Insights into the Rich Polymorphism of the Na+Ion Conductor Na3PS4from the Perspective of Variable-Temperature Diffraction and Spectroscopy

Theodosios Famprikis; Houssny Bouyanfif; Pieremanuele Canepa; Mohamed Zbiri; James A. Dawson; Emmanuelle Suard; François Fauth; Helen Y. Playford; Damien Dambournet; Olaf J. Borkiewicz; Matthieu Courty; Oliver Clemens; Jean Noël Chotard; M. Saiful Islam; Christian Masquelier

doi:10.1021/acs.chemmater.1c01113

Insights into the Rich Polymorphism of the Na⁺Ion Conductor Na₃PS₄from the Perspective of Variable-Temperature Diffraction and Spectroscopy

Theodosios Famprikis, Houssny Bouyanfif, Pieremanuele Canepa, Mohamed Zbiri, James A. Dawson, Emmanuelle Suard, François Fauth, Helen Y. Playford, Damien Dambournet, Olaf J. Borkiewicz, Matthieu Courty, Oliver Clemens, Jean Noël Chotard, M. Saiful Islam, Christian Masquelier

Research output: Contribution to journal › Article › peer-review

31 Citations (SciVal)

Abstract

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, P4¯ 21c) to the cubic polymorph (β, I4¯ 3m) 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.

Original language	English
Pages (from-to)	5652–5667
Journal	Chemistry of Materials
Volume	33
Issue number	14
Early online date	16 Jul 2021
DOIs	https://doi.org/10.1021/acs.chemmater.1c01113
Publication status	Published - 27 Jul 2021

Bibliographical note

Funding Information:
The authors are grateful to the Institut Laue-Langevin (ILL) for providing beam time on the D2B diffractometer for the powder diffraction measurements and the IN6 spectrometer for the INS measurements, to the ALBA synchrotron for providing beam time on the MSPD diffractometer for powder diffraction measurements, to the Argonne National Laboratory (ANL) for providing beam time on the 11-ID-B beamline of the Advanced Photon Source (APS) for the powder total scattering measurements, and to the ISIS neutron and muon source for providing beam time on the POLARIS diffractometer for powder total scattering measurements. T.F. is thankful to the ALISTORE ERI and the German Academic Exchange Service (DAAD) for funding in the form of PhD scholarships. J.A.D. and M.S.I. gratefully acknowledge the EPSRC Programme Grant EP/M009521/1 for funding and the MCC/Archer consortium (EP/L000202/1) for computational resources. J.A.D. also gratefully acknowledges Newcastle University for funding through a Newcastle Academic Track (NUAcT) Fellowship. P.C. acknowledges funding from the National Research Foundation under his NRFF NRFF12-2020-0012 and the ANR-NRF NRF2019-NRF-ANR073 Na-MASTER. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by the Argonne National Laboratory under contract no. DE-AC02-06CH11357. a

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

Access to Document

10.1021/acs.chemmater.1c01113Licence: CC BY-NC-ND

Cite this

Famprikis, T., Bouyanfif, H., Canepa, P., Zbiri, M., Dawson, J. A., Suard, E., Fauth, F., Playford, H. Y., Dambournet, D., Borkiewicz, O. J., Courty, M., Clemens, O., Chotard, J. N., Islam, M. S., & Masquelier, C. (2021). Insights into the Rich Polymorphism of the Na⁺Ion Conductor Na₃PS₄from the Perspective of Variable-Temperature Diffraction and Spectroscopy. Chemistry of Materials, 33(14), 5652–5667. https://doi.org/10.1021/acs.chemmater.1c01113

Famprikis, T, Bouyanfif, H, Canepa, P, Zbiri, M, Dawson, JA, Suard, E, Fauth, F, Playford, HY, Dambournet, D, Borkiewicz, OJ, Courty, M, Clemens, O, Chotard, JN, Islam, MS & Masquelier, C 2021, 'Insights into the Rich Polymorphism of the Na⁺Ion Conductor Na₃PS₄from the Perspective of Variable-Temperature Diffraction and Spectroscopy', Chemistry of Materials, vol. 33, no. 14, pp. 5652–5667. https://doi.org/10.1021/acs.chemmater.1c01113

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title = "Insights into the Rich Polymorphism of the Na+Ion Conductor Na3PS4from the Perspective of Variable-Temperature Diffraction and Spectroscopy",

abstract = "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, P4¯ 21c) to the cubic polymorph (β, I4¯ 3m) 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.",

author = "Theodosios Famprikis and Houssny Bouyanfif and Pieremanuele Canepa and Mohamed Zbiri and Dawson, {James A.} and Emmanuelle Suard and Fran{\c c}ois Fauth and Playford, {Helen Y.} and Damien Dambournet and Borkiewicz, {Olaf J.} and Matthieu Courty and Oliver Clemens and Chotard, {Jean No{\"e}l} and Islam, {M. Saiful} and Christian Masquelier",

note = "Funding Information: The authors are grateful to the Institut Laue-Langevin (ILL) for providing beam time on the D2B diffractometer for the powder diffraction measurements and the IN6 spectrometer for the INS measurements, to the ALBA synchrotron for providing beam time on the MSPD diffractometer for powder diffraction measurements, to the Argonne National Laboratory (ANL) for providing beam time on the 11-ID-B beamline of the Advanced Photon Source (APS) for the powder total scattering measurements, and to the ISIS neutron and muon source for providing beam time on the POLARIS diffractometer for powder total scattering measurements. T.F. is thankful to the ALISTORE ERI and the German Academic Exchange Service (DAAD) for funding in the form of PhD scholarships. J.A.D. and M.S.I. gratefully acknowledge the EPSRC Programme Grant EP/M009521/1 for funding and the MCC/Archer consortium (EP/L000202/1) for computational resources. J.A.D. also gratefully acknowledges Newcastle University for funding through a Newcastle Academic Track (NUAcT) Fellowship. P.C. acknowledges funding from the National Research Foundation under his NRFF NRFF12-2020-0012 and the ANR-NRF NRF2019-NRF-ANR073 Na-MASTER. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by the Argonne National Laboratory under contract no. DE-AC02-06CH11357. a ",

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AU - Canepa, Pieremanuele

AU - Zbiri, Mohamed

AU - Dawson, James A.

AU - Suard, Emmanuelle

AU - Fauth, François

AU - Playford, Helen Y.

AU - Dambournet, Damien

AU - Borkiewicz, Olaf J.

AU - Courty, Matthieu

AU - Clemens, Oliver

AU - Chotard, Jean Noël

AU - Islam, M. Saiful

AU - Masquelier, Christian

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N2 - 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, P4¯ 21c) to the cubic polymorph (β, I4¯ 3m) 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.

AB - 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, P4¯ 21c) to the cubic polymorph (β, I4¯ 3m) 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.

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Insights into the Rich Polymorphism of the Na⁺Ion Conductor Na₃PS₄from the Perspective of Variable-Temperature Diffraction and Spectroscopy

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Insights into the Rich Polymorphism of the Na+Ion Conductor Na3PS4from the Perspective of Variable-Temperature Diffraction and Spectroscopy

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Bibliographical note

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Insights into the Rich Polymorphism of the Na⁺Ion Conductor Na₃PS₄from the Perspective of Variable-Temperature Diffraction and Spectroscopy