An Entropically Stabilized Fast-Ion Conductor: Li3.25[Si0.25P0.75]S4
| Autor: | Ashfia Huq, Qiang Zhang, Joern Kulisch, Abdeljalil Assoud, Pascal Hartmann, Abhinandan Shyamsunder, Linda F. Nazar, Laidong Zhou |
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| Rok vydání: | 2019 |
| Předmět: |
Materials science
Nanoporous General Chemical Engineering Neutron diffraction 02 engineering and technology General Chemistry Conductivity 010402 general chemistry 021001 nanoscience & nanotechnology 7. Clean energy 01 natural sciences 0104 chemical sciences Ion Chemical physics Materials Chemistry Fast ion conductor 0210 nano-technology Single crystal Order of magnitude Solid solution |
| Zdroj: | Chemistry of Materials. 31:7801-7811 |
| ISSN: | 1520-5002 0897-4756 |
| DOI: | 10.1021/acs.chemmater.9b00657 |
| Popis: | 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 increasin... |
| Databáze: | OpenAIRE |
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