Under pressure: Mechanochemical effects on structure and ion conduction in the sodium-ion solid electrolyte Na3PS4

Theodosios Famprikis; O. Ulaş Kudu; James A. Dawson; Pieremanuele Canepa; François Fauth; Emmanuelle Suard; Mohamed Zbiri; Damien Dambournet; Olaf J. Borkiewicz; Houssny Bouyanfif; Steffen P. Emge; Sorina Cretu; Jean Noel Chotard; Clare P. Grey; Wolfgang G. Zeier; M. Saiful Islam; Christian Masquelier

doi:10.1021/jacs.0c06668

Under pressure: Mechanochemical effects on structure and ion conduction in the sodium-ion solid electrolyte Na₃PS₄

Theodosios Famprikis, O. Ulaş Kudu, James A. Dawson, Pieremanuele Canepa, François Fauth, Emmanuelle Suard, Mohamed Zbiri, Damien Dambournet, Olaf J. Borkiewicz, Houssny Bouyanfif, Steffen P. Emge, Sorina Cretu, Jean Noel Chotard, Clare P. Grey, Wolfgang G. Zeier, M. Saiful Islam, Christian Masquelier

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

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Abstract

Fast-ion conductors are critical to the development of solid-state batteries. The effects of mechanochemical synthesis that lead to increased ionic conductivity in an archetypical sodiumion conductor Na3PS4 are not fully understood. We present here a comprehensive analysis based on diffraction (Bragg and pair distribution function), spectroscopy (impedance, Raman, NMR and INS), and ab initio simulations aimed at elucidating the synthesis-property relationships in Na3PS4. We consolidate previously reported interpretations regarding the local structure of ball-milled samples, underlining the sodium disorder and showing that a local tetragonal framework more accurately describes the structure than the originally proposed cubic one. Through variable-pressure impedance spectroscopy measurements, we report for the first time the activation volume for Na+ migration in Na3PS4, which is ∼30% higher for the ball-milled samples. Moreover, we show that the effect of ball-milling on increasing the ionic conductivity of Na3PS4 to ∼10-4 S/cm can be reproduced by applying external pressure on a sample from conventional high-temperature ceramic synthesis. We conclude that the key effects of mechanochemical synthesis on the properties of solid electrolytes can be analyzed and understood in terms of pressure, strain, and activation volume.

Original language	English
Pages (from-to)	18422-18436
Number of pages	15
Journal	Journal of the American Chemical Society
Volume	142
Issue number	43
Early online date	15 Oct 2020
DOIs	https://doi.org/10.1021/jacs.0c06668
Publication status	Published - 28 Oct 2020

Funding

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 inelastic neutron scattering (INS) measurements; to the ALBA synchrotron for providing beam time on the MSPD diffractometer for powder diffraction measurements; and 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. 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 Argonne National Laboratory under Contract DE-AC02-06CH11357. S.P.E. was funded via an EPSRC iCASE (Award 1834544) and via the Royal Society (RP\R1\180147).

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.0c06668

Na3PS4_mechanical_v11
This document is the Accepted Manuscript version of a Published Work that appeared in final form in J. Am. Chem. Soc., copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/jacs.0c06668
Accepted author manuscript, 2.16 MB
SI_Na3PS4_mechanical_v14
This document is the Accepted Manuscript version of a Published Work that appeared in final form in J. Am. Chem. Soc., copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/jacs.0c06668
Accepted author manuscript, 2.5 MB

Cite this

Famprikis, T., Kudu, O. U., Dawson, J. A., Canepa, P., Fauth, F., Suard, E., Zbiri, M., Dambournet, D., Borkiewicz, O. J., Bouyanfif, H., Emge, S. P., Cretu, S., Chotard, J. N., Grey, C. P., Zeier, W. G., Islam, M. S., & Masquelier, C. (2020). Under pressure: Mechanochemical effects on structure and ion conduction in the sodium-ion solid electrolyte Na₃PS₄. Journal of the American Chemical Society, 142(43), 18422-18436. https://doi.org/10.1021/jacs.0c06668

Famprikis, T, Kudu, OU, Dawson, JA, Canepa, P, Fauth, F, Suard, E, Zbiri, M, Dambournet, D, Borkiewicz, OJ, Bouyanfif, H, Emge, SP, Cretu, S, Chotard, JN, Grey, CP, Zeier, WG, Islam, MS & Masquelier, C 2020, 'Under pressure: Mechanochemical effects on structure and ion conduction in the sodium-ion solid electrolyte Na₃PS₄', Journal of the American Chemical Society, vol. 142, no. 43, pp. 18422-18436. https://doi.org/10.1021/jacs.0c06668

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