Oxygen Nonstoichiometry in Layered Cobaltite Ca3Co4Oy
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概要
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Oxygen nonstoichiometry of Ca3Co4Oy was precisely measured by thermogravimetry. Combining the result of thermal decomposition analysis, this compound was found to be expressed as (CoO2)1.62(Ca2CoO3-δ) with $\delta=0--0.14$. The observed oxygen nonstoichiometry in the present system was much larger than those of other layered cobaltites having the CdI2-type CoO2 layer. Three regions showing different oxygen nonstoichiometry behaviors were found in the equilibrium oxygen phase diagram. Thermodynamic analyses revealed that dependencies of $\Delta h_{\text{O$_{2}$}}$ and $\Delta s_{\text{O$_{2}$}}$ on $\delta$ are apparently different in the three regions and the generation of oxygen defect accompanies a decrease of the valence of cobalt ions at the Ca2CoO3-δ block in the main region.
- 2003-02-15
著者
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Kishio Kohji
Department Of Applied Chemistry Faculty Of Engineering University Of Tokyo
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Sano Mitsuhiro
Department Of Applied Chemistry School Of Engineering University Of Tokyo
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Otzschi Kenji
Department Of Applied Chemistry School Of Engineering University Of Tokyo
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Shimoyama Jun-ichi
Department Of Applied Chemistry School Of Engineering University Of Tokyo
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Horii Shigeru
Department Of Applied Chemistry School Of Engineering University Of Tokyo
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Shimoyama Jun-ichi
Department of Applied Chemistry, School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
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Kishio Kohji
Department of Applied Chemistry, School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
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Horii Shigeru
Department of Applied Chemistry, School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
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Sano Mitsuhiro
Department of Applied Chemistry, School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
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