Demands for high energy-density batteries have sharpened with the increased use of portable electronic devices, as has the focus global warming is now placing on the need for electric and electric-hybrid vehicles. Li-ion battery technology is superior to other rechargeable battery technologies in both energy- and power-density. A remaining challenge, however, is to find an alternative candidate to graphite as the commercial anode. Several metals can store more lithium than graphite, e.g., Al, Sn, Si and Sb. The main problem is the large volume changes that these metals undergo during the lithiation process, leading to degradation and pulverization of the anode with resulting limitations in cycle-life. The Li-ion battery is studied in this thesis with the goal of better understanding the critical parameters determining high and stable electrochemical performance when using a metal or a metal-alloy anode. Various antimony-containing systems will be presented. These represent different routes to circumvent the problems caused by volume change. Sb-compounds exhibit a high lithium storage capability. At most, three Li-ions can be stored per Sb atom, leading to a theoretical gravimetric capacity of 660 mAh/g. Model systems with stepwise increasing complexity have been designed to better understand the factors influencing lithium insertion/extraction. It is demonstrated that the microstructure of the anode material is crucial to stable cycling performance and high reversibility. The relative importance of the various factors controlling stability, such as particle-size, oxide content and morphology, varies strongly with the type of system studied. The cycling performance of pure Sb is improved dramatically by incorporating a second component, Sb2O3. With a critical oxide concentration of ~25%, a stable capacity close to the theoretical value of 770 mAh/g is obtained for over 50 cycles. Cu2Sb shows stable cycling performance in the absence of oxide. Cu9Sb2 has been presented for the first time as an anode material in a Li-ion battery context. Studies of the Solid Electrolyte Interphase (SEI) formed on AlSb composite electrodes show an SEI layer thinner than graphite, and with a clearly dynamic character.

The maximum theoretical energy efficiency of fuel cells is much larger than those of the steam-power-turbine cycles that are currently used for generating electrical power. Similarly, direct hydrocarbon fuel cells, DHFCs, can theoretically be much more efficient than hydrogen fuel cells. Unfortunately the current densities (overall reaction rates) of DHFCs are substantially smaller than those of hydrogen fuel cells. The problem is that the exchange current density (catalytic reaction rate) is orders of magnitude smaller for DHFCs. Other work at the University of Ottawa has been directed toward the development of polymer electrolytes for DHFCs that operate above the boiling point of water, making corrosion rates much slower so that precious metal catalysts are not required. Propane (liquefied petroleum gas, LPG) was the hydrocarbon chosen for this research partly because infrastructure for its transportation and storage in rural areas already exists. In this work nickel based catalysts, an inexpensive replacement for the platinum based catalysts used in conventional fuel cells, were examined using density functional theory, DFT. The heats of propane adsorption for 3d metals, when plotted as a function of the number of 3d electrons in the metal atom, had the shape of a volcano plot, with the value for nickel being the peak value of the volcano plot. Also the C-H bond of the central carbon atom was longer for propane adsorbed on nickel than when adsorbed on any of the other metals, suggesting that the species adsorbed on nickel was less likely to desorb than those on other metals. The selectivity of the propyl radical reaction was examined. It was found that propyl radicals

Une grande 'Chambre à Projection Temporelle' (TPC) est un candidat pour la détection et la mesure des traces chargées auprès de l'ILC, collisionneur linéaire d'électrons et de positons de 31 km permettant d'atteindre des énergies dans le centre de masse de 250 GeV à 1 TeV. Le travail de R&D décrit dans cette thèse porte sur un type nouveau de TPC, dont la lecture est assurée par des Micromégas à anode résistive. Ce dispositif permet de répartir le signal électrique sur plusieurs carreaux, même lorsque la charge est déposée sur un seul carreau. Il permet aussi de protéger l'électronique, ce qui est utilisé dans notre prototype pour miniaturiser les cartes de lecture. Dans ce travail, des modules Micromégas ont été testés et caractérisés, dans un premier temps, en faisceau, un par un au centre de la chambre, puis 7 modules montés en même temps de façon à couvrir la surface. Egalement, des tests sur un banc équipé d'une source de ⁵⁵Fe ont permis de caractériser les 7 modules utilisés. Une résolution en position de 60 microns par ligne de carreaux est obtenue à petite distance de dérive. L'uniformité est aussi évaluée, et des distorsions pouvant atteindre environ 500 microns sont observées. L'ensemble des résultats démontre l'adéquation de ce type de lecture à la TPC pour l'ILC. La fraction de retour des ions est également mesurée à l'aide d'un détecteur de même géométrie et avec le même gaz que ceux utilisés dans ces tests, et la loi en rapport inverse des champs est validée à nouveau dans ces conditions. La même technique est appliquée à la réalisation d'un imageur neutron, consistant en une TPC Micromégas 'plate' précédée d'un film convertisseur de 1mm d'épaisseur. Les protons éjectés par les neutrons sont 'suivis à la trace' dans le volume gazeux, ce qui permet de reconstruire avec une précision meilleure que le millimètre le point d'origine du neutron.

A solid oxide fuel cell (SOFC) is an energy conversion device that has the potential to efficiently generate electricity in an environmentally-friendly manner. In general, a SOFC operates between 750&deg;C and 1000&deg;C utilizing hydrogen or hydrocarbons as fuel and air as an oxidant. The three major components comprising a fuel cell are the electrolyte, the cathode, and the anode. At present, the state-of-the-art SOFC is made from a dense yttria-stabilized zirconia (YSZ) electrolyte, a porous lanthanum manganite cathode, and a porous nickel/YSZ composite anode. With the advent of the anode-supported SOFC and the increased interest in using a wider range of fuels, such as those containing sulphur, knowledge of the anode properties is becoming more important. <br /> The properties of the current anodes are limited due to the narrow range of nickel loadings imposed by the minimum nickel content for electrical conductivity and the maximum allowable nickel loading to avoid thermal mismatch with the YSZ electrolyte. In addition, there is little research presented in the literature regarding the use of nickel metal as a starting anode material, rather than the traditional nickel oxide powder, and how porosity may affect the anode properties. <br /> The purpose of this investigation is to determine the influence nickel morphology and porosity distribution have on the processing and properties of tape cast Ni/YSZ composites. Specifically, the sintering characteristics, electrical conductivity, and thermal expansion behaviour of tape cast composites created from YSZ, nickel, nickel oxide (NiO), nickel coated graphite (NiGr), and/or graphite (Gr) powders are investigated. In addition to samples made from 100% YSZ, 100% Ni, and 100% NiO powders, five composite types were created for this investigation: NiO/YSZ, NiO&Gr/YSZ, Ni/YSZ, NiGr/YSZ, and Ni&Gr/YSZ each with nickel loadings varying between 4 vol% Ni of total solids and 77 vol% Ni of total solids. Another set of composites with a fixed nickel loading of 27 vol% Ni and 47 vol% Ni of total solids and varying graphite loadings were also created. <br /> During the burnout stage, the composites made from nickel oxide powder shrink slightly while the composites made from nickel metal expand due to nickel oxidation. Graphite additions below 20 vol% of the green volume do not alter the dimensional changes of the composites during burnout, but graphite loadings greater than 25 vol% of the green volume cause significant expansion in the thickness of the composites. <br /> After sintering, the amount of volumetric sintering shrinkage decreases with higher nickel loadings and is greater for the composites made with nickel oxide compared to the composites made from nickel metal. The porosity generated in the composites containing graphite is slightly higher than the volume of graphite added to the composite and is much greater than the porosity contained in the graphite-free composites. <br /> Dimensional changes of the porous Ni/YSZ and NiO/YSZ composites during both burnout and sintering were analysed based on concepts of constrained sintering of composite powder mixtures. In some cases constrained sintering was evident, while in others, a more simple rule of mixtures behaviour for shrinkage as a function of YSZ content was observed. <br /> When nickel oxide is reduced to nickel metal during the reduction stage there is essentially no change in the composite volume for the composites containing YSZ because the YSZ prevents the composites from shrinking. After reduction the additional porosity generated in the composites is equivalent to the change in volume due to the reduction of nickel oxide to nickel metal. <br /> When measuring the electrical conductivity, each composite type demonstrated classic percolation behaviour. The NiGr/YSZ composites had the lowest percolation threshold, followed by the Ni/YSZ and NiO/YSZ composites. When graphite was added with a nickel coating, the added porosity did not disrupt the nickel percolation network and allowed the nickel to occupy a larger effective volume compared to a composite made with similar sized solid nickel particles. When graphite was added to the composites, the electrical conductivity was reduced and the percolation threshold increased. <br /> Generally, the coefficient of thermal expansion (CTE) for Ni/YSZ composites are expected to follow the rule of mixtures prediction since the elastic properties for nickel and YSZ are similar. However when porosity is distributed unevenly between the YSZ and nickel phases, the CTE prediction will deviate from the rule of mixtures. When cornstarch was added to the NiGr/YSZ composites, the CTE increased as the amount of porosity in the YSZ phase increased. The CTE of the NiGr/YSZ composites followed the rule of mixtures indicating that the porosity was evenly distributed between the nickel and YSZ phases. For the other composite types, the measured CTE was higher than the rule of mixtures prediction suggesting that more porosity was contained within the YSZ phase.

A solid oxide fuel cell (SOFC) is an energy conversion device that has the potential to efficiently generate electricity in an environmentally-friendly manner. In general, a SOFC operates between 750&deg;C and 1000&deg;C utilizing hydrogen or hydrocarbons as fuel and air as an oxidant. The three major components comprising a fuel cell are the electrolyte, the cathode, and the anode. At present, the state-of-the-art SOFC is made from a dense yttria-stabilized zirconia (YSZ) electrolyte, a porous lanthanum manganite cathode, and a porous nickel/YSZ composite anode. With the advent of the anode-supported SOFC and the increased interest in using a wider range of fuels, such as those containing sulphur, knowledge of the anode properties is becoming more important. <br /> The properties of the current anodes are limited due to the narrow range of nickel loadings imposed by the minimum nickel content for electrical conductivity and the maximum allowable nickel loading to avoid thermal mismatch with the YSZ electrolyte. In addition, there is little research presented in the literature regarding the use of nickel metal as a starting anode material, rather than the traditional nickel oxide powder, and how porosity may affect the anode properties. <br /> The purpose of this investigation is to determine the influence nickel morphology and porosity distribution have on the processing and properties of tape cast Ni/YSZ composites. Specifically, the sintering characteristics, electrical conductivity, and thermal expansion behaviour of tape cast composites created from YSZ, nickel, nickel oxide (NiO), nickel coated graphite (NiGr), and/or graphite (Gr) powders are investigated. In addition to samples made from 100% YSZ, 100% Ni, and 100% NiO powders, five composite types were created for this investigation: NiO/YSZ, NiO&Gr/YSZ, Ni/YSZ, NiGr/YSZ, and Ni&Gr/YSZ each with nickel loadings varying between 4 vol% Ni of total solids and 77 vol% Ni of total solids. Another set of composites with a fixed nickel loading of 27 vol% Ni and 47 vol% Ni of total solids and varying graphite loadings were also created. <br /> During the burnout stage, the composites made from nickel oxide powder shrink slightly while the composites made from nickel metal expand due to nickel oxidation. Graphite additions below 20 vol% of the green volume do not alter the dimensional changes of the composites during burnout, but graphite loadings greater than 25 vol% of the green volume cause significant expansion in the thickness of the composites. <br /> After sintering, the amount of volumetric sintering shrinkage decreases with higher nickel loadings and is greater for the composites made with nickel oxide compared to the composites made from nickel metal. The porosity generated in the composites containing graphite is slightly higher than the volume of graphite added to the composite and is much greater than the porosity contained in the graphite-free composites. <br /> Dimensional changes of the porous Ni/YSZ and NiO/YSZ composites during both burnout and sintering were analysed based on concepts of constrained sintering of composite powder mixtures. In some cases constrained sintering was evident, while in others, a more simple rule of mixtures behaviour for shrinkage as a function of YSZ content was observed. <br /> When nickel oxide is reduced to nickel metal during the reduction stage there is essentially no change in the composite volume for the composites containing YSZ because the YSZ prevents the composites from shrinking. After reduction the additional porosity generated in the composites is equivalent to the change in volume due to the reduction of nickel oxide to nickel metal. <br /> When measuring the electrical conductivity, each composite type demonstrated classic percolation behaviour. The NiGr/YSZ composites had the lowest percolation threshold, followed by the Ni/YSZ and NiO/YSZ composites. When graphite was added with a nickel coating, the added porosity did not disrupt the nickel percolation network and allowed the nickel to occupy a larger effective volume compared to a composite made with similar sized solid nickel particles. When graphite was added to the composites, the electrical conductivity was reduced and the percolation threshold increased. <br /> Generally, the coefficient of thermal expansion (CTE) for Ni/YSZ composites are expected to follow the rule of mixtures prediction since the elastic properties for nickel and YSZ are similar. However when porosity is distributed unevenly between the YSZ and nickel phases, the CTE prediction will deviate from the rule of mixtures. When cornstarch was added to the NiGr/YSZ composites, the CTE increased as the amount of porosity in the YSZ phase increased. The CTE of the NiGr/YSZ composites followed the rule of mixtures indicating that the porosity was evenly distributed between the nickel and YSZ phases. For the other composite types, the measured CTE was higher than the rule of mixtures prediction suggesting that more porosity was contained within the YSZ phase.

Solid oxide fuel cells (SOFCs) conventionally operate between 800 and 1000°C. The barriers for full-scale commercialization of SOFCs are the high cost and relatively poor long-term stability due to the high temperatures used in current state-of-the-art SOFCs. One solution is to decrease the operating temperature, e.g. to 550-750°C but this requires developing new electrolytes and electrode materials. Also, to increase efficiency and practicality, the anode should be able to internally reform hydrocarbon fuels especially methane because it is the most common hydrocarbon in natural gas. The overall goal of this research is to develop a coke-tolerant Ni1-x-yCuxMgyO-SDC anode for methane fuelled IT-SOFCs. The Ni-Cu-Mg-O-SDC anode has been chosen based on the premises that doped-ceria is suitable for intermediate operating temperatures (550-800°C), Ni is known as an active metal and good electronic conductor, Cu increases resistance to coking, MgO helps prevent agglomeration of Ni during reduction, and finally SDC improves oxide ion transport to the cell at this intermediate temperature range. In this work, these materials were characterized in three primary ways: material physical and chemical properties, methane steam reforming activity and electrochemical performance. Two different methods have been used to add Cu to Ni1-yMgyO: a one-step co-precipitation method and a two-step co-precipitation/impregnation method. For the first method, Ni1-x-yCuxMgyO was synthesized via co-precipitation of Ni, Mg and Cu. In the two-step method, Ni0.9Mg0.1O was first prepared by co-precipitation, followed by addition of copper to Ni0.9Mg0.1O by impregnation. However, co-precipitation of all metal in one step limits the sintering temperature of the anode in the cell fabrication due to the low boiling point of CuO. Therefore, co-precipitation of Cu is not a practical method and only Cu impregnation should be considered for practical SOFC applications. It was found that the addition of Mg (Ni0.9Mg0.1O) lowers the reducibility of NiO. Addition of Cu to Ni0.9Mg0.1O up to 5% shows similar reducibility as Ni0.9Mg0.1O. The reducibility of Ni1-x-yCuxMgyO becomes lower when the Cu content is increased to 10%. Nonetheless, all materials are fully reduced at 750ºC. The XRD patterns of pure NiO, Ni0.9Mg0.1O, and the Cu-containing material when Cu is less than 10 mol% are similar. The lower reducibility of Ni-Mg-O and Ni-Cu-Mg-O compared to NiO indicates that they form a solid solution with NiO as the matrix. Solid oxide fuel cells (SOFCs) conventionally operate between 800 and 1000°C. The barriers for full-scale commercialization of SOFCs are the high cost and relatively poor long-term stability due to the high temperatures used in current state-of-the-art SOFCs. One solution is to decrease the operating temperature, e.g. to 550-750°C but this requires developing new electrolytes and electrode materials. Also, to increase efficiency and practicality, the anode should be able to internally reform hydrocarbon fuels especially methane because it is the most common hydrocarbon in natural gas. The overall goal of this research is to develop a coke-tolerant Ni1-x-yCuxMgyO-SDC anode for methane fuelled IT-SOFCs. The Ni-Cu-Mg-O-SDC anode has been chosen based on the premises that doped-ceria is suitable for intermediate operating temperatures (550-800°C), Ni is known as an active metal and good electronic conductor, Cu increases resistance to coking, MgO helps prevent agglomeration of Ni during reduction, and finally SDC improves oxide ion transport to the cell at this intermediate temperature range. In this work, these materials were characterized in three primary ways: material physical and chemical properties, methane steam reforming activity and electrochemical performance. Two different methods have been used to add Cu to Ni1-yMgyO: a one-step co-precipitation method and a two-step co-precipitation/impregnation method. For the first method, Ni1-x-yCuxMgyO was synthesized via co-precipitation of Ni, Mg and Cu. In the two-step method, Ni0.9Mg0.1O was first prepared by co-precipitation, followed by addition of copper to Ni0.9Mg0.1O by impregnation. However, co-precipitation of all metal in one step limits the sintering temperature of the anode in the cell fabrication due to the low boiling point of CuO. Therefore, co-precipitation of Cu is not a practical method and only Cu impregnation should be considered for practical SOFC applications. It was found that the addition of Mg (Ni0.9Mg0.1O) lowers the reducibility of NiO. Addition of Cu to Ni0.9Mg0.1O up to 5% shows similar reducibility as Ni0.9Mg0.1O. The reducibility of Ni1-x-yCuxMgyO becomes lower when the Cu content is increased to 10%. Nonetheless, all materials are fully reduced at 750ºC. The XRD patterns of pure NiO, Ni0.9Mg0.1O, and the Cu-containing material when Cu is less than 10 mol% are similar. The lower reducibility of Ni-Mg-O and Ni-Cu-Mg-O compared to NiO indicates that they form a solid solution with NiO as the matrix. Addition of Mg also lowers the BET specific surface area from 11.5 m2/g for NiO:SDC to 10.4 m2/g for Ni0.9Mg0.1O. The surface area is further reduced when Cu is added; for example, at 10% Cu, the surface area is 8.2 m2/g. The activity of 50wt% Ni1-x-yCuxMgyO/50wt% SDC samples for methane steam reforming (SMR) and water-gas-shift reaction (WGS) was evaluated in a fully automated catalytic fixed-bed reactor where the exiting gases were analyzed online by a gas chromatograph (GC). The tests were performed at steam-to-carbon ratios (S/C) of 3, 2 and 1, and at temperatures of 750°C and 650°C for twenty hours. Higher methane conversions were obtained at the higher temperature and higher S/C ratio. Higher methane conversion are obtained using NiO:SDC and Ni0.9Mg0.1O:SDC than Ni-Cu-Mg-O. The conversion decreases with increasing Cu content. Over NiO:SDC and Ni0.9Mg0.1O:SDC the methane conversions are the same; for example 85% at 750°C for S/C of 3. At the same conditions, impregnation of 5%Cu and 10%Cu yields lower conversions: 62% and 48%, respectively. The activity for the WGS reaction was determined by mornitoring CO2/(CO+CO2) ratio. As expected because WGS is a moderately exothermic reaction, this ratio decreases when increasing the temperature. However, the CO2/(CO+CO2) ratio increases with higher S/C. The results indicate that adding Mg does not affect the WGS activity of NiO. The WGS activity of Ni0.9Mg0.1O:SDC is higher when Cu is added. The effect of additional Cu is more pronounced at 650ºC. At 750°C, changing the amount of Cu does not change the WGS activity because the WGS reaction rapidly reaches equilibrium at this high temperature. At 750°C for S/C of 1, carbon filaments were found in all samples. At 650ºC, different types of deposited carbon were observed: carbon fibers and thin graphite layers. Spent NiO:SDC had the longest carbon fibers. Addition of Mg significantly reduced the formation of carbon fibers. Impregnating 5% Cu on Ni0.9Mg0.1O:SDC did not change the type of deposited carbon. Monitoring the amount of deposited carbon on Ni0.9Mg0.1O:SDC, 3%Cu and 5%Cu impregnated on Ni0.9Mg0.1O:SDC for S/C of 0 at 750ºC showed that Cu addition deactivated methane cracking causing a reduction in the amount of carbon deposited. Electrochemical performance in the presence of dry and humidified hydrogen was determined at 600, 650, 700 and 750ºC. Electrolyte-supported cells constructed with four different anodes were tested using polarization curve and electrochemical impedance spectra. The four anodes were NiO:SDC, Ni0.9Mg0.1O:SDC, 3%Cu and 5%Cu on Ni0.9Mg0.1O:SDC. Adding Mg improved the maximum power density from 356 mW.cm-2 with NiO:SDC to 369 mW.cm-2 with Ni0.9Mg0.1O:SDC at 750ºC in dry hydrogen. Addition of Cu, on the other hand, lowered the maximum power density to 325 mW.cm-2 with 3%Cu impregnated and to 303 mW.cm-2 with 5% Cu impregnated. The cell with Ni0.9Mg0.1O:SDC was also tested under dry methane. To minimize methane cracking under this extreme condition, a current density of 0.10 A.cm-2 was always drawn when methane was present in the feed. The voltage decreased during the first hour from 0.8 to 0.5 V, then remained stable for 10 hours, and then started to drop again. Many small cracks were observed on the anode after completion of the electrochemical test, but there was no evidence of much carbon being deposited. In addition to dry methane, tests were also carried out, using the same material, with a H2O/CH4 mixture of 1/6 in order to generate a polarization curve at 750°C. Under these conditions, the maximum power density was 226 mW.cm-2. This is lower than the maximum power density obtained with humidified hydrogen, which was 362 mW.cm-2.

<p>Fuel cells are promising candidates for converting chemical energy into electrical energy. The Molten Carbonate Fuel Cell (MCFC) is a high temperature fuel cell that produces electrical energy from a variety of fuels containing hydrogen, hydrocarbons and carbon monoxide. Since the waste heat has a high temperature it can also be used leading to a high overall efficiency.</p><p>Material degradation and the cost of the components are the problems for the commercialisation of MCFC. Although there are companies around the world starting to commercialise MCFC some further cost reduction is needed before MCFC can be fully introduced at the market.</p><p>In this work, alternative materials for three different components of MCFC have been investigated. The alternative materials should have a lower cost compared to the state-of-the-art materials but also meet the life-time goal of MCFC, which is around 5 years. The nickel dissolution of the cathode is a problem and a cathode with lower solubility is needed. The dissolution of nickel for three alternative cathode materials was investigated, where one of the materials had a lower solubility than the state-of-the-art nickel oxide. This material was also tested in a cell and the electrochemical performance was found to be comparable with nickel oxide and is an interesting candidate.</p><p>An inexpensive anode current collector material is also desired. For the anode current collector, the contact resistance should be low and it should have good corrosion properties. The two alternative materials tested had low contact resistance, but some chromium enrichment was seen at the grain boundaries. This can lead to a decreased mechanical stability of the material. In the wet-seal area, the stainless steel used as bipolar/separator plate should be coated. An alternative process to coat the stainless steel, that is less expensive, was evaluated. This process can be a suitable process, but today, when the coating process is done manually there seems to be a problem with the adherence.</p><p>This work has been a part of the IRMATECH project, which was financed by the European Commission, where the partners have been universities, research institutes and companies around Europe.</p>

<p>In the chlorate process, natural convection arises thanks to the hydrogen evolving cathode. This increases the mass transport of the different species in the chlorate electrolyte. There is a strong connection between mass transport and the kinetics of the electrode reactions. A better knowledge about these phenomena and their interactions is desirable in order to understand e.g. the reasons for deactivation of anode coatings and what process conditions give the longest lifetime and the highest efficiency.</p><p>One of the aims of his work was to understand how the chlorate process has to be run to avoid exceeding the critical anode potential (<em>E</em>_cr) in order to keep the potential losses low and to achieve a long lifetime of the DSAs. At <em>E</em>_cr anodic polarisation curves in chlorate electrolyte bend to higher Tafel slopes, causing increasing potential losses and accelerated ageing of the anode. Therefore the impact on the anode potential and on <em>E</em>_cr of different electrolyte parameters and electrolyte impurities was investigated. Additionally, the work aimed to investigate the impact of an addition of chromate on oxygen evolution and concentration profiles under conditions reminiscent of those in the chlorate process (high ionic strength, 70 °C, ruthenium based DSA, neutral pH), but without chloride in order to avoid hypochlorite formation. For this purpose a model, taking into account mass transport as well as potential- and concentration-dependent electrode reactions and homogeneous reactions was developed. Water oxidation is one of the side reactions considered to decrease the current efficiency in chlorate production. The results from the study increase the understanding of how a buffer/weak base affects a pH dependent electrode reaction in a pH neutral electrolyte in general. This could also throw light on the link between electrode reactions and homogeneous reactions in the chlorate process.</p><p>It was found that the mechanism for chloride oxidation is likely to be the same for potentials below <em>E</em>_cr as well as for potentials above <em>E</em>_cr. This was based on the fact that the apparent reaction order as well as α_a seem to be of the same values even if the anode potential exceeds<em> E</em>_cr. The reason for the higher slope of the polarisation curve above <em>E</em>_cr could then be a potential dependent deactivation of the active sites. Deactivation of active ruthenium sites could occur if ruthenium in a higher oxidation state were inactive for chloride oxidation.</p><p>Concentration gradients of H⁺, OH^-, CrO₄ ^2- and HCrO₄ ^-during oxygen evolution on a rotating disk electrode (RDE) were predicted by simulations. The pH dependent currents at varying potentials calculated by the model were verified in experiments. It was found that an important part of the chromate buffering effect at high current densities occurs in a thin (in the order of nanometers) reaction layer at the anode. From comparisons between the model and experiments a reaction for the chromate buffering has been proposed. Under conditions with bulk pH and chromate concentration similar to those in the chlorate process, the simulations show that the current density for oxygen evolution from OH^- would be approximately 0.1 kA m^-2, which corresponds to about 3% of the total current in chlorate production.</p>

Natural graphite from cheap and abundant natural sources is an attractive anode material for lithium ion batteries. We report on modifications of such a common natural graphite, whose electrochemical performance is very poor, with solutions of (NH4)2S2O8, concentrated nitric acid, and green chemical solutions such of e.g. hydrogen peroxide and ceric sulfate. These treatments resulted in markedly im-proved electrochemical performance (reversible capacity, coulombic efficiency in the first cycle and cycling behavior). This is attributed to the effective removal of active defects, formation of a new dense surface film consisting of oxides, improvement of the graphite stability, and introduction of more nanochannels/micropores. These changes inhibit the decomposition of electrolyte solution, pre-vent the movement of graphene planes along a-axis direction, and provide more passage and storage sites for lithium. The methods are mild, and the uniformity of the product can be well controlled. Pilot experiments show promising results for their application in industry.

Lithium-ion batteries are most commonly employed as power sources for portable electronic devices. Limited capacity, high cost, and safety problems associated with the commercially used graphite anode materials are hampering the use of lithium-ion batteries in larger-scale applications such as the electric vehicle. Nanocomposite alloys have shown promise as new anode materials because of their better safety due to higher operating potential, increased energy density, low cost, and straightforward synthesis as compared to graphite. The purpose of this dissertation is to investigate and understand the electrochemical properties of several types of nanocomposite alloys and to assess their viability as replacement anode materials for lithium-ion batteries. Tin and antimony are two elements that are active toward lithium. Accordingly, this dissertation is focused on tin-based and antimony-based nanocomposite alloy materials. Tin and antimony each have larger theoretical capacities than commercially available anodes, but the capacity fades dramatically in the first few cycles when metallic tin or antimony is used as the anode in a lithium-ion battery. This capacity fade is largely due to the agglomeration of particles in the anode material and the formation of a barrier layer between the surface of the anode and the electrolyte. In order to suppress agglomeration, the active anode material can be constrained by an inactive matrix of material that makes up the nanocomposite. By controlling the surface of the particles in the nanocomposite via methods such as the addition of additives to the electrolyte, the detrimental effects of the solid-electrolyte interphase layer (SEI) can be minimized, and the capacity of the material can be maintained. Moreover, the nanocomposite alloys described in this dissertation can be used above the voltage where lithium plating occurs, thereby enhancing the safety of lithium-ion batteries. The alloy anodes in this study are synthesized by high-energy mechanical milling and furnace heating. The materials are characterized by X-ray diffraction, scanning and transmission electron microscopies, and X-ray photoelectron spectroscopy. Electrochemical performances are assessed at various temperatures, potential ranges, and charge rates. The lithiation/delithiation reaction mechanisms for these nanocomposite materials are explored with ex-situ X-ray diffraction. Specifically, three different nanocomposite alloy anode materials have been developed: Mo3Sb7-C, Cu2Sb-Al2O3-C, and Cu6Sn5-TiC-C. Mo3Sb7-C has high gravimetric capacity and involves a reaction mechanism whereby crystalline Mo3Sb7 disappears and is reformed during each cycle. Cu2Sb-Al2O3-C with small particles (2 - 10 nm) of Cu2Sb dispersed in the Al2O3-C matrix is made by a single-step ball milling process. It exhibits long cycle life (+ 500 cycles), and the reversibility of the reaction of Cu2Sb-Al2O3-C with lithium is improved when longer milling times are used for synthesis. The reaction mechanism for Cu2Sb-Al2O3-C appears to be dependent upon the size of the crystalline Cu2Sb particles. The coulombic efficiency of Cu2Sb-Al2O3-C is improved through the addition of 2 % vinylethylene carbonate to the electrolyte. With a high tap density of 2.2 g/cm3, Cu6Sn5-TiC-C exhibits high volumetric capacity. The reversibility of the reaction of Cu6Sn5-TiC-C with lithium is improved when the material is cycled above 0.2 V vs. Li/Li+. / text