The demand for Lithium-ion batteries (LIBs) has been growing exponentially in recent years due to the proliferation of electric vehicles (EV). A large amount of lithium-ion batteries are expected to reach their end-of-life (EOL) within five to seven years. The improper disposal of EOL lithium-ion batteries generates enormous amounts of flammable and explosive hazardous waste. Therefore, cost-effectively recycling LIBs becomes urgent needs. Lithium nickel cobalt manganese oxides (NCM) are one of the most essential cathode materials for EV applications due to their long cycle life, high capacity, and low cost. In 2008, 18.9% of Lithium-ion batteries used NCM cathode material worldwide while this number increased to 31% six years later. An environment–friendly and low-cost direct recycling process for NCM has been developed in this project. The goal of this project is to recycle the EOL NCM and yield battery-grade NCM with equivalent electrochemical performance compared to virgin materials. In order to achieve this goal, four different heat treatment conditions are investigated during the direct recycling process. From the experimental results, the charge and discharge capacities of the recycled material are stable (between 151-155 mAh/g) which is similar to that of the commercial MTI NCM when sintered at 850 °C for 12 hours in the air. In addition, the cycling performance of recycled NCM is better than the commercial MTI NCM up to 100 cycles. / Master of Science / The demand for Lithium-ion batteries has been growing exponentially in recent years due to the proliferation of electric vehicles. A large amount of lithium-ion batteries are expected to reach their end-of-life within five to seven years. The improper disposal of end-of-life lithium-ion batteries generates enormous amounts of flammable and explosive hazardous waste. Therefore, cost-effectively recycling Lithium-ion batteries becomes urgent needs. Lithium nickel cobalt manganese oxides are one of the most essential cathode materials for electric vehicles applications due to their long cycle life, high capacity, and low cost. In 2008, 18.9% of Lithium-ion batteries used Lithium nickel cobalt manganese oxides cathode material worldwide while this number increased to 31% six years later. An environment–friendly and low-cost direct recycling process for Lithium nickel cobalt manganese oxides material has been developed in this project. The goal of this project is to recycle the end-of-life manganese oxides cathode material. In order to achieve this goal, four different heat treatment conditions are investigated during the direct recycling process. From the experimental results, the cycling performance of recycled NCM is better than the commercial MTI NCM.

Understanding and establishing reaction mechanisms is an important area in heterogeneous catalysis. This dissertation describes the use of in situ laser Raman spectroscopy combined with kinetic measurements and dynamic experiments to determine the mechanism of catalytic reactions. Two cases involving ozone reactions on manganese oxide catalysts were treated. Manganese oxide was chosen because it is the most active of the transition metal oxides for ozone decomposition and because it is a well-known catalyst for complete oxidation reactions. The first case studied was that of the ozone decomposition reaction on a supported manganese oxide catalyst. An adsorbed species with a Raman signal at 884 cm-1 was observed and assigned to a peroxide species based on results of in situ Raman spectroscopy, 18O isotopic substitution measurements, and ab initio MO calculations. The reaction pathway of ozone decomposition was elucidated with carefully designed isotopic experiments. The reaction sequence was found to involve two irreversible, kinetically significant steps: 1) dissociative adsorption of ozone to form a peroxide species and an atomic oxygen species, and 2) desorption of the peroxide intermediate. The kinetic behavior of the peroxide species and the overall decomposition reaction were investigated to test the validity of the proposed sequence. The transient kinetics were found to be consistent with the steady state kinetics, and both were well represented by the two-step sequence, indicating that the proposed reaction sequence accurately described the mechanism of decomposition. The surface was found to be non-uniform, with activation energies that varied linearly with coverage. At zero surface coverage the activation energy for ozone adsorption was found to be 6.2 kJ mol-1, while that for desorption of the peroxide species was found to be 69.0 kJ mol-1. The second case investigated was that of ethanol oxidation using ozone on alumina and silica supported manganese oxide catalysts. Ethanol was found to react with ozone at lower temperatures than with oxygen, and also with a lower activation energy. The reaction kinetics was found to be well described by a power law equation with the reaction orders on ozone and ethanol being 0.89 and 0.81 respectively. The oxidation reactivity was found to be closely related to that of ozone decomposition, suggesting an important role of ozone decomposition in the reaction mechanism. In situ laser Raman spectroscopic studies showed the existence of adsorbed ethoxide species on the catalyst surface under reaction conditions, however, at a much lower concentration than when oxygen alone was used as the oxidant. Transient experiments provided direct evidence that surface peroxide (an adsorbed species due to ozone) and surface ethoxide (an adsorbed species due to ethanol) reacted with each other on the catalyst surface. / Ph. D.

by Tsai Yau Moon = 錳氧化物的金屬-絶緣體轉變 : 多層薄膜及異構結 / 蔡友滿. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references. / Text in English; abstracts in English and Chinese. / by Tsai Yau Moon = Meng yang hua wu de jin shu-jue yuan ti zhuan bian : duo ceng bo mo ji yi gou jie / Cai Youman. / Abstract / 論文摘要 / Acknowledgements / Table of Contents / List of Figures / List of Tables / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Perovskite-type structure / Chapter 1.2 --- Metal-insulator transition / Chapter 1.3 --- Magnetoresistance / Chapter 1.3.1 --- Giant magnetoresistance (GMR) / Chapter 1.3.2.1 --- Colossal magnetoresistance (CMR) in perovskite manganites / Chapter 1.3.2.2 --- Possible origin of CMR / Chapter 1.4 --- Brief review of p-n junction between perovskite manganites and STON (001) / Chapter 1.5 --- Our project / Chapter 1.6 --- Scope of this thesis work / References / Chapter Chapter 2 --- Preparation and characterization of manganite thin films / Chapter 2.1 --- Thin film deposition / Chapter 2.1.1 --- Facing-target sputtering (FTS) / Chapter 2.1.2 --- Vacuum system / Chapter 2.1.3 --- Deposition procedure / Chapter 2.1.4 --- Deposition conditions / Chapter 2.1.5 --- Oxygen annealing system / Chapter 2.1.6 --- Silver electrode coating system / Chapter 2.2 --- Characterization / Chapter 2.2.1 --- Alpha step profilometer / Chapter 2.2.2 --- X-ray diffraction (XRD) / Chapter 2.2.3 --- Transport property measurement / References / Chapter Chapter 3 --- [LCSMO/PCMO] multilayers / Chapter 3.1 --- [LCSMO (100 A)/PCMO (X A)] multilayers / Chapter 3.1.1 --- Sample preparation / Chapter 3.1.2 --- Results and discussion / Chapter 3.1.2.1 --- Structural analysis / Chapter 3.1.2.2 --- Transport properties / Chapter 3.2 --- [LCSMO (50 A)/PCMO (X A)] multilayers / Chapter 3.2.1 --- Sample preparation / Chapter 3.2.2 --- Results and discussion / Chapter 3.2.2.1 --- Structural analysis / Chapter 3.2.2.2 --- Transport properties / References / Chapter Chapter 4 --- [LSMO/PCMO] multilayers and LSMO/STON p-n junction / Chapter 4.1 --- [LSMO/PCMO] multilayers / Chapter 4.1.1 --- Sample preparation / Chapter 4.1.2 --- Results and discussion / Chapter 4.1.2.1 --- Structural analysis / Chapter 4.1.2.2 --- Magnetization / Chapter 4.2 --- LSMO/STON heterojunction / Chapter 4.2.1 --- Sample preparation / Chapter 4.2.2 --- Results and discussion / Chapter 4.2.2.1 --- Structural analysis / Chapter 4.2.2.2 --- Metal insulator transition of LSMO revealed by four point I-V measurement / Chapter 4.3 --- Conclusion / References / Chapter 5 Conclusion / Chapter 5.1 --- Conclusion / Chapter 5.2 --- Future outlook

Durant ce travail de thèse, d’importants paramètres concernant la synthèse de matériaux catalytiques nanostructurés à base de manganèse et d’oxydes de cobalt ont été établis. La corrélation entre les propriétés structurales du catalyseur et l’activité catalytique, ainsi que le mécanisme d’oxydation du CO ont été analysé au moyen d’une grande variété de méthodes expérimentales physico-chimiques.<p>De l’oxyde de manganèse non-stœchiométrique (MnOx) a été préparé par décomposition spinodale d’oxalate de manganèse trihydraté en ayant recours à la technique d’oxydation programmée en température (TPO). Tant l’analyse quantitative relatives à ces données TPO que les résultats obtenus par spectroscopie de structure au front d’absorption des rayons X (XANES), ainsi que par spectroscopie des photoélectrons X (XPS) ont permis d’estimer la stœchiométrie de l’oxyde avec un x situé entre 1.61 et 1.67. En accord avec à la fois la surface spécifique élevée et la combinaison d’isothermes d’adsorption/désorption de type I et IV, la microscopie électronique à transmission à haute résolution (HRTEM) démontre la présence de micro-bâtonnets caractéristiques et « imbriqués » les uns dans les autres, accompagné de particules nanocristalline à l’extrémité de ces bâtonnets.<p>Les découvertes faites par spectroscopie infra-rouge de réflexion diffuse par transformée de Fourier (DRIFTS), par études isotopiques et cinétiques suggère que l’adsorption des deux molécules, CO et O2, est suivie par leur réaction en surface via des intermédiaires de type carbonate/formate, pour finalement produire du CO2. Nous supposons un mécanisme de type Mars-van Krevelen où l’oxygène appartenant à la structure de type MnOx prend part dans l’oxydation catalytique du CO à basse température. Cependant, ces espèces mobiles d’oxygènes ne faisaient pas partie du cœur de phase du réseau d’oxyde, et de ce fait, ont été capables de « sauter » sur la surface et approvisionner les espèces oxygénées nécessaires à l’oxydation du CO déjà adsorbé.<p>Une structure spinelle d’oxyde de cobalt Co3O4 dans lequel le cobalt présente deux états de valence (+2 et +3) a été choisie pour élucider l’effet de la taille des particules sur l’activité lors de la réaction d’oxydation du CO. Tout d’abord, des nanoparticules monodispersées de cobalt métallique présentant une déviation standard en taille inférieure à 8% ont été synthétisées à partir de carbonyle de cobalt (Co2(CO)8) par une méthode optimisée «d’injection chaude». Un contrôle de la taille des nanoparticules dans la gamme 3 à 11 nm a pu être obtenu en variant la température d’injection du carbonyle de cobalt dans une solution de dichlorobenzène et d’acide oléique. La microscopie électronique à transmission (TEM) nous montre que ces particules de cobalt sont quasiment hémisphériques. Ensuite, de la silice poreuse (de type MCF-17) a été imprégnée par des nanoparticules de cobalt, et ensuite activée par TPO menant à des nanoparticules d’oxyde de cobalt. Des études par diffraction des rayons X (XRD) et spectroscopie des photoélectrons X (XPS) ont démontré la structure spinelle Co3O4. Finalement, l’activité des catalyseurs obtenus vis-à-vis de l’oxydation du monoxyde de carbone fut mesurée à 423 K et ce en fonction de la taille des particules. Les particules de Co3O4 présentant une taille allant de 5 à 8 nm se sont révélées les plus actives. Ceci peut s’expliquer par une plus grande mobilité des atomes d’oxygène en surface des nanoparticules d’oxyde de cobalt.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

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A reação de redução de oxigênio (RRO) e a reação de oxidação do borohidreto (ROB) foram estudadas em eletrólito alcalino em eletrodos formados por diversos tipos de óxidos de manganês dopados com Ni (II) dispersos sobre carbonos Monarch 1000, MM225 e E350. As técnicas de caracterização físico-química foram difração de raios X (DRX), microscopia eletrônica de transmissão de alta resolução (HR-TEM) equipado com espectrômetro de energia dispersiva de raios X (EDX). Já os estudos eletroquímicos compreenderam voltametria cíclica, curvas de polarização de estado quase estacionário além das técnicas de Espectroscopia de massas diferencial on line (DEMS) e Infravermelho com transformada de Fourier in situ (FTIR). Foi observada pequena inserção dos átomos de Ni na estrutura dos MnOx. A fase correspondente a NiMnOx/C está presente na forma de aglomerados nanocristalinos ou em forma de agulhas com tamanhos da ordem de 1,5 a 6,7 nm dependendo do tipo de carbono utilizado como substrato. Manganita (MnOOH) apresentou-se como fase preponderante para óxido de manganês disperso sobre carbono Monarch 1000 enquanto que para materiais dispersos sobre carbono MM225 e E350G a fase MnO2 esta presente em maior quantidade. Estudos eletroquímicos em camada fina utilizando eletrodo disco rotatório revelaram melhores atividade para a RRO e estabilidade para MnOx dopados com níquel. A RRO procede segundo o mecanismo peróxido, seguida pela reação de desproporcionação do íon HO2- formado. A extensão da reação de desproporcionação do íon HO2- aumenta com o aumento da quantidade de Ni. Sobre eletrocatalisadores suportados em carbonos MM225 e E350 a reação de desproporcionação é mais rápida e envolve um total de 4 e- por oxigênio molecular. As curvas de polarização para RRO obtidas na presença do íon BH4- mostraram que todos os materiais são tolerantes à presença do borohidreto. Resultados de DEMS on line e FTIR in situ mostraram que óxidos de manganês dopados com Ni além de serem ativos para RRO são também ativos para a ROB, porém há uma grande influência da composição e da morfologia dos materiais uma vez que, quando fases segregadas de Ni estão presentes nas amostras, a reação compete com a hidrólise heterogênea do BH4- levando a uma diminuição da eficiência faradaica. / The oxygen reduction reaction (ORR) and the borohydride oxidation reaction (BOR) were studied in alkaline medium on Ni (II) doped MnOx catalysts supported on different carbon powder substrates. Characterizations of physico chemical properties were made by X ray diffraction (XRD), high resolution transmition electronic microscopy (HR-TEM) equipped with X ray dispersive energy spectroscopy (EDS). Electrochemical studies involved cyclic voltammetry and oxygen reduction voltammograms. Also it was used Differential Electrochemical Mass Spectrometry on line (DEMS) and Fourier Transform Infra Red Spectrometry (FTIR) in situ. A small insertion of Ni atoms in the MnOx lattice was observed, this consisting of a true doping of the manganese oxide phase. The corresponding NiMnOx phase is present in the form of needles or agglomerates, with crystallite sizes in the order of 1.5-6.7 nm. Layered manganite (MnOOH) phase has been detected for the Monarch1000 supported NiMnOx material, while different species of MnOx phases are present at the E350G and MM225 carbons. Electrochemical studies in thin porous coating active layers in the rotating ring-disk electrode setup revealed that the MnOx catalysts present better ORR kinetics and electrochemical stability upon Ni doping. The ORR follows the so-called peroxide mechanism on MnOx/C catalysts, with the occurrence of minority HO2- disproportionation reaction. The HO2- disproportionation reaction progressively increases with the Ni content in NiMnOx materials. The catalysts supported on the MM225 and E350G carbons promote faster disproportionation reaction, thus leading to an overall four-electron ORR pathway. The results towards ORR in presence of sodium borohydride showed that all materials are tolerant to the presence of BH4- ion into some extent. DEMS on line and FTIR in situ showed that NiMnOx/C are also active toward the BOR, but there is a strong influence of the nature of the electrocatalysts with respect to the morphology, composition, the nature of the carbon substrate and the Ni load. Results indicate that the electrocatalysts containing segregate Ni phases, the bohohydride oxidation occurs together with the heterogeneous hydrolysis of the BH4- ion resulting in a decrease of the faradaic efficiency.

Reactions of aqueous Fe(II) with Fe and Mn oxides influence heavy metal mobility, transformation of trace organics, and important elemental cycles as Fe precipitates form or dissolve, and as electrons move between aqueous and solid phases. Our objective was to characterize reactions of Fe(II) with important metal oxides, using a suite of complementary tools to investigate the extent and underlying mechanisms of Fe(II)-metal oxide redox activity. Nanoscale materials (1-100 nm) may have fundamentally different surface or electronic properties than larger solids. Goethite was synthesized with primary particle dimensions above or below the nanoscale. Despite large differences in particle surface area, goethite nanorods and microrods had similar net Fe(II) sorption and electron transfer properties. Experimental evidence suggested particle aggregation resulted in particle complexes of a similar size, meaning considerations of available reactive surface area could explain our results. Kinetics and extent of Fe(II)-Fe(III) redox reactions between aqueous Fe(II) and goethite were examined using a stable isotope tracer approach. Aqueous Fe(II) that had been enriched in 57Fe was mixed with isotopically-normal goethite. Convergence of Fe isotope ratios in aqueous and solid phases to values predicted by complete Fe atom exchange provided evidence that all goethite Fe(III) atoms could eventually react with Fe(II), despite no evidence for complete atom exchange from bulk measurements of the aqueous or solid phase. Fe isotope data at different experimental conditions was combined with theoretical considerations governing electron transfer in goethite to provide evidence for redox-driven atom exchange involving bulk conduction of electrons between spatially distinct Fe(II) sorption and release sites. Procedures for stable Fe isotope tracer studies have been adapted to investigate redox transformations of magnetite solids with different divalent cation content. Evolution of aqueous Fe(II)-Mn(IV) redox reactions was examined using complementary techniques. After pyrolusite particles were exposed to aqueous Fe(II), aqueous Fe and Mn were analyzed, and X-ray diffraction was utilized with electron microscopy to assess solid phase evolution during continued exposure to Fe(II). Selective use of Fe isotopes during Fe(II) resuspensions allowed us to track chemical changes occurring to one particular Fe addition using 57Fe Mössbauer spectroscopy.

The biogenic reduction of Mn(IV) oxides is one of the most favorable anaerobic electron transfer processes in aquatic systems and likely plays an important role in the redox cycle of both carbon and nitrogen in anaerobic environments; yet, the different pathways involved in the microbial transformation of Mn(IV) oxides remain unclear. The coupling between the reduction of Mn(IV) to Mn(II) and the oxidation of organic carbon to CO₂ is largely catalyzed by microorganisms in various environments such as redox stratified water columns and sediments. The recent discovery that soluble Mn(III) exists in natural systems and is formed during biological oxidation of Mn(II) implies the possibility that Mn(III) is formed as an intermediate during the microbial reduction of Mn(IV). In this dissertation, mutagenesis studies and kinetic analysis were combined to study the mechanism of microbial reduction of Mn(IV) by Shewanella oneidensis MR-1, one of the most studied metal-respiring prokaryotes. We show for the first time that the microbial reduction of Mn(IV) proceeds step-wise via two successive one-electron transfer reactions with soluble Mn(III) as intermediate produced in solution. The point mutant strain Mn3, generated via random chemical mutagenesis, presents a unique phenotype that reduces solid Mn(IV) to Mn(III) but not to Mn(II), suggesting that these two reduction steps proceed via different electron transport pathways. Mutagenesis studies on various in-frame deletion mutant strains demonstrate that the reduction of both solid Mn(IV) and soluble Mn(III) occurs at the outer membrane of the cell and Mn(IV) respiration involves only one of the two potential terminal reductases (c-type cytochrome MtrC and OmcA) involved in Fe(III) respiration. Interestingly, only the second electron transfer step is coupled to the respiration of organic carbon, which opposes the long-standing paradigm that microbial reduction of Mn(IV) proceeds via the single transfer of two electrons coupled to the mineralization of carbon substrates. The coupling between anaerobic nitrification and Mn reduction has been demonstrated to be thermodynamically favorable. However, the existence of this process in natural system is still in debate. In this dissertation, characterization of coastal marine sediments was combined with laboratory incubations of the same sediments to investigate the effect of Mn oxides on the redox cycle of nitrogen. Our slurry incubations demonstrate that anaerobic nitrification is catalyzed by Mn oxides. In addition, mass balance calculations on NH₄⁺ link the consumption of NH₄⁺ to anaerobic ammonium oxidation in the presence of Mn oxides and confirm the occurrence of Mn(IV)-catalyzed anaerobic nitrification. The activity of anaerobic nitrification is greatly affected by the initial ratio of Mn(IV) to NH₄⁺, the reactivity of Mn oxides, and the reducing potential of the system. Overall, Mn(IV)-catalyzed anaerobic nitrification may be an important source of nitrite/nitrate in anaerobic marine sediments and provide an alternative pathway for subsequent nitrogen losses in the marine nitrogen cycle.

In this thesis, we have performed systematical study of the complex impedance spectra(CIS) with the manganeses oxide thin films by the equivalent circuit model(ECM) composed of resistance and capacitance. The ECM has been utilized in analog of the electrical and dielectric properties of the granular films. The purpose of this research is to understand how the electrical- and magneto-transport properties in La0.67Ca0.33MnO3(LCMO),La0.8Ba0.2MnO3(LBMO),La0.67Sr0.33MnO3(LSMO(113)) and La0.67Sr1.33MnO4 (LSMO(214)) thin films, at various magnetic fields and temperatures. First of all, we demonstrate that the LSMO(214) and LSMO(113) can be sensitively affected by magnetic states on the manganite films. Our result provides further understanding of the dielectrics variation during the phase transition from an AFM insulating phase and/or a ferromagnetic metallic phase to a paramagnetic PM metallic phase. It is known that the strong correlation between the itinerant carriers and the local magnetic moments is the mechanism for FM/PM phase transition for LSMO(113), while the direct magnetic exchange coupling governed the AFM/PM phase transition and an indirect coupling to the status of intrinsic carriers for LSMO(214) films. These transitions can not be concludes directly by using a dc resistance measurement but can be clearly distinguished by the CIS measurement. On the other hand, the dc resistance (Rdc) and the relaxation time(£n) have the same tendency that this indicates the changes of £n matches to the electric transport properties for LCMO_90min and LSMO(214) thin films. We focus on the the dielectric properties of both samples are insensitive to temperature, revealing that the dielectric behavior is independent of magnetic phase transition but strongly associated with the transport properties. Therefore, the magnetic transitions can be most thoroughly investigated by combining CIS measurements and RC ECM, as well as by making dc resistance measurements. Moreover, the relative change of M£q(ac) is nearly larger than the dc resistive variation. This phenomenon, called giant magneto-impedance effect (GMI), implies that thehigh-frequency magnetotransport effect may enhance the performance of these manganese oxides for sensing the magnetic field. The CMI, have been analyzed by ECM, including two sets of parallel R and capacitance (C) components in series. The analyzing results the specific feature of grain boundaries(GBs) can be attributed to the interplay of magnetic moment spin disorder to ordering. The grain boundary (GB) effect can enhance low field magnetoresitance (LFMR) for artificial GBs, but shows very limited enhancement for those GBs in epitaxial films. This study finds that artificial GBs, which exhibit large LFMR, can be modeled as a non-conductive layer which disconnects the lattice periodicity of adjacent grains and contains no magnetic ions. The GBs in the present fully strained epitaxial film, which shows a relatively smaller LFMR, are more similar to a semi-continuous grain with continuous distribution of magnetic ions that align loosely parallel to the grain magnetic moment. In addition, we report in this study the high frequency magneto-transport properties, based on the classical model, of La0.8Ba0.2MnO3 and La0.67Ca0.33MnO3 thin films around their ferromagnetic transitions and under an external magnetic field. It is found that the specific features of magneto-impedance can be correlated with the complex magnetization response and the dielectric relaxation in corresponding phase states. The fast dielectric relaxation time, £nE, and the slow magnetic response, £nH, reflect the interplay of itinerant carriers and the magnetic coupling to the ac electromagnetic wave, indicating that the double exchange, or hopping, of carriers between O 2P and Mn 3d-eg states occur prior to the indirect magnetic coupling of adjacent Mn ions via strong Hunt¡¦s rules. Applied magnetic field enhances both electric and magnetic dipoles are now responding faster to the electromagnetic wave. The results of our work may provide a fundamental understanding of high frequency magnetic and electrical properties of the manganite films, and imply tips for device application of the films.