10.1021/jacs.0c06668Journal of the American Chemical Society1424318422-1843

Borkiewicz, Olaf J.

Bouyanfif, Houssny

Canepa, Pieremanuele

Chotard, Jean Noel

Cretu, Sorina

Dambournet, Damien

Dawson, James A.

Emge, Steffen P.

Famprikis, Theodosios

Fauth, François

Grey, Clare P.

Islam, M. Saiful

Kudu, O. Ulaş

Masquelier, Christian

Suard, Emmanuelle

Zbiri, Mohamed

Zeier, Wolfgang G.

Journal of the American Chemical Society

English

Theodosios Famprikis

Ö. 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-Noël Chotard

Clare P. Grey

Wolfgang G. Zeier

M. Saiful Islam

Christian Masquelier

ScholarBank@NUS

Under Pressure: Mechanochemical Effects on Structure and Ion Conduction in the Sodium-Ion Solid Electrolyte Na3PS4

International audienceFast-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 sodium-ion 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 similar to 30% higher for the ball-milled samples. Moreover, we show that the effect of ball-milling on increasing the ionic conductivity of Na(3)PS(4 )to similar 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

Kudu, O. Ulas

Fauth, Francois

Chotard, Jean-Noel

HAL-Univ-Nantes

HAL AMU

Hal-Diderot

HAL Descartes

Hal - Université Grenoble Alpes

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. </p

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