<p>There are today clear indications that the Li-ion battery of the type currently used worldwide in mobile-phones and lap-tops is also destined to soon become the battery of choice in more energy-demanding concepts such as electric and electric hybrid vehicles (EVs and EHVs). Since the currently used cathode materials (typically of the Li(Ni,Co)O₂-type) are too expensive in large-scale applications, these new batteries will have to exploit some much cheaper transition-metal. Ideally, this should be the very cheapest - iron(Fe) - in combination with a graphite(C)-based anode. In this context, the obvious Fe-based active cathode of choice appears to be LiFePO₄. A second and in some ways even more attractive material - Li₂FeSiO₄ - has emerged during the course of this work.</p><p>An effort has here been made to understand the Li extraction/insertion mechanism on electrochemical cycling of Li₂FeSiO₄. A fascinating picture has emerged (following a complex combination of Mössbauer, X-ray diffraction and electrochemical studies) in which the material is seen to cycle between Li₂FeSiO₄ and LiFeSiO₄, but with the structure of the original Li₂FeSiO₄ transforming from a metastable short-range ordered solid-solution into a more stable long-range ordered structure during the first cycle. Density Functional Theory calculations on Li₂FeSiO₄ and the delithiated on LiFeSiO₄ structure provide an interesting insight into the experimental result.</p><p>Photoelectron spectroscopy was used to study the surface chemistry of both carbon-treated LiFePO₄ and Li₂FeSiO₄ after electrochemical cycling. The surface-layer on both materials was concluded to be very thin and with incomplete coverage, giving the promise of good long-term cycling.</p><p>LiFePO₄ and Li₂FeSiO₄ should both be seen as highly promising candidates as positive-electrode materials for large-scale Li-ion battery applications.</p>

There are today clear indications that the Li-ion battery of the type currently used worldwide in mobile-phones and lap-tops is also destined to soon become the battery of choice in more energy-demanding concepts such as electric and electric hybrid vehicles (EVs and EHVs). Since the currently used cathode materials (typically of the Li(Ni,Co)O2-type) are too expensive in large-scale applications, these new batteries will have to exploit some much cheaper transition-metal. Ideally, this should be the very cheapest - iron(Fe) - in combination with a graphite(C)-based anode. In this context, the obvious Fe-based active cathode of choice appears to be LiFePO4. A second and in some ways even more attractive material - Li2FeSiO4 - has emerged during the course of this work. An effort has here been made to understand the Li extraction/insertion mechanism on electrochemical cycling of Li2FeSiO4. A fascinating picture has emerged (following a complex combination of Mössbauer, X-ray diffraction and electrochemical studies) in which the material is seen to cycle between Li2FeSiO4 and LiFeSiO4, but with the structure of the original Li2FeSiO4 transforming from a metastable short-range ordered solid-solution into a more stable long-range ordered structure during the first cycle. Density Functional Theory calculations on Li2FeSiO4 and the delithiated on LiFeSiO4 structure provide an interesting insight into the experimental result. Photoelectron spectroscopy was used to study the surface chemistry of both carbon-treated LiFePO4 and Li2FeSiO4 after electrochemical cycling. The surface-layer on both materials was concluded to be very thin and with incomplete coverage, giving the promise of good long-term cycling. LiFePO4 and Li2FeSiO4 should both be seen as highly promising candidates as positive-electrode materials for large-scale Li-ion battery applications.

Les diverses perovskites de strontium-fer présentent de très fortes corrélations entre la structurecristalline et les phénomènes d’ordre de lacunes d’oxygènes, de charge, de spin et d’orbitales. Danscette thèse, nous avons réalisé une étude systématique des relations entre les ordres de charges etles ordres de spins selon les différents environnements cristallographiques rencontrés pour lescations Fe3+ et Fe4+ dans la phase Sr4Fe4O11, pour le cation Fe3+ dans les phases Sr3Fe2O6 et Sr2Fe2O10et pour le cation Fe2+ dans la phase SrFeO2. Les synthèses des phases polycristallines furent réaliséesvia des voies « solide » ou « sol-gel » en complément de la synthèse de cristaux préparés à l’aide d’unfour à image à fusion de zone verticale pour les phases Sr4Fe4O11 et Sr2Fe2O10. La qualité cristalline etchimique des oxydes fut contrôlée par diffraction de rayons X sur poudre et spectroscopieMössbauer alors que l’étude de la structure électronique de chaque phase a été réalisée à l’aide despectroscopie d’absorption de rayons X. Finalement, les structures magnétiques des phases Sr3Fe2O6et Sr4Fe4O11 sont aussi présentées. / The relationship of the crystallographic, magnetic, and electronic structure have long been of highinterest in research. Strontium iron oxides have structural, charge, spin, and orbital degrees offreedom, and thus give rich information to study for the condensed matter scientists. In this thesis,we have systematically studied the strontium iron oxides based on the freedom of the iron charge:Fe3+ and Fe4+ mixed valence compound SrFeO2,75 , Fe3+ compound Sr3Fe2O6 and SrFeO2,5 with differentcoordination around Fe3+ and Fe2+ compound SrFeO2. The synthesis of the polycrystalline compoundsare through either solid state reaction or sol-gel method. Single crystals of SrFeO2,75 and SrFeO2,5have been prepared by floating zone furnace. The purity of all the compounds is checked by lab x-raydiffraction and Mössbauer spectroscopy. Electronic structures have been studied by x-ray absorptionspectroscopy for all these compounds. Special efforts have been used to investigate the magneticstructure of SrFeO2,75 and Sr3Fe2O6 .

Ce mémoire est consacré à l’étude des composites à base de phosphates de type NASICON comme matériaux d’électrode pour batteries sodium-ion : Na1+xFexTi2-x(PO4)3/C et Na1+xFexSn2-x(PO4)3/C avec 0 ≤ x ≤ 1. Ces composites ont été synthétisés par voie solide suivie d’une pyrolyse avec le saccharose. Ils sont constitués de particules ayant une porosité élevée et enrobées par du carbone conférant à l’électrode une bonne conductivité ionique et électronique. Les mécanismes réactionnels se produisant lors des cycles de charge-décharge ont été analysés en mode operando par diffraction des rayons X, spectroscopies Mössbauer du 57Fe et de 119Sn et spectroscopie d’absorption X. Pour les composites fer-titane, ces mécanismes sont essentiellement basés sur la diffusion des ions Na+ dans les canaux des phases cristallisées avec changements d’état d’oxydation des métaux. Pour les composites fer-étain, les mécanismes sont plus complexes incluant insertion, conversion conduisant à la destruction des phases NASICON, puis formation d’alliages NaxSn. Les meilleures performances électrochimiques ont été obtenues pour Na1,5Fe0,5Ti1,5(PO4)3/C avec un potentiel de fonctionnement de 2,2 V vs Na+/Na0. Même si ces deux familles de matériaux peuvent être utilisées à plus bas potentiel, les performances doivent être améliorées pour envisager leur application comme électrode négative. / This thesis is devoted to the study of phosphate based composites with NASICON type structure, that are used as electrode materials for sodium-ion batteries: Na1+xFexTi2-x (PO4)3/C et Na1+xFexSn2-x(PO4)3/C with 0 ≤ x ≤ 1. These composites were synthesized by solid state route followed by a pyrolysis reaction with sucrose. They consist of particles having high porosity and coated with carbon giving to the electrode good ionic and electronic conductivity. The reaction mechanisms occurring during charge-discharge cycles were analyzed in operando mode, by X-ray diffraction, 57Fe and 119Sn Mössbauer spectroscopies and X-ray absorption spectroscopy. For the iron-titanium composites, the mechanisms are essentially based on the diffusion of Na+ in the channels of the crystalline phases with changes of transition metal oxidation state. For iron-tin composites, the mechanisms are more complex including insertion, conversion leading to the destruction of the NASICON phases and then reversible formation of NaxSn alloys. The best electrochemical performances were obtained for Na1,5Fe0,5Ti1,5(PO4)3/C with an operating potential of 2.2 V vs. Na+/Na0. Although these two types of materials can be used at lower potential, the performances must be improved to consider their application as the negative electrode.

No description available.

Diploma thesis Iron Functionalized Nanoparticles of Titanium Dioxide Lenka Volfová 2017, ABSTRACT Iron-functionalized TiO2 were obtained by hydrolysis of aqueous solutions of titanyl sulfate with addition of ferric nitrate with ammonium hydroxide and the reaction filtered and washed with hydrogen peroxide. The colloid solutions thus prepared were lyophilized and the products were subsequently annealed at three different temperatures of 650 řC, 800 řC and 950 řC. The prepared doped materials were characterized by powder X-ray diffractometry, electron microscopy, infrared spectroscopy, Mössbauer spectroscopy, UV/VIS spectroscopy, thermogravimetric analysis and differential thermal analysis, and measurement of the specific surface area. Photocatalytic activity was determined by measuring of the decomposition of kinetics of 4-chlorophenol in an aqueous solution in the ultraviolet and visible area. For comparison of activity in the UV area and in the visible area were used a previously prepared highly photoactive specimen and standard TiO2 from Kronos, respectively. Keywords: Doped titanium dioxide, nanostructure, X-ray diffraction, electron microscopy, Mössbauer spectroscopy, suppression of photoactivity

Dans cette thèse nous démontrons le travail fait sur deux matériaux de cathodes pour les piles lithium-ion. Dans la première partie, nous avons préparé du phosphate de fer lithié (LiFePO4) par deux méthodes de lithiation présentées dans la littérature qui utilisent du phosphate de fer (FePO4) amorphe comme précurseur. Pour les deux méthodes, le produit obtenu à chaque étape de la synthèse a été analysé par la spectroscopie Mössbauer ainsi que par diffraction des rayons X (DRX) pour mieux comprendre le mécanisme de la réaction. Les résultats de ces analyses ont été publiés dans Journal of Power Sources. Le deuxième matériau de cathode qui a été étudié est le silicate de fer lithié (Li2FeSiO4). Une nouvelle méthode de synthèse a été développée pour obtenir le silicate de fer lithié en utilisant des produits chimiques peu couteux ainsi que de l’équipement de laboratoire de base. Le matériau a été obtenu par une synthèse à l’état solide. Les performances électrochimiques ont été obtenues après une étape de broyage et un dépôt d’une couche de carbone. Un essai a été fait pour synthétiser une version substituée du silicate de fer lithié dans le but d’augmenter les performances électrochimiques de ce matériau. / In this thesis, we demonstrate work on two different cathode materials for lithium-ion batteries. First, the synthesis of lithium iron phosphate (LiFePO4) is reproduced from literature using two lithiation methods starting with amorphous iron phosphate (FePO4). For both reactions, the product at each step of the synthesis was analyzed using Mössbauer Spectroscopy and X-ray diffraction in order to gain further insight of the reaction mechanism. The results of this work were published in Journal of Power Sources. The second cathode material of interest was lithium iron silicate (Li2FeSiO4). A novel synthetic method was developed to produce lithium iron silicate cost effectively starting with low cost precursors and basic laboratory equipment. The material was synthesized using a solid- state synthesis after milling and carbon coating, electrochemical performance was evaluated. An attempt was made to synthesize off-stoichiometric lithium iron silicate in order to increase the electrochemical performance of the material.

No description available.

M.Tech. (Department of Chemistry, Faculty of Applied Sciences), Vaal University of Technology / Many oxidic iron compounds—iron oxides; oxy-hydroxides and hydroxides—not only play an important role in a variety of disciplines but also serve as a model system of reduction and catalytic reactions. There are more than 16 identifiable oxidic iron compounds. The reduction of these compounds has been investigated for centuries. Despite this, the reduction behavior of the oxides is not fully understood as yet. To date the reduction mechanism is still plagued with uncertainties and conflicting theories, partly due to the complex nature of these oxides and intermediates formed during the reduction. Thermodynamically, the reduction of iron oxide occurs in steps. For example, during the reduction of hematite (a-Fe2O3) magnetite (Fe3O4) is first formed followed by non-stoichiometric wüstite (Fe1-yO) and lastly metallic iron (a-Fe). The rate of transformation depends on the reduction conditions. Further, this reduction is accompanied by changes in the crystal structure. The reduction behavior of iron oxides using graphite under ball-milling conditions was investigated using Planetary mono mill (Fritsch Pulverisette 6), Mössbauer Spectroscopy (MS), X-ray Diffraction (XRD), Scanning electron microscopy (SEM) and Transmission Electron Microscopy (TEM). It was found that hematite transformed into magnetite, Wüstite and or cementite depending on the milling conditions. The study shows that by increasing the milling time, the rotational speed and / or the ball to powder ratio, the extent of the conversion of hematite to its reduction products increased. Further investigations are required for the elucidation of the reduction mechanism. The reaction og magnetite and graphite at different milling conditions lead to the formation of Fe2+ and Fe3+ species, the former increasing at the expense of Fe3O4. Fe3O4 completely disappeared after a BPR of 50:1 and beyond. The Fe2+ species was confirmed to be due to FeO using XRD analysis. HRSEM images Fe2O3 using scanning electron microscopy prior to and after milling at different times showed significant changes while the milling period was increased, HRSEM images showed that the once well defined hematite particles took ill-defined shapes and also became smaller in size, which was a results of the milling action that induced reaction between the two powders to form magnetite. EDX spectra at different milling times also confirmed formation of magnetite. EDX elemental analysis and quantification confirmed the elemental composition of starting material consisting mainly of iron. Similarly, HRSEM images of Fe3O4 using Scanning electron microscopy (SEM) prior to and after milling at different BPR showed significant changes when the milling period was increased. EDX spectra at different milling times also confirmed formation of partial FeO and EDX elemental analysis and quantification confirmed the elemental composition of starting material consisting mainly of iron than Fe2O3. TEM images of both Fe2O3 and Fe3O4 particles at different milling conditions displayed observable particle damages as a function of milling period.The once well - defined particles (Fe2O3 and Fe3O4 ) successively took ill – defined shapes, possibly accompanied by crystallite size reduction. MAS showed that the reactive milling of α- Fe2O3 and C resulted in reduction to Fe3O4 , FeO and or cementite depending on the milling conditions etc Time, milling speed and BPR variation which influenced the reduction. The study shows that by increasing the milling time, the rotational speed and / or the ball to powder ratio, the extent of the conversion of hematite to its reduction products increased. XRD study investigations even though were unable to detect spm species (Fe2+ and Fe3+ ) which has smaller crystallites below detection limits ,the variation in time showed an increment in the magnetite peaks accompanied by recession of hematite and graphite peaks as the milling time was increased which relates to the MAS observation.XRD also corroborated the data obtained from MAS that showed that the main constituent was magnetite and further evidence in support of the reduction of hematite to magnetite under reactive milling was obtained using XRD . Overall, the work demonstrated selective reduction of Fe2O3 to Fe3O4 and Fe3O4 to FeO by fine tuning the milling conditions. It is envisaged that the reduction of FeO to Fe and possible carburization to FexC could also be achieved.

<p>Proces pečenja u proizvodnji keramičkog crepa u većini slučajeva se izvodi u<br />oksidavionoj atmosferi. Dobijena mikrostruktura koja obezbeđuje najvažnije osobine<br />primene zavisi od mineralo&scaron;kog sastava polaznog materijala i temperature termičkog<br />tretmana.<br />Sa stanovi&scaron;ta proizvodnje glinenog crepa, sirovina sa značajnim sadržajem karbonata kao &scaron;to je kop gline u Kanjiži, predstavlja problem te se ne može koristiti u njenom prirodnom sastavu. U oksidacionom termičkom tretmanu, staklasta faza koja se formira razgradnjom lakotopivih glinenih minerala ne kvasi u dovoljnoj meri zemnoalkalne okside nastale razgradnjom karbonata. Očekivane nove kristalne faze, kao &scaron;to su gelenit i anortit, koje predstavljaju osnovu dobrih tehničkih osobina crepa, ne mogu nastati u potrebnoj količini. Jedno od re&scaron;enja ovog problema je pobolj&scaron;anje interakcije između silikata i CaO/MgO promenom kvaliteta atmosfere pečenja.<br />Cilj je bio da se dobije odgovor na pitanje, da li se mogu promenom tehnolo&scaron;kih<br />parametara pečenja pobolj&scaron;ati karakteristike finalnog proizvoda dobijenog od sirovinske sme&scaron;e sa visokim masenim udelom karbonata.<br />Dati su rezultati pečenja u oksidacionoj i redukcionoj atmosferi u pogledu fizičkomehaničkih karakteristika i nastanka novih kristalnih faza. U radu su primenjene metode 57Fe M&ouml;ssbauer spektroskopije, difrakcija X zraka i dilatometrijska analiza za<br />identifikaciju promena faza tokom pečenja u oksidacionoj i redukcionoj atmosferi<br />(CO/N2 atmosfera) na temperaturama od 700-1060&deg;C. Ove promene reflektuju<br />dehidroksilaciju glinenih minerala, dekompoziciju karbonata, denzifikaciju i formiranje<br />novih kristalnih faza (plagioklasi). U cilju analize industrijskih uzoraka, pored 57Fe<br />M&ouml;ssbauer spektroskopije, primenjene su i sledeće metode: skenirajuća elektronska<br />mikroskopija (SEM) sa EDS analizom, živina porozimetrija, fotoelektronska spektroskopija (XPS) i karakterizacija apsorbcije vode, otpornosti na mraz i nosivosti.<br />Primena redukujuće atmosfere pokazala se kao opravdana, dobijen je glineni crep<br />pobolj&scaron;anih karakteristika u odnosu na standardni proizvod pečen u oksidacionoj<br />atmosferi.</p> / <p>The firing process in clay roofing tile production is normally carried out in oxidizing<br />firing atmosphere. The obtained microstructure which provides the most important<br />properties of the application depends on the mineralogical composition of the starting raw material and the firing temperature.<br />Concerning the production of roofing tiles, clay raw materials with a high content of<br />carbonates such as the Kanjiza clay material, possess an inappropriate composition. The melt phase is formed after the decomposition of clay minerals during the common firing process. This liquid phase, due to its extent wetting characteristics, is not able to wet properly the earth alkali oxides obtained after the decomposition of the carbonates. The expected new crystalline phases, like gehlenite and anorthite, which are needed for the favorable technical properties of the roofing tiles, can not be formed in the required quality and quantity. One solution to this problem is the limebonding improvement by changing the conditions of the firing atmosphere.<br />The main aim of this work is to examine the effects of firing conditions on the<br />properties of clay roofing tiles with high carbonate content. The obtained physical and<br />mechanical properties and the obtained new crystalline phases are described in detail.<br />The experiment used dilatometry, X-ray diffractometry, 57Fe M&ouml;ssbauer<br />spectroscopy to identify the changes during the firing process in oxidizing and<br />reducing atmosphere (CO/N2 atmosphere) at temperatures between 700 and 1060&deg;C.<br />Furthermore, for industrial sample analysis, scanning electronmicroscopy with EDS,<br />XPS, Hg porosimetry, water absorption procedure, frost resistance and bending<br />measurements were applied.<br />The application of reducing atmosphere was proved to be valid. The obtained<br />roofing tiles had improved properties compared to the standard production which uses<br />oxidizing firing atmosphere.</p>