Single-step synthesis of highly conductive Na3PS4 solid electrolyte for sodium all solid-state batteries

Nguyen, Han; Banerjee, Abhik; Wang, Xuefeng; Tan, Darren H. S.; Wu, Erik A.; Doux, Jean-Marie; Stephens, Ryan; Verbist, G.; Meng, Ying Shirley

doi:10.1016/j.jpowsour.2019.05.031

“…Inspired by previous work 7,15 we also synthesized an "intermediate" sample prepared by rapid high temperature annealing of a ball-milled sample, also resulting in tetragonal long-range symmetry (BM-tet-Na3PS4); which we invoke in certain parts of this paper. In agreement with previous studies, the ball-milled samples exhibit significantly higher room-temperature ionic conductivity (BM-tet and BM-cub, ~10 -4 S/cm) [4][5][6][7]15,16 compared to the high-temperature-synthesized material (HT-tet, ~10 -5 S/cm) 1,7,11,12,15 .…”

Section: Resultssupporting

confidence: 92%

“…In all spectra, we observe invariantly the splitting of the PS4 3normal modes indicating the same tetragonal local structure for all samples, including the BM-cub one. These observations are consistent with the PDF interpretation and also in agreement with all reported Raman spectra for ball-milled Na3PS4 samples in the literature 16,37 . Vibrational modes below 200 cm -1 (~25 meV) are not fundamental but pertain to interactions of the anionic and cationic lattices.…”

Section: Micro- Average-and Local Structures Of Ht-and Bm-na3ps4 Sysupporting

confidence: 93%

“…The conductivity-enhancing effect of mechanochemistry is quite reproducible in Na3PS4 16 and similar observations have been reported for several mechanically soft solid-electrolytes (e.g.…”

Section: Introductionsupporting

confidence: 85%

“…4 ̅ 2 as proposed recently 35 . We are not the first to measure this; practically every diffractogram of ball-milled "cubic" Na3PS4 reported in the literature features these reflections [4][5][6][7]9,11,[14][15][16]30,36 . However, this observation has never been adequately explained: it is unclear whether these reflections originate from a secondary tetragonal phase, are indicative of a tetragonal average structure or whether they originate from ordering of the main phase.…”

Section: Micro- Average-and Local Structures Of Ht-and Bm-na3ps4 Symentioning

confidence: 99%

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

Famprikis¹,

Kudu²,

Dawson³

et al. 2020

Preprint

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<div> 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 sodium-ion conductor Na3PS4 are not fully understood. We present here a comprehensive analysis based on diffraction (Bragg, pair distribution function), spectroscopy (impedance, Raman, NMR, INS) and ab-initio simulations aimed at elucidating the synthesis-property relationships in Na3PS4. We consolidate previously reported interpretations about 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. </div>

show abstract

“…Inspired by previous work 7,15 we also synthesized an "intermediate" sample prepared by rapid high temperature annealing of a ball-milled sample, also resulting in tetragonal long-range symmetry (BM-tet-Na3PS4); which we invoke in certain parts of this paper. In agreement with previous studies, the ball-milled samples exhibit significantly higher room-temperature ionic conductivity (BM-tet and BM-cub, ~10 -4 S/cm) [4][5][6][7]15,16 compared to the hightemperature-synthesized material (HT-tet, ~10 -5 S/cm) 1,7,11,12,15 .…”

Section: Resultssupporting

confidence: 92%

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

Famprikis

¹

,

Kudu²,

Dawson³

et al. 2020

Preprint

0

View full text Add to dashboard Cite

<div> 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 sodium-ion conductor Na3PS4 are not fully understood. We present here a comprehensive analysis based on diffraction (Bragg, pair distribution function), spectroscopy (impedance, Raman, NMR, INS) and ab-initio simulations aimed at elucidating the synthesis-property relationships in Na3PS4. We consolidate previously reported interpretations about 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. </div>

show abstract

Solid‐State and Gel Electrolytes for Sodium‐Ion Batteries

2022

Sodium‐Ion Batteries

0

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Single-step synthesis of highly conductive Na3PS4 solid electrolyte for sodium all solid-state batteries

Abstract: Single-step synthesis of highly conductive sodium solid-state electrolyte. � Facile synthesis process for large batch production of solid-state electrolyte. � All solid-state battery constructed with Na 3 PS 4 .

Cited by 71 publications

References 34 publications

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

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

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

Solid‐State and Gel Electrolytes for Sodium‐Ion Batteries

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