Nanostructured materials have received a surge of interest in recent years since it has become apparent that reducing the size of a material often leads to heightened mechanical behavior. From a fundamental standpoint, this stems from the confinement of dislocations. Applications in microelectromechanical devices, lithium ion batteries, gas sensing and catalysis are realized by combining the improvements in mechanical behavior from material size reduction with the heightened chemical activity offered by materials with a high surface-area-to-volume ratio. In this study, films of nanoporous Si-Mg were produced through magnetron sputtering, followed by dealloying using an environmentally benign process with distilled water. The film composition and structure was characterized both at the surface and throughout the film thickness, while the mechanical behavior was explored with nanoindentation. Dispenser cathodes operate via thermionic emission and are an important area of interest in vacuum electron devices. While scientists have known for many years what elemental constituents are used to manufacture dispenser cathodes of excellent emission behavior, a fundamental understanding has yet to be realized. In this study, components of a scandate cathode that exhibited excellent emission behavior were characterized and used to inform the study of model thin films. Isolating relevant components of the scandate cathode for careful study could help inform future breakthroughs in understanding the working mechanism(s) of the scandate cathode. The structure, composition and electronic behavior of model W-Al alloy films were characterized experimentally and compared to computation. Moreover, a unique vacuum chamber was designed to activate modern thermionic dispenser cathodes, observe residual gas species present, and measure the work function through various state-of-the-art techniques.

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.

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La pile à combustible H+-SOFC (Protonic Conducting Solid Oxide Fuel Cell) basée surl'utilisation d'un électrolyte conducteur protonique peut représenter une alternative intéressanteà la pile SOFC qui présente actuellement le meilleur rendement. Cependant, la surtension à lacathode reste élevée et ce travail est dédié à la compréhension du mécanisme de réductionl'oxygène à cette électrode.Différents matériaux conducteurs mixtes O2- / e- de structures dérivées de la perovskite ABO3,tels que les doubles perovskites LnBaM2O5+d (Ln = Pr, Nd et Gd et M = Co et Fe) ainsi que lesphases de Ruddlesden-Popper A2MO4+d (Ln = Pr et Sr et M = Ni), ont été étudiés. Leur niveaude conductivité électronique ainsi que leur non-stoechiométrie en oxygène ont d'abord étédéterminées. Puis, à l'aide de la détermination des coefficients de diffusion de l'oxygène par laméthode de relaxation de conductivité électrique, leur conductivité ionique O2- a été estimée.Une étude électrochimique et plus spécialement la détermination des étapes limitant la réactionde réduction de l'oxygène à la cathode de pile H+-SOFC a ensuite permis de démontrer le rôledu proton dans le mécanisme de réaction pour les matériaux présentant les meilleuresperformances électrochimiques.Enfin, dans le cadre d'un projet ANR HPAC 2009 " CONDOR ", des mono-cellules de piles H+-SOFC ont été mises en forme et des densités de puissance proche de 180 mW/cm² à 0.6 V à600°C ont été obtenues.

<p>LiMn₂O₄ is ideal as a high-capacity Li-ion battery cathode material by virtue of its low toxicity, low cost, and the high natural abundance of Mn. Surface related reactions and bulk kinetics have been the major focus of this work. The main techniques exploited have been: electrochemical cycling, X-ray diffraction, X-ray photoelectron spectroscopy, infrared spectroscopy and thermal analysis.</p><p>Interface formation between the LiMn₂O₄cathode and carbonate-based electrolytes has been followed under different pre-treatment conditions. The variables have been: number of charge/discharge cycles, storage time, potential, electrolyte salt and temperature. The formation of the surface layer was found not to be governed by electrochemical cycling. The species precipitating on the surface of the cathodes at ambient temperature have been determined to comprise a mixture of organic and inorganic compounds: LiF, Li_xPF_y (or Li_xBF_y, depending on the electrolyte salt used), Li_xPO_yF_z (or Li_xBO_yF_z) and poly(oxyethylene). Additional compounds were found at elevated temperatures: phosphorous oxides (or boron oxides) and polycarbonates. A model has been presented for the formation of these surface species at elevated temperatures. </p><p>The cathode surface structure was found to change towards a lithium-rich and Mn³⁺-rich compound under self-discharge. The reduction of LiMn₂O₄, in addition to the high operating potential, induces oxidation of the electrolyte at the cathode surface.</p><p>A novel <i>in situ</i> electrochemical/structural set-up has facilitated a study of the kinetics in the LiMn₂O₄ electrode. The results eliminate solid-phase diffusion as the rate-limiting factor in electrochemical cycling. The electrode preparation method used results in good utilisation of the electrode, even at high discharge rates.</p>

<p>Thin films of metals and compounds have a very wide range of applications today. Many of the deposition methods used for the production of such films utilize plasma to support the growth the film, e.g. by the supply of energy and the enhancement of reactivity. This thesis focuses on the physical vapor deposition (PVD) of thin films by high density plasma sources based on hollow cathodes and aims to increase the understanding of the deposition process and its influence on the film properties.</p><p>Titanium nitride films reactively deposited by the low-pressure hybrid plasma (HYP LP) source exhibited excellent properties and was deposited at considerable higher rates than films deposited by conventional methods.</p><p>An original finding in this work is the influence of substrate material on the deposition process and consequently on the properties of the deposited film. In the deposition of TiN films by the HYP LP source it was found that the substrate temperature was higher for Si substrates than for steel substrates due to a more efficient absorption of microwave power in Si than in steel. Further, it was found that ferromagnetic substrates influence the film growth in magnetized plasma systems. An effect of the ferromagnetic substrates is the enhancement of ion bombardment that increases the growth temperature and affects the texture and morphology of the growing films. It was also found that a DC bias can change the TiN film properties considerably and compensate the effect of ferromagnetic substrates.</p><p>High rate depositions of chromium and chromium nitride films by the RF hollow cathode plasma jet (RHCPJ) source were studied. The performance of the reactive diffuse arc process and the CrN film properties indicates that the process can be transferred from small cylindrical cathodes to linear magnetized hollow cathodes which allow deposition on considerable larger areas and this is important for industrial applications.</p>

Ab Initio calculations suggest that partially lithiated layered LixMnO₂ transforms to spinel in a two-stage process. In the first stage, a significant fraction of the Mn and Li ions rapidly occupy tetrahedral sites, forming a metastable intermediate. The second stage involves a more difficult coordinated rearrangement of Mn and Li ions to form spinel. This behavior is contrasted to LixCoO₂. The susceptibility of Mn for migration into the Li layer is found to be controlled by oxidation state which suggests various means of inhibiting the transformation. These strategies could prove useful in the creation of superior Mn based cathode materials. / Singapore-MIT Alliance (SMA)

LiMn2O4 is ideal as a high-capacity Li-ion battery cathode material by virtue of its low toxicity, low cost, and the high natural abundance of Mn. Surface related reactions and bulk kinetics have been the major focus of this work. The main techniques exploited have been: electrochemical cycling, X-ray diffraction, X-ray photoelectron spectroscopy, infrared spectroscopy and thermal analysis. Interface formation between the LiMn2O4 cathode and carbonate-based electrolytes has been followed under different pre-treatment conditions. The variables have been: number of charge/discharge cycles, storage time, potential, electrolyte salt and temperature. The formation of the surface layer was found not to be governed by electrochemical cycling. The species precipitating on the surface of the cathodes at ambient temperature have been determined to comprise a mixture of organic and inorganic compounds: LiF, LixPFy (or LixBFy, depending on the electrolyte salt used), LixPOyFz (or LixBOyFz) and poly(oxyethylene). Additional compounds were found at elevated temperatures: phosphorous oxides (or boron oxides) and polycarbonates. A model has been presented for the formation of these surface species at elevated temperatures. The cathode surface structure was found to change towards a lithium-rich and Mn3+-rich compound under self-discharge. The reduction of LiMn2O4, in addition to the high operating potential, induces oxidation of the electrolyte at the cathode surface. A novel in situ electrochemical/structural set-up has facilitated a study of the kinetics in the LiMn2O4 electrode. The results eliminate solid-phase diffusion as the rate-limiting factor in electrochemical cycling. The electrode preparation method used results in good utilisation of the electrode, even at high discharge rates.

Thin films of metals and compounds have a very wide range of applications today. Many of the deposition methods used for the production of such films utilize plasma to support the growth the film, e.g. by the supply of energy and the enhancement of reactivity. This thesis focuses on the physical vapor deposition (PVD) of thin films by high density plasma sources based on hollow cathodes and aims to increase the understanding of the deposition process and its influence on the film properties. Titanium nitride films reactively deposited by the low-pressure hybrid plasma (HYP LP) source exhibited excellent properties and was deposited at considerable higher rates than films deposited by conventional methods. An original finding in this work is the influence of substrate material on the deposition process and consequently on the properties of the deposited film. In the deposition of TiN films by the HYP LP source it was found that the substrate temperature was higher for Si substrates than for steel substrates due to a more efficient absorption of microwave power in Si than in steel. Further, it was found that ferromagnetic substrates influence the film growth in magnetized plasma systems. An effect of the ferromagnetic substrates is the enhancement of ion bombardment that increases the growth temperature and affects the texture and morphology of the growing films. It was also found that a DC bias can change the TiN film properties considerably and compensate the effect of ferromagnetic substrates. High rate depositions of chromium and chromium nitride films by the RF hollow cathode plasma jet (RHCPJ) source were studied. The performance of the reactive diffuse arc process and the CrN film properties indicates that the process can be transferred from small cylindrical cathodes to linear magnetized hollow cathodes which allow deposition on considerable larger areas and this is important for industrial applications.