Exploring the Temperature‐Dependent Structural Evolution of Mechanically Synthesized Na3PS4 Solid Electrolyte through In Situ X‐Ray Diffraction

Exploring the potential of sodium‐based materials is of utmost importance, especially for next‐generation solid‐state batteries. Herein, Na3PS4 thiophosphate solid electrolyte is focused on. While its tetragonal α phase is initially studied for Na solid‐state batteries, the impact of heat treatment...

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Main Authors: Sergio Federico Mayer, Marta Mirolo, Alisson Andrea Iles Velez, Ove Korjus, Emmanuelle Suard, Laureline Lecarme, Jean‐Baptiste Ducros, Claire Villevieille
Format: Article
Language:English
Published: Wiley-VCH 2024-11-01
Series:Small Structures
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Online Access:https://doi.org/10.1002/sstr.202400225
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author Sergio Federico Mayer
Marta Mirolo
Alisson Andrea Iles Velez
Ove Korjus
Emmanuelle Suard
Laureline Lecarme
Jean‐Baptiste Ducros
Claire Villevieille
author_facet Sergio Federico Mayer
Marta Mirolo
Alisson Andrea Iles Velez
Ove Korjus
Emmanuelle Suard
Laureline Lecarme
Jean‐Baptiste Ducros
Claire Villevieille
author_sort Sergio Federico Mayer
collection DOAJ
description Exploring the potential of sodium‐based materials is of utmost importance, especially for next‐generation solid‐state batteries. Herein, Na3PS4 thiophosphate solid electrolyte is focused on. While its tetragonal α phase is initially studied for Na solid‐state batteries, the impact of heat treatment and the phase transitions of amorphous and semicrystalline polymorphs obtained by mechanochemical synthesis remains poorly understood. The structural evolution is evaluated as function of the temperature of amorphous and semicrystalline Na3PS4 polymorphs obtained by mechanochemical processes. Both samples are heat‐treated during an in situ synchrotron X‐ray diffraction measurement, and multiple phase transitions are detected, some of them being irreversible. A novel and abundant orthorhombic intermediary phase is observed when the heat treatment is performed on the amorphous sample. The ionic conductivity of both amorphous and semicrystalline samples undergoes significant enhancement after heat treatment, reaching 0.09 and 0.16 × 10−3 S cm−1, respectively. This research sheds light on the thermal dynamics of Na3PS4 polymorphs, providing valuable insights into their crystallization processes, especially in the amorphous‐to‐cubic transition. The discovered intermediate phases underscore the potential for further advancements in sodium‐based solid‐state battery technologies.
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spelling doaj-art-b669e7ea93a1475a81e5e1ae62fdeaf92025-08-20T02:12:29ZengWiley-VCHSmall Structures2688-40622024-11-01511n/an/a10.1002/sstr.202400225Exploring the Temperature‐Dependent Structural Evolution of Mechanically Synthesized Na3PS4 Solid Electrolyte through In Situ X‐Ray DiffractionSergio Federico Mayer0Marta Mirolo1Alisson Andrea Iles Velez2Ove Korjus3Emmanuelle Suard4Laureline Lecarme5Jean‐Baptiste Ducros6Claire Villevieille7University Grenoble Alpes University of Savoie Mont Blanc CNRS Grenoble INP LEPMI Grenoble 38000 FranceEuropean Synchrotron Radiation Facility (ESRF) Experimental division Grenoble 38000 FranceEuropean Synchrotron Radiation Facility (ESRF) Experimental division Grenoble 38000 FranceInstitut Laue Langevin (ILL) Grenoble 38042 FranceInstitut Laue Langevin (ILL) Grenoble 38042 FranceUniversity Grenoble Alpes University of Savoie Mont Blanc CNRS Grenoble INP LEPMI Grenoble 38000 FranceUniversity Grenoble Alpes CEA Liten DEHT Grenoble 38000 FranceUniversity Grenoble Alpes University of Savoie Mont Blanc CNRS Grenoble INP LEPMI Grenoble 38000 FranceExploring the potential of sodium‐based materials is of utmost importance, especially for next‐generation solid‐state batteries. Herein, Na3PS4 thiophosphate solid electrolyte is focused on. While its tetragonal α phase is initially studied for Na solid‐state batteries, the impact of heat treatment and the phase transitions of amorphous and semicrystalline polymorphs obtained by mechanochemical synthesis remains poorly understood. The structural evolution is evaluated as function of the temperature of amorphous and semicrystalline Na3PS4 polymorphs obtained by mechanochemical processes. Both samples are heat‐treated during an in situ synchrotron X‐ray diffraction measurement, and multiple phase transitions are detected, some of them being irreversible. A novel and abundant orthorhombic intermediary phase is observed when the heat treatment is performed on the amorphous sample. The ionic conductivity of both amorphous and semicrystalline samples undergoes significant enhancement after heat treatment, reaching 0.09 and 0.16 × 10−3 S cm−1, respectively. This research sheds light on the thermal dynamics of Na3PS4 polymorphs, providing valuable insights into their crystallization processes, especially in the amorphous‐to‐cubic transition. The discovered intermediate phases underscore the potential for further advancements in sodium‐based solid‐state battery technologies.https://doi.org/10.1002/sstr.202400225energy storageNa3PS4sodium‐ionsolid electrolytessolid‐state batteriesstructure refinement
spellingShingle Sergio Federico Mayer
Marta Mirolo
Alisson Andrea Iles Velez
Ove Korjus
Emmanuelle Suard
Laureline Lecarme
Jean‐Baptiste Ducros
Claire Villevieille
Exploring the Temperature‐Dependent Structural Evolution of Mechanically Synthesized Na3PS4 Solid Electrolyte through In Situ X‐Ray Diffraction
Small Structures
energy storage
Na3PS4
sodium‐ion
solid electrolytes
solid‐state batteries
structure refinement
title Exploring the Temperature‐Dependent Structural Evolution of Mechanically Synthesized Na3PS4 Solid Electrolyte through In Situ X‐Ray Diffraction
title_full Exploring the Temperature‐Dependent Structural Evolution of Mechanically Synthesized Na3PS4 Solid Electrolyte through In Situ X‐Ray Diffraction
title_fullStr Exploring the Temperature‐Dependent Structural Evolution of Mechanically Synthesized Na3PS4 Solid Electrolyte through In Situ X‐Ray Diffraction
title_full_unstemmed Exploring the Temperature‐Dependent Structural Evolution of Mechanically Synthesized Na3PS4 Solid Electrolyte through In Situ X‐Ray Diffraction
title_short Exploring the Temperature‐Dependent Structural Evolution of Mechanically Synthesized Na3PS4 Solid Electrolyte through In Situ X‐Ray Diffraction
title_sort exploring the temperature dependent structural evolution of mechanically synthesized na3ps4 solid electrolyte through in situ x ray diffraction
topic energy storage
Na3PS4
sodium‐ion
solid electrolytes
solid‐state batteries
structure refinement
url https://doi.org/10.1002/sstr.202400225
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