High-entropy argyrodite glass–ceramic electrolytes for all-solid-state batteries

Lithium argyrodite superionic conductors with the general formula Li _6 PS _5 X (X = Cl, Br, I) have been intensively investigated in recent years and successfully adopted in the field of solid-state batteries (SSBs). The transport properties of argyrodite solid electrolytes (SEs) usually strongly d...

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Main Authors: Jing Lin, Mareen Schaller, Ruizhuo Zhang, Volodymyr Baran, Hao Liu, Ziming Ding, Sylvio Indris, Aleksandr Kondrakov, Torsten Brezesinski, Florian Strauss
Format: Article
Language:English
Published: IOP Publishing 2025-01-01
Series:Materials Futures
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Online Access:https://doi.org/10.1088/2752-5724/adde76
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Summary:Lithium argyrodite superionic conductors with the general formula Li _6 PS _5 X (X = Cl, Br, I) have been intensively investigated in recent years and successfully adopted in the field of solid-state batteries (SSBs). The transport properties of argyrodite solid electrolytes (SEs) usually strongly depend on the degree of occupational disorder. Increasing disorder through complex doping or substitution has been shown to directly affect ionic conductivity. Herein, we explore a high-entropy lithium argyrodite of nominal composition Li _6.6 [P _0.2 Si _0.2 Sn _0.2 Ge _0.2 Sb _0.2 ]S _5 I. This material can be readily prepared by mechanochemistry. Using complementary diffraction techniques, nuclear magnetic resonance spectroscopy, and charge-transport measurements, we show that upon tailoring crystallinity and defect concentration by post-annealing at temperatures up to 220 °C, a high room-temperature ionic conductivity of about 0.9 mS cm ^−1 (∼4.4 mS cm ^−1 bulk conductivity) can be achieved. Both the as-prepared and annealed (at 220 °C) samples were tested in pellet-stack SSB cells. The mechanochemically prepared glass–ceramic SE was found to exhibit superior performance, even outperforming commercially available Li _6 PS _5 Cl. Collectively, the results highlight the importance of considering structural aspects across different length scales when optimizing the properties of lithium argyrodites for SSB applications.
ISSN:2752-5724