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Rapid Crystallization and Kinetic Freezing of Site-Disorder in the Lithium Superionic Argyrodite Li6PS5Br

Gautam, Ajay and Sadowski, Marcel and Prinz, Nils and Eickhoff, Henrik and Minafra, Nicolò and Ghidiu, Michael and Culver, Sean P. and Albe, Karsten and Fässler, Thomas F. and Zobel, Mirijam and Zeier, Wolfgang G. (2019):
Rapid Crystallization and Kinetic Freezing of Site-Disorder in the Lithium Superionic Argyrodite Li6PS5Br.
In: Chemistry of Materials, 31 (24), 2019. American Chemical Society, pp. 10178-10185, ISSN 0897-4756,
DOI: 10.1021/acs.chemmater.9b03852,
[Online-Edition: https://doi.org/10.1021/acs.chemmater.9b03852],
[Article]

Abstract

Lithium argyrodite superionic conductors are currently being investigated as solid electrolytes for all-solid-state batteries. Recently, in the lithium argyrodite Li6PS5X (X = Cl, Br, and I), a site-disorder between the anions S2– and X– has been observed, which strongly affects the ionic transport and appears to be a function of the halide present. In this work, we show how such a disorder in Li6PS5Br can be engineered via the synthesis method. By comparing fast cooling (i.e., quenching) to more slowly cooled samples, we find that the anion site-disorder is higher at elevated temperatures, and that fast cooling can be used to kinetically trap the desired disorder, leading to higher ionic conductivities as shown by impedance spectroscopy in combination with ab initio molecular dynamics. Furthermore, we observe that after milling, a crystalline lithium argyrodite can be obtained within 1 min of heat treatment. This rapid crystallization highlights the reactive nature of mechanical milling and shows that long reaction times with high energy consumption are not needed in this class of materials. The fact that site-disorder induced via quenching is beneficial for ionic transport provides an additional approach for the optimization and design of lithium superionic conductors.

Item Type: Article
Erschienen: 2019
Creators: Gautam, Ajay and Sadowski, Marcel and Prinz, Nils and Eickhoff, Henrik and Minafra, Nicolò and Ghidiu, Michael and Culver, Sean P. and Albe, Karsten and Fässler, Thomas F. and Zobel, Mirijam and Zeier, Wolfgang G.
Title: Rapid Crystallization and Kinetic Freezing of Site-Disorder in the Lithium Superionic Argyrodite Li6PS5Br
Language: English
Abstract:

Lithium argyrodite superionic conductors are currently being investigated as solid electrolytes for all-solid-state batteries. Recently, in the lithium argyrodite Li6PS5X (X = Cl, Br, and I), a site-disorder between the anions S2– and X– has been observed, which strongly affects the ionic transport and appears to be a function of the halide present. In this work, we show how such a disorder in Li6PS5Br can be engineered via the synthesis method. By comparing fast cooling (i.e., quenching) to more slowly cooled samples, we find that the anion site-disorder is higher at elevated temperatures, and that fast cooling can be used to kinetically trap the desired disorder, leading to higher ionic conductivities as shown by impedance spectroscopy in combination with ab initio molecular dynamics. Furthermore, we observe that after milling, a crystalline lithium argyrodite can be obtained within 1 min of heat treatment. This rapid crystallization highlights the reactive nature of mechanical milling and shows that long reaction times with high energy consumption are not needed in this class of materials. The fact that site-disorder induced via quenching is beneficial for ionic transport provides an additional approach for the optimization and design of lithium superionic conductors.

Journal or Publication Title: Chemistry of Materials
Volume: 31
Number: 24
Publisher: American Chemical Society
Divisions: 11 Department of Materials and Earth Sciences
11 Department of Materials and Earth Sciences > Material Science
11 Department of Materials and Earth Sciences > Material Science > Materials Modelling
Zentrale Einrichtungen
Zentrale Einrichtungen > University IT-Service and Computing Centre (HRZ)
Zentrale Einrichtungen > University IT-Service and Computing Centre (HRZ) > Hochleistungsrechner
Date Deposited: 28 Jan 2020 07:23
DOI: 10.1021/acs.chemmater.9b03852
Official URL: https://doi.org/10.1021/acs.chemmater.9b03852
Projects: BMBF Projekt FESTBATT unter den Förderkennzeichen 03XP0177A und 03XP0174A, SPP2080, Förderkennzeichen ZO 369/2-1
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