An Entropically Stabilized Fast-Ion Conductor: Li 3.25[Si 0.25P 0.75]S4
Abstract
We report on a family of lithium fast ion conductors, Li3+x[SixP1–x]S4, that exhibit an entropically stabilized structure type in a solid solution regime (0.15 < x < 0.33) with superionic conductivity above 1 mS·cm–1. Exploration of the influence of aliovalent substitution in the thermodynamically unstable β-Li3PS4 lattice using a combination of single crystal X-ray and powder neutron diffraction, the maximum entropy method, and impedance spectroscopy reveals that substitution induces structural splitting of the localized Li sites, effectively stabilizing bulk β-Li3PS4 at room temperature and delocalizing lithium ion density. The optimal material, Li3.25[Si0.25P0.75]S4, exhibits inherent entropic site disorder and a frustrated energy landscape, resulting in a high conductivity of 1.22 mS·cm–1 that represents an increase of three orders of magnitude compared to bulk β-Li3PS4 and one order of magnitude higher than the nanoporous form. The enhanced ion conduction and lowered activation barrier with increasing site disorder as a result of aliovalent “tuning” reveals an important strategy toward the design of fast ion conductors that are vital as solid state electrolytes.
- Authors:
-
[1];
[2];
[2];
[1]
- Univ. of Waterloo, ON (Canada). Waterloo Inst. for Nanotechnology
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- BASF SE, Ludwigshafen (Germany)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1606882
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 31; Journal Issue: 19; 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; Diffusion; Crystal structure; Ions; Physical and chemical processes; Electrical conductivity
Citation Formats
Zhou, Laidong, Assoud, Abdeljalil, Shyamsunder, Abhinandan, Huq, Ashfia, Zhang, Qiang, Hartmann, Pascal, Kulisch, Joern, and Nazar, Linda F. An Entropically Stabilized Fast-Ion Conductor: Li 3.25[Si 0.25P 0.75]S4. United States: N. p., 2019.
Web. doi:10.1021/acs.chemmater.9b00657.
Zhou, Laidong, Assoud, Abdeljalil, Shyamsunder, Abhinandan, Huq, Ashfia, Zhang, Qiang, Hartmann, Pascal, Kulisch, Joern, & Nazar, Linda F. An Entropically Stabilized Fast-Ion Conductor: Li 3.25[Si 0.25P 0.75]S4. United States. https://doi.org/10.1021/acs.chemmater.9b00657
Zhou, Laidong, Assoud, Abdeljalil, Shyamsunder, Abhinandan, Huq, Ashfia, Zhang, Qiang, Hartmann, Pascal, Kulisch, Joern, and Nazar, Linda F. Wed .
"An Entropically Stabilized Fast-Ion Conductor: Li 3.25[Si 0.25P 0.75]S4". United States. https://doi.org/10.1021/acs.chemmater.9b00657. https://www.osti.gov/servlets/purl/1606882.
@article{osti_1606882,
title = {An Entropically Stabilized Fast-Ion Conductor: Li 3.25[Si 0.25P 0.75]S4},
author = {Zhou, Laidong and Assoud, Abdeljalil and Shyamsunder, Abhinandan and Huq, Ashfia and Zhang, Qiang and Hartmann, Pascal and Kulisch, Joern and Nazar, Linda F.},
abstractNote = {We report on a family of lithium fast ion conductors, Li3+x[SixP1–x]S4, that exhibit an entropically stabilized structure type in a solid solution regime (0.15 < x < 0.33) with superionic conductivity above 1 mS·cm–1. Exploration of the influence of aliovalent substitution in the thermodynamically unstable β-Li3PS4 lattice using a combination of single crystal X-ray and powder neutron diffraction, the maximum entropy method, and impedance spectroscopy reveals that substitution induces structural splitting of the localized Li sites, effectively stabilizing bulk β-Li3PS4 at room temperature and delocalizing lithium ion density. The optimal material, Li3.25[Si0.25P0.75]S4, exhibits inherent entropic site disorder and a frustrated energy landscape, resulting in a high conductivity of 1.22 mS·cm–1 that represents an increase of three orders of magnitude compared to bulk β-Li3PS4 and one order of magnitude higher than the nanoporous form. The enhanced ion conduction and lowered activation barrier with increasing site disorder as a result of aliovalent “tuning” reveals an important strategy toward the design of fast ion conductors that are vital as solid state electrolytes.},
doi = {10.1021/acs.chemmater.9b00657},
journal = {Chemistry of Materials},
number = 19,
volume = 31,
place = {United States},
year = {Wed Sep 04 00:00:00 EDT 2019},
month = {Wed Sep 04 00:00:00 EDT 2019}
}
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