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Low-temperature paddlewheel effect in glassy solid electrolytes

Glasses are promising electrolytes for use in solid-state batteries. Nevertheless, due to their amorphous structure, the mechanisms that underlie their ionic conductivity remain poorly understood. Here, ab initio molecular dynamics is used to characterize migration processes in the prototype glass,...

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Autores principales: Smith, Jeffrey G., Siegel, Donald J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7083903/
https://www.ncbi.nlm.nih.gov/pubmed/32198363
http://dx.doi.org/10.1038/s41467-020-15245-5
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author Smith, Jeffrey G.
Siegel, Donald J.
author_facet Smith, Jeffrey G.
Siegel, Donald J.
author_sort Smith, Jeffrey G.
collection PubMed
description Glasses are promising electrolytes for use in solid-state batteries. Nevertheless, due to their amorphous structure, the mechanisms that underlie their ionic conductivity remain poorly understood. Here, ab initio molecular dynamics is used to characterize migration processes in the prototype glass, 75Li(2)S–25P(2)S(5). Lithium migration occurs via a mechanism that combines concerted motion of lithium ions with large, quasi-permanent reorientations of PS(4)(3−) anions. This latter effect, known as the ‘paddlewheel’ mechanism, is typically observed in high-temperature crystalline polymorphs. In contrast to the behavior of crystalline materials, in the glass paddlewheel dynamics contribute to Lithium-ion mobility at room temperature. Paddlewheel contributions are confirmed by characterizing spatial, temporal, vibrational, and energetic correlations with Lithium motion. Furthermore, the dynamics in the glass differ from those in the stable crystalline analogue, γ-Li(3)PS(4), where anion reorientations are negligible and ion mobility is reduced. These data imply that glasses containing complex anions, and in which covalent network formation is minimized, may exhibit paddlewheel dynamics at low temperature. Consequently, these systems may be fertile ground in the search for new solid electrolytes.
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spelling pubmed-70839032020-03-23 Low-temperature paddlewheel effect in glassy solid electrolytes Smith, Jeffrey G. Siegel, Donald J. Nat Commun Article Glasses are promising electrolytes for use in solid-state batteries. Nevertheless, due to their amorphous structure, the mechanisms that underlie their ionic conductivity remain poorly understood. Here, ab initio molecular dynamics is used to characterize migration processes in the prototype glass, 75Li(2)S–25P(2)S(5). Lithium migration occurs via a mechanism that combines concerted motion of lithium ions with large, quasi-permanent reorientations of PS(4)(3−) anions. This latter effect, known as the ‘paddlewheel’ mechanism, is typically observed in high-temperature crystalline polymorphs. In contrast to the behavior of crystalline materials, in the glass paddlewheel dynamics contribute to Lithium-ion mobility at room temperature. Paddlewheel contributions are confirmed by characterizing spatial, temporal, vibrational, and energetic correlations with Lithium motion. Furthermore, the dynamics in the glass differ from those in the stable crystalline analogue, γ-Li(3)PS(4), where anion reorientations are negligible and ion mobility is reduced. These data imply that glasses containing complex anions, and in which covalent network formation is minimized, may exhibit paddlewheel dynamics at low temperature. Consequently, these systems may be fertile ground in the search for new solid electrolytes. Nature Publishing Group UK 2020-03-20 /pmc/articles/PMC7083903/ /pubmed/32198363 http://dx.doi.org/10.1038/s41467-020-15245-5 Text en © The Author(s) 2020 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
spellingShingle Article
Smith, Jeffrey G.
Siegel, Donald J.
Low-temperature paddlewheel effect in glassy solid electrolytes
title Low-temperature paddlewheel effect in glassy solid electrolytes
title_full Low-temperature paddlewheel effect in glassy solid electrolytes
title_fullStr Low-temperature paddlewheel effect in glassy solid electrolytes
title_full_unstemmed Low-temperature paddlewheel effect in glassy solid electrolytes
title_short Low-temperature paddlewheel effect in glassy solid electrolytes
title_sort low-temperature paddlewheel effect in glassy solid electrolytes
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7083903/
https://www.ncbi.nlm.nih.gov/pubmed/32198363
http://dx.doi.org/10.1038/s41467-020-15245-5
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