Insights into the Rich Polymorphism of the Na+ Ion Conductor Na3PS4 from the Perspective of Variable-Temperature Diffraction and Spectroscopy

Insights into the Rich Polymorphism of the Na+ Ion Conductor Na3PS4 from the Perspective of Variable-Temperature Diffraction and Spectroscopy

© 2021 The Authors. Published by American Chemical Society.

Bibliographische Detailangaben
Veröffentlicht in:Chemistry of materials : a publication of the American Chemical Society. - 1998. - 33(2021), 14 vom: 27. Juli, Seite 5652-5667
1. Verfasser: Famprikis, Theodosios (VerfasserIn)
Weitere Verfasser: Bouyanfif, Houssny, Canepa, Pieremanuele, Zbiri, Mohamed, Dawson, James A, Suard, Emmanuelle, Fauth, François, Playford, Helen Y, Dambournet, Damien, Borkiewicz, Olaf J, Courty, Matthieu, Clemens, Oliver, Chotard, Jean-Noël, Islam, M Saiful, Masquelier, Christian
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2021
Zugriff auf das übergeordnete Werk:Chemistry of materials : a publication of the American Chemical Society
Schlagworte:Journal Article
Beschreibung
Zusammenfassung:© 2021 The Authors. Published by American Chemical Society.
Solid electrolytes are crucial for next-generation solid-state batteries, and Na3PS4 is one of the most promising Na+ conductors for such applications, despite outstanding questions regarding its structural polymorphs. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na3PS4 over a wide temperature range 30 < T < 600 °C through combined experimental-computational analysis. Although Bragg diffraction experiments indicate a second-order phase transition from the tetragonal ground state (α, P4̅21 c) to the cubic polymorph (β, I4̅3m) above ∼250 °C, pair distribution function analysis in real space and Raman spectroscopy indicate remnants of a tetragonal character in the range 250 < T < 500 °C, which we attribute to dynamic local tetragonal distortions. The first-order phase transition to the mesophasic high-temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid-like dynamics for sodium-cations (translational) and thiophosphate-polyanions (rotational) evident by inelastic neutron and Raman spectroscopies, as well as pair-distribution function and molecular dynamics analyses. These results shed light on the rich polymorphism of Na3PS4 and are relevant for a range host of high-performance materials deriving from the Na3PS4 structural archetype
Beschreibung:Date Revised 07.09.2021
published: Print-Electronic
Citation Status PubMed-not-MEDLINE
ISSN:0897-4756
DOI:10.1021/acs.chemmater.1c01113