High-efficiency thermoelectric Ba 8 Cu 14 Ge 6 P 26 : bridging the gap between tetrel-based and tetrel-free clathrates
Abstract
A new type-I clathrate, Ba8Cu14Ge6P26, was synthesized by solid-state methods as a polycrystalline powder and grown as a cm-sized single crystal via the vertical Bridgman method. Single-crystal and powder X-ray diffraction show that Ba8Cu14Ge6P26 crystallizes in the cubic space group Pm$$\bar{3}$$n (no. 223). Ba8Cu14Ge6P26 is the first representative of anionic clathrates whose framework is composed of three atom types of very different chemical natures: a transition metal, tetrel element, and pnicogen. Uniform distribution of the Cu, Ge, and P atoms over the framework sites and the absence of any superstructural or local ordering in Ba8Cu4Ge6P26 were confirmed by synchrotron X-ray diffraction, electron diffraction and high-angle annular dark field scanning transmission electron microscopy, and neutron and X-ray pair distribution function analyses. Characterization of the transport properties demonstrate that Ba8Cu14Ge6P26 is a p-type semiconductor with an intrinsically low thermal conductivity of 0.72 W m-1K-1 at 812 K. The thermoelectric figure of merit, ZT, for a slice of the Bridgman-grown crystal of Ba8Cu14Ge6P26 approaches 0.63 at 812 K due to a high power factor of 5.62 μW cm-1 K-2. The thermoelectric efficiency of Ba8Cu14Ge6P26 is on par with the best optimized p-type Ge-based clathrates and outperforms the majority of clathrates in the 700–850 K temperature region, including all tetrel-free clathrates. Ba8Cu14Ge6P26 expands clathrate chemistry by bridging conventional tetrel-based and tetrel-free clathrates. Advanced transport properties, in combination with earth-abundant framework elements and congruent melting make Ba8Cu14Ge6P26 a strong candidate as a novel and efficient thermoelectric material.
- Authors:
-
- Department of Chemistry, Iowa State University, Ames, USA, Department of Chemistry
- Laboratoire CRISMAT, ENSICAEN, CNRS, UMR 6508, F-14050 Caen
- Department of Chemistry, University of California, Davis, USA, Thermal Energy Conversion Research and Advancement Group
- Department of Chemistry, University of California, Davis, USA
- Department of Physics, University of California, Davis, USA
- Thermal Energy Conversion Research and Advancement Group, Jet Propulsion Laboratory, Pasadena, USA
- Publication Date:
- Research Org.:
- Univ. of California, Davis, CA (United States); Univ., of Chicago, Chicago, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1409482
- Alternate Identifier(s):
- OSTI ID: 1506077
- Grant/Contract Number:
- SC0008931; AC02-06CH11357
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 8 Journal Issue: 12; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
Citation Formats
Wang, Jian, Lebedev, Oleg I., Lee, Kathleen, Dolyniuk, Juli-Anna, Klavins, Peter, Bux, Sabah, and Kovnir, Kirill. High-efficiency thermoelectric Ba 8 Cu 14 Ge 6 P 26 : bridging the gap between tetrel-based and tetrel-free clathrates. United Kingdom: N. p., 2017.
Web. doi:10.1039/C7SC03482B.
Wang, Jian, Lebedev, Oleg I., Lee, Kathleen, Dolyniuk, Juli-Anna, Klavins, Peter, Bux, Sabah, & Kovnir, Kirill. High-efficiency thermoelectric Ba 8 Cu 14 Ge 6 P 26 : bridging the gap between tetrel-based and tetrel-free clathrates. United Kingdom. https://doi.org/10.1039/C7SC03482B
Wang, Jian, Lebedev, Oleg I., Lee, Kathleen, Dolyniuk, Juli-Anna, Klavins, Peter, Bux, Sabah, and Kovnir, Kirill. Sun .
"High-efficiency thermoelectric Ba 8 Cu 14 Ge 6 P 26 : bridging the gap between tetrel-based and tetrel-free clathrates". United Kingdom. https://doi.org/10.1039/C7SC03482B.
@article{osti_1409482,
title = {High-efficiency thermoelectric Ba 8 Cu 14 Ge 6 P 26 : bridging the gap between tetrel-based and tetrel-free clathrates},
author = {Wang, Jian and Lebedev, Oleg I. and Lee, Kathleen and Dolyniuk, Juli-Anna and Klavins, Peter and Bux, Sabah and Kovnir, Kirill},
abstractNote = {A new type-I clathrate, Ba8Cu14Ge6P26, was synthesized by solid-state methods as a polycrystalline powder and grown as a cm-sized single crystal via the vertical Bridgman method. Single-crystal and powder X-ray diffraction show that Ba8Cu14Ge6P26 crystallizes in the cubic space group Pm$\bar{3}$n (no. 223). Ba8Cu14Ge6P26 is the first representative of anionic clathrates whose framework is composed of three atom types of very different chemical natures: a transition metal, tetrel element, and pnicogen. Uniform distribution of the Cu, Ge, and P atoms over the framework sites and the absence of any superstructural or local ordering in Ba8Cu4Ge6P26 were confirmed by synchrotron X-ray diffraction, electron diffraction and high-angle annular dark field scanning transmission electron microscopy, and neutron and X-ray pair distribution function analyses. Characterization of the transport properties demonstrate that Ba8Cu14Ge6P26 is a p-type semiconductor with an intrinsically low thermal conductivity of 0.72 W m-1K-1 at 812 K. The thermoelectric figure of merit, ZT, for a slice of the Bridgman-grown crystal of Ba8Cu14Ge6P26 approaches 0.63 at 812 K due to a high power factor of 5.62 μW cm-1 K-2. The thermoelectric efficiency of Ba8Cu14Ge6P26 is on par with the best optimized p-type Ge-based clathrates and outperforms the majority of clathrates in the 700–850 K temperature region, including all tetrel-free clathrates. Ba8Cu14Ge6P26 expands clathrate chemistry by bridging conventional tetrel-based and tetrel-free clathrates. Advanced transport properties, in combination with earth-abundant framework elements and congruent melting make Ba8Cu14Ge6P26 a strong candidate as a novel and efficient thermoelectric material.},
doi = {10.1039/C7SC03482B},
journal = {Chemical Science},
number = 12,
volume = 8,
place = {United Kingdom},
year = {Sun Jan 01 00:00:00 EST 2017},
month = {Sun Jan 01 00:00:00 EST 2017}
}
https://doi.org/10.1039/C7SC03482B
Web of Science
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