove to be a promising material as a negative electrode, due to their better chemical and thermal stability in comparison with metallic lithium. This PhD work was devoted to the development of germanium electrode coatings and the optimisation of their synthesis by magnetron sputtering. Their physical properties have been correlated to their electrochemical performances. The influence of the morphology and doping of the films on their electrochemical behaviour at different current densities and on the cyclability was established. Despite huge volumic variations of the electrode, this study showed the feasibility of integrating these films in Ge lithiated/ LiPON /Li microbatteries deposited by low temperature processes (Above IC compatibility). With this stack configuration, a stable specific capacity of 50 µAh/cm² (» 800 µAh/cm².µm) has been maintained during forty cycles. Different solutions have been suggested to improve the cyclability of all solid state microbatteries and the techniques used for directly depositing them on the electronic microcomponents.

Orientadores: Lauro Tatsuo Kubota, Graciliano de Oliveira Neto / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-08T00:59:06Z (GMT). No. of bitstreams: 1 Ribeiro_PauloJoseFernandes_M.pdf: 3526765 bytes, checksum: d7527897c70e194a6207d1020f2ce8bc (MD5) Previous issue date: 2006 / Resumo: Nesse trabalho é apresentado o desenvolvimento de um eletrodo íon-seletivo para determinação de ibuprofeno, utilizando-se membrana do copolímero poli(etileno co-acetato de vinila) (EVA), tentando minimizar o uso de plastificantes. A membrana foi preparada diretamente sobre um suporte condutor constituído de uma mistura de resina epóxi, endurecedor e grafite. Na preparação da membrana foram estudadas diversas proporções de seus componentes, como concentração de par-iônico, influência do plastificante e quantidades de matriz polimérica. As melhores respostas foram obtidas com uma membrana composta de 115 mg do par-iônico aliquat-ibuprofeno, 170 mg de EVA e 150 mg do plastificante o-NPOE (orto-nitrofeniloctil-éter), não sendo possível eliminar o plastificante. Com o objetivo de otimizar as condições analíticas, foram feitos estudos da influência do pH, da natureza e concentração do tampão e de interferentes, além do tempo de reposta e de vida do eletrodo. As melhores respostas em estado estacionário foram obtidas em tampão Fosfato com concentração de 0,5 mol L a pH 7.0. Nestas condições foi verificado um bom desempenho do eletrodo na faixa de concentração de 2,93 10 a 10mol L, com limite de detecção de 8,7 10 mol L, sensibilidade de 127 mV década, tempo médio de resposta de 56 s e capacidade para aproximadamente 100 determinações. O eletrodo foi aplicado para determinação de ibuprofeno em amostras de medicamento obtendo bons resultados, sendo estes estatisticamente igual aos obtidos com o método de referência a um nível de 95% de confiança. / Abstract: In this work is presented the development of an ion-selective electrode for ibuprofen determination, using the poly(ethylene-co-vinyl-acetate) copolymer (EVA) membrane, trying to minimize the use of plasticizer. The membrane was prepared directly on a conducting support consisting of an epóxi resin, hardener and graphite mixture. In the preparation of the membrane several ratios of its components were investigated, such as concentration of ion-pair, influence of the plasticizer and polymeric matrix. The best performance was reached with a membrane composed with 115 mg of the ibuprofen-aliquat ion-pair, 170 mg of EVA and 150 mg of the o-NPOE (orto-nitrophenyloctyl-ether), being impossible to eliminate the plasticizer. Studies of the influence of pH, nature and concentration of the buffer and the interfering were carried out looking for the optimized conditions for the electrode performance like sensitivity, fast response and lifetime. The best response was obtained with Phosphate buffer in a concentration of 0,5 mol L at pH 7.0. In these conditions the electrode showed a good performance in the concentration range between 2,93 10 and 10 mol L, with a sensitivity of 127 mV/decade, a detection limit of 8,7 10 mol L, response time of 56 s and capacity for 100 determinations. The electrode was employed to determine ibuprofen in medicine samples obtaining good results, being statistically equal at 95% confidence level, when compared with the results obtained with the reference method for the same samples. / Mestrado / Quimica Analitica / Mestre em Química

The problem with which this research is concerned is the determination of inorganic anions and cations with single injection ion chromatography. Direct detection of the separated analyte ions occurs after the analyte ions have passed through ion-exchange resins where they are separated according to their affinity for the ion-exchange resin active sites. The techniques involve the use of essentially a non-suppressed ion chromatographic system followed by a suppressed ion chromatographic system. With this system it is possible to accomplish both qualitative and quantitative determinations.

Accelerator Mass Spectrometry (AMS) is a sensitive technique for the analysis of rare isotopes. Optimizing the output of the cesium-sputter ion source is a fundamental method for improving measurement precision, efficiency, and reliability. Several strategies for improving the ion source are discussed and lead to an understanding of the electrodynamics within the ion source to inform further improvement in design and operating parameters. At the Andr´e E. Lalonde Accelerator Mass Spectrometry Laboratory (Lalonde AMS), the High Voltage Engineering Europa (HVEE) SO-110C ion source was modelled using Integrated Engineering Software (IES)’s Lorentz-2E ion trajectory simulation software. Lorentz-2E incorporates the mutual space-charge interaction between the positively charged cesium ion beam and the sputtered negative ion beam. A critical component of this work was the development of the Rijke code. Rijke communicates with Lorentz-2E to initiate, generate, and run varied sequences of simulations, as well as analyze and record the input and output data in formats convenient for timely analysis. This software and its interconnection with Lorentz- 2E is described in extensive detail for a prospective user. Initial simulation work examined the effects of modifying various electrode geometries within the source such as the extraction cone, the target aperture, a simple cratered sample model as well as examining the effects of varying the cesium ion current. The self-repulsion of cesium was found to be important at currents of 250 µA and above. At high enough cesium currents, the expansion of the cesium beam is such that parts of it impinge outside the extents of the sample material. Through both simulation and experiment, it was demonstrated that this effect can be mitigated by either recessing (translating along the axis of symmetry away from the ionizer) the target holding the sample or by adjusting the potential difference between the target and ionizer. Experimentally, at routine settings (6 kV target to ionizer potential, 115 ◦C cesium oven temperature, and 35 keV output energy), a target recess of 1 mm gave the most stable and sustained output of 12C from graphite blanks. While the peak current was less than the unrecessed case, the total measured charge from the recessed target was higher. Cesium currents at these routine settings were found to be below the theoretical space-charge limited maximum. Using 10Be standards, a multi-dimensional experimental study examined the effects of increasing the cesium current, adjusting the target-ionizer potential from 4 to 11 kV, while also examining target recesses of 0 to 4 mm. Multiple combinations of these settings produced enhanced currents of 9Be2+, measured at the high-energy offset Faraday cup, as high as 13.5 µA. This was higher than previously observed, resulting in the most precise measurement of 10Be performed to date at Lalonde AMS. The electrodynamics within the ion source can be characterized as three competing processes: a) a strong locus of positive space charge located at the centre of the sample, depending primarily on the focusing of the cesium beam, which draws negative ions across the axis of symmetry; b) a bulk positive space charge external to the negative ion beam, depending primarily on the magnitude of the cesium current, draws the outer-most negative ions away from the axis; and c) the raw field from the electrode potentials and geometry which is mainly defocusing for negative ions. These effects are mitigated the most when the cesium beam is distributed across the entire sample surface with the additional critical benefit of maximizing the sample material accessed for sputtering. This thesis work has demonstrated that both the mutual and self space-charge interaction of the cesium and negative ion beams were critically important and that the use of the simulation software can inform both improved design and operation settings of the ion source.