Anisotropic Structural Collapse of Mg3Sb2 and Mg3Bi2 at High Pressure
Abstract
Alloys between Mg3Sb2 and Mg3Bi2 have recently been shown to be exceptional thermoelectric materials due in part to their anomalously low thermal conductivity. In the present study, in situ high-pressure synchrotron X-ray diffraction was used to investigate the structure and bonding in Mg3Sb2 and Mg3Bi2 at pressures up to 50 GPa. Our results confirm prior predictions of isotropic in-plane and out-of-plane compressibility but reveal large disparities between the bond strength of the two distinct Mg sites. Using single-crystal diffraction, we show that the octahedral Mg–Sb bonds are significantly more compressible than the tetrahedral Mg–Sb bonds in Mg3Sb2, which lends support to prior arguments that the weaker octahedral Mg bonds are responsible for the anomalous thermal properties of Mg3Sb2 and Mg3Bi2. Further, we report the discovery of a displacive and reversible phase transition in both Mg3Sb2 and Mg3Bi2 above 7.8 and 4.0 GPa, respectively. Furthermore, the transition to the high-pressure structure involves a highly anisotropic volume collapse, in which the out-of-plane axis compresses significantly more than the in-plane axes. Single-crystal diffraction at high pressure was used to solve the monoclinic high-pressure structure (C2/m), which is a distorted variant of the ambient-pressure structure containing four unique Mg coordination environments.
- Authors:
-
[1];
[2];
[1];
[4];
[1]
- Michigan State Univ., East Lansing, MI (United States)
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Duke Univ., Durham, NC (United States)
- Univ. of Massachusetts, Amherst, MA (United States)
- Publication Date:
- Research Org.:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Univ. of Illinois, Chicago, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1765294
- Alternate Identifier(s):
- OSTI ID: 1774968
- Report Number(s):
- LLNL-JRNL-814732
Journal ID: ISSN 0897-4756; 1023098
- Grant/Contract Number:
- AC52-07NA27344; NA0003975; SC0019252; SC0019299; FG02-94ER14466; AC02-06CH11357; EAR-1634415
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 33; Journal Issue: 2; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Chemical structure; physical and chemical processes; granular materials; phase transitions; crystal structure
Citation Formats
Calderón-Cueva, Mario, Peng, Wanyue, Clarke, Samantha M., Ding, Jingxuan, Brugman, Benjamin L., Levental, Gill, Balodhi, Ashiwini, Rylko, Megan, Delaire, Olivier, Walsh, James S., Dorfman, Susannah M., and Zevalkink, Alexandra. Anisotropic Structural Collapse of Mg3Sb2 and Mg3Bi2 at High Pressure. United States: N. p., 2021.
Web. doi:10.1021/acs.chemmater.0c03678.
Calderón-Cueva, Mario, Peng, Wanyue, Clarke, Samantha M., Ding, Jingxuan, Brugman, Benjamin L., Levental, Gill, Balodhi, Ashiwini, Rylko, Megan, Delaire, Olivier, Walsh, James S., Dorfman, Susannah M., & Zevalkink, Alexandra. Anisotropic Structural Collapse of Mg3Sb2 and Mg3Bi2 at High Pressure. United States. https://doi.org/10.1021/acs.chemmater.0c03678
Calderón-Cueva, Mario, Peng, Wanyue, Clarke, Samantha M., Ding, Jingxuan, Brugman, Benjamin L., Levental, Gill, Balodhi, Ashiwini, Rylko, Megan, Delaire, Olivier, Walsh, James S., Dorfman, Susannah M., and Zevalkink, Alexandra. Tue .
"Anisotropic Structural Collapse of Mg3Sb2 and Mg3Bi2 at High Pressure". United States. https://doi.org/10.1021/acs.chemmater.0c03678. https://www.osti.gov/servlets/purl/1765294.
@article{osti_1765294,
title = {Anisotropic Structural Collapse of Mg3Sb2 and Mg3Bi2 at High Pressure},
author = {Calderón-Cueva, Mario and Peng, Wanyue and Clarke, Samantha M. and Ding, Jingxuan and Brugman, Benjamin L. and Levental, Gill and Balodhi, Ashiwini and Rylko, Megan and Delaire, Olivier and Walsh, James S. and Dorfman, Susannah M. and Zevalkink, Alexandra},
abstractNote = {Alloys between Mg3Sb2 and Mg3Bi2 have recently been shown to be exceptional thermoelectric materials due in part to their anomalously low thermal conductivity. In the present study, in situ high-pressure synchrotron X-ray diffraction was used to investigate the structure and bonding in Mg3Sb2 and Mg3Bi2 at pressures up to 50 GPa. Our results confirm prior predictions of isotropic in-plane and out-of-plane compressibility but reveal large disparities between the bond strength of the two distinct Mg sites. Using single-crystal diffraction, we show that the octahedral Mg–Sb bonds are significantly more compressible than the tetrahedral Mg–Sb bonds in Mg3Sb2, which lends support to prior arguments that the weaker octahedral Mg bonds are responsible for the anomalous thermal properties of Mg3Sb2 and Mg3Bi2. Further, we report the discovery of a displacive and reversible phase transition in both Mg3Sb2 and Mg3Bi2 above 7.8 and 4.0 GPa, respectively. Furthermore, the transition to the high-pressure structure involves a highly anisotropic volume collapse, in which the out-of-plane axis compresses significantly more than the in-plane axes. Single-crystal diffraction at high pressure was used to solve the monoclinic high-pressure structure (C2/m), which is a distorted variant of the ambient-pressure structure containing four unique Mg coordination environments.},
doi = {10.1021/acs.chemmater.0c03678},
journal = {Chemistry of Materials},
number = 2,
volume = 33,
place = {United States},
year = {Tue Jan 12 00:00:00 EST 2021},
month = {Tue Jan 12 00:00:00 EST 2021}
}
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