Thermoelectric misfit-layered cobalt oxides with interlayers of hydroxide and peroxide species
- Laboratory of Inorganic Chemistry, Department of Chemistry, Aalto University, FI-00076 Aalto (Finland)
- National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan (China)
- Program for Science and Technology of Accelerator Light Source, National Chiao Tung University, Hsinchu 30076, Taiwan (China)
Among the thermoelectric misfit-layered cobalt oxides, [M{sub m}A{sub 2}O{sub m+2}]{sub q}CoO{sub 2}, the parent m=0 phases exhibit divergent chemical features but are less understood than the more common m>0 members of the series. Here we synthesize Sr-for-Ca substituted [(Ca{sub 1−x}Sr{sub x}){sub z}(O,OH){sub 2}]{sub q}CoO{sub 2} zero phases up to x=0.2 through low-temperature hydrothermal conversion of precursor powders of the m=1 misfit system, [Co(Ca{sub 1−x}Sr{sub x}){sub 2}O{sub 3}]{sub q}CoO{sub 2}. In the zero-phase [(Ca{sub 1−x}Sr{sub x}){sub z}(O,OH){sub 2}]{sub q}CoO{sub 2} system, as the Sr content x increases the lattice expands anisotropically along the c axis such that the ab-plane dimension and the misfit parameter q remain essentially constant. X-ray absorption spectroscopy data suggest the presence of peroxide-type oxygen species in the (Ca{sub 1−x}Sr{sub x}){sub z}(O,OH){sub 2} rock-salt block and together with infrared spectroscopy, thermogravimetric and low-temperature resistivity and thermopower measurements evidence that the isovalent Sr-for-Ca substitution controls the balance between the peroxide and hydroxide species in the (Ca{sub 1−x}Sr{sub x}){sub z}(O,OH){sub 2} block but leaves the valence of Co essentially intact in the CoO{sub 2} block. The higher electrical conductivity of the Sr-substituted phases is explained as a consequence of increased carrier mobility. - Graphical abstract: Among the thermoelectric misfit-layered cobalt oxides, [M{sub m}A{sub 2}O{sub m+2}]{sub q}CoO{sub 2}, the parent zero (m=0) phases exhibit divergent chemical features. For [(Ca{sub 1−x}Sr{sub x}){sub z}(O,OH){sub 2}]{sub q}CoO{sub 2}, X-ray absorption spectroscopy data suggest the presence of peroxide-type oxygen species in the (Ca{sub 1−x}Sr{sub x}){sub z}(O,OH){sub 2} rock-salt block and together with thermogravimetric and low-temperature transport-property measurements evidence that the isovalent Sr-for-Ca substitution controls the balance between the peroxide and hydroxide species in the (Ca{sub 1−x}Sr{sub x}){sub z}(O,OH){sub 2} block but leaves the valence of Co essentially intact in the CoO{sub 2} block. - Highlights: • Parent m=0 [M{sub m}A{sub 2}O{sub m+2}]{sub q}CoO{sub 2} misfit-layer oxides exhibit divergent chemical features. • [(Ca,Sr){sub z}(O,OH){sub 2}]{sub q}CoO{sub 2} is found to contain both peroxide and hydroxide species. • Hydrothermal synthesis yields [(Ca{sub 1−x}Sr{sub x}){sub z}(O,OH){sub 2}]{sub q}CoO{sub 2} samples up to x=0.2. • With increasing x, the c axis expands but the misfit parameter q remains constant. • Co valence remains intact, but peroxide and hydroxide contents may be affected.
- OSTI ID:
- 22309074
- Journal Information:
- Journal of Solid State Chemistry, Vol. 208; Other Information: Copyright (c) 2013 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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