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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...

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Autores principales: Deng, Chuting, Bennington, Peter, Sánchez-Leija, Regina J., Patel, Shrayesh N., Nealey, Paul F., de Pablo, Juan J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
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.
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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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