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Title: Structures and thermoelectric properties of double-filled (Ca{sub x}Ce{sub 1−x})Fe{sub 4}Sb{sub 12} skutterudites

The structures and thermoelectric properties of the double-filled (Ca{sub x}Ce{sub 1−x})Fe{sub 4}Sb{sub 12} series (x=0, 0.25, 0.5, 0.75, and 1) have been studied using a combined experimental and computational methods. Compounds of (Ca{sub x}Ce{sub 1−x})Fe{sub 4}Sb{sub 12} were obtained only for x=0, 0.5, and 1. Composition with x=0.25 was found to be a mixture of x=0 and 0.5 compounds, and composition with x=0.75 was found to be a mixture of x=1 and 0.5 compounds, respectively. Our conclusions on phase formation are supported by density functional theory (DFT) calculations. In Ca{sub 0.5}Ce{sub 0.5}Fe{sub 4}Sb{sub 12,} Ca substitution in the Ce site of CeFe{sub 4}Sb{sub 12} leads to high hole concentrations, resulting in stronger semimetal transport as compared to CeFe{sub 4}Sb{sub 12}. Ca{sub 0.5}Ce{sub 0.5}Fe{sub 4}Sb{sub 12} yields a slightly higher ZT value than that of CeFe{sub 4}Sb{sub 12}, which is attributed to its lower lattice thermal conductivity. Phonon mode calculations adopting a three-particle bending model suggest that thermal conductivity is reduced upon Ca substitution because of an additional vibration mode which involves both Ca and Ce atoms. - Graphical abstract: Detailed structural information to correlate with thermoelectric properties in a series of double-filled (Ca{sub x}Ce{sub 1−x})Fe{sub 4}Sb{sub 12} skutterudite samples weremore » obtained using synchrotron X-ray diffraction and first principle calculations. - Highlights: • Research focus on phase stability of CaCe double-filled p-type skutterudite. • Stable structure forms for an equiatomic occupancy of the voids by Ca and Ce. • Samples feature two-phase mixtures with variations of filling atoms ratio. • Phase stablility is investigated by DFT total energy calculations. • Sample with Equiatomic occupancy of Ca and Ce show higher ZT.« less
Authors:
 [1] ;  [2] ; ; ;  [3] ;  [4] ;  [5] ; ;  [1] ;  [1]
  1. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, Hubei 430070 (China)
  2. (United States)
  3. Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States)
  4. Department of Biological and Chemical Sciences, Illinois Institute of Technology, Chicago, IL 60616 (United States)
  5. Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439 (United States)
Publication Date:
OSTI Identifier:
22443432
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 218; Other Information: Copyright (c) 2014 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DENSITY FUNCTIONAL METHOD; MIXTURES; OSCILLATION MODES; PARTICLES; PHASE STABILITY; PHONONS; SYNCHROTRONS; THERMAL CONDUCTIVITY; THERMOELECTRIC PROPERTIES; X-RAY DIFFRACTION