Synthesis, crystal structure and physical properties of layered cobalt oxide CaxCoO2 (x- 0.47)

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  • MIYAZAKI Yuzuru
    Department of Applied Physics, Graduate School of Engineering, Tohoku University
  • HUANG Xiangyang
    Core Research for Evolutional Science and Technology, Japan Science and Technology Agency
  • KAJIWARA Takashi
    Department of Chemistry, Graduate School of Science, Tohoku University
  • YAMANE Hisanori
    Institute of Multidisciplinary Research for Advanced Materials, Tohoku University
  • KAJITANI Tsuyoshi
    Department of Applied Physics, Graduate School of Engineering, Tohoku University

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説明

We have synthesized a single-phase sample of the compound known as CaCo2O4 and investigated its crystal structure by means of a single crystal X-ray diffraction technique. The compound crystallizes in a triclinic system (space group P1) with lattice parameters of a = 492.4(2) pm, b = 568.3(3) pm, c = 568.5(3) pm, α = 75.400(9)°, β = 89.974(9)° and γ = 81.261(9)° at 293(2) K. The structure consists of an alternate stack of a CdI2-type CoO2 triangular sheet and a layer of Ca atoms, showing great similarity to that of β-NaxCoO2 (x∼ 0.67). However, the Ca atom has four crystallographic sites with different occupation probabilities, leading to the structure formula Ca1.87(5)Co4O8 (Ca0.47(1)CoO2). Due to a low bulk density as well as a small number of hole carriers, equivalent to the nominal valence state of Co ions close to 3.06, a polycrystalline sample of the Ca-phase exhibits much higher electrical resistivity ρ = 680 μΩ m, relative to that of the Na-phase ρ = 1.2 μΩ m, with a large positive Seebeck coefficient of S = 145 μV/K at 300 K.

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