Made available in DSpace on 2014-10-09T12:27:23Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:51Z (GMT). No. of bitstreams: 0 / Os filmes cerâmicos de manganito de lantânio dopado com estrôncio (LSM) e de manganito de lantânio dopado com estrôncio/zircônia estabilizada com ítria (LSM/YSZ) são utilizados como catodos das células a combustível de óxido sólido de temperatura alta (CaCOSTA). Estes filmes cerâmicos porosos foram depositados sobre o substrato cerâmico denso de YSZ, utilizado como eletrólito, componente estrutural do módulo, assim conferindo uma configuração de meia-célula denominada auto-suporte. O estudo da meia-célula é fundamental, pois na interface catodo/eletrólito ocorre a reação de redução do oxigênio, conseqüentemente influenciando no desempenho da CaCOSTA. Neste sentido, o presente trabalho contribui para a síntese de pós de LSM e LSM/YSZ e para o processamento de filmes finos, utilizando a técnica de pulverização de pó úmido, adotada para a conformação dos filmes cerâmicos por permitir a obtenção de camadas porosas com espessuras variadas na ordem de micrômetros. Os pós de LSM foram sintetizados pela técnica de citratos e os pós de LSM/YSZ pela técnica de mistura de sólidos. Na etapa de conformação foram preparadas suspensões orgânicas de LSM e LSM/YSZ alimentada por gravidade em um aerógrafo manual. Para a conformação do substrato de YSZ utilizou-se uma prensa uniaxial hidráulica. Foram possíveis a obtenção das meia-células de óxido sólido catodo/eletrólito de estruturas cristalinas hexagonal para a fase LSM e cúbica para a fase YSZ. E as micrografias das meia-células mostram que o substrato YSZ é denso, suficiente para ser utilizado como eletrólito sólido, e os filmes de LSM e LSM/YSZ apresentam-se porosos com espessura de aproximadamente 30 μm e com boa aderência entre os catodos e o eletrólito. A presença do catodo compósito entre o catodo LSM e o substrato YSZ, possibilitou um aumento no desempenho eletroquímico na reação de redução do oxigênio. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Batteries play a pivotal role in the modern world, powering everything from portable electronics to electric vehicles, and are critical in the shift towards renewable energy sources by enabling efficient energy storage. This thesis presents new computational strategies to understand and predict surface degradation and stacking faults in battery cathodes, phenomena that have crucial impact on the battery lifetime. The starting point is a detailed first-principles analysis of LiNiO₂ surface degradation, assessing the thermodynamics of oxygen release and its impact on the surface integrity of this prospective cathode material. This research led to the development of a method for the automated enumeration of surface reconstructions and the development of a Python software package implementing the methodology, thereby greatly accelerating the computational surface characterization of electrode materials. The methodology made it feasible to extend the investigation to LiCoO₂ surfaces, comparing their oxygen retention and surface stability with LiNiO₂ and identifying the unique properties of the two transition metals that control their behavior during battery operation. In addition to surface phase changes, stacking faults are another important class of two-dimensional defects that can affect the properties of cathode materials. Combining information from first principles calculations with 17O nuclear magnetic resonance (NMR) spectroscopy provided by collaborators, we uncovered how stacking faults affect the capacity and cyclability of Li₂MnO₃ cathodes, a prototypical lithium-rich material with oxygen redox activity. Although automated first-principles calculations are, in principle, an ideal tool for understanding atomic-scale degradation phenomena in batteries, they are computationally demanding and, therefore, limited to materials with simple compositions. In the final chapter, we explore the application of machine learning for further accelerating computational battery degradation simulations by leveraging existing data first-principles calculations for predicting the stability of new surface reconstructions. This chapter points toward a new direction that should be further explored in the future. The research presented in this thesis not only advances the understanding of lithium-ion battery cathode materials but also introduces more-widely applicable computational methodologies that lay a foundation for the development of advanced materials for energy storage applications. This work demonstrates the benefits of integrating traditional computational methods with machine learning, contributing to ongoing progress in materials science and opening up new possibilities for advancements in energy technology and material engineering.

Le revêtement d'une cuve d'électrolyse est constitué en grande partie de matériaux à base de carbone. La caractérisation thermomécanique de ces matériaux est essentielle afin de modéliser leur comportement lors du préchauffage et en phase de production d'aluminium. Une vaste étude expérimentale a ainsi été élaborée afin de caractériser les cathodes de carbone et se veut une collaboration entre l'Université Laval et Carbone Savoie. Cette étude porte sur la détermination du module d'Young et de l'en-dommagemciit et ce, pour des températures allant de 25°C à 1000'C. Les échantillons cylindriques utilisés ont un diamètre de 50 mm, soit des échantillons de très grandes tailles considérant les contraintes techniques dans un contexte de caractérisation à haute température. Ce mémoire présente donc les résultats obtenus sur des échantillons de cathode de type graphitique pour des températures allant de la température ambiante jusqu'à la température d'opération.

The global energy transition, involving the widespread adoption of electric vehicles and grid-scale energy storage, demands energy storage devices made up of abundant, inexpensive minerals. For this to be achieved, the large Co content in conventional Li-ion battery cathodes (e.g., LiCoO₂) must be replaced while also maintaining or improving the energy density of the battery. Alternative low-Co and Co-free materials (e.g., layered LiNixMnyCozO₂, spinel LiNi₀.₅Mn₁.₅O₄, and olivine LiFePO₄) are promising alternatives due to their theoretically higher energy densities or improved safety properties from the industry standards. However, in practice, these materials exhibit both bulk and interfacial instabilities that limit their practical energy density and cycle lifetime. It is well known that reactions between the delithiated (charged) cathode surface with the electrolyte generates electrolyte decomposition species that form an interphase layer called the cathode electrolyte interphase (CEI), where such reactions are concomitant with a crystallographic reconstruction of the surface of the bulk material. The CEI is air sensitive, disordered, nanometers thick and evolves as a function of state of charge and cycle number, making it difficult to fully understand its composition and effect on device performance. The dynamic nature of the CEI necessitates development of chemical characterization tools that can analyze surface reactivity during battery operation. Commercial cathode films are also composites including not just the electrochemically active material but also conductive carbon additive and polymer binder, meaning we need spatially resolved tools to study CEI composition across the film to isolate reactivity by film component. In this thesis, we have developed and applied spatially resolved and operando characterization tools to study the CEI of low-Co and Co-free cathode materials and use these data to pinpoint the degradation reactions at play during battery operation. In the first chapter, we introduce the three most prevalent types of cathode materials (layered, spinels, and olivines) used in Li-ion batteries. We then highlight recent progress in the analytical characterization tools that have been developed to elucidate CEI composition, spatial arrangement, and formation pathways during battery operation while discussing the difference in surface reactivity between each cathode active material as revealed by these techniques. Major findings from my own thesis work, detailed in following chapters, are discussed in parallel within this broader context. Finally, equipped with a deeper understanding of the CEI and the processes that lead to its formation, we discuss what remains to be discovered and enabled by optimizing these complex interfaces. The second chapter investigates the composition of the CEI formed by the Li-rich layered cathode material, Li₂RuO₃, to better understand performance decline in this class of materials. To bridge this gap in understanding, we use solid-state NMR (SSNMR) and surface-sensitive dynamic nuclear polarization (DNP) NMR to achieve high resolution compositional assignment of the CEI. We show that the CEI that forms on Li₂RuO₃, when cycled in carbonate-containing electrolytes, is similar to the solid electrolyte interphase (SEI) that has been observed on anode materials, containing components such as polyethylene oxide (PEO) structures, Li acetate, carbonates, and LiF. The CEI composition deposited on the cathode surface on charge is chemically distinct from that observed upon discharge, supporting the notion of crosstalk between the SEI and the CEI, with Li+-coordinating species leaving the CEI during delithiation. We use electrochemical impedance spectroscopy (EIS) to assess the impedance of the CEI on Li₂RuO₃ as a function of state of charge in connection with the migration of CEI species as identified with NMR. Migration of the outer CEI combined with the accumulation of poor ionic conducting components on the static inner CEI may contribute to the loss of performance over time in Li-excess cathode materials. This work demonstrates the utility of SSNMR for studying electrolyte decomposition at the cathode-electrolyte interface which is then applied in the following chapter to more commercially relevant materials. In the third chapter, we study the CEI and surface reactivity of the Ni-rich layered material LiNi₀.₈Mn₀.₁Co₀.₁O₂ (NMC811). The high specific capacities of Ni-rich transition-metal oxides have garnered immense interest for improving the energy density of Li-ion batteries. However, Ni-rich cathodes suffer from interfacial instabilities that lead to formation of electrochemically inactive phases at the cathode particle surface as well as the formation of a CEI layer on the composite surface during electrochemical cycling. We use a combination of ex situ SSNMR spectroscopy and X-ray photoemission electron microscopy (XPEEM) to provide chemical and spatial information, on the nanometer length scale, on the CEI deposited on NMC811 composite cathode films. XPEEM elemental maps offer insight into the lateral arrangement of the electrolyte decomposition products that comprise the CEI and paramagnetic interactions (assessed with electron paramagnetic resonance (EPR) and relaxation measurements) in 13C SSNMR provide information on the radial arrangement of the CEI from the NMC811 particles outward. Using this approach, we find that LiF, Li₂CO₃, and carboxy-containing structures are directly appended to NMC811 active particles, whereas soluble species detected during in situ 1H and 19F solution NMR experiments (e.g., alkyl carbonates, HF, and vinyl compounds) are randomly deposited on the composite surface. We show that the combined approach of ex situ SSNMR and XPEEM, in conjunction with in situ solution NMR, allows spatially resolved, molecular-level characterization of paramagnetic surfaces and new insights into electrolyte oxidation mechanisms in porous electrode films. The in situ solution NMR cell developed here is one of the first of its kind developed specifically for studying electrolyte decomposition products during or directly after battery operation, which is further developed in the next chapter. The fourth chapter focuses on studying the surface reactivity of the high-voltage LiNi₀.₅Mn₁.₅O₄ (LNMO) spinel cathode material. Unfortunately, LNMO-containing batteries suffer from poor cycling performance because of the intrinsically coupled processes of electrolyte oxidation and transition metal dissolution that occurs at high voltage. In this work, we use operando EPR and NMR spectroscopies to study these high voltage reactions, applying the in situ cell design from the previous chapter to operando conditions (characterization during battery charging). We demonstrate that transition metal dissolution in LNMO is tightly coupled to HF formation (and thus, electrolyte oxidation reactions as detected with operando and in situ solution NMR), indicative of an acid-driven disproportionation reaction that occurs during delithiation (battery charging). Leveraging the temporal resolution (s-min) of magnetic resonance, we find that the LNMO particles accelerate the rate of LiPF6 decomposition and subsequent Mn²⁺ dissolution, possibly due to the acidic nature of terminal Mn-OH groups and protic species generated upon oxidizing the solvents. X-ray photoemission electron microscopy (XPEEM) provides surface-sensitive and localized X-ray absorption spectroscopy (XAS) measurements, in addition to X-ray photoelectron spectroscopy (XPS), that indicate disproportionation is enabled by surface reconstruction upon charging, which leads to surface Mn³⁺ sites on the LNMO particle surface that can disproportionate into Mn²⁺(dissolved) and Mn⁴⁺(s). During discharge of the battery, we observe high quantities of metal fluorides (in particular, MnF₂) in the cathode electrolyte interphase (CEI) on LNMO as well as the conductive carbon additives in the composite. Electronic conductivity measurements indicate that the MnF₂ decreases film conductivity by threefold compared to LiF, suggesting that this CEI component may impede both the ionic and electronic properties of the cathode. Ultimately, to prevent transition metal dissolution and the associated side reactions in spinel-type cathodes (particularly those that operate at high voltages like LNMO), the use of electrolytes that offer improved anodic stability and prevent acid byproducts will likely be necessary. In the fifth chapter, we conduct an in situ X-ray spectroscopy, electron microscopy, and electron diffraction experiment to study the oxidation of the surface of Li metal, which is of critical importance for next generation Li metal batteries. Elemental Li is one of the most promising anode materials for high energy density Li batteries if it can replace graphite because it increases the specific capacity by an order of magnitude. However, Li metal is extremely reactive and is easily oxidized by air and moisture, even under inert conditions (e.g., in argon-filled gloveboxes, ultrahigh vacuum chambers). The industrial production of Li metal anodes, their surface evolution upon contact with the electrolyte, and electrodeposition behavior upon battery cycling all rely on the initial oxidative processes that take place prior to cell assembly. To better understand Li metal oxidation, we deposit pure Li on a Cu substrate and dose the Li deposit with various amounts of oxygen gas. During this experiment, we monitor the surface composition in situ using low-energy electron microscopy (LEEM), low-energy electron diffraction (LEED), and XPS measurements. We show that by evaporating Li onto Cu substrates, we can bypass long sputtering times needed to study commercial Li foils that usually exhibit alkali metal impurities and thick contamination layers from their external environment. Combined insights from LEED, LEEM and DFT calculations indicate that upon oxygen dosing of this ultrapure Li film, oxygen adsorbs to Li, forming a disordered layer, followed by (111) oriented polycrystalline Li₂O growth. DFT was particularly instrumental in elucidating the precise work function of the surface for the intermediate oxide phases (timescale of seconds) to correlate with trends observed via in situ LEEM imaging experiments. To conclude, we reflect on the overarching insight on cathode degradation that we have learned from these studies and discuss remaining knowledge gaps in the field. We highlight promising future avenues to study for stabilizing the cathode-electrolyte interface of these materials, such as adapting the characterization methods developed here for more high throughput study of next generation electrolyte formulations.

Cette thèse présente les résultats de travaux de recherches menés sur les décharges luminescentes pulsées de néon xénon destinées à être utilisées en remplacement des décharges gaz rares-mercure pour les applications d'enseignes lumineuses publicitaires ou architecturales. Les enseignes lumineuses sont formées par des tubes fluorescents à cathodes froides fonctionnant à haute tension. Ceci les distingue notamment des tubes fluorescents pour l'éclairage général qui fonctionnent avec le même type de mélange mais à basse tension avec des cathodes chaudes préchauffées. Ces recherches ont bénéficié d'un partenariat GREMI-ADEME-Région Centre- Aupem Sefli, et sont motivées par la volonté de proposer une technologie sans mercure, qui est un élément toxique pour l'environnement et qui nécessite la mise en place de filières de récupération et de valorisation lourdes. On s'est attaché à vérifier et préciser certains mécanismes fondamentaux de la décharge. Ces travaux ont aussi permis de dégager des conditions permettant d'optimiser les caractéristiques des enseignes néon-xénon en terme de flux lumineux, d'efficacité énergétique, et de durée de vie. A l'issue de cette thèse, la durée de vie et l'efficacité des tubes fluorescents à cathodes froides basés sur une décharge pulsée de néon xénon les placent entre les lampes à incandescence et les tubes fluorescents au mercure. Des pistes existent pour poursuivre l'amélioration de l'efficacité lumineuse.

In this thesis, the discharge products formed at the cathode and the performance and cell chemistry of sodium-oxygen batteries have been studied. This was carried out using different NaOTf salt concentrations. The influence of different salt concentrations on sodium-oxygen batteries was investigated since it has been shown that increasing the salt concentration beyond conventional concentrations could result in advantages such as increased stability of the electrolytes towards decomposition, higher thermal stability and lower volatility. An increase in salt concentration has also been shown to influence the electrochemical potential window. The solubility of NaOTf was investigated in two different solvents, DME and diglyme. NaOTf was found to be more soluble in DME compared to diglyme but due to the volatile nature of DME, three different concentrations of NaOTf were prepared with diglyme as solvent. Experimentation involved discharging the batteries to either maximum or limited capacity. The discharge products were examined and characterized using XRD and SEM. The main discharge product was identified as sodium superoxide although sodium peroxide dihydrate was also identified in one battery. A trend of higher capacity and voltage plateaus with higher salt concentration was also found. The influence of trace amounts of water was suggested as one explanation as it works as a catalyst, promoting sodium superoxide cube growth due to improved transportation of superoxide. Another or contributing explanation could be a possible change in donor number with increased salt concentration, resulting in higher solubility and longer lifetime of superoxide, promoting the growth of sodium superoxide cubes.

Laser Chemical Vapor Deposition (LCVD) has been shown to have great potential for the manufacture of small, complex, two or three dimensional metal and ceramic parts. One of the most promising applications of the technology is in the fabrication of an integrated dispenser cathode assembly. This application requires the deposition of a boron nitridemolybdenum composite structure. In order to realize this structure, work was done to improve the control and understanding of the LCVD process and to determine experimental conditions conducive to the growth of the required materials. A series of carbon fiber and line deposition studies were used to characterize processshape relationships and study the kinetics of carbon LCVD. These studies provided a foundation for the fabrication of the first high aspect ratio multilayered LCVD wall structures. The kinetics studies enabled the formulation of an advanced computational model in the FLUENT CFD package for studying energy transport, mass and momentum transport, and species transport within a forced flow LCVD environment. The model was applied to two different material systems and used to quantify deposition rates and identify ratelimiting regimes. A computational thermalstructural model was also developed using the ANSYS software package to study the thermal stress state within an LCVD deposit during growth. Georgia Techs LCVD system was modified and used to characterize both boron nitride and molybdenum deposition independently. The focus was on understanding the relations among process parameters and deposit shape. Boron nitride was deposited using a B3N3H6-N2 mixture and growth was characterized by sporadic nucleation followed by rapid bulk growth. Molybdenum was deposited from the MoCl5-H2 system and showed slow, but stable growth. Each material was used to grow both fibers and lines. The fabrication of a boron nitridemolybdenum composite was also demonstrated. In sum, this work served to both advance the general science of Laser Chemical Vapor Deposition and to elucidate the practicality of fabricating ceramicmetal composites using the process.

Solid oxide fuel cells (SOFCs) offer the advantages of (i) employing less expensive catalysts compared to the expensive Pt catalyst used in proton exchange membrane fuel cells and (ii) directly using hydrocarbon fuels without requiring external fuel reforming due to the high operating temperature. However, the conventional high operating temperatures of 800 - 1000 °C lead to interfacial reactions and thermal expansion mismatch among the components and limitations in the choice of electrode and interconnect materials. These problems have prompted a lowering of the operating temperature to an intermediate range of 500 - 800 °C, but the poor oxygen reduction reaction kinetics of the conventional La[subscript 1-x]Sr[subscript x]MnO₃ perovskite cathode remains a major obstacle for the intermediate temperature SOFC. In this regard, cobalt-containing oxides with perovskite or perovskite-related structures have been widely investigated, but they suffer from large thermal expansion coefficient (TEC) mismatch with the electrolytes. With an aim to lower the TEC and maximize the electrochemical performance, this dissertation focuses on perovskite-related and trigonal RBaCo₄O₇-based oxide cathode materials. First, the effect of M = Fe and Cu in the perovskite-related layered LnBaCo₂₋xMxO₊[delta] (Ln = Nd and Gd) oxides has been investigated. The Fe and Cu substitutions lower the polarization resistance and offer fuel cell performance comparable to that of La[subscript 1-x]Sr[subscript x]CoO₃₋[delta] perovskite due to improved chemical stability with the electrolyte and a better matching of the TEC with those of standard electrolytes. Second, the perovskite-related intergrowth oxides Ln(Sr,Ca)₃Fe₁.₅Co₁.₅O₀ and La₁.₈₅Sr₁.₁₅Cu[subscript 2-x]Co[subscript x]O[subscript 6 +delta] and their composites with gadolinia-doped ceria (GDC) have been investigated. The electrical conductivity, TEC, and catalytic activity increase with increasing Co content. The composite cathodes exhibit enhanced electrochemical performance due to lower TEC and increased triple-phase boundary. Third, RBa(Co,Zn)₄O₇ (R = Y, Ca, and In) oxides with a trigonal structure and tetrahedral-site Con+ ions have been investigated. The chemical instability normally encountered with this class of oxides has been overcome by appropriate cationic substitutions as in (Y₀.₅Ca₀.₅)Ba(Co₂.₅Zn₁.₅)O₇ and (Y₀.₅In₀.₅)BaCo₃ZnO₇. With an ideal matching of TEC with those of standard electrolytes, the RBa(Co,Zn)₄O₇ (R = Y, Ca, and In) + GDC composite cathodes exhibit low polarization resistance and electrochemical performance comparable to that of perovskite oxides. / text

Polymer-based carbide-derived carbons (CDCs) with combined micro- and mesopores are prepared by an advantageous sacrificial templating approach using poly(methylmethacrylate) (PMMA) spheres as the pore forming material. Resulting CDCs reveal uniform pore size and pore shape with a specific surface area of 2434 m2 g−1 and a total pore volume as high as 2.64 cm3 g−1. The bimodal CDC material is a highly attractive host structure for the active material in lithium–sulfur (Li–S) battery cathodes. It facilitates the utilization of high molarity electrolytes and therefore the cells exhibit good rate performance and stability. The cathodes in the 5 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) electrolyte show the highest discharge capacities (up to 1404 mA h gs−1) and capacity retention (72% after 50 cycles at C/5). The unique network structure of the carbon host enables uniform distribution of sulfur through the conductive media and at the same time it facilitates rapid access for the electrolyte to the active material.

Two novel lithium host materials were investigated using structural and electrochemical analysis; the cathode material Li₂CoSiO₄ and the LiMO₂ class of anodes (where M is a transition metal ion). Li₂CoSiO₄ materials were produced utilising a combination of solid state and hydrothermal synthesis conditions. Three Li₂CoSiO₄ polymorphs were synthesised; β[subscript(I)], β[subscript(II)] and γ₀. The Li₂CoSiO₄ polymorphs formed structures based around a distorted Li₃PO₄ structure. The β[subscript(II)] material was indexed to a Pmn2₁ space group, the β[subscript(I)] polymorph to Pbn2₁ and the γ₀ material was indexed to the P2₁/n space group. A varying degree of cation mixing between lithium and cobalt sites was observed across the polymorphs. The β[subscript(II)] polymorph produced 210mAh/g of capacity on first charge, with a first discharge capacity of 67mAh/g. It was found that the β[subscript(I)] material converted to the β[subscript(II)] polymorph during first charge. The γ₀ polymorph showed almost negligible electrochemical performance. Capacity retention of all polymorphs was poor, diminishing significantly by the tenth cycle. The effect of mechanical milling and carbon coating upon β[subscript(II)], β[subscript(I)] and γ₀ materials was also investigated. Various Li[subscript(1+x)]V[subscript(1-x)]O₂ materials (where 0≤X≤0.2) were produced through solid state synthesis. LiVO₂ was found to convert to Li₂VO₂ on discharge, this process was found to be strongly dependent on the amount of excess lithium in the system. The Li₁.₀₈V₀.₉₂O₂ material had the highest first discharge capacity at 310mAh/g. It was found that the initial discharge consisted of several distinct electrochemical processes, connected by a complicated relationship, with significant irreversible capacity on first discharge. Several other LiMO₂ systems were investigated for their ability to convert to layered Li₂MO₂ structures on low voltage discharge. While LiCoO₂ failed to convert to a Li₂CoO₂ structure, LiMn₀.₅Ni₀.₅O₂ underwent an addition type reaction to form Li₂Mn₀.₅Ni₀.₅O₂. A previously unknown Li₂Ni[subscript(X)]Co[subscript(1-X)]O₂ structure was observed, identified during the discharge of LiNi₀.₃₃Co₀.₆₆O₂.