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Nouvelles données sur les systèmes graphite-lithium-europium et graphite-lithium-calcium

Abstract : The molten alloy solid-liquid method containing lithium has recently enabled the synthesis of several bulk graphite intercalation compounds (GICs) in graphite-lithium-alkaline earth metal systems. As part of this thesis, this synthesis method was extended to graphite-lithium-lanthanide systems, with an additional difficulty which is the lack of knowledge of lithium-lanthanide binary phase diagrams whose data are crucial for determining the temperature range and chemical composition of alloys that may lead to GICs. The immersion of pyrographite platelets in some europium-lithium alloys wisely chosen led to a binary EuC6 compound as well as a graphite-lithium-europium first stage ternary compound. Kinetics study of EuC6 compound was followed by ex situ X-ray diffraction in order to understand the different reaction steps and identify intermediate phases leading to the thermodynamically stable final compound. This mechanism revealed a reaction process more "cooperative" than that leading to CaC6 binary compound and was described by a succession of steps that contribute to the bulk insertion of europium. The elementary composition of the ternary compound was determined by ions beam analysis allowing the simultaneous quantification of the three elements lithium, carbon and europium. The refinement of these analyses led to the chemical formula Li0,25Eu1,95C6 for the ternary compound. EuC6 has also been studied by nuclear microprobe analysis, and especially the C/Eu atomic ratio equal to 6 has been confirmed. Structural studies have been undertaken for binary and ternary compounds. On one hand, it was possible to fully resolve the three-dimensional structure of the binary EuC6, which crystallizes in a hexagonal unit cell with P63/mmc space group. On the other hand, the c axis stacking sequence of the poly-layered intercalated sheet of the ternary compound was modeled by combining structural data with information from the ions beam analysis. The graphite intercalation compounds are low-dimensional solids that are ideal for the study of structure-properties relations. Thus in graphite-lithium-calcium system, superconducting character has been studied for CaC6 and Li3Ca2C6 compounds by muons spin spectroscopy ([mu]SR). For the graphite-lithium-europium system, previous magnetic measurements have been continued and supplemented by [mu]SR analysis (for Li0,25Eu1,95C6 and EuC6) and by low temperature 151Eu Mössbauer spectroscopy (for Li0,25Eu1,95C6).
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Submitted on : Thursday, March 29, 2018 - 10:25:31 AM
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  • HAL Id : tel-01746162, version 1


Hania Rida. Nouvelles données sur les systèmes graphite-lithium-europium et graphite-lithium-calcium. Autre. Université Henri Poincaré - Nancy 1, 2011. Français. ⟨NNT : 2011NAN10019⟩. ⟨tel-01746162⟩



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