How Certain Are the Reported Ionic Conductivities of Thiophosphate-Based Solid Electrolytes? An Interlaboratory Study

Ohno, Saneyuki; Bernges, Tim; Buchheim, Johannes; Duchardt, Marc; Hatz, Anna Katharina; Kraft, Marvin; Kwak, Hiram; Santhosha, A. L.; Liu, Zhantao; Minafra, Nicolò; Tsuji, Fumika; Sakuda, Atsushi; Schlem, Roman; Xiong, Shiqin; Zhang, Zhenggang; Adelhelm, Philipp; Chen, Hailong; Hayashi, Akitoshi; Jung, Yoon Seok; Lotsch, Bettina V.; Roling, Bernhard; Vargas‐Barbosa, Nella M.; Zeier, Wolfgang G.

doi:10.1021/acsenergylett.9b02764

Cited by 126 publications

(153 citation statements)

References 34 publications

(39 reference statements)

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“…Similar observations of increased conductivity upon pressing were found from recent variable-pressure conductivity measurements on the isostructural Na3SbS4 44 . These observations are analogous to variations of measured ionic conductivity as a function of pellet preparation which has been reported for several solid electrolytes [64][65][66] , including ball-milled Na3PS4 56 . We attribute this to extrinsic effects on macroscopic ionic percolation through the consolidation of the pellet, improving particle-particle and pellet-electrode contact.…”

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

confidence: 85%

“…In particular, impedance spectroscopy on pelletized samples largely depends on the procedure of pellet preparation and the conductivities measured should not necessarily reflect the intrinsic behavior of the material on the atomic scale. Impedance spectroscopy experiments performed at low temperatures 64,67 and/or on single-crystals 68,69 can distinguish or eliminate the microstructural effects, respectively, thus revealing the "real" intrinsic ion-transport at the atomic scale.…”

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>

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

confidence: 85%

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

confidence: 99%

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

Famprikis¹,

Kudu²,

Dawson³

et al. 2020

Preprint

View full text Add to dashboard Cite

show abstract

“…In particular, impedance spectroscopy on pelletized samples largely depends on the procedure of pellet preparation and the conductivities measured should not necessarily reflect the intrinsic behavior of the material on the atomic scale. Impedance spectroscopy experiments performed at low temperatures 65,68 and/or on single-crystals 69,70 can distinguish or eliminate the microstructural effects, respectively, thus revealing the "real"…”

Section: Micro- Average-and Local Structures Of Ht-and Bm-na3ps4mentioning

confidence: 99%

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

et al. 2020

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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 Na 3 PS 4 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 Na 3 PS 4. 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 Na 3 PS 4 , which is ~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 ~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. File list (2) download file view on ChemRxiv Na3PS4_mechanical_v10.1.pdf (2.18 MiB) download file view on ChemRxiv SI_Na3PS4_mechanical_v10.1.pdf (2.38 MiB)

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“…Subsequently, many research groups explored the composition of LPS, to elucidate the crystal structure, ionic conductivity, and fabrication of LPS-based ASSBs. Garcia-Mendez et al [219] reported the effect of molding pressure on mechanical and ionic conductivity values of LPS electrolyte, and recently, Ohno et al [220] summarized various other factors which influence the electrical properties of sulfate electrolytes.…”

Section: Lithium Phosphorus Sulfide Electrolytementioning

confidence: 99%

Sulfide and Oxide Inorganic Solid Electrolytes for All-Solid-State Li Batteries: A Review

et al. 2020

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Energy storage materials are finding increasing applications in our daily lives, for devices such as mobile phones and electric vehicles. Current commercial batteries use flammable liquid electrolytes, which are unsafe, toxic, and environmentally unfriendly with low chemical stability. Recently, solid electrolytes have been extensively studied as alternative electrolytes to address these shortcomings. Herein, we report the early history, synthesis and characterization, mechanical properties, and Li+ ion transport mechanisms of inorganic sulfide and oxide electrolytes. Furthermore, we highlight the importance of the fabrication technology and experimental conditions, such as the effects of pressure and operating parameters, on the electrochemical performance of all-solid-state Li batteries. In particular, we emphasize promising electrolyte systems based on sulfides and argyrodites, such as LiPS5Cl and β-Li3PS4, oxide electrolytes, bare and doped Li7La3Zr2O12 garnet, NASICON-type structures, and perovskite electrolyte materials. Moreover, we discuss the present and future challenges that all-solid-state batteries face for large-scale industrial applications.

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How Certain Are the Reported Ionic Conductivities of Thiophosphate-Based Solid Electrolytes? An Interlaboratory Study

Cited by 126 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

Sulfide and Oxide Inorganic Solid Electrolytes for All-Solid-State Li Batteries: A Review

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