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KMID : 1059519950390060446
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Journal of the Korean Chemical Society
1995 Volume.39 No. 6 p.446 ~ p.452
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Electronic Structure of Iron and Molybdenum in Li2FeMoO4Cl and Its Crystal Symmetry
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Choy Jin-Ho
Park Nam-Gyu
Chang Soon-Ho
Park Hyung-Ho
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Abstract
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Lithium intercalates, LixFeMoO4Cl (1≤X≤2) prepared by electrochemical lithiation of FeMoO4Cl crystallizes in monoclinic structure for all x values as revealed by x-ray diffraction and galvanostatic discharge experiments. According to the x-ray photoelectron spectroscopic study, Fe(Ⅲ) is at first reduced to Fe(Ⅱ) upon lithium intercalation with the x domain of 0≤X≤1, where the crystal symmetry is changed from tetragonal to monoclinic. On the other hand, Mo(Ⅵ) is reduced to lower valent state upon further lithium intercalation (1≤X≤2), where no crystal symmetry transformation and reduction of Fe(Ⅱ) to lower valent state are observed. The Mo 3d spectrum for Li2FeMoO4Cl appears as a complex shape, but can be deconvoluted into the three sets of the doublet on the basis of Gaussian function, those which correspond to Mo(Ⅵ), Mo(Ⅴ) and Mo(Ⅳ) states, respectively. The mixed valent states of molybdenum after further lithiation may be due to a competitive reaction between the formation of Mo(Ⅴ) and its disproportionation to Mo(Ⅳ) and Mo(Ⅵ).
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