Famprikis, Theodosios ; Dawson, James A. ; Fauth, François ; Clemens, Oliver ; Suard, Emmanuelle ; Fleutot, Benoit ; Courty, Matthieu ; Chotard, Jean-Noël ; Islam, M. Saiful ; Masquelier, Christian (2019):
A New Superionic Plastic Polymorph of the Na+ Conductor Na3PS4.
In: ACS Materials Letters, 1 (6), pp. 641-646. American Chemical Society, ISSN 2639-4979,
DOI: 10.1021/acsmaterialslett.9b00322,
[Article]
Abstract
Na3PS4 is one of the most promising Na+ conductors, relevant for applications that can leverage its high ionic conductivity, such as solid-state batteries. Currently, two crystalline phases of the material have been identified, and it has been thought to melt above 500 °C. In contrast, based on diffraction, ab initio simulations, impedance spectroscopy, and thermal analysis, we show that Na3PS4 remains solid above this temperature and transforms to a third polymorph, γ, exhibiting fast-ion conduction and an orthorhombic crystal structure. We show that the fast Na+-conduction is associated with rotational motion of the thiophosphate polyanions pointing to a plastic crystal. These findings are of major importance for the development and understanding of new polyanion-based solid electrolytes.
| Item Type: | Article |
|---|---|
| Erschienen: | 2019 |
| Creators: | Famprikis, Theodosios ; Dawson, James A. ; Fauth, François ; Clemens, Oliver ; Suard, Emmanuelle ; Fleutot, Benoit ; Courty, Matthieu ; Chotard, Jean-Noël ; Islam, M. Saiful ; Masquelier, Christian |
| Title: | A New Superionic Plastic Polymorph of the Na+ Conductor Na3PS4 |
| Language: | English |
| Abstract: | Na3PS4 is one of the most promising Na+ conductors, relevant for applications that can leverage its high ionic conductivity, such as solid-state batteries. Currently, two crystalline phases of the material have been identified, and it has been thought to melt above 500 °C. In contrast, based on diffraction, ab initio simulations, impedance spectroscopy, and thermal analysis, we show that Na3PS4 remains solid above this temperature and transforms to a third polymorph, γ, exhibiting fast-ion conduction and an orthorhombic crystal structure. We show that the fast Na+-conduction is associated with rotational motion of the thiophosphate polyanions pointing to a plastic crystal. These findings are of major importance for the development and understanding of new polyanion-based solid electrolytes. |
| Journal or Publication Title: | ACS Materials Letters |
| Volume of the journal: | 1 |
| Issue Number: | 6 |
| Publisher: | American Chemical Society |
| Uncontrolled Keywords: | Plastics Thermodynamic modeling, Physical and chemical processes, Ionic conductivity, Phase transitions |
| Divisions: | 11 Department of Materials and Earth Sciences 11 Department of Materials and Earth Sciences > Material Science 11 Department of Materials and Earth Sciences > Material Science > Fachgebiet Materialdesign durch Synthese |
| Date Deposited: | 19 Feb 2020 07:31 |
| DOI: | 10.1021/acsmaterialslett.9b00322 |
| URL / URN: | https://doi.org/10.1021/acsmaterialslett.9b00322 |
| PPN: | |
| Projects: | T.F. acknowledges the Alistore ERI and CNRS for their financial support in the form of a joint Ph.D. project between Amiens (France) and Bath (UK)., M.S.I. and J.A.D. acknowledge the EPSRC Programme Grant (No. EP/M009521/1) and the MCC-Archer consortium (No. EP/L000202/1). |
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