Electronegative Guests in CoSb3
Abstract
Introducing guests into a host framework to form a so called inclusion compound can be used to design materials with new and fascinating functionalities. The vast majority of inclusion compounds have electropositive guests with neutral or negatively charged frameworks. Here, we show a series of electronegative guest filled skutterudites with inverse polarity. The strong covalent guest-host interactions observed for the electronegative group VIA guests, i.e., S and Se, feature a unique localized cluster vibration which significantly influences the lattice dynamics, together with the point-defect scattering caused by element substitutions, resulting in very low lattice thermal conductivity values. The findings of electronegative guests provide a new perspective for guest-filling in skutterudites, and the covalent filler/lattice interactions lead to an unusual lattice dynamics phenomenon which can be used for designing high-efficiency thermoelectric materials and novel functional inclusion compounds with open structures.
- Authors:
-
- Univ. of Washington, Seattle, WA (United States)
- General Motors (GM), Warren, MI (United States). Global Research and Development
- Univ. of Pittsburgh, PA (United States)
- Chinese Academy of Sciences (CAS), Shanghai (China). Shanghai Inst. of Ceramics
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Wuhan Univ. (China)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1261362
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energy & Environmental Science
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 6; Journal ID: ISSN 1754-5692
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Duan, Bo, Yang, Jiong, Salvador, James R., He, Yang, Zhao, Bo, Wang, Shanyu, Wei, Ping, Ohuchi, Fumio, Zhang, Wenqing, Hermann, Raphael P., Gourdon, Olivier, Mao, Scott, Cheng, Yingwen, Wang, Chongmin, Liu, Jun, Zhai, Pengcheng, Tang, Xinfeng, Zhang, Qingjie, and Yang, Jihui. Electronegative Guests in CoSb3. United States: N. p., 2016.
Web. doi:10.1039/C6EE00322B.
Duan, Bo, Yang, Jiong, Salvador, James R., He, Yang, Zhao, Bo, Wang, Shanyu, Wei, Ping, Ohuchi, Fumio, Zhang, Wenqing, Hermann, Raphael P., Gourdon, Olivier, Mao, Scott, Cheng, Yingwen, Wang, Chongmin, Liu, Jun, Zhai, Pengcheng, Tang, Xinfeng, Zhang, Qingjie, & Yang, Jihui. Electronegative Guests in CoSb3. United States. https://doi.org/10.1039/C6EE00322B
Duan, Bo, Yang, Jiong, Salvador, James R., He, Yang, Zhao, Bo, Wang, Shanyu, Wei, Ping, Ohuchi, Fumio, Zhang, Wenqing, Hermann, Raphael P., Gourdon, Olivier, Mao, Scott, Cheng, Yingwen, Wang, Chongmin, Liu, Jun, Zhai, Pengcheng, Tang, Xinfeng, Zhang, Qingjie, and Yang, Jihui. Tue .
"Electronegative Guests in CoSb3". United States. https://doi.org/10.1039/C6EE00322B. https://www.osti.gov/servlets/purl/1261362.
@article{osti_1261362,
title = {Electronegative Guests in CoSb3},
author = {Duan, Bo and Yang, Jiong and Salvador, James R. and He, Yang and Zhao, Bo and Wang, Shanyu and Wei, Ping and Ohuchi, Fumio and Zhang, Wenqing and Hermann, Raphael P. and Gourdon, Olivier and Mao, Scott and Cheng, Yingwen and Wang, Chongmin and Liu, Jun and Zhai, Pengcheng and Tang, Xinfeng and Zhang, Qingjie and Yang, Jihui},
abstractNote = {Introducing guests into a host framework to form a so called inclusion compound can be used to design materials with new and fascinating functionalities. The vast majority of inclusion compounds have electropositive guests with neutral or negatively charged frameworks. Here, we show a series of electronegative guest filled skutterudites with inverse polarity. The strong covalent guest-host interactions observed for the electronegative group VIA guests, i.e., S and Se, feature a unique localized cluster vibration which significantly influences the lattice dynamics, together with the point-defect scattering caused by element substitutions, resulting in very low lattice thermal conductivity values. The findings of electronegative guests provide a new perspective for guest-filling in skutterudites, and the covalent filler/lattice interactions lead to an unusual lattice dynamics phenomenon which can be used for designing high-efficiency thermoelectric materials and novel functional inclusion compounds with open structures.},
doi = {10.1039/C6EE00322B},
journal = {Energy & Environmental Science},
number = 6,
volume = 9,
place = {United States},
year = {Tue Apr 19 00:00:00 EDT 2016},
month = {Tue Apr 19 00:00:00 EDT 2016}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 79 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Avoided crossing of rattler modes in thermoelectric materials
journal, August 2008
- Christensen, Mogens; Abrahamsen, Asger B.; Christensen, Niels B.
- Nature Materials, Vol. 7, Issue 10
Recognition of Electron-Donating Guests by Carborane-Supported Multidentate Macrocyclic Lewis Acid Hosts: Mercuracarborand Chemistry
journal, July 1997
- Hawthorne, M. Frederick; Zheng, Zhiping
- Accounts of Chemical Research, Vol. 30, Issue 7
Synthesis, Structure, and Transport Properties of Type-I Derived Clathrate Ge 46– x P x Se 8– y ( x = 15.4(1); y = 0–2.65) with Diverse Host–Guest Bonding
journal, December 2012
- Kirsanova, Maria A.; Mori, Takao; Maruyama, Satofumi
- Inorganic Chemistry, Vol. 52, Issue 2
New mercury-contained cationic frameworks stabilized by (GaCl4)− unit via weak electrostatic forces in supramolecular compounds (Hg11P4)(GaCl4)4 and (Hg3AsS)(GaCl4)
journal, January 2013
- Jiang, Xiao-Ming; Li, Xiao-Guo; Fan, Yu-Hang
- Dalton Transactions, Vol. 42, Issue 43
Anion Driven [Cu II L 2 ] n Frameworks: Crystal Structures, Guest-Encapsulation, Dielectric, and Possible Ferroelectric Properties
journal, June 2014
- Srivastava, Anant Kumar; Praveenkumar, B.; Mahawar, Indra Kumar
- Chemistry of Materials, Vol. 26, Issue 12
Cooling, Heating, Generating Power, and Recovering Waste Heat with Thermoelectric Systems
journal, September 2008
- Bell, L. E.
- Science, Vol. 321, Issue 5895, p. 1457-1461
Skutterudites as thermoelectric materials: revisited
journal, January 2015
- Rull-Bravo, M.; Moure, A.; Fernández, J. F.
- RSC Advances, Vol. 5, Issue 52
Synthesis of iodine filled CoSb 3 with extremely low thermal conductivity
journal, December 2014
- Li, Xiaodong; Xu, Bo; Zhang, Long
- Journal of Alloys and Compounds, Vol. 615
High-Pressure Synthesis, Structure, and Electrical Property of Iodine-Filled Skutterudite I 0.9 Rh 4 Sb 12 —First Anion-Filled Skutterudite
journal, January 2010
- Fukuoka, Hiroshi; Yamanaka, Shoji
- Chemistry of Materials, Vol. 22, Issue 1
Multiple-Filled Skutterudites: High Thermoelectric Figure of Merit through Separately Optimizing Electrical and Thermal Transports
journal, May 2011
- Shi, Xun; Yang, Jiong; Salvador, James R.
- Journal of the American Chemical Society, Vol. 133, Issue 20
Filling Fraction Limit for Intrinsic Voids in Crystals: Doping in Skutterudites
journal, October 2005
- Shi, X.; Zhang, W.; Chen, L. D.
- Physical Review Letters, Vol. 95, Issue 18
Alkali-metal-filled skutterudites as thermoelectric materials: Theoretical study
journal, January 2008
- Mei, Z. G.; Yang, Jiong; Pei, Y. Z.
- Physical Review B, Vol. 77, Issue 4
Synthesis and thermoelectric properties of KyCo4Sb12
journal, November 2006
- Pei, Y. Z.; Chen, L. D.; Zhang, W.
- Applied Physics Letters, Vol. 89, Issue 22
Anomalous barium filling fraction and n -type thermoelectric performance of BayCo4Sb12
journal, August 2001
- Chen, L. D.; Kawahara, T.; Tang, X. F.
- Journal of Applied Physics, Vol. 90, Issue 4
Synthesis of YbyCo4Sb12∕Yb2O3 composites and their thermoelectric properties
journal, August 2006
- Zhao, X. Y.; Shi, X.; Chen, L. D.
- Applied Physics Letters, Vol. 89, Issue 9
High figure of merit in partially filled ytterbium skutterudite materials
journal, January 2000
- Nolas, G. S.; Kaeser, M.; Littleton, R. T.
- Applied Physics Letters, Vol. 77, Issue 12
Thermoelectric property enhancement in Yb-doped n-type skutterudites YbxCo4Sb12
journal, August 2014
- Dahal, Tulashi; Jie, Qing; Joshi, Giri
- Acta Materialia, Vol. 75
Coupled vibrational modes in multiple-filled skutterudites and the effects on lattice thermal conductivity reduction
journal, March 2013
- Guo, L.; Xu, X.; Salvador, J. R.
- Applied Physics Letters, Vol. 102, Issue 11
Complex doping of group 13 elements In and Ga in caged skutterudite CoSb3
journal, February 2015
- Xi, Lili; Qiu, Yuting; Zheng, Shan
- Acta Materialia, Vol. 85
Charge-Compensated Compound Defects in Ga-containing Thermoelectric Skutterudites
journal, February 2013
- Qiu, Yuting; Xi, Lili; Shi, Xun
- Advanced Functional Materials, Vol. 23, Issue 25
Phase diagram of In–Co–Sb system and thermoelectric properties of In-containing skutterudites
journal, January 2014
- Tang, Yinglu; Qiu, Yuting; Xi, Lili
- Energy Environ. Sci., Vol. 7, Issue 2
Thermoelectric properties of Te-doped CoSb3 by spark plasma sintering
journal, October 2005
- Li, X. Y.; Chen, L. D.; Fan, J. F.
- Journal of Applied Physics, Vol. 98, Issue 8
Thermoelectric properties of CoSb 3 and related alloys
journal, July 1995
- Sharp, J. W.; Jones, E. C.; Williams, R. K.
- Journal of Applied Physics, Vol. 78, Issue 2
Improving thermoelectric performance of caged compounds through light-element filling
journal, July 2009
- Pei, Y. Z.; Yang, Jiong; Chen, L. D.
- Applied Physics Letters, Vol. 95, Issue 4
Properties of single crystalline semiconducting CoSb 3
journal, October 1996
- Caillat, T.; Borshchevsky, A.; Fleurial, J. ‐P.
- Journal of Applied Physics, Vol. 80, Issue 8
Significant Reduction of Lattice Thermal Conductivity by the Electron-Phonon Interaction in Silicon with High Carrier Concentrations: A First-Principles Study
journal, March 2015
- Liao, Bolin; Qiu, Bo; Zhou, Jiawei
- Physical Review Letters, Vol. 114, Issue 11
Structure and Transport Properties of Double-Doped CoSb 2.75 Ge 0.25– x Te x ( x = 0.125–0.20) with in Situ Nanostructure
journal, June 2011
- Su, Xianli; Li, Han; Wang, Guoyu
- Chemistry of Materials, Vol. 23, Issue 11
Structure and Thermoelectric Properties of Te- and Ge-Doped Skutterudites CoSb2.875−x Ge0.125Te x
journal, March 2011
- Su, XianLi; Li, Han; Guo, QuanSheng
- Journal of Electronic Materials, Vol. 40, Issue 5
Full-potential band-structure calculation of iron pyrite
journal, November 1999
- Opahle, I.; Koepernik, K.; Eschrig, H.
- Physical Review B, Vol. 60, Issue 20
Direct Experimental Evidence for Atomic Tunneling of Europium in Crystalline
journal, July 2006
- Hermann, Raphaël P.; Keppens, Veerle; Bonville, Pierre
- Physical Review Letters, Vol. 97, Issue 1
Enhanced thermoelectric performance of dual-element-filled skutterudites BaxCeyCo4Sb12
journal, June 2009
- Bai, S. Q.; Pei, Y. Z.; Chen, L. D.
- Acta Materialia, Vol. 57, Issue 11
Electrical Transport Properties of Filled CoSb3 Skutterudites: A Theoretical Study
journal, February 2009
- Yang, Jiong; Xi, L.; Zhang, W.
- Journal of Electronic Materials, Vol. 38, Issue 7
Skutterudite antimonides: Quasilinear bands and unusual transport
journal, October 1994
- Singh, David J.; Pickett, Warren E.
- Physical Review B, Vol. 50, Issue 15
Beneficial effect of Se substitution on thermoelectric properties of Co4Sb11.9−xTexSe0.1 skutterudites
journal, September 2012
- Duan, Bo; Zhai, Pengcheng; Liu, Lisheng
- Journal of Solid State Chemistry, Vol. 193
Thermoelectric Performance of Multiple-Doped Co4Sb12−x−y−z Ge x Te y S z Skutterudite Compounds
journal, October 2012
- Duan, Bo; Zhai, Pengcheng; Liu, Lisheng
- Journal of Electronic Materials, Vol. 42, Issue 7
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
First-principles calculations of the ferroelastic transition between rutile-type and -type at high pressures
journal, October 2008
- Togo, Atsushi; Oba, Fumiyasu; Tanaka, Isao
- Physical Review B, Vol. 78, Issue 13
Works referencing / citing this record:
Compromise and Synergy in High-Efficiency Thermoelectric Materials
journal, March 2017
- Zhu, Tiejun; Liu, Yintu; Fu, Chenguang
- Advanced Materials, Vol. 29, Issue 14
Design of Highly Efficient Thermoelectric Materials: Tailoring Reciprocal-Space Properties by Real-Space Modification
journal, September 2018
- Zhu, Hao; Xiao, Chong; Xie, Yi
- Advanced Materials, Vol. 30, Issue 48
Thermoelectric GeTe with Diverse Degrees of Freedom Having Secured Superhigh Performance
journal, February 2019
- Hong, Min; Zou, Jin; Chen, Zhi‐Gang
- Advanced Materials, Vol. 31, Issue 14
Intrinsically High Thermoelectric Performance in AgInSe 2 n-Type Diamond-Like Compounds
journal, December 2017
- Qiu, Pengfei; Qin, Yuting; Zhang, Qihao
- Advanced Science, Vol. 5, Issue 3
Multiscale Defects as Strong Phonon Scatters to Enhance Thermoelectric Performance in Mg 2 Sn 1– x Sb x Solid Solutions
journal, July 2019
- Xin, Jiazhan; Zhang, Yang; Wu, Haijun
- Small Methods, Vol. 3, Issue 12
Improved electrical transport properties and optimized thermoelectric figure of merit in lithium-doped copper sulfides
journal, March 2018
- Guan, Meng-Jia; Qiu, Peng-Fei; Song, Qing-Feng
- Rare Metals, Vol. 37, Issue 4
Determining ideal strength and failure mechanism of thermoelectric CuInTe 2 through quantum mechanics
journal, January 2018
- Li, Guodong; An, Qi; Morozov, Sergey I.
- Journal of Materials Chemistry A, Vol. 6, Issue 25
Study of thermal stability of p-type skutterudites DD 0.7 Fe 3 CoSb 12 by Knudsen effusion mass spectrometry
journal, January 2019
- Zelenka, František; Brož, Pavel; Vřešťál, Jan
- RSC Advances, Vol. 9, Issue 37
Thermal, electronic and thermoelectric properties of TiNiSn and TiCoSb based quaternary half Heusler alloys obtained from ab initio calculations
journal, January 2020
- Choudhary, Mukesh K.; Ravindran, P.
- Sustainable Energy & Fuels, Vol. 4, Issue 2
Thermoelectric properties of electronegatively filled S y Co 4−x Ni x Sb 12 skutterudites
journal, January 2019
- Li, Jialiang; Duan, Bo; Yang, Houjiang
- Journal of Materials Chemistry C, Vol. 7, Issue 26
New insights into the role of dislocation engineering in N-type filled skutterudite CoSb 3
journal, January 2019
- Liu, Zihang; Meng, Xianfu; Qin, Dandan
- Journal of Materials Chemistry C, Vol. 7, Issue 43
Thermoelectric transport properties of Ni-, Pd-, and Pt- doped skutterudites with S-filling as charge compensation
journal, April 2019
- Tu, Zhikang; Sun, Xin; Li, Xin
- AIP Advances, Vol. 9, Issue 4
High performance p-type half-Heusler thermoelectric materials
journal, February 2018
- Yu, Junjie; Xia, Kaiyang; Zhao, Xinbing
- Journal of Physics D: Applied Physics, Vol. 51, Issue 11
Thermoelectric properties of Co 4 Sb 12 with Bi 2 Te 3 nanoinclusions
journal, February 2018
- Ghosh, Sanyukta; Bisht, Anuj; Karati, Anirudha
- Journal of Physics: Condensed Matter, Vol. 30, Issue 9
Thermal transport in thermoelectric materials with chemical bond hierarchy
journal, March 2019
- Yang, Jiong; Wang, Yancheng; Yang, Hongliang
- Journal of Physics: Condensed Matter, Vol. 31, Issue 18
Enhanced thermoelectric properties of CoSb 3 -based skutterudites by filling Se as electronegative element
journal, November 2018
- Bao, Xin; Wu, Zihua; Xie, Huaqing
- Materials Research Express, Vol. 6, Issue 2