Grain Boundary Transport in the Argyrodite‐Type Li6PS5Br Solid Electrolyte: Influence of Misorientation and Anion Disorder on Li Ion Mobility

Abstract To realize efficient solid‐state batteries, many efforts are directed toward maximizing the bulk Li+ conductivity of sulfide superionic conductors, as demonstrated for the argyrodite‐type materials Li6PS5Cl and Li6PS5Br. Notably, in these archetype materials, the fast Li+ transport benefits...

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Main Authors: Marcel Sadowski, Karsten Albe
Format: Article
Language:English
Published: Wiley-VCH 2024-11-01
Series:Advanced Materials Interfaces
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Online Access:https://doi.org/10.1002/admi.202400423
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author Marcel Sadowski
Karsten Albe
author_facet Marcel Sadowski
Karsten Albe
author_sort Marcel Sadowski
collection DOAJ
description Abstract To realize efficient solid‐state batteries, many efforts are directed toward maximizing the bulk Li+ conductivity of sulfide superionic conductors, as demonstrated for the argyrodite‐type materials Li6PS5Cl and Li6PS5Br. Notably, in these archetype materials, the fast Li+ transport benefits from considerable anion disorder on the halide and sulfur sublattices. To further improve the Li+ conductivity, however, one must consider not only the bulk properties of the solid electrolyte (SE) but also microstructural aspects. It is, however, controversially discussed whether grain boundary (GB) transport is generally detrimental for the overall ion conductivity in agyrodite‐type SEs. Thus, by means of atomistic computer simulations, the Li+ ion transport is studied in twist and tilt GBs of Li6PS5Br, revealing that the Br/S site exchange determines whether the presence of GBs deteriorates the ionic conductivity: Whereas the material with 0% Br/S site exchange only shows locally limited bulk diffusion but enhanced GB conductivity, at higher degrees of site exchange, GBs deteriorate Li+ diffusion. These results show that the interplay of GB transport directly depends on the degree of site exchange in argyrodite‐type materials.
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spelling doaj-art-e62553187e5743aa80eb6d7c294be43b2025-08-20T02:23:44ZengWiley-VCHAdvanced Materials Interfaces2196-73502024-11-011133n/an/a10.1002/admi.202400423Grain Boundary Transport in the Argyrodite‐Type Li6PS5Br Solid Electrolyte: Influence of Misorientation and Anion Disorder on Li Ion MobilityMarcel Sadowski0Karsten Albe1Institute of Materials Science Technical University of Darmstadt Otto‐Bernd‐Straße 3 64287 Darmstadt GermanyInstitute of Materials Science Technical University of Darmstadt Otto‐Bernd‐Straße 3 64287 Darmstadt GermanyAbstract To realize efficient solid‐state batteries, many efforts are directed toward maximizing the bulk Li+ conductivity of sulfide superionic conductors, as demonstrated for the argyrodite‐type materials Li6PS5Cl and Li6PS5Br. Notably, in these archetype materials, the fast Li+ transport benefits from considerable anion disorder on the halide and sulfur sublattices. To further improve the Li+ conductivity, however, one must consider not only the bulk properties of the solid electrolyte (SE) but also microstructural aspects. It is, however, controversially discussed whether grain boundary (GB) transport is generally detrimental for the overall ion conductivity in agyrodite‐type SEs. Thus, by means of atomistic computer simulations, the Li+ ion transport is studied in twist and tilt GBs of Li6PS5Br, revealing that the Br/S site exchange determines whether the presence of GBs deteriorates the ionic conductivity: Whereas the material with 0% Br/S site exchange only shows locally limited bulk diffusion but enhanced GB conductivity, at higher degrees of site exchange, GBs deteriorate Li+ diffusion. These results show that the interplay of GB transport directly depends on the degree of site exchange in argyrodite‐type materials.https://doi.org/10.1002/admi.202400423batteriesdiffusiongrain boundariesion disorderlithiumsulfide solid electrolytes
spellingShingle Marcel Sadowski
Karsten Albe
Grain Boundary Transport in the Argyrodite‐Type Li6PS5Br Solid Electrolyte: Influence of Misorientation and Anion Disorder on Li Ion Mobility
Advanced Materials Interfaces
batteries
diffusion
grain boundaries
ion disorder
lithium
sulfide solid electrolytes
title Grain Boundary Transport in the Argyrodite‐Type Li6PS5Br Solid Electrolyte: Influence of Misorientation and Anion Disorder on Li Ion Mobility
title_full Grain Boundary Transport in the Argyrodite‐Type Li6PS5Br Solid Electrolyte: Influence of Misorientation and Anion Disorder on Li Ion Mobility
title_fullStr Grain Boundary Transport in the Argyrodite‐Type Li6PS5Br Solid Electrolyte: Influence of Misorientation and Anion Disorder on Li Ion Mobility
title_full_unstemmed Grain Boundary Transport in the Argyrodite‐Type Li6PS5Br Solid Electrolyte: Influence of Misorientation and Anion Disorder on Li Ion Mobility
title_short Grain Boundary Transport in the Argyrodite‐Type Li6PS5Br Solid Electrolyte: Influence of Misorientation and Anion Disorder on Li Ion Mobility
title_sort grain boundary transport in the argyrodite type li6ps5br solid electrolyte influence of misorientation and anion disorder on li ion mobility
topic batteries
diffusion
grain boundaries
ion disorder
lithium
sulfide solid electrolytes
url https://doi.org/10.1002/admi.202400423
work_keys_str_mv AT marcelsadowski grainboundarytransportintheargyroditetypeli6ps5brsolidelectrolyteinfluenceofmisorientationandaniondisorderonliionmobility
AT karstenalbe grainboundarytransportintheargyroditetypeli6ps5brsolidelectrolyteinfluenceofmisorientationandaniondisorderonliionmobility