A New Superionic Plastic Polymorph of the Na+ Conductor Na3PS4

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 diff...

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Bibliographic Details
Published inACS materials letters Vol. 1; no. 6; pp. 641 - 646
Main Authors Famprikis, Theodosios, Dawson, James A, Fauth, François, Clemens, Oliver, Suard, Emmanuelle, Fleutot, Benoit, Courty, Matthieu, Chotard, Jean-Noël, Islam, M. Saiful, Masquelier, Christian
Format Journal Article
LanguageEnglish
Published American Chemical Society 02.12.2019
Subjects
Chemical Sciences
Material chemistry
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Summary: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.
ISSN:2639-4979
2639-4979
DOI:10.1021/acsmaterialslett.9b00322