Bonding Hierarchy Gives Rise to High Thermoelectric Performance in Layered Zintl Compound BaAu2P4
Abstract
The search for new thermoelectric materials has gained rapid progress in recent years as thermoelectric technology offers the potential for environmentally friendly and sustainable energy conversion methods from waste heat to electricity. In this work, we use first-principles calculations based on density functional theory to predict high thermoelectric performance in BaAu2P4, a layered Zintl compound with a small band gap. BaAu2P4 exhibits crystallographic heterogeneity in which rigid [Au2P4]2– units are separated by layers of Ba2+ cations, which are bonded relatively weakly to the lattice through electrostatic interactions. The phosphorus atoms are covalently bonded to each other and form infinite chains within the crystal. While the phosphorus chains facilitate large electrical conductivity, the presence of multiple bands near the Fermi level gives rise to an enhanced Seebeck coefficient. On the other hand, the loosely bound Ba along with Au strongly scatter the heat carrying acoustic phonons, significantly reducing the lattice thermal conduction along the stacking direction. As a consequence of this bonding hierarchy (i.e., coexisting rigid and fluctuating sublattices), BaAu2P4 exhibits a large power factor and low lattice thermal conductivity, which results in a high thermoelectric figure of merit ($zT$). Thus, our findings should encourage the exploration of new thermoelectric materialsmore »
- Authors:
-
[1];
[1];
[1]
- Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Northwestern Univ., Evanston, IL (United States); Citrine Informatics, Inc., Redwood City, CA (United States); Univ. of California, Oakland, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
- OSTI Identifier:
- 1543613
- Alternate Identifier(s):
- OSTI ID: 1775430
- Grant/Contract Number:
- SC0014520; SC0015106; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 30; Journal Issue: 21; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Materials Science; Thermal conductivity; Phonons; Gold; Lattices; Electrical conductivity
Citation Formats
Pal, Koushik, He, Jiangang, and Wolverton, C. Bonding Hierarchy Gives Rise to High Thermoelectric Performance in Layered Zintl Compound BaAu2P4. United States: N. p., 2018.
Web. doi:10.1021/acs.chemmater.8b03130.
Pal, Koushik, He, Jiangang, & Wolverton, C. Bonding Hierarchy Gives Rise to High Thermoelectric Performance in Layered Zintl Compound BaAu2P4. United States. https://doi.org/10.1021/acs.chemmater.8b03130
Pal, Koushik, He, Jiangang, and Wolverton, C. Fri .
"Bonding Hierarchy Gives Rise to High Thermoelectric Performance in Layered Zintl Compound BaAu2P4". United States. https://doi.org/10.1021/acs.chemmater.8b03130. https://www.osti.gov/servlets/purl/1543613.
@article{osti_1543613,
title = {Bonding Hierarchy Gives Rise to High Thermoelectric Performance in Layered Zintl Compound BaAu2P4},
author = {Pal, Koushik and He, Jiangang and Wolverton, C.},
abstractNote = {The search for new thermoelectric materials has gained rapid progress in recent years as thermoelectric technology offers the potential for environmentally friendly and sustainable energy conversion methods from waste heat to electricity. In this work, we use first-principles calculations based on density functional theory to predict high thermoelectric performance in BaAu2P4, a layered Zintl compound with a small band gap. BaAu2P4 exhibits crystallographic heterogeneity in which rigid [Au2P4]2– units are separated by layers of Ba2+ cations, which are bonded relatively weakly to the lattice through electrostatic interactions. The phosphorus atoms are covalently bonded to each other and form infinite chains within the crystal. While the phosphorus chains facilitate large electrical conductivity, the presence of multiple bands near the Fermi level gives rise to an enhanced Seebeck coefficient. On the other hand, the loosely bound Ba along with Au strongly scatter the heat carrying acoustic phonons, significantly reducing the lattice thermal conduction along the stacking direction. As a consequence of this bonding hierarchy (i.e., coexisting rigid and fluctuating sublattices), BaAu2P4 exhibits a large power factor and low lattice thermal conductivity, which results in a high thermoelectric figure of merit ($zT$). Thus, our findings should encourage the exploration of new thermoelectric materials in the family of layered compounds with small band gaps and crystallographic heterogeneity.},
doi = {10.1021/acs.chemmater.8b03130},
journal = {Chemistry of Materials},
number = 21,
volume = 30,
place = {United States},
year = {Fri Oct 12 00:00:00 EDT 2018},
month = {Fri Oct 12 00:00:00 EDT 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 23 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:
Complex thermoelectric materials
journal, February 2008
- Snyder, G. Jeffrey; Toberer, Eric S.
- Nature Materials, Vol. 7, Issue 2, p. 105-114
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
Thermoelectric Cooling and Power Generation
journal, July 1999
- DiSalvo, F. J.
- Science, Vol. 285, Issue 5428, p. 703-706
Nanostructured Thermoelectrics: Big Efficiency Gains from Small Features
journal, July 2010
- Vineis, Christopher J.; Shakouri, Ali; Majumdar, Arun
- Advanced Materials, Vol. 22, Issue 36, p. 3970-3980
Thinking Like a Chemist: Intuition in Thermoelectric Materials
journal, April 2016
- Zeier, Wolfgang G.; Zevalkink, Alex; Gibbs, Zachary M.
- Angewandte Chemie International Edition, Vol. 55, Issue 24
Thermoelectric performance of lanthanum telluride produced via mechanical alloying
journal, September 2008
- May, Andrew F.; Fleurial, Jean-Pierre; Snyder, G. Jeffrey
- Physical Review B, Vol. 78, Issue 12
Ultralow Thermal Conductivity in Full Heusler Semiconductors
journal, July 2016
- He, Jiangang; Amsler, Maximilian; Xia, Yi
- Physical Review Letters, Vol. 117, Issue 4
Bi 2 PdO 4 : A Promising Thermoelectric Oxide with High Power Factor and Low Lattice Thermal Conductivity
journal, November 2016
- He, Jiangang; Hao, Shiqiang; Xia, Yi
- Chemistry of Materials, Vol. 29, Issue 6
Convergence of electronic bands for high performance bulk thermoelectrics
journal, May 2011
- Pei, Yanzhong; Shi, Xiaoya; LaLonde, Aaron
- Nature, Vol. 473, Issue 7345, p. 66-69
Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals
journal, April 2014
- Zhao, Li-Dong; Lo, Shih-Han; Zhang, Yongsheng
- Nature, Vol. 508, Issue 7496, p. 373-377
Ultrahigh power factor and thermoelectric performance in hole-doped single-crystal SnSe
journal, November 2015
- Zhao, L.-D.; Tan, G.; Hao, S.
- Science, Vol. 351, Issue 6269, p. 141-144
Thermoelectric properties of materials with nontrivial electronic topology
journal, January 2015
- Pal, Koushik; Anand, Shashwat; Waghmare, Umesh V.
- Journal of Materials Chemistry C, Vol. 3, Issue 46
Band Engineering of Thermoelectric Materials
journal, October 2012
- Pei, Yanzhong; Wang, Heng; Snyder, G. J.
- Advanced Materials, Vol. 24, Issue 46
All-scale hierarchical thermoelectrics: MgTe in PbTe facilitates valence band convergence and suppresses bipolar thermal transport for high performance
journal, January 2013
- Zhao, L. D.; Wu, H. J.; Hao, S. Q.
- Energy & Environmental Science, Vol. 6, Issue 11
3D charge and 2D phonon transports leading to high out-of-plane ZT in n-type SnSe crystals
journal, May 2018
- Chang, Cheng; Wu, Minghui; He, Dongsheng
- Science, Vol. 360, Issue 6390
Convergence of multi-valley bands as the electronic origin of high thermoelectric performance in CoSb3 skutterudites
journal, October 2015
- Tang, Yinglu; Gibbs, Zachary M.; Agapito, Luis A.
- Nature Materials, Vol. 14, Issue 12
Strain induced Z2 topological insulating state of β -As 2 Te 3
journal, August 2014
- Pal, Koushik; Waghmare, Umesh V.
- Applied Physics Letters, Vol. 105, Issue 6
Low-Dimensional Transport and Large Thermoelectric Power Factors in Bulk Semiconductors by Band Engineering of Highly Directional Electronic States
journal, March 2015
- Bilc, Daniel I.; Hautier, Geoffroy; Waroquiers, David
- Physical Review Letters, Vol. 114, Issue 13
Inverse Band Structure Design via Materials Database Screening: Application to Square Planar Thermoelectrics
journal, February 2018
- Isaacs, Eric B.; Wolverton, Chris
- Chemistry of Materials, Vol. 30, Issue 5
High-performance bulk thermoelectrics with all-scale hierarchical architectures
journal, September 2012
- Biswas, Kanishka; He, Jiaqing; Blum, Ivan D.
- Nature, Vol. 489, Issue 7416, p. 414-418
High-Thermoelectric Performance of Nanostructured Bismuth Antimony Telluride Bulk Alloys
journal, May 2008
- Poudel, B.; Hao, Q.; Ma, Y.
- Science, Vol. 320, Issue 5876, p. 634-638
High Thermoelectric Performance via Hierarchical Compositionally Alloyed Nanostructures
journal, May 2013
- Zhao, Li-Dong; Hao, Shiqiang; Lo, Shih-Han
- Journal of the American Chemical Society, Vol. 135, Issue 19
First-Principles Theory of Competing Order Types, Phase Separation, and Phonon Spectra in Thermoelectric Alloys
journal, October 2008
- Barabash, S. V.; Ozolins, V.; Wolverton, C.
- Physical Review Letters, Vol. 101, Issue 15
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
Phonon-glass electron-crystal thermoelectric clathrates: Experiments and theory
journal, June 2014
- Takabatake, Toshiro; Suekuni, Koichiro; Nakayama, Tsuneyoshi
- Reviews of Modern Physics, Vol. 86, Issue 2
Lone pair electrons minimize lattice thermal conductivity
journal, January 2013
- Nielsen, Michele D.; Ozolins, Vidvuds; Heremans, Joseph P.
- Energy Environ. Sci., Vol. 6, Issue 2
Intrinsically Minimal Thermal Conductivity in Cubic Semiconductors
journal, July 2008
- Morelli, D. T.; Jovovic, V.; Heremans, J. P.
- Physical Review Letters, Vol. 101, Issue 3, Article No. 035901
Part-crystalline part-liquid state and rattling-like thermal damping in materials with chemical-bond hierarchy
journal, October 2014
- Qiu, Wujie; Xi, Lili; Wei, Ping
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 42
First-principles description of anomalously low lattice thermal conductivity in thermoelectric Cu-Sb-Se ternary semiconductors
journal, February 2012
- Zhang, Yongsheng; Skoug, Eric; Cain, Jeffrey
- Physical Review B, Vol. 85, Issue 5
The Origin of Ultralow Thermal Conductivity in InTe: Lone-Pair-Induced Anharmonic Rattling
journal, February 2016
- Jana, Manoj K.; Pal, Koushik; Waghmare, Umesh V.
- Angewandte Chemie International Edition, Vol. 55, Issue 27
Intrinsic Rattler-Induced Low Thermal Conductivity in Zintl Type TlInTe 2
journal, March 2017
- Jana, Manoj K.; Pal, Koushik; Warankar, Avinash
- Journal of the American Chemical Society, Vol. 139, Issue 12
Promising Thermoelectric Bulk Materials with 2D Structures
journal, July 2017
- Zhou, Yiming; Zhao, Li-Dong
- Advanced Materials, Vol. 29, Issue 45
Discovery of high-performance low-cost n-type Mg3Sb2-based thermoelectric materials with multi-valley conduction bands
journal, January 2017
- Zhang, Jiawei; Song, Lirong; Pedersen, Steffen Hindborg
- Nature Communications, Vol. 8, Issue 1
Observation of valence band crossing: the thermoelectric properties of CaZn 2 Sb 2 –CaMg 2 Sb 2 solid solution
journal, January 2018
- Wood, Max; Aydemir, Umut; Ohno, Saneyuki
- Journal of Materials Chemistry A, Vol. 6, Issue 20
Clathrate Ba 8 Au 16 P 30 : The “Gold Standard” for Lattice Thermal Conductivity
journal, August 2013
- Fulmer, James; Lebedev, Oleg I.; Roddatis, Vladimir V.
- Journal of the American Chemical Society, Vol. 135, Issue 33
Resonant Bonding, Multiband Thermoelectric Transport, and Native Defects in n-Type BaBiTe 3– x Se x ( x = 0, 0.05, and 0.1)
journal, December 2017
- Maier, S.; Ohno, S.; Yu, G.
- Chemistry of Materials, Vol. 30, Issue 1
Metal phosphides as potential thermoelectric materials
journal, January 2017
- Pöhls, Jan-Hendrik; Faghaninia, Alireza; Petretto, Guido
- Journal of Materials Chemistry C, Vol. 5, Issue 47
BaAu 2 P 4 : Layered Zintl Polyphosphide with Infinite ∞ 1 ( P – ) Chains
journal, June 2013
- Fulmer, James; Kaseman, Derrick C.; Dolyniuk, Juli-Anna
- Inorganic Chemistry, Vol. 52, Issue 12
Black phosphorus field-effect transistors
journal, March 2014
- Li, Likai; Yu, Yijun; Ye, Guo Jun
- Nature Nanotechnology, Vol. 9, Issue 5
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
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
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
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
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008
- Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.
- Physical Review Letters, Vol. 100, Issue 13
Hybrid functionals based on a screened Coulomb potential
journal, May 2003
- Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
- The Journal of Chemical Physics, Vol. 118, Issue 18
Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]
journal, June 2006
- Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
- The Journal of Chemical Physics, Vol. 124, Issue 21
BoltzTraP. A code for calculating band-structure dependent quantities
journal, July 2006
- Madsen, Georg K. H.; Singh, David J.
- Computer Physics Communications, Vol. 175, Issue 1
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009
- Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
- Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
EPW: A program for calculating the electron–phonon coupling using maximally localized Wannier functions
journal, December 2010
- Noffsinger, Jesse; Giustino, Feliciano; Malone, Brad D.
- Computer Physics Communications, Vol. 181, Issue 12, p. 2140-2148
EPW: Electron–phonon coupling, transport and superconducting properties using maximally localized Wannier functions
journal, December 2016
- Poncé, S.; Margine, E. R.; Verdi, C.
- Computer Physics Communications, Vol. 209
Phonons and related crystal properties from density-functional perturbation theory
journal, July 2001
- Baroni, Stefano; de Gironcoli, Stefano; Dal Corso, Andrea
- Reviews of Modern Physics, Vol. 73, Issue 2
First principles phonon calculations in materials science
journal, November 2015
- Togo, Atsushi; Tanaka, Isao
- Scripta Materialia, Vol. 108
Thermal conductivity of bulk and nanowire Mg Si Sn alloys from first principles
journal, November 2012
- Li, Wu; Lindsay, L.; Broido, D. A.
- Physical Review B, Vol. 86, Issue 17
ShengBTE: A solver of the Boltzmann transport equation for phonons
journal, June 2014
- Li, Wu; Carrete, Jesús; A. Katcho, Nebil
- Computer Physics Communications, Vol. 185, Issue 6
Prediction of New Stable Compounds and Promising Thermoelectrics in the Cu–Sb–Se System
journal, May 2014
- Zhang, Yongsheng; Ozoliņš, Vidvuds; Morelli, Donald
- Chemistry of Materials, Vol. 26, Issue 11
Material descriptors for predicting thermoelectric performance
journal, January 2015
- Yan, Jun; Gorai, Prashun; Ortiz, Brenden
- Energy & Environmental Science, Vol. 8, Issue 3
High-throughput exploration of alloying as design strategy for thermoelectrics
journal, August 2015
- Bhattacharya, Sandip; Madsen, Georg K. H.
- Physical Review B, Vol. 92, Issue 8
Electron mean-free-path filtering in Dirac material for improved thermoelectric performance
journal, January 2018
- Liu, Te-Huan; Zhou, Jiawei; Li, Mingda
- Proceedings of the National Academy of Sciences, Vol. 115, Issue 5
Electronic fitness function for screening semiconductors as thermoelectric materials
journal, November 2017
- Xing, Guangzong; Sun, Jifeng; Li, Yuwei
- Physical Review Materials, Vol. 1, Issue 6
Atomistic Design of Thermoelectric Properties of Silicon Nanowires
journal, April 2008
- Vo, Trinh T. M.; Williamson, Andrew J.; Lordi, Vincenzo
- Nano Letters, Vol. 8, Issue 4
First-principles Debye–Callaway approach to lattice thermal conductivity
journal, September 2016
- Zhang, Yongsheng
- Journal of Materiomics, Vol. 2, Issue 3
ELF: The Electron Localization Function
journal, September 1997
- Savin, Andreas; Nesper, Reinhard; Wengert, Steffen
- Angewandte Chemie International Edition in English, Vol. 36, Issue 17
Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations
journal, August 1993
- Dronskowski, Richard; Bloechl, Peter E.
- The Journal of Physical Chemistry, Vol. 97, Issue 33
Crystal Orbital Hamilton Population (COHP) Analysis As Projected from Plane-Wave Basis Sets
journal, June 2011
- Deringer, Volker L.; Tchougréeff, Andrei L.; Dronskowski, Richard
- The Journal of Physical Chemistry A, Vol. 115, Issue 21
Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids
journal, September 2013
- Maintz, Stefan; Deringer, Volker L.; Tchougréeff, Andrei L.
- Journal of Computational Chemistry, Vol. 34, Issue 29
Efficient PAW-based bond strength analysis for understanding the In/Si(111)(8 × 2) - (4 × 1) phase transition
journal, July 2017
- Lücke, Andreas; Gerstmann, Uwe; Kühne, Thomas D.
- Journal of Computational Chemistry, Vol. 38, Issue 26
Localized Vibrations of Bi Bilayer Leading to Ultralow Lattice Thermal Conductivity and High Thermoelectric Performance in Weak Topological Insulator n- Type BiSe
journal, April 2018
- Samanta, Manisha; Pal, Koushik; Pal, Provas
- Journal of the American Chemical Society, Vol. 140, Issue 17
Phonon-phonon interactions in transition metals
journal, September 2011
- Chaput, Laurent; Togo, Atsushi; Tanaka, Isao
- Physical Review B, Vol. 84, Issue 9
Distributions of phonon lifetimes in Brillouin zones
journal, March 2015
- Togo, Atsushi; Chaput, Laurent; Tanaka, Isao
- Physical Review B, Vol. 91, Issue 9
Enhancement of Thermoelectric Efficiency in PbTe by Distortion of the Electronic Density of States
journal, July 2008
- Heremans, J. P.; Jovovic, V.; Toberer, E. S.
- Science, Vol. 321, Issue 5888, p. 554-557
Works referencing / citing this record:
Powering the Hydrogen Economy from Waste Heat: A Review of Heat‐to‐Hydrogen Concepts
journal, August 2019
- Mulla, Rafiq; Dunnill, Charles W.
- ChemSusChem, Vol. 12, Issue 17
Bonding heterogeneity and lone pair induced anharmonicity resulted in ultralow thermal conductivity and promising thermoelectric properties in n-type AgPbBiSe 3
journal, January 2019
- Dutta, Moinak; Pal, Koushik; Waghmare, Umesh V.
- Chemical Science, Vol. 10, Issue 18
Bonding heterogeneity and lone pair induced anharmonicity resulted in ultralow thermal conductivity and promising thermoelectric properties in n-type $AgPbBiSe_{3}$
text, January 2019
- Dutta, Moinak; Pal, Koushik; Waghmare, Umesh V.
- Deutsches Elektronen-Synchrotron, DESY, Hamburg