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...

Descripción completa

Guardado en:

Detalles Bibliográficos
Autores principales:	Semino, Rocio, Calvo, Ernesto Julio, Laria, Daniel Hector
Publicado:	2014
Materias:	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
Acceso en línea:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00219606_v141_n21_p_Semino http://hdl.handle.net/20.500.12110/paper_00219606_v141_n21_p_Semino
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	paper:paper_00219606_v141_n21_p_Semino
record_format	dspace
spelling	paper:paper_00219606_v141_n21_p_Semino2023-06-08T14:44:26Z Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures Semino, Rocio Calvo, Ernesto Julio Laria, Daniel Hector 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. 2014 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00219606_v141_n21_p_Semino http://hdl.handle.net/20.500.12110/paper_00219606_v141_n21_p_Semino
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	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, Rocio Calvo, Ernesto Julio Laria, Daniel Hector 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.
author	Semino, Rocio Calvo, Ernesto Julio Laria, Daniel Hector
author_facet	Semino, Rocio Calvo, Ernesto Julio Laria, Daniel Hector
author_sort	Semino, Rocio
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
publishDate	2014
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00219606_v141_n21_p_Semino http://hdl.handle.net/20.500.12110/paper_00219606_v141_n21_p_Semino
work_keys_str_mv	AT seminorocio lithiumsolvationindimethylsulfoxideacetonitrilemixtures AT calvoernestojulio lithiumsolvationindimethylsulfoxideacetonitrilemixtures AT lariadanielhector lithiumsolvationindimethylsulfoxideacetonitrilemixtures
_version_	1768543977343025152

Lithium solvation in dimethyl sulfoxide-acetonitrile mixtures

Ejemplares similares