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

Journal Article · · Chemistry of Materials
 [1];  [2];  [3];  [4];  [5];  [4];  [6];  [7];  [8];  [9];  [10];  [11];  [10];  [12];  [10]
  1. Univ. de Picardie Jules Verne, Amiens (France). Lab. de Réactivité et Chimie des Solides (LRCS); University of Bath (United Kingdom); ALISTORE European Research Inst., Amiens (France); Réseau sur le Stockage Électrochimique de l’Énergie (RS2E), Amiens (France)
  2. Univ. de Picardie Jules Verne, Amiens (France). Lab. de Physique de la Matière Condensée (LPMC)
  3. National Univ. of Singapore (Singapore)
  4. Institut Laue-Langevin (ILL), Grenoble (France)
  5. Newcastle Univ., Newcastle upon Tyne (United Kingdom); Newcastle Univ., Newcastle upon Tyne (United Kingdom). Centre for Energy
  6. CELLS—ALBA Synchrotron, ILL, Barcelona (Spain)
  7. Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Rutherford Appleton Lab., ISIS Neutron Source
  8. Sorbonne Univ., Paris (France). Physico-Chimie des Electrolytes et Nano-systèmes Interfaciaux (PHENIX); Réseau sur le Stockage Électrochimique de l’Énergie (RS2E), Amiens (France)
  9. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  10. Univ. de Picardie Jules Verne, Amiens (France). Lab. de Réactivité et Chimie des Solides (LRCS); Réseau sur le Stockage Électrochimique de l’Énergie (RS2E), Amiens (France)
  11. Univ. of Stuttgart (Germany). Inst. of Materials Science,
  12. University of Bath (United Kingdom); ALISTORE European Research Inst., Amiens (France)
+ Show Author Affiliations
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 < TT < 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. Overall, 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.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
Engineering and Physical Sciences Research Council (EPSRC); National Research Foundation (NRF) Singapore; Newcastle University; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1833596
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 14 Vol. 33; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical structure
Group theory
Lattices
Phase transitions
Raman spectroscopy