Tunable Lithium-Ion Transport in Mixed-Halide Argyrodites Li6–xPS5–xClBrx: An Unusual Compositional Space
Abstract
Argyrodites, with fast lithium-ion conduction, are promising for applications in rechargeable solid-state lithium-ion batteries. In this article, we report a new compositional space of argyrodite superionic conductors, Li6–xPS5–xClBrx [0 ≤ x ≤ 0.8], with a remarkably high ionic conductivity of 24 mS/cm at 25 °C for Li5.3PS4.3ClBr0.7. In addition, the extremely low lithium migration barrier of 0.155 eV makes Li5.3PS4.3ClBr0.7 highly promising for low-temperature operation. Average and local structure analyses reveal that bromination (x > 0) leads to (i) retention of the parent Li6PS5Cl structure for a wide range of x in Li6–xPS5–xClBrx (0 ≤ x ≤ 0.7), (ii) co-occupancy of Cl–, Br–, and S2– at 4a/4d sites, and (iii) gradually increased Li+-ion dynamics, eventually yielding a “liquid-like” Li-sublattice with a flattened energy landscape when x approaches 0.7. In addition, the diversity of anion species and Li-deficiency in halogen-rich Li6–xPS5–xClBrx induce hypercoordination and coordination entropy for the Li-sublattice, also leading to enhanced Li+-ion transport in Li6–xPS5–xClBrx. This study demonstrates that mixed-anion framework can help stabilize highly conductive structures in a compositional space otherwise unstable with lower anion diversity.
- Authors:
-
[1];
[2];
[3];
[3];
[2];
[4]
- Florida State Univ., Tallahassee, FL (United States)
- Univ. of California, San Diego, CA (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
- Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Science Foundation (NSF)
- OSTI Identifier:
- 1772860
- Grant/Contract Number:
- AC05-00OR22725; AC02-05-CH11231; DMR-1847038; DMR-1720139; DMR-1644779; ACI-1053575; PT78832
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 33; Journal Issue: 4; 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; chemical structure; ionic conductivity; anions; activation energy; ions
Citation Formats
Patel, Sawankumar V., Banerjee, Swastika, Liu, Haoyu, Wang, Pengbo, Chien, Po-Hsiu, Feng, Xuyong, Liu, Jue, Ong, Shyue Ping, and Hu, Yan-Yan. Tunable Lithium-Ion Transport in Mixed-Halide Argyrodites Li6–xPS5–xClBrx: An Unusual Compositional Space. United States: N. p., 2021.
Web. doi:10.1021/acs.chemmater.0c04650.
Patel, Sawankumar V., Banerjee, Swastika, Liu, Haoyu, Wang, Pengbo, Chien, Po-Hsiu, Feng, Xuyong, Liu, Jue, Ong, Shyue Ping, & Hu, Yan-Yan. Tunable Lithium-Ion Transport in Mixed-Halide Argyrodites Li6–xPS5–xClBrx: An Unusual Compositional Space. United States. https://doi.org/10.1021/acs.chemmater.0c04650
Patel, Sawankumar V., Banerjee, Swastika, Liu, Haoyu, Wang, Pengbo, Chien, Po-Hsiu, Feng, Xuyong, Liu, Jue, Ong, Shyue Ping, and Hu, Yan-Yan. Wed .
"Tunable Lithium-Ion Transport in Mixed-Halide Argyrodites Li6–xPS5–xClBrx: An Unusual Compositional Space". United States. https://doi.org/10.1021/acs.chemmater.0c04650. https://www.osti.gov/servlets/purl/1772860.
@article{osti_1772860,
title = {Tunable Lithium-Ion Transport in Mixed-Halide Argyrodites Li6–xPS5–xClBrx: An Unusual Compositional Space},
author = {Patel, Sawankumar V. and Banerjee, Swastika and Liu, Haoyu and Wang, Pengbo and Chien, Po-Hsiu and Feng, Xuyong and Liu, Jue and Ong, Shyue Ping and Hu, Yan-Yan},
abstractNote = {Argyrodites, with fast lithium-ion conduction, are promising for applications in rechargeable solid-state lithium-ion batteries. In this article, we report a new compositional space of argyrodite superionic conductors, Li6–xPS5–xClBrx [0 ≤ x ≤ 0.8], with a remarkably high ionic conductivity of 24 mS/cm at 25 °C for Li5.3PS4.3ClBr0.7. In addition, the extremely low lithium migration barrier of 0.155 eV makes Li5.3PS4.3ClBr0.7 highly promising for low-temperature operation. Average and local structure analyses reveal that bromination (x > 0) leads to (i) retention of the parent Li6PS5Cl structure for a wide range of x in Li6–xPS5–xClBrx (0 ≤ x ≤ 0.7), (ii) co-occupancy of Cl–, Br–, and S2– at 4a/4d sites, and (iii) gradually increased Li+-ion dynamics, eventually yielding a “liquid-like” Li-sublattice with a flattened energy landscape when x approaches 0.7. In addition, the diversity of anion species and Li-deficiency in halogen-rich Li6–xPS5–xClBrx induce hypercoordination and coordination entropy for the Li-sublattice, also leading to enhanced Li+-ion transport in Li6–xPS5–xClBrx. This study demonstrates that mixed-anion framework can help stabilize highly conductive structures in a compositional space otherwise unstable with lower anion diversity.},
doi = {10.1021/acs.chemmater.0c04650},
journal = {Chemistry of Materials},
number = 4,
volume = 33,
place = {United States},
year = {Wed Feb 03 00:00:00 EST 2021},
month = {Wed Feb 03 00:00:00 EST 2021}
}
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