Three-dimensional macroporous structures (‘opals’ and ‘inverse opals’) can be produced by colloidal crystal templating, one of the most intensively studied areas in materials science today. There are several potential advantages of lithium-ion battery electrodes based on inverse opal structures. High electrode surface, easier electrolyte access to the bulk of electrode and reduced lithium diffusion lengths allow higher discharge rates. Highly open structures provide for better mechanical stability to volume swings during cycling. Silicon is one of the most promising anode materials for lithium-ion batteries. Its theoretical capacity exceeds capacities of all other materials besides metallic lithium. Silicon is abundant, cheap, and its use would allow for incorporation of microbattery production into the semiconductor manufacturing. Performance of silicon is restricted mainly by large volume changes during cycling. The objective of this work was to investigate how the inverse opal structures influence the performance of silicon electrodes. Several types of silicon-based inverse opal films were synthesised, and their electrochemical performance was studied. Amorphous silicon inverse opals were fabricated via chemical vapour deposition and characterised by various techniques. Galvanostatic cycling of these materials confirmed the feasibility of the approach taken, since the electrodes demonstrated high capacities and decent capacity retentions. The rate performance of amorphous silicon inverse opals was unsatisfactory due to low conductivity of silicon. The conductivity of silicon inverse opals was improved by crystallisation. Nanocrystalline silicon inverse opals demonstrated much better rate capabilities, but the capacities faded to zero after several cycles. Silicon-carbon composite inverse opal materials were synthesised by depositing a thin layer of carbon via pyrolysis of a sucrose-based precursor onto the silicon inverse opals in an attempt to further increase conductivity and achieve mechanical stabilisation of the structures. The amount of carbon deposited proved to be insufficient to stabilise the structures, and silicon-carbon composites demonstrated unsatisfactory electrochemical behaviour. Carbon inverse opals were coated with amorphous silicon producing another type of macroporous composites. These electrodes demonstrated significant improvement both in capacity retentions and in rate capabilities. The inner carbon matrix not only increased the material conductivity, but also resulted in lower silicon pulverisation during cycling.

Η παρούσα διπλωματική εργασία έχει ως αντικείμενο την μελέτη της επίδρασης της μορφής της ανόδου στην παραγωγή εκκενώσεων τύπου αίγλης. Για τον σκοπό αυτό μελετώνται οι εκκενώσεις που παράγονται στο εσωτερικό ενός αντιδραστήρα παραγωγής ψυχρού πλάσματος, μεταξύ μιας μη συμμετρικής διάταξης ηλεκτροδίων (διάκενο ακίδας-πλάκας), ο οποίος βρίσκεται στο εργαστήριο Ηλεκτροτεχνικών Υλικών του τμήματος Ηλεκτρολόγων Μηχανικών και Τεχνολογίας Υπολογιστών. Ειδικότερα, μελετώνται οι εκκενώσεις για τρεις διαφορετικούς τύπους ανόδου, κατασκευασμένες από διαφορετικό υλικό κάθε φορά, πραγματοποιώντας μια σειρά μετρήσεων από τις οποίες εξάγονται οι χαρακτηριστικές τάσης-ρεύματος για διάφορες τιμές της πίεσης εντός του αντιδραστήρα και για δύο διαφορετικές τιμές του μήκους του διακένου. Επιπρόσθετα, για τις παραπάνω συνθήκες, λαμβάνονται παλμοί ρεύματος και φωτός(με την βοήθεια ενός φωτοπολλαπλασιαστή) της εκκένωσης, οι οποίοι απεικονίζουν την φωτεινή δραστηριότητα κατά μήκος του διακένου. Από την επεξεργασία όλων των παραπάνω μετρήσεων, γίνεται προσπάθεια εξαγωγής συμπερασμάτων σχετικά με την επίδραση που δύναται να έχει η μορφή της ανόδου, στην παραγωγή μιας εκκένωσης αίγλης. Ειδικότερα: •Στο πρώτο κεφάλαιο, γίνεται μια σύντομη ιστορική αναφορά και αναφέρονται κάποιες βασικές γνώσεις και χαρακτηριστικά που αφορούν στο πλάσμα. •Στο δεύτερο κεφάλαιο, παρατίθενται συνοπτικά τα καθεστώτα λειτουργίας μιας εκκένωσης αίγλης και συγχρόνως αναλύεται η εκκένωση, από φαινομενολογικής άποψης. •Στο τρίτο κεφάλαιο, περιγράφεται αναλυτικά η πειραματική διάταξη στην οποία έγινε το σύνολο των μετρήσεων. Παρουσιάζονται τα επιμέρους όργανα, που χρησιμοποιούνται για την μέτρηση συγκεκριμένων μεγεθών και ταυτόχρονα παρατίθενται διάφορες φωτογραφίες που απεικονίζουν οπτικά τα επιμέρους τμήματα που την απαρτίζουν. •Στο τέταρτο κεφάλαιο, παρουσιάζεται το σύνολο των μετρήσεων, το οποίο περιλαμβάνει χαρακτηριστικές τάσης-ρεύματος, παλμούς ρεύματος και παλμούς φωτός για τις τρεις διαφορετικές ακίδες, για μια σειρά συνθηκών καθώς και συγκρίσεις διαφόρων μεγεθών που εξάγονται από τα παραπάνω. / In this thesis, the effect of the anode’s geometry on the production of glow discharges is studied. For this purpose, glow discharges produced inside a cold plasma reactor, between a non-symmetrical set-up of electrodes, are investigated. In particular, we study glow discharges for three types of anode, which are made of different materials. Initially, a series of measurements of the gap voltage and current is taken and the V-I characteristics are extracted, each for different values of pressure inside the reactor and two different values of gap length (d=1cm, d=2cm). Furthermore, for the above conditions, several current and light impulses (using a photomultiplier) are recorded, demonstrating the light distribution and light emission among the gap. Using all the above measurement, the effect of the anode’s geometry on the glow discharge production is analyzed. In summary, the following subjects are treated: • Basic characteristics of plasma and short historical reference. •Short reference to different functional regimes of a glow discharge and phenomenological analysis of the discharge. •Description of the experimental set-up and measuring instruments. •Experimental measurements of current and gap voltage (V-I characteristics), current pulses, light pulses, conclusions.

O dióxido de cério (CeO2), pode apresentar condutividade iônica e eletrônica (condutor misto) em temperaturas relativamente baixas (considerando a faixa de trabalho 1000°C de uma SOFC). Esta característica torna este material promissor para uso em células a combustível de óxido sólido (SOFC ou CCOS) assim como em catalisadores. Vale destacar que em altas temperaturas o dióxido de cério puro é um mau condutor iônico, contudo pode-se obter um aumento significativo com a substituição estrutural do íon cério (Ce+4) por outro íon metálico de menor valência (La+3 e Ca+2). O estudo proposto consiste em sintetizar óxido de cério dopado com lantânio e cálcio com características microestruturais e elétricas adequadas para uso em uma CCOS. Utilizando o método de síntese de combustão foi estudado a influência que o excesso de combustível (sacarose) pode proporcionar nas características finais dos pós cerâmicos. A caracterização dos pós foi realizada pelas técnicas de raios-X (DRX), área superficial especifica (BET), análise termogravimétrica (TGA), Microscopia Eletrônica de: Varredura (MEV) e Transmissão (MET), Microscopia de Calefação (MC) e por fim a análise elétrica por meio da Espectroscopia de Impedância Eletroquímica (EIE). Os principais resultados mostraram que a técnica de síntese por combustão é um método eficiente para obtenção de pós nanoparticulados, bem dispersos e com elevada homogeneidade. Observou-se ainda que a troca do tipo de dopante assim como o teor de combustível utilizado na síntese interfere diretamente nas propriedades microestruturais, físicas e elétricas dos compostos finais a base de céria dopada. As amostras apresentaram comportamento condutor em baixas temperaturas (500°C) o que viabiliza sua utilização como catalizadores e também em CCOS após tratamentos térmicos em atmosferas adequadas para aplicação como eletrodos ou eletrólitos. Os resultados também demonstram que a céria dopada com cálcio tem características que se torna viável a substituição do lantânio para uso em uma CCOS. / The cerium dioxide (CeO2) has ionic and electronic conductivity (mixed conductor) properties at relatively low temperatures (considering a working range of 1000°C for a SOFC). These characteristics make this material appropriate for use as anode in solid oxide fuel cells (SOFC or CCOS). It should be mentioned that pure cerium dioxide is a bad ionic conductor in high temperatures, but we have a significant increase with the structural substitution of the cerium ion (Ce+4) by another metal ion of lower valence (in its crystalline lattice). The proposed study consisted in the synthesis of ceria oxide with lanthanum and/ or calcium with microstructural and electrical characteristics, suitable for use in a CCOS. Using the combustion synthesis, the influence of excess of fuel (sucrose) on the final characteristics of the ceramic powder has been analyzed. The characterization of the powders was realized using X-ray (XRD), specific surface area (BET), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), Electron Microscope Transmission (TEM), Microscope Heating (HSM) and Electrochemical Impedance Spectroscopy (EIS). The main results showed that the combustion synthesis technique is an efficient method to obtain nanoparticulate and well dispersed powders with high homogeneity. It was observed that the exchange of the dopant type as well as the fuel content used in the synthesis interferes directly in the microstructural, physical and electrical properties of the final compounds of ceria doped. Therefore, the calcium doped ceria has interesting characteristics for use in a CCOS.

abstract: Microbial Electrochemical Cell (MXC) technology harnesses the power stored in wastewater by using anode respiring bacteria (ARB) as a biofilm catalyst to convert the energy stored in waste into hydrogen or electricity. ARB, or exoelectrogens, are able to convert the chemical energy stored in wastes into electrical energy by transporting electrons extracellularly and then transferring them to an electrode. If MXC technology is to be feasible for ‘real world’ applications, it is essential that diverse ARB are discovered and their unique physiologies elucidated- ones which are capable of consuming a broad spectrum of wastes from different contaminated water sources. This dissertation examines the use of Gram-positive thermophilic (60 ◦C) ARB in MXCs since very little is known regarding the behavior of these microorganisms in this setting. Here, we begin with the draft sequence of the Thermincola ferriacetica genome and reveal the presence of 35 multiheme c-type cytochromes. In addition, we employ electrochemical techniques including cyclic voltammetry (CV) and chronoamperometry (CA) to gain insight into the presence of multiple pathways for extracellular electron transport (EET) and current production (j) limitations in T. ferriacetica biofilms. Next, Thermoanaerobacter pseudethanolicus, a fermentative ARB, is investigated for its ability to ferment pentose and hexose sugars prior to using its fermentation products, including acetate and lactate, for current production in an MXC. Using CA, current production is tracked over time with the generation and consumption of fermentation products. Using CV, the midpoint potential (EKA) of the T. pseudethanolicus EET pathway is revealed. Lastly, a cellulolytic microbial consortium was employed for the purpose ofassessing the feasibility of using thermophilic MXCs for the conversion of solid waste into current production. Here, a highly enriched consortium of bacteria, predominately from the Firmicutes phylum, is capable of generating current from solid cellulosic materials. / Dissertation/Thesis / Doctoral Dissertation Biological Design 2015

O dióxido de cério (CeO2), pode apresentar condutividade iônica e eletrônica (condutor misto) em temperaturas relativamente baixas (considerando a faixa de trabalho 1000°C de uma SOFC). Esta característica torna este material promissor para uso em células a combustível de óxido sólido (SOFC ou CCOS) assim como em catalisadores. Vale destacar que em altas temperaturas o dióxido de cério puro é um mau condutor iônico, contudo pode-se obter um aumento significativo com a substituição estrutural do íon cério (Ce+4) por outro íon metálico de menor valência (La+3 e Ca+2). O estudo proposto consiste em sintetizar óxido de cério dopado com lantânio e cálcio com características microestruturais e elétricas adequadas para uso em uma CCOS. Utilizando o método de síntese de combustão foi estudado a influência que o excesso de combustível (sacarose) pode proporcionar nas características finais dos pós cerâmicos. A caracterização dos pós foi realizada pelas técnicas de raios-X (DRX), área superficial especifica (BET), análise termogravimétrica (TGA), Microscopia Eletrônica de: Varredura (MEV) e Transmissão (MET), Microscopia de Calefação (MC) e por fim a análise elétrica por meio da Espectroscopia de Impedância Eletroquímica (EIE). Os principais resultados mostraram que a técnica de síntese por combustão é um método eficiente para obtenção de pós nanoparticulados, bem dispersos e com elevada homogeneidade. Observou-se ainda que a troca do tipo de dopante assim como o teor de combustível utilizado na síntese interfere diretamente nas propriedades microestruturais, físicas e elétricas dos compostos finais a base de céria dopada. As amostras apresentaram comportamento condutor em baixas temperaturas (500°C) o que viabiliza sua utilização como catalizadores e também em CCOS após tratamentos térmicos em atmosferas adequadas para aplicação como eletrodos ou eletrólitos. Os resultados também demonstram que a céria dopada com cálcio tem características que se torna viável a substituição do lantânio para uso em uma CCOS. / The cerium dioxide (CeO2) has ionic and electronic conductivity (mixed conductor) properties at relatively low temperatures (considering a working range of 1000°C for a SOFC). These characteristics make this material appropriate for use as anode in solid oxide fuel cells (SOFC or CCOS). It should be mentioned that pure cerium dioxide is a bad ionic conductor in high temperatures, but we have a significant increase with the structural substitution of the cerium ion (Ce+4) by another metal ion of lower valence (in its crystalline lattice). The proposed study consisted in the synthesis of ceria oxide with lanthanum and/ or calcium with microstructural and electrical characteristics, suitable for use in a CCOS. Using the combustion synthesis, the influence of excess of fuel (sucrose) on the final characteristics of the ceramic powder has been analyzed. The characterization of the powders was realized using X-ray (XRD), specific surface area (BET), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), Electron Microscope Transmission (TEM), Microscope Heating (HSM) and Electrochemical Impedance Spectroscopy (EIS). The main results showed that the combustion synthesis technique is an efficient method to obtain nanoparticulate and well dispersed powders with high homogeneity. It was observed that the exchange of the dopant type as well as the fuel content used in the synthesis interferes directly in the microstructural, physical and electrical properties of the final compounds of ceria doped. Therefore, the calcium doped ceria has interesting characteristics for use in a CCOS.

abstract: Novel materials for Li-ion batteries is one of the principle thrust areas for current research in energy storage, more so than most, considering its widespread use in portable electronic gadgets and plug-in electric and hybrid cars. One of the major limiting factors in a Li-ion battery's energy density is the low specific capacities of the active materials in the electrodes. In the search for high-performance anode materials for Li-ion batteries, many alternatives to carbonaceous materials have been studied. Both cubic and amorphous silicon can reversibly alloy with lithium and have a theoretical capacity of 3500 mAh/g, making silicon a potential high density anode material. However, a large volume expansion of 300% occurs due to changes in the structure during lithium insertion, often leading to pulverization of the silicon. To this end, a class of silicon based cage compounds called clathrates are studied for electrochemical reactivity with lithium. Silicon-clathrates consist of silicon covalently bonded in cage structures comprised of face sharing Si20, Si24 and/or Si28 clusters with guest ions occupying the interstitial positions in the polyhedra. Prior to this, silicon clathrates have been studied primarily for their superconducting and thermoelectric properties. In this work, the synthesis and electrochemical characterization of two categories of silicon clathrates - Type-I silicon clathrate with aluminum framework substitution and barium guest ions (Ba8AlxSi46-x) and Type-II silicon clathrate with sodium guest ions (Nax Si136), are explored. The Type-I clathrate, Ba8AlxSi46-x consists of an open framework of aluminium and silicon, with barium (guest) atoms occupying the interstitial positions. X-ray diffraction studies have shown that a crystalline phase of clathrate is obtained from synthesis, which is powdered to a fine particle size to be used as the anode material in a Li-ion battery. Electrochemical measurements of these type of clathrates have shown that capacities comparable to graphite can be obtained for up to 10 cycles and lower capacities can be obtained for up to 20 cycles. Unlike bulk silicon, the clathrate structure does not undergo excessive volume change upon lithium intercalation, and therefore, the crystal structure is morphologically stable over many cycles. X-ray diffraction of the clathrate after cycling showed that crystallinity is intact, indicating that the clathrate does not collapse during reversible intercalation with lithium ions. Electrochemical potential spectroscopy obtained from the cycling data showed that there is an absence of formation of lithium-silicide, which is the product of lithium alloying with diamond cubic silicon. Type II silicon clathrate, NaxSi136, consists of silicon making up the framework structure and sodium (guest) atoms occupying the interstitial spaces. These clathrates showed very high capacities during their first intercalation cycle, in the range of 3,500 mAh/g, but then deteriorated during subsequent cycles. X-ray diffraction after one cycle showed the absence of clathrate phase and the presence of lithium-silicide, indicating the disintegration of clathrate structure. This could explain the silicon-like cycling behavior of Type II clathrates. / Dissertation/Thesis / M.S. Materials Science and Engineering 2013

abstract: In engineering, buckling is mechanical instability of walls or columns under compression and usually is a problem that engineers try to prevent. In everyday life buckles (wrinkles) on different substrates are ubiquitous -- from human skin to a rotten apple they are a commonly observed phenomenon. It seems that buckles with macroscopic wavelengths are not technologically useful; over the past decade or so, however, thanks to the widespread availability of soft polymers and silicone materials micro-buckles with wavelengths in submicron to micron scale have received increasing attention because it is useful for generating well-ordered periodic microstructures spontaneously without conventional lithographic techniques. This thesis investigates the buckling behavior of thin stiff films on soft polymeric substrates and explores a variety of applications, ranging from optical gratings, optical masks, energy harvest to energy storage. A laser scanning technique is proposed to detect micro-strain induced by thermomechanical loads and a periodic buckling microstructure is employed as a diffraction grating with broad wavelength tunability, which is spontaneously generated from a metallic thin film on polymer substrates. A mechanical strategy is also presented for quantitatively buckling nanoribbons of piezoelectric material on polymer substrates involving the combined use of lithographically patterning surface adhesion sites and transfer printing technique. The precisely engineered buckling configurations provide a route to energy harvesters with extremely high levels of stretchability. This stiff-thin-film/polymer hybrid structure is further employed into electrochemical field to circumvent the electrochemically-driven stress issue in silicon-anode-based lithium ion batteries. It shows that the initial flat silicon-nanoribbon-anode on a polymer substrate tends to buckle to mitigate the lithiation-induced stress so as to avoid the pulverization of silicon anode. Spontaneously generated submicron buckles of film/polymer are also used as an optical mask to produce submicron periodic patterns with large filling ratio in contrast to generating only ~100 nm edge submicron patterns in conventional near-field soft contact photolithography. This thesis aims to deepen understanding of buckling behavior of thin films on compliant substrates and, in turn, to harness the fundamental properties of such instability for diverse applications. / Dissertation/Thesis / Ph.D. Mechanical Engineering 2014

Este trabalho investigou a oxidação eletroquímica do ácido tânico em eletrodos do tipo Ânodo Dimensionalmente Estáveis (ADE) a base de SnO2 e IrO2 e eletrodos de Diamante Dopado com Boro (BDD). As eletrólises foram feitas em modo galvanostático em função de parâmetros como densidade de corrente e concentração de cloreto. A oxidação eletroquímica do ácido tânico foi capaz de promover a diminuição da concentração de fenóis totais, Carbono Orgânico Total (COT) e Demanda Química de oxigênio (DQO). Para os ADE os melhores resultados de remoção de Carbono Orgânico Total (COT) foram nas condições em que se utilizou 300 mg L-1 de cloreto e densidade de corrente de 25 mA cm-2. No entanto houve a formação de compostos organoclorados que não foram degradados com maiores tempo de reação. Para os eletrodos de BDD, obteve-se a remoção de aproximadamente 98% de COT após 10 horas de reação à 75 mA cm-2, na ausência de cloreto. Maiores remoções de COT são obtidas com o aumento da densidade de corrente. Eletrólises na presença de cloreto removeram quase 100% do COT em tempos menores de reação. Análises de compostos organohalogenados (AOX) mostraram que não houve a formação de compostos organoclorados. Menores densidades de corrente apresentaram maiores Eficiência de Corrente (EC) e menor Consumo de Energia (CE). As eletrólises na presença de cloro apresentaram melhores resultados de EC que na ausência do mesmo. A oxidação fotoeletroquímia do ácido tânico em eletrodos do tipo ADE de composição nominal Ti/ Sn0,7 Ir0,3 O2 também foi investigada nesse trabalho. O tratamento fotoeletroquímico foi realizado utilizando uma lâmpada de vapor de mercúrio de alta pressão de 125 W como fonte de irradiação. A variação da corrente não mostrou diferença significativa na oxidação do ácido tânico. A variação da concentração de cloreto no eletrólito suporte influenciou de forma acentuada a oxidação do ácido tânico. O tratamento fotoeletroquímico se mostrou mais eficiente na remoção de COT que os tratamentos eletroquímico e fotoquímico. No tratamento fotoeletroquímico ocorreu a formação de AOX no início da reação, no entanto com o passar do tempo esses compostos foram degradados. / This study investigated the electrochemical oxidation of tannic acid on electrodes of the Dimensionally Stable Anode (DSA) type based on SnO2 and IrO2 as well as on boron doped diamond (BDD) electrodes. The electrolyses were performed in the galvanostatic mode, as a function of such parameters as current density and chloride concentration. The electrochemical oxidation of tannic acid was able to promote the reduction of the concentration of total phenolics, total organic carbon (TOC), and chemical oxygen demand (COD). For the DSA the best results of Total Organic Carbon (TOC) removal were achieved at 300 ppm chloride and current density of 25 mA cm-2. However, organochlorine compounds were formed and were not degraded with increased reaction times. For the BDD electrodes, the removal of approximately 98% TOC was obtained after 10 hours of reaction at 75 mA cm-2, in the absence of chloride. Major TOC removals were obtained with increasing current density. Electrolyses in the presence of chloride removed almost 100% TOC in shorter reaction times. Analysis of organohalogen compounds (AOX) showed no formation of organochlorine compounds. Lower current densities led to higher current efficiency (CE) and lower Energy Consumption (EC). The electrolyses in the presence of chlorine produced better CE results than those performed in the absence of chlorine. The photoelectrochemical oxidation of tannic acid in ADE-type electrodes of nominal composition Ti / Sn0.9 Ir0.3 O2 was also investigated in this work. The photoelectrochemical treatment was performed using a high pressure mercury vapor lamp 125 W as the source of irradiation. The variation in current revealed no significant difference in the oxidation of tannic acid. The variation in chloride concentration in the electrolyte markedly influenced the oxidation of tannic acid. The photoelectrochemical treatment was more efficient for TOC removal than the electrochemical and photochemical treatments. Formation of AOX occurred at the beginning of the photoelectrochemical treatment, but over time these compounds were degraded.

Le silicium est un matériau étudié depuis plusieurs années comme une sérieuse alternative au graphite dans les batteries Li-ion. Ce travail de thèse vise à développer des approches alternatives et complémentaires à celles déjà existantes afin de mieux comprendre les mécanismes de lithiation et de dégradation. L'analyse croisée entre plusieurs techniques, principalement FIB-ToF-SIMS, Auger, XPS et FIB-MEB, point central de l'étude, nécessite la mise en place de protocoles spécifiques prenant en compte la forte réactivité des échantillons lithiés. En premier lieu, un couplage entre ToF-SIMS et XPS sur des couches minces de silicium, permet de mettre en évidence la présence d'une phase riche en lithium ségrégée à l'interface entre la couche de matériau actif et le collecteur de courant en cuivre. Un mécanisme particulier de lithiation du silicium, basé sur l'existence de chemins de diffusion rapide pour le lithium, est suggéré. La réalisation de coupes FIB effectuées in situ dans la chambre d'analyse du ToF-SIMS sur des électrodes à base de poudre micrométrique de Si permet ensuite de proposer un mécanisme de lithiation analogue à celui mis en évidence précédemment. En outre, la présence de grains déconnectés du réseau percolant de l'électrode au cours du cyclage et piégeant le lithium est mise en évidence et contribue à la défaillance rapide de la batterie. Enfin, la méthodologie développée est appliquée à l'étude d'électrodes composées de Si nanométrique et de composite Si/C. Elle participe à l'établissement d'un modèle de croissance de SEI à la surface de grains de silicium nanométriques et permet d'identifier les raisons de la défaillance de ces électrodes. / Silicon is a serious option to replace graphite in anodes for Li-ion batteries since it offers a specific capacity almost ten times higher. However, silicon anodes suffer from a drastic capacity fading, making it unusable after a few cycles. The work presented here aims at the development of new alternative and complementary approaches to those currently used, in order to better understand lithiation and degradation mechanisms. These methods are based on cross-analysis between several surface characterizations techniques, including FIB-ToF-SIMS, AES, XPS and FIB-MEB, which require specific procedures to deal with the extreme sensitivity of lithiated materials. Coupling XPS and ToF-SIMS on silicon thin films revealed the presence of a Li-rich phase segregated at the interface between silicon and Cu current collector. A mechanism based on fast diffusion paths for lithium is suggested. In situ FIB milling, performed in the analysis chamber of the ToF-SIMS on anodes using micrometer-sized silicon particles, revealed a similar mechanism involving fast diffusion paths for lithium. Additional TEM observations suggest that, in the case of micrometer-sized particles, these paths result from sub-grain boundaries. Additionally, the presence of Li trapped in Si particles which are disconnected from the conductive grid along cycling is shown, contributing to the poor battery lifespan. Finally, the developed method has been applied to electrodes based on nanometer-sized Si particles and Si/C composite. Despite of the small size of the involved particles, it is possible to get information about SEI growth on the surface of nano-sized silicon particles and to identify causes of failure.

This master thesis work examines whether it is possible to separate lead from an electrolytic sludge rich in manganese using pyrometallurgical treatment, and also attempts to determine the optimum process parameters for such a treatment. It also includes a theoretical study of the possible applications for lead and manganese, as well as thermodynamic calculations predicting the behaviour of the material at increasing temperatures. The experimental work completed includes characterisation and agglomeration of the raw material, as well as tests in a chamber furnace and a rotary furnace. The anode sludge was characterised using chemical analysis, XRD, SEM and PSD. The anode sludge was agglomerated into pellets using either both bentonite and water, or only water as binder. The smaller scale tests in the chamber furnace examined the impact of several variables on lead removal. These variables included type and amount of reduction agent used, temperature, and whether the anode sludge was added as untreated material or pellets. The most promising of these results were further tested in the rotary furnace at a slightly larger scale. The variables used for the rotary furnace tests were amount of reduction agent added, whether the anode sludge was added as untreated material or pellets, and whether the reduction agent was added at the start of or during the experiment. All samples were sent for chemical analysis, and selected samples were further analysed using XRD and SEM. The conclusions drawn from the results of the thermodynamic calculations and experimental work are as follows: In the untreated anode sludge the primary phases are MnO2, CaSO4, and (Pb,Sr)SO4. The anode sludge can be agglomerated into pellets, with or without added binder. After treatment the primary phases present are MnO and (Ca,Sr)2SiO4. Lead is present as small separate grains. The most effective treatment method should adhere to the following parameters:Use of a rotating furnace. Anode sludge added in the form of pellets, to simplify materials handling. Temperature of 1400-1500 °C. Reduction agent added in batches after initial smoke formation has stopped. Total addition of reduction agent should be 10 wt% of anode sludge. Significant weight loss occurs during treatment. The amount of reduction agent added to the anode sludge has the greatest effect on the removal of lead and zinc. Charcoal is a potential candidate for a renewable reduction agent, but leads to increased weight loss. It is possible to separate lead from the manganese anode sludge using pyrometallurgical treatment, down to 100 ppm. Zinc can also be separated, down to 600 ppm. / Detta examensarbete undersöker huruvida det är möjligt att separera bly från ett anodslam rikt i mangan med hjälp av pyrometallurgiska behandlingsmetoder, och försöker även avgöra de optimala processparametrarna för en sådan behandling. Arbetet inkluderar även en teoristudie av möjliga användningsområden för bly och mangan, samt termodynamiska beräkningar som förutser materialets beteende vid ökande temperaturer. Det experimentella arbetet som utförts inkluderar karakterisering och agglomerering av råmaterialet, samt försök i en kammarugn och en rullugn. Anodslammet karakteriserades med hjälp av kemisk analys, XRD, SEM, och partikelstorleksfördelning. Anodslammet agglomererades till pellets med antingen bentonit och vatten eller bara vatten som bindemedel. Försöken i mindre skala i kammarugnen undersökte hur flera variabler påverkade blyavdrivningen. Dessa variabler inkluderade typ och mängd av reduktionsmedel som tillsattes, temperatur, och huruvida anodslammet som användes var obehandlat material eller pellets. De mest lovande av dessa resultat användes för vidare försök i rullugnen i något större skala. Variablerna som undersöktes vid rullugnsförsöken var mängd reduktionsmedel som tillsattes, huruvida anodslammet som användes var obehandlat material eller pellets, samt huruvida reduktionsmedlet tillsattes vid start eller under försökets gång. Alla prover skickades för kemisk analys, och utvalda prover analyserades ytterligare med XRD och SEM. Slutsatserna som dragits utifrån resultaten av de termodynamiska beräkningarna och det experimentella arbetet är som följande: I det obehandlade anodslammet är de primära faserna MnO2, CaSO4, och (Pb,Sr)SO4. Anodslammet kan agglomereras till pellets. Efter behandling är de primära faserna i materialet MnO och (Ca,Sr)2SiO4. Kvarvarande bly är närvarande som små separata korn. Den mest effektiva behandlingsmetoden bör använda följande parametrar: Användning av en roterande ugn. Anodslam bör tillsättas i form av pellets för att underlätta materialhantering. Temperatur mellan 1400-1500 °C. Reduktionsmedel tillsatt i omgångar efter att initial rökbildningen avstannat. Total tillsats av reduktionsmedel bör vara 10 vikt% av anodslammets vikt. Signifikanta viktförluster under behandling. Mängden tillsatt reduktionsmedel är den faktor som har störst effekt på avlägsnandet av bly och zink. Träkol är en potentiell kandidat för ett förnyelsebart reduktionsmedel, men orsakar ökade viktförluster. Det är möjligt att separera bly från mangan med hjälp av pyrometallurgiska metoder, ned till 100 ppm bly. Zink kan också separeras, ned till 600 ppm.