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Entropic Penalty Switches Li(+) Solvation Site Formation and Transport Mechanisms in Mixed Polarity Copolymer Electrolytes
[Image: see text] Emerging solid polymer electrolyte (SPE) designs for efficient Li-ion (Li(+)) conduction have relied on polarity and mobility contrast to improve conductivity. To further develop this concept, we employ simulations to examine Li(+) solvation and transport in poly(oligo ethylene met...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10569096/ https://www.ncbi.nlm.nih.gov/pubmed/37841534 http://dx.doi.org/10.1021/acs.macromol.3c00804 |
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author | Deng, Chuting Bennington, Peter Sánchez-Leija, Regina J. Patel, Shrayesh N. Nealey, Paul F. de Pablo, Juan J. |
author_facet | Deng, Chuting Bennington, Peter Sánchez-Leija, Regina J. Patel, Shrayesh N. Nealey, Paul F. de Pablo, Juan J. |
author_sort | Deng, Chuting |
collection | PubMed |
description | [Image: see text] Emerging solid polymer electrolyte (SPE) designs for efficient Li-ion (Li(+)) conduction have relied on polarity and mobility contrast to improve conductivity. To further develop this concept, we employ simulations to examine Li(+) solvation and transport in poly(oligo ethylene methacrylate) (POEM) and its copolymers with poly(glycerol carbonate methacrylate) (PGCMA). We find that Li(+) is solvated by ether oxygens instead of the highly polar PGCMA, due to lower entropic penalties. The presence of PGCMA promotes single-chain solvation, thereby suppressing interchain Li(+) hopping. The conductivity difference between random copolymer PGCMA-r-POEM and block copolymer PGCMA-b-POEM is explained in terms of a hybrid solvation site mechanism. With diffuse microscopic interfaces between domains, PGCMA near the POEM contributes to Li(+) transport by forming hybrid solvation sites. The formation of such sites is hindered when PGCMA is locally concentrated. These findings help explain how thermodynamic driving forces govern Li(+) solvation and transport in mixed SPEs. |
format | Online Article Text |
id | pubmed-10569096 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-105690962023-10-13 Entropic Penalty Switches Li(+) Solvation Site Formation and Transport Mechanisms in Mixed Polarity Copolymer Electrolytes Deng, Chuting Bennington, Peter Sánchez-Leija, Regina J. Patel, Shrayesh N. Nealey, Paul F. de Pablo, Juan J. Macromolecules [Image: see text] Emerging solid polymer electrolyte (SPE) designs for efficient Li-ion (Li(+)) conduction have relied on polarity and mobility contrast to improve conductivity. To further develop this concept, we employ simulations to examine Li(+) solvation and transport in poly(oligo ethylene methacrylate) (POEM) and its copolymers with poly(glycerol carbonate methacrylate) (PGCMA). We find that Li(+) is solvated by ether oxygens instead of the highly polar PGCMA, due to lower entropic penalties. The presence of PGCMA promotes single-chain solvation, thereby suppressing interchain Li(+) hopping. The conductivity difference between random copolymer PGCMA-r-POEM and block copolymer PGCMA-b-POEM is explained in terms of a hybrid solvation site mechanism. With diffuse microscopic interfaces between domains, PGCMA near the POEM contributes to Li(+) transport by forming hybrid solvation sites. The formation of such sites is hindered when PGCMA is locally concentrated. These findings help explain how thermodynamic driving forces govern Li(+) solvation and transport in mixed SPEs. American Chemical Society 2023-09-22 /pmc/articles/PMC10569096/ /pubmed/37841534 http://dx.doi.org/10.1021/acs.macromol.3c00804 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/). |
spellingShingle | Deng, Chuting Bennington, Peter Sánchez-Leija, Regina J. Patel, Shrayesh N. Nealey, Paul F. de Pablo, Juan J. Entropic Penalty Switches Li(+) Solvation Site Formation and Transport Mechanisms in Mixed Polarity Copolymer Electrolytes |
title | Entropic Penalty
Switches Li(+) Solvation
Site Formation and Transport Mechanisms in Mixed Polarity Copolymer
Electrolytes |
title_full | Entropic Penalty
Switches Li(+) Solvation
Site Formation and Transport Mechanisms in Mixed Polarity Copolymer
Electrolytes |
title_fullStr | Entropic Penalty
Switches Li(+) Solvation
Site Formation and Transport Mechanisms in Mixed Polarity Copolymer
Electrolytes |
title_full_unstemmed | Entropic Penalty
Switches Li(+) Solvation
Site Formation and Transport Mechanisms in Mixed Polarity Copolymer
Electrolytes |
title_short | Entropic Penalty
Switches Li(+) Solvation
Site Formation and Transport Mechanisms in Mixed Polarity Copolymer
Electrolytes |
title_sort | entropic penalty
switches li(+) solvation
site formation and transport mechanisms in mixed polarity copolymer
electrolytes |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10569096/ https://www.ncbi.nlm.nih.gov/pubmed/37841534 http://dx.doi.org/10.1021/acs.macromol.3c00804 |
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