Les applications portables et stationnaires des accumulateurs Ni-MH nécessitent sans cesse des autonomies de plus en plus importantes. Cet accroissement d’autonomie peut être obtenu en développant de nouveaux composés intermétalliques hydrurables de type ABx (3<x<4) de plus grande capacité massique. Le groupe A de ces composés est constitué de La partiellement substitué par du Mg, qui est beaucoup plus léger et diminue la masse molaire de l’alliage, et le groupe B contenant du Ni partiellement substitué par d’autres éléments de transition. Après une étude bibliographique approfondie, le travail de cette thèse consiste à rechercher tout d’abord les conditions optimales d’élaboration d’intermétalliques de composition La1-yMgyNix (0<y<1 ; 3<x<4). Puis ces composés sont caractérisés du point de vue structural et physico chimique (diffraction des rayons X et microsonde électronique), et leurs propriétés vis-à-vis de l’hydrogène (réaction solide-gaz et électrochimique) sont étudiées / Mobile and stationary applications for Ni-MH batteries require continuously more and more energy density. This increased autonomy can be obtained by developing new hydride-forming compounds of ABx-type (3<x<4) with larger weight capacities. The A element of these compounds is constituted of La partially substituted by light Mg, allowing a reduced molar weight. The B element is made of Ni that can be partially substituted by other transition metals. After an extensive bibliographic study, this thesis presents the research work to find optimum conditions for the synthesis of Mg-containing intermetallic compounds La1-yMgyNix (0<y<1; 3<x<4). These compounds are then characterized from the structural and chemical point of views (X-ray diffraction and microprobe analysis) and their hydrogen-related properties are studied and compared (solid-gas and electrochemical reactions)

Les Hydroxydes Doubles Lamellaires (HDL) sont des matériaux en couches à forte potentialité pour de nombreux domaines d’applications, cependant, leur caractère d’isolants électriques limite les possibilités d’applications en électrochimie. Il est donc intéressant de chercher des moyens d’améliorer leurs propriétés conductrices. Dans ce but, trois approches ont été envisagées : - l’insertion de cations de métaux de transition 3d dans les feuillets, - l’intercalation de médiateurs redox entre les feuillets ou - l’ajout de percolant électronique dans le système afin d’obtenir des HDL « électroactifs ». Même si les combinaisons possibles de cations divalents et trivalents dans le feuillet HDL sont nombreuses, toutes les études ont été centrées sur le rôle d’un élément principalement, le cobalt. La composition chimique des matériaux ainsi que leurs propriétés physico-chimiques en termes de morphologie et de structure globale et locale ont été étudiées par le couplage de différentes techniques d’analyse (DRX, IRTF, MEB, ATG, XAS, PDF, XPS) avant de réaliser la caractérisation des propriétés électrochimiques par voltammétrie cyclique et spectroscopie d’impédance électrochimique. Ces analyses ont alors montré les potentialités applicatives de certaines compositions des matériaux HDL choisis. Les propriétés capacitives des phases CoIICoIII-CO3 ont été étudiées pour une utilisation en tant que matériaux d’électrodes de supercondensateurs alors que la présence d’un médiateur redox ainsi que les propriétés d’immobilisation d’enzymes de la phase hybride Co2Al-ABTS ont permis d’élaborer des bioélectrodes potentiellement adaptables dans une biopile. / Layered Double Hydroxides (LDH) are lamellar materials with strong potentiality for numerous fields of application, however, their insulating electric character limits the possibilities for electrochemical applications. It is thus necessary to investigate for ways to improve their conductive properties. In this purpose, three approaches were envisaged: - insertion of cations of 3d transition metals into the lamellar sheets, - insertion of redox mediators between the layers or - addition of electronic percolants in the system to obtain “electroactive” LDH. Even if the possibilities of combination of divalent and trivalent metal cations within the LDH layer are tunable, all the studies were centered on the role of an element mainly, the cobalt. The chemical compositions of materials as well as their physico-chemical properties, in terms of morphology and global and local structure, were then studied by coupling various analytical techniques before realizing the characterization of the electrochemical properties by cyclic voltammetry and electrochemical impedance spectroscopy. These analyses then showed the application potentialities of certain type of LDH materials. The capacitive properties of CoIICoIII-CO3 phases were studied as supercapacitor electrode materials while the presence of a redox mediator as well as the immobilization properties for enzymes of the hybrid phase Co2Al-ABTS allowed constructing bioelectrodes potentially applicable in biofuel cell.

One of the major directions of research in the area of materials science is to impart multifunctionalities to materials. Carbon stands on the top of the list to provide various multifunctional materials. It exists in all dimensions, zero (fullerene), one (carbon nanotube, CNT), two (graphene) and three (graphite) dimensions are very well-known for their versatility in various studies. They are also used in various applications in nanoelectronics, polymer composites, hydrogen production and storage, intercalation materials, drug delivery, sensing, catalysis, photovoltaics etc. Electrical conductivity of carbon can be tuned from insulator (diamond) to semiconductor (graphene) to conductor (graphite) with varying band gap. The main reason for this versatility and varied properties is that carbon can be involved in different hybridizations. Graphene, a single layer of graphite has fascinated the world during the last several years culminating in a Nobel prize for Physics in 2010. The present study is an attempt to understand the physicochemical and electrochemical properties of graphite oxide and its reduced form. Graphene oxide (GO) possesses oxygen containing functional groups such as carbonyl, carboxyl and epoxy groups distributed very randomly in the extended graphene sheet which makes it ionically conducting and electrically insulating. The AFM images of single layer of graphite (graphene) obtained from micromechanical cleavage method and that of EGO are shown in figure 1. EGO is a layered material similar to graphite and can form very stable aqueous colloids over a wide pH range of 2-11. The stability of the colloid is due to electrostatic repulsive interactions between the functional groups. EGO behaves like a molecule due to its thickness (~1 nm) and like a particle due to its two dimensional nature (lateral size can vary from nm to few microns). It behaves as amphiphilic molecule having both hydrophilic and hydrophobic nature. Figure 1d shows the STM image of EGO which clearly indicates oxidized and unoxidized regions which will impart hydrophilic and hydrophobic regions respectively. Figure 1: AFM image of (a) graphene (b) EGO. STM image of (c) HOPG and (d) EGO. The present work is related to exploring EGO as a multifunctional material. Both hydrophilic and amphiphilic nature is explored for various studies. Reduced GO (rGO) is synthesized from EGO by assembling at different interfaces (solid-liquid and liquid-air) followed by reduction. Since EGO is hydrophilic, it is brought to the air-water interface with the help of a surfactant (CTAB) through electrostatic interactions. It is reduced chemically by hydrazine vapour to rGO and electrochemically by assembling EGO on gold through electrostatic interactions between EGO and amine groups of cystamine (figure 2). The reduction process is followed by AFM, UV-Visible and in-situ Raman spectroelectrochemistry. Figure 2: Schematic of EGO self assembly, cyclic voltammogram showing electrochemical reduction and schematic for in-situ Raman spectroelectrochemistry. The next section deals with composites of EGO and polymers. EGO/polyaniline (PANI) composite is formed by electrochemical polymerization under applied surface pressure. The in-situ electrochemical polymerization of aniline in the sub-phase of Langmuir-Blodgett trough under applied surface pressure in presence of EGO at the air-water interface leads to preferential orientation of PANI in the polaronic form. This is followed by electrochemistry and Raman spectroscopy. Figure 3 shows differential pulse voltammograms of EGO/PANI obtained under two different conditions. Externally polymerized sample shows three redox peaks at 0.086/0.064 V (A/A‟), 0.390/0.430 V (B/B‟) and 0.520/0.560 mV (C/C‟) which correspond to leucoemaraldine/emaraldine, quinone/hydroquinone and emaraldine/pernigraniline redox states respectively. The peak at C/C‟ vanishes when aniline is polymerized in-trough under applied surface pressure. This implies that oxidation of emaraldine to pernigraniline becomes difficult when sample is prepared in-trough. The Raman spectroscopy clearly reveals the preferential orientation of PANI in planar polaronic structure. Figure 3. Differential pulse voltammograms for EGO/PANI complex obtained through external polymerization (black) and in-trough polymerization (red). In the next part, EGO is used as a proton conducting material for polymer electrolyte membrane fuel cell (PEMFC). EGO possesses hydrophilic and hydrophobic regions similar to nafion (sulfonated tetrafluoroethylene based fluoropolymer-copolymer) and hence it can act as a good ionically conducting membrane. EGO is incorporated in poly(vinyl alcohol) (PVA) matrix and used in the present studies. The ionic conductivity increases from 10 μS cm-1 to 370 μS cm-1 when EGO content is increased from 1wt% to 7wt% in PVA matrix. Power densities of 25 and 90 mW cm-2 are obtained for PVA and PVA/EGO membranes in H2-O2 fuel cell at 40 0C respectively. In the next section, EGO is used as receptor for simultaneous electrochemical detection of heavy metal ions such as Cd, Pb, Cu and Hg with detection limit of 5 μM, 1 pM, 5 μM and 5 μM respectively. During the process it is observed that the EGO/PbO composite can give rise to detection limit of 10 nM for arsenic. Along with detection, EGO can also be used as an effective adsorbent for inorganics (metal ions) as well as organics (dye molecules). EGO behaves as good adsorbent for heavy metal ions and cationic dyes and rGO adsorbs anionic dyes effectively. Spectroscopic techniques are used to understand the interactions between adsorbent and adsorbates. The thesis is presented as follows: Chapter 1 gives general introduction about graphene and graphite oxide with particular emphasis on the latter one. Chapter 2 gives details on the experimental methods followed, along with schematics for various adsorption processes. Chapter 3 focuses on assembling EGO at interfaces (solid-liquid and liquid-air) followed by reduction with chemical and electrochemical methods. Chapter 4 explores EGO as an amphiphilic material where EGO is assembled at air-water interface with anilinium and subsequent electropolymerization to EGO/PANI composites. EGO/PVA composite is used as electrolyte for PEMFC. Chapter 5 explores EGO as receptor for heavy metal ion detection (Cd, Pb, Cu and Hg). Chapter 6 deals with EGO as adsorbent for adsorption of inorganics (metal ions) as well as organics (dye molecules). This is followed by summary and conclusions. The appendix section gives details on the studies on preparation of exfoliated graphite with various metal ion intercalation. The covalent functionalization of EGO with metal phthalocyanines and its assembly at air-water interface forms second part of the appendix. (For figures pl see the abstract pdf file)

La demande en énergie ne cesse d'augmenter et elle satisfaite essentiellement par les énergies fossiles qui présentent une contrainte environnementale vue ses émissions de gaz à effet de serre. Considéré comme vecteur énergétique, l'hydrogène possède l'immense avantage de ne pas émettre de gaz à effet de serre et notamment du CO2. Son stockage dans des intermétalliques permet d’obtenir des capacités massiques et volumiques supérieures à celles obtenues en voie liquide ou sous pression. Dans ce travail, nous avons élaboré le composé intermétallique quaternaire LaCaMgNi9 par mécanosynthèse et ce selon différents schémas réactionnels. Ce procédés de synthèse est employé pour la première fois, pour la synthèse de cet intermétallique, afin de s'affranchir des difficultés que présentent les autres techniques de synthèse (co-fusion, frittage). Les caractérisations structurales et morphologiques des alliages obtenus ont été réalisées afin de tester leurs performances en tant que matériaux pour électrode négative d’accumulateur Ni-MH par divers techniques de caractérisation électrochimiques et solide-gaz / The increasing energy demand is mainly supplied by fossil sources which had environmental drawback essentially greenhouse gas emission. Considered as an energy carrier, hydrogen has the huge advantage to be clean. Its storage in intermetallic compound leads too higher hydration capacities than liquid and compressed storage. In this work, LaCaMgNi9 quaternary type alloy has been synthesized, for the first time, by mechanical alloying in order to avoid the inherent difficulties of the fusion technique. The structural and morphological characterization of the obtained alloys were performed. Their hydrogen related properties were examined (solid-gas and electrochemical reactions) in order to study their performance as negative electrode material in Ni-MH batteries

Neste trabalho avaliou-se a ação positiva da substituição de lantânio por praseodímio e de lantânio por magnésio na performance eletroquímica de eletrodos de ligas de armazenamento de hidrogênio em estado bruto de fusão e com tratamento térmico. O La foi substituído por Mg nas ligas La0,7-xMgxPr0,3Al0,3Mn0,4Co0,5Ni3,8 (x=0,0-0,7) e por Pr nas ligas La0,7-yPryMg0,3Al0,3Mn0,4Co0,5Ni3,8 (y=0,0-0,7). Os parâmetros eletroquímicos analisados foram ativação, capacidade de descarga, retenção da capacidade de descarga, autodescarga e alta taxa de descarga. As ligas apresentaram comportamento passivo em relação à corrosão. As análises por MEV/EDS e por DRX com refinamento por Rietveld revelaram a presença majoritária de fases similares às fases LaNi5, PrNi5, LaMg2Ni9 e PrMg2Ni9 em função das composições das ligas estudadas. Os parâmetros de rede e os volumes da célula unitária das fases diminuíram com a substituição crescente de La por Mg e de La por Pr. As capacidades de descarga máxima decresceram com a substituição crescente de La por Mg e de La por Pr, acompanhando o decréscimo da abundância da fase similar à fase LaNi5 e o aumento da abundância da fase similar à fase LaMg2Ni9. Comparativamente, menores taxas de autodescarga e maior estabilidade cíclica foram observadas para o eletrodo da liga na condição x=0,1, ao passo que o eletrodo da liga na condição y=0,0 apresentou maiores valores de alta taxa de descarga, indicando melhor performance cinética. / In this work, the positive action of the substitution of lanthanum by praseodymium and lanthanum by magnesium in the electrochemical performance of the as-cast and annealed hydrogen storage alloys electrodes had been evaluated. La was replaced by Mg in La0.7-xMgxPr0.3Al0.3Mn0.4Co0.5Ni3.8 (x=0.0-0.7) alloys and by Pr in La0.7-yPryMg0.3Al0.3Mn0.4Co0.5Ni3.8 (y=0.0-0.7) alloys. The electrochemical parameters analyzed were activation, discharge capacity, discharge capacity retention, self-discharge rate and high-rate dischargeability. The alloys showed a passive corrosion behavior. The analyses by SEM/EDS and XRD with Rietveld refinement revealed the majority presence of LaNi5, PrNi5, LaMg2Ni9 and PrMg2Ni9 similar reference phases depending on the compositions of the studied alloys. The lattice parameters and cell volumes of the component phases decreased with increasing substitution of La for Mg and with La for Pr. The maximum discharge capacity decreased with increasing substitution of La for Mg and with La for Pr, following the decrease in the abundance of LaNi5 similar phase and the increase in the abundance of to the LaMg2Ni9 similar phase. Lower self-discharge rates were observed for the alloy electrode when x=0.1, while higher high-rate dischargeability for the alloy electrode when y=0.0 indicated better kinetic performance, comparatively.

Neste trabalho, avaliou-se o efeito da substituição parcial do Ni pelos elementos Co, Cu e Sn, e do La e Mg pelo Pr em ligas do tipo AB5 para as ligas nominais La0,7Mg0,3Al0,3Mn0,4Cu0,5Ni3,8, La0,7Mg0,3Al0,3Mn0,4Co0,5Ni3,8 e La0,7Mg0,3Al0,3Mn0,4Sn0,5Ni3,8, La0,7Pr0,3Al0,3Mn0,4Co0,5Ni3,8, Pr0,7Mg0,3Al0,3Mn0,4Co0,5Ni3,8 sem e com tratamento térmico de 750° e 850°C por 9 e 16 horas. Estas ligas absorvedoras de hidrogênio foram utilizadas como material ativo em eletrodos negativos de baterias de Ni-HM. Avaliou-se a influência destas substituições e do tratamento térmico na microestrutura e nas propriedades eletroquímicas nas ligas. A substituição parcial do Ni pelo Co com o tratamento térmico de 750°C por 16 horas apresentou duas novas fases Al6Mn e PrCo13. Na substituição parcial do Ni pelo Sn formou a fase LaNi2Sn2 na liga. Utilizou-se caracterização de raios-X com refinamento de Rietveld para quantificar as fases em cada composição. Mediu-se a absorção de hidrogênio utilizando um Aparato Sieverts para obtenção das curvas PCT. Observou-se que as ligas La0,7Mg0,3Al0,3Mn0,4Co0,5Ni3,8 e La0,7Pr0,3Al0,3Mn0,4Co0,5Ni3,8 apresentaram as melhores capacidades de absorção de hidrogênio. Verificou-se o comportamento destas ligas na capacidade de descarga, estabilidade cíclica das baterias de Ni-HM. Comparando as ligas, a maior capacidade de descarga medida foi para a substituição parcial do Ni pelo Co, alcançando 406,1 mAh após o tratamento térmico de 850° C por 16 horas. A melhor capacidade de absorção obtida na analise de PCT, foi para a liga La0,7Pr0,3Al0,3Mn0,4Co0,5Ni3,8 com valor de H/M de 0,980. Também, foi avaliada uma correlação das propriedades eletroquímicas com a capacidade de absorção obtida na analise da curva PCT. / In this work, it was evaluated the effect of the partial substitution of Ni by the elements Co, Cu and Sn and of the La and Mg by the Pr in type AB5 alloys to the nominal alloys La0,7Mg0,3Al0,3Mn0,4Cu0,5Ni3,8, La0,7Mg0,3Al0,3Mn0,4Co0,5Ni3,8, La0,7Mg0,3Al0,3Mn0,4Sn0,5Ni3,8, La0,7Pr0,3Al0,3Mn0,4Co0,5Ni3,8 and Pr0,7Mg0,3Al0,3Mn0,4Co0,5Ni3,8, as castting and with annealing treatment of 750 °C and 850 °C for 9 and 16 hours. These hydrogen-absorbing alloys were used as active material on negative electrodes of Ni-HM batteries. The influence of these substitutions and the annealing treatment on the microstructure and on the electrochemical properties in the alloys was evaluated. The partial substitution of Ni by Co with the annealing treatment of 750 °C for 16 hours presented two new phases Al6Mn and PrCo13. In the partial substitution of Ni by Sn formed the LaNi2Sn2 phase in the alloy. It was characterized by X-ray diffraction using Rietveld\'s refinement to quantify the phases in each composition. Hydrogen absorption was measured using the Sieverts apparatus to obtain the PCT curves. It was observed that the alloys La0,7Mg0,3Al0,3Mn0,4Co0,5Ni3,8 and La0,7Pr0,3Al0,3Mn0,4Co0,5Ni3,8, presented the best capacities of hydrogen absorption. The behavior of these alloys in the discharge capacity, the cyclic stability of the Ni-HM batteries, was verified. Comparing the alloys, the biggest discharge capacity measured was for the partial substitution of Ni by Co alloy, reaching 406.1 mAh after the annealing treatment of 850 °C for 16 hours. The finest absorption capacity obtained in the PCT analysis was for the La0,7Pr0,3Al0,3Mn0,4Co0,5Ni3,8 alloy with an H/M value of 0.980. Also, a correlation of the electrochemical properties with the absorption capacity obtained in the analysis of the PCT curve was evaluated.

Ce travail est consacré à la synthèse de phases d’Hydroxydes Doubles Lamellaire (HDL) [NiAl-CO32-] à morphologies contrôlées et à l’étude de la relation entre leurs propriétés structurales / microstructurales et leurs propriétés électrochimiques. Les phases HDL sont préparées par un nouveau procédé de synthèse, basé sur un traitement hydrothermal en présence d’acides aminés. Nous avons mis en évidence l’influence de plusieurs paramètres de synthèse tels que la quantité d’acide aminé, la concentration de sels métalliques, le pH du milieu ainsi que la température et le temps du traitement hydrothermal ou encore la nature de l’acide aminé. Trois phases présentant différents degrés de cristallinité et différentes morphologies et représentatives des échantillons synthétisés, ont été plus particulièrement étudiées. Leur structure et microstructure ont été déterminées par affinement Rietveld en utilisant des données de diffraction des rayons X à haute résolution enregistrées au synchrotron. Ces résultats de DRX combinés avec les observations en microscopie électronique à transmission (MET) indiquent que l'élargissement des raies de diffraction 00l est principalement dû à des effets de taille, tandis que les effets, à la fois de taille et de micro-contrainte contribuent à l’élargissement anisotrope des autres réflexions hkl. Les micro-contraintes sont attribuées à un phénomène d’interstratification (CO32-/SO42-) et d’intercroissance de deux polytypes 2H1 et 3R1, confirmés et quantifiés à l’aide du logiciel DIFFaX. L’étude des propriétés électrochimiques de ces phases par voltammétrie cyclique a permis de montrer que la présence du motif d’empilement 2H1 induit une nette augmentation du signal électrochimique. / This work is devoted to the synthesis of NiAl-CO32- Layered Double Hydroxide phases (LDH) with controlled morphology and to the study of the relationship between the structural / microstructural and electrochemical properties. The LDH phases are prepared by a new synthetic method, based on the hydrothermal synthesis in presence of amino acids. We have highlighted the influence of various synthetic parameters such as the amount of amino acid, the concentration of metal salts, the pH of the medium, the temperature and time of hydrothermal treatment as well as the amino acid nature. Three phases of different degrees of crystallinity and different morphologies, representative of synthesized samples were particularly studied. Their structures and microstructures were determined by Rietveld refinement using high-resolution synchrotron powder X-ray diffraction (XRD) data. These XRD results combined with transmission electron microscopy (TEM) observations indicate that the broadening of 00l diffraction lines is mainly due to size effects, while both size and micro-strain effects contribute to the anisotropic broadening of the other hkl reflections. The micro-strain are attributed to an interstratification phenomena (CO32-/SO42-) and intergrowth between rhombohedral 3R1 and hexagonal 2H1 polytypes, confirmed and quantified using the software DIFFaX. The electrochemical properties of these phases are also studied by cyclic voltammetry showing that the presence of the 2H1 stacking motifs results in a net increase of the electrochemical signal.

Neste trabalho avaliou-se a ação positiva da substituição de lantânio por praseodímio e de lantânio por magnésio na performance eletroquímica de eletrodos de ligas de armazenamento de hidrogênio em estado bruto de fusão e com tratamento térmico. O La foi substituído por Mg nas ligas La0,7-xMgxPr0,3Al0,3Mn0,4Co0,5Ni3,8 (x=0,0-0,7) e por Pr nas ligas La0,7-yPryMg0,3Al0,3Mn0,4Co0,5Ni3,8 (y=0,0-0,7). Os parâmetros eletroquímicos analisados foram ativação, capacidade de descarga, retenção da capacidade de descarga, autodescarga e alta taxa de descarga. As ligas apresentaram comportamento passivo em relação à corrosão. As análises por MEV/EDS e por DRX com refinamento por Rietveld revelaram a presença majoritária de fases similares às fases LaNi5, PrNi5, LaMg2Ni9 e PrMg2Ni9 em função das composições das ligas estudadas. Os parâmetros de rede e os volumes da célula unitária das fases diminuíram com a substituição crescente de La por Mg e de La por Pr. As capacidades de descarga máxima decresceram com a substituição crescente de La por Mg e de La por Pr, acompanhando o decréscimo da abundância da fase similar à fase LaNi5 e o aumento da abundância da fase similar à fase LaMg2Ni9. Comparativamente, menores taxas de autodescarga e maior estabilidade cíclica foram observadas para o eletrodo da liga na condição x=0,1, ao passo que o eletrodo da liga na condição y=0,0 apresentou maiores valores de alta taxa de descarga, indicando melhor performance cinética. / In this work, the positive action of the substitution of lanthanum by praseodymium and lanthanum by magnesium in the electrochemical performance of the as-cast and annealed hydrogen storage alloys electrodes had been evaluated. La was replaced by Mg in La0.7-xMgxPr0.3Al0.3Mn0.4Co0.5Ni3.8 (x=0.0-0.7) alloys and by Pr in La0.7-yPryMg0.3Al0.3Mn0.4Co0.5Ni3.8 (y=0.0-0.7) alloys. The electrochemical parameters analyzed were activation, discharge capacity, discharge capacity retention, self-discharge rate and high-rate dischargeability. The alloys showed a passive corrosion behavior. The analyses by SEM/EDS and XRD with Rietveld refinement revealed the majority presence of LaNi5, PrNi5, LaMg2Ni9 and PrMg2Ni9 similar reference phases depending on the compositions of the studied alloys. The lattice parameters and cell volumes of the component phases decreased with increasing substitution of La for Mg and with La for Pr. The maximum discharge capacity decreased with increasing substitution of La for Mg and with La for Pr, following the decrease in the abundance of LaNi5 similar phase and the increase in the abundance of to the LaMg2Ni9 similar phase. Lower self-discharge rates were observed for the alloy electrode when x=0.1, while higher high-rate dischargeability for the alloy electrode when y=0.0 indicated better kinetic performance, comparatively.

Les batteries Li-ion, découvertes depuis presque 40 ans, et dont les inventeurs viennent d’être récompensés par le prix Nobel 2019 de Chimie, font encore l’objet de nombreuses recherches visant à développer leurs composantes et leurs méthodes de synthèse afin de garantir des batteries plus performantes. Dans cette optique, ce mémoire vise à étudier la synthèse des matériaux de cathode de LiFe1-xMnxPO4 (0<x<1) en utilisant, pour la première fois, la méthode de synthèse par fusion. En effet, cette méthode de synthèse pourrait offrir des matériaux de haute pureté avec des bonnes performances électrochimiques et tout cela à des coûts réduits. Ainsi, nous avons comparé la méthode de synthèse par fusion avec la méthode de synthèse classique par voie solide pour différentes compositions de LiFe1-xMnxPO4. Les résultats montrent que la rétention de la capacité et la capacité à se charger/décharger à différentes densités de courant sont similaires pour les deux méthodes et sont proches des résultats rapportés dans la littérature. Cependant, les composés riches en manganèse synthétisés par fusion présentent une capacité de décharge légèrement plus élevée que celles synthétisées par voie solide. Nous avons aussi étudié l’impact de la composition chimique, des conditions de synthèse (température, durée, atmosphère), de la source des réactifs (commerciaux de haute pureté ou des minerais de base) et du processus de revêtement de carbone sur la pureté et les propriétés électrochimiques de LiFe1-xMnxPO4 synthétisé. D’après les résultats obtenus, les conditions de synthèse ont plus d’effet sur la pureté alors que la composition chimique et la méthode de revêtement de carbone ont un impact plus important sur les propriétés électrochimiques du LiFe1-xMnxPO4. Ces résultats prometteurs ouvrent la porte à de nouvelles perspectives pour la production à grande échelle des matériaux de cathode de hautes performances en utilisant la méthode de synthèse par fusion. / Li-ion batteries, discovered for almost 40 years ago, and whose inventors have just been awarded the 2019 Nobel Prize for Chemistry, are still the subject of a large body of research aiming to develop their components and their synthesis methods in order to improve their performances. In this context, this thesis aims at studying the synthesis of LiFe1-xMnxPO4 (0<x<1) cathode materials using, for the first time, the melting synthesis method. Indeed, this synthesis method could offer high purity materials with good electrochemical performance while ensuring reduced costs. We hence compared the melt synthesis method with the conventional solid-state synthesis method for different compositions of LiFe1-xMnxPO4. The results show that the retention of capacity and the rate capability are similar for both methods and are close to the results reported in the literature. However, manganese-rich compounds have a slightly higher discharge capacity than those synthesized by the solid-state method. We also studied the impact of the chemical composition, the synthesis conditions (temperature, time, atmosphere), the reagents source (commercial with high purity or ores) and the carbon coating process on the purity and the electrochemical properties of the synthesized LiFe1-xMnxPO4. According to the obtained results, the synthesis conditions have more effect on the purity whereas the chemical composition and the carbon coating method have a greater impact on the electrochemical properties of LiFe1-xMnxPO4. These promising results open the door to new perspectives for large-scale production of high-performance cathodic materials using melt synthesis method.

La microscopie optique sur substrats antireflets est un outil de caractérisation simple et puissant qui a notamment permis l'isolation du graphène en 2004. Depuis, le domaine d'étude des matériaux bidimensionnels (2D) s'est rapidement développé, tant au niveau fondamental qu'appliqué. Ces matériaux ultraminces présentent des inhomogénéités (bords, joints de grains, multicouches, etc.) qui impactent fortement leurs propriétés physiques et chimiques. Ainsi leur caractérisation à l'échelle locale est primordiale. Cette thèse s'intéresse à une technique récente de microscopie optique à fort contraste, nommée BALM, basée sur l'utilisation originale de couches antireflets très minces (2-5 nm) et fortement absorbantes (métalliques). Elle a notamment pour but d'évaluer les mérites de cette technique pour l'étude des matériaux 2D et de leur réactivité chimique. Ainsi, les différents leviers permettant d'améliorer les conditions d'observation des matériaux 2D ont tout d'abord été étudiés et optimisés pour deux matériaux modèles : l'oxyde de graphène et les monocouches de MoS₂. L'étude de la dynamique de dépôt de couches moléculaires a notamment permis de montrer à la fois l'extrême sensibilité de BALM pour ce type de mesures et l'apport significatif des multicouches antireflets pour l'augmentation du contraste lors de l'observation des matériaux 2D. L'un des atouts principaux de BALM venant de sa combinaison à d'autres techniques, nous nous sommes particulièrement intéressés au couplage de mesures optiques et électrochimiques pour lesquelles le revêtement antireflet sert d'électrode de travail. Nous avons ainsi pu étudier optiquement la dynamique de réduction électrochimique de l'oxyde de graphène (GO), l'électro-greffage de couches minces organiques par réduction de sels de diazonium sur le GO et sa forme réduite (r-GO), ainsi que l'intercalation d'ions métalliques entre feuillets de GO. En combinant versatilité et fort-contraste, BALM est ainsi établi comme un outil prometteur pour l'étude des matériaux 2D et en particulier pour la caractérisation locale et in situ de leur réactivité chimique et électrochimique. / Optical microscopy based on anti-reflective coatings is a simple yet powerful characterization tool which notably allowed the first observation of graphene in 2004. Since then, the field of two-dimensional (2D) materials has developed rapidly both at the fundamental and applied levels. These ultrathin materials present inhomogeneities (edges, grain boundaries, multilayers, etc.) which strongly impact their physical and chemical properties. Thus their local characterization is essential. This thesis focuses on a recent enhanced-contrast optical microscopy technique, named BALM, based on ultrathin (2-5 nm) and strongly light-absorbing (metallic) anti-reflective layers. The goal is notably to evaluate the benefits of this technique for the study of 2D materials and their chemical reactivity. The various levers to improve 2D materials observation were investigated and optimized for two model materials: graphene oxide and MoS₂ monolayers. The investigation of molecular layer deposition dynamic notably showed the extreme sensitivity of BALM for such measurements and the significant contribution of multilayers anti-reflective coatings to enhance contrast during the observation of 2D materials. One of the main assets of BALM comes from its combination to other techniques. We particularly considered the coupling between optical measurements and electrochemistry for which the anti-reflective layer serves as working electrode. We investigated optically the dynamic of electrochemical reduction of Graphene Oxide (GO), the electrografting of organic layers by diazonium salts reduction on GO and its reduced form (rGO), as well as the intercalation of metallic ions within GO sheets. By combining versatility and high-contrast, BALM is established as a promising tool for the study of 2D materials, especially for the local and in situ characterization of their chemical and electrochemical reactivity.