Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures
We present molecular dynamics simulation results pertaining to the solvation of Li+ in dimethyl sulfoxide-acetonitrile binary mixtures. The results are potentially relevant in the design of Li-air batteries that rely on aprotic mixtures as solvent media. To analyze effects derived from differences i...
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Acceso en línea: | http://hdl.handle.net/20.500.12110/paper_00219606_v141_n21_p_Semino |
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todo:paper_00219606_v141_n21_p_Semino2023-10-03T14:24:34Z Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures Semino, R. Zaldívar, G. Calvo, E.J. Laria, D. Acetonitrile Dimethyl sulfoxide Free energy Lithium Molecular dynamics Solvation Solvents Stabilization Acetonitrile binary mixtures Concentration dependence Concentration trends Gradual modifications Ionic transports Li-air batteries Molecular dynamics simulations Non-linear trends Binary mixtures We present molecular dynamics simulation results pertaining to the solvation of Li+ in dimethyl sulfoxide-acetonitrile binary mixtures. The results are potentially relevant in the design of Li-air batteries that rely on aprotic mixtures as solvent media. To analyze effects derived from differences in ionic size and charge sign, the solvation of Li+ is compared to the ones observed for infinitely diluted K+ and Cl- species, in similar solutions. At all compositions, the cations are preferentially solvated by dimethyl sulfoxide. Contrasting, the first solvation shell of Cl- shows a gradual modification in its composition, which varies linearly with the global concentrations of the two solvents in the mixtures. Moreover, the energetics of the solvation, described in terms of the corresponding solute-solvent coupling, presents a clear non-ideal concentration dependence. Similar nonlinear trends were found for the stabilization of different ionic species in solution, compared to the ones exhibited by their electrically neutral counterparts. These tendencies account for the characteristics of the free energy associated to the stabilization of Li+Cl-, contact-ion-pairs in these solutions. Ionic transport is also analyzed. Dynamical results show concentration trends similar to those recently obtained from direct experimental measurements. © 2014 AIP Publishing LLC. Fil:Semino, R. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Calvo, E.J. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Laria, D. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00219606_v141_n21_p_Semino |
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Universidad de Buenos Aires |
institution_str |
I-28 |
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R-134 |
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
topic |
Acetonitrile Dimethyl sulfoxide Free energy Lithium Molecular dynamics Solvation Solvents Stabilization Acetonitrile binary mixtures Concentration dependence Concentration trends Gradual modifications Ionic transports Li-air batteries Molecular dynamics simulations Non-linear trends Binary mixtures |
spellingShingle |
Acetonitrile Dimethyl sulfoxide Free energy Lithium Molecular dynamics Solvation Solvents Stabilization Acetonitrile binary mixtures Concentration dependence Concentration trends Gradual modifications Ionic transports Li-air batteries Molecular dynamics simulations Non-linear trends Binary mixtures Semino, R. Zaldívar, G. Calvo, E.J. Laria, D. Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures |
topic_facet |
Acetonitrile Dimethyl sulfoxide Free energy Lithium Molecular dynamics Solvation Solvents Stabilization Acetonitrile binary mixtures Concentration dependence Concentration trends Gradual modifications Ionic transports Li-air batteries Molecular dynamics simulations Non-linear trends Binary mixtures |
description |
We present molecular dynamics simulation results pertaining to the solvation of Li+ in dimethyl sulfoxide-acetonitrile binary mixtures. The results are potentially relevant in the design of Li-air batteries that rely on aprotic mixtures as solvent media. To analyze effects derived from differences in ionic size and charge sign, the solvation of Li+ is compared to the ones observed for infinitely diluted K+ and Cl- species, in similar solutions. At all compositions, the cations are preferentially solvated by dimethyl sulfoxide. Contrasting, the first solvation shell of Cl- shows a gradual modification in its composition, which varies linearly with the global concentrations of the two solvents in the mixtures. Moreover, the energetics of the solvation, described in terms of the corresponding solute-solvent coupling, presents a clear non-ideal concentration dependence. Similar nonlinear trends were found for the stabilization of different ionic species in solution, compared to the ones exhibited by their electrically neutral counterparts. These tendencies account for the characteristics of the free energy associated to the stabilization of Li+Cl-, contact-ion-pairs in these solutions. Ionic transport is also analyzed. Dynamical results show concentration trends similar to those recently obtained from direct experimental measurements. © 2014 AIP Publishing LLC. |
format |
JOUR |
author |
Semino, R. Zaldívar, G. Calvo, E.J. Laria, D. |
author_facet |
Semino, R. Zaldívar, G. Calvo, E.J. Laria, D. |
author_sort |
Semino, R. |
title |
Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures |
title_short |
Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures |
title_full |
Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures |
title_fullStr |
Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures |
title_full_unstemmed |
Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures |
title_sort |
lithium solvation in dimethyl sulfoxide-acetonitrile mixtures |
url |
http://hdl.handle.net/20.500.12110/paper_00219606_v141_n21_p_Semino |
work_keys_str_mv |
AT seminor lithiumsolvationindimethylsulfoxideacetonitrilemixtures AT zaldivarg lithiumsolvationindimethylsulfoxideacetonitrilemixtures AT calvoej lithiumsolvationindimethylsulfoxideacetonitrilemixtures AT lariad lithiumsolvationindimethylsulfoxideacetonitrilemixtures |
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1782029378219147264 |