Ionic Transport and Speciation of Lithium Salts in Glymes: Experimental and Theoretical Results for Electrolytes of Interest for Lithium-Air Batteries

Autores
Horwitz, Gabriela; Factorovich, Matias Hector; Rodriguez, Javier; Laria, Daniel Hector; Corti, Horacio Roberto
Año de publicación
2018
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Glycol ethers, or glymes, have been recognized as good candidates as solvents for lithium-air batteries because they exhibit relatively good stability in the presence of superoxide radicals. Diglyme (bis(2-methoxy-ethyl)ether), in spite of its low donor number, has been found to promote the solution mechanism for the formation of Li2O2 during the discharge reaction, leading to large deposits, that is, high capacities. It has been suggested that lithium salt association in these types of solvents could be responsible for this behavior. Thus, the knowledge of the speciation and transport behavior of lithium salts in these types of solvents is relevant for the optimization of the lithium-air battery performance. In this work, a comprehensive study of lithium trifluoromethanesulfonate (LiTf) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in 1,2-di-methoxyethane (DME) and diglyme, over a wide range of concentrations, have been performed. Consistent ion pairs and triplet ions formation constants have been obtained by resorting to well-known equations that describe the concentration dependence of the molar conductivities in highly associated electrolytes, and we found that the system LiTf/DME would be the best to promote bulky Li2O2 deposits. Unexpected differences are observed for the association constants of LiTf and, to a lesser extent, for LiTFSI, in DME and diglyme, whose dielectric constants are similar. Molecular dynamics (MD) simulations allowed us to rationalize these differences in terms of the competing interactions of the O-sites of the ethers and the SOx groups of the corresponding anions with Li+ ion. The limiting Li+ diffusivity derived from the fractional Walden rule agrees quite well with those obtained from MD simulations, when solvent viscosity is conveniently rescaled.
Fil: Horwitz, Gabriela. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Factorovich, Matias Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Rodriguez, Javier. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina
Fil: Laria, Daniel Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Comisión Nacional de Energía Atómica; Argentina
Fil: Corti, Horacio Roberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Materia
Litio
Diglimas
Conductividad Ionica
Dinamica Molecular
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
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oai:ri.conicet.gov.ar:11336/89329
Acceder
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spelling Ionic Transport and Speciation of Lithium Salts in Glymes: Experimental and Theoretical Results for Electrolytes of Interest for Lithium-Air BatteriesHorwitz, GabrielaFactorovich, Matias HectorRodriguez, JavierLaria, Daniel HectorCorti, Horacio RobertoLitioDiglimasConductividad IonicaDinamica Molecularhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Glycol ethers, or glymes, have been recognized as good candidates as solvents for lithium-air batteries because they exhibit relatively good stability in the presence of superoxide radicals. Diglyme (bis(2-methoxy-ethyl)ether), in spite of its low donor number, has been found to promote the solution mechanism for the formation of Li2O2 during the discharge reaction, leading to large deposits, that is, high capacities. It has been suggested that lithium salt association in these types of solvents could be responsible for this behavior. Thus, the knowledge of the speciation and transport behavior of lithium salts in these types of solvents is relevant for the optimization of the lithium-air battery performance. In this work, a comprehensive study of lithium trifluoromethanesulfonate (LiTf) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in 1,2-di-methoxyethane (DME) and diglyme, over a wide range of concentrations, have been performed. Consistent ion pairs and triplet ions formation constants have been obtained by resorting to well-known equations that describe the concentration dependence of the molar conductivities in highly associated electrolytes, and we found that the system LiTf/DME would be the best to promote bulky Li2O2 deposits. Unexpected differences are observed for the association constants of LiTf and, to a lesser extent, for LiTFSI, in DME and diglyme, whose dielectric constants are similar. Molecular dynamics (MD) simulations allowed us to rationalize these differences in terms of the competing interactions of the O-sites of the ethers and the SOx groups of the corresponding anions with Li+ ion. The limiting Li+ diffusivity derived from the fractional Walden rule agrees quite well with those obtained from MD simulations, when solvent viscosity is conveniently rescaled.Fil: Horwitz, Gabriela. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Factorovich, Matias Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Rodriguez, Javier. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; ArgentinaFil: Laria, Daniel Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Comisión Nacional de Energía Atómica; ArgentinaFil: Corti, Horacio Roberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaAmerican Chemical Society2018-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/89329Horwitz, Gabriela; Factorovich, Matias Hector; Rodriguez, Javier; Laria, Daniel Hector; Corti, Horacio Roberto; Ionic Transport and Speciation of Lithium Salts in Glymes: Experimental and Theoretical Results for Electrolytes of Interest for Lithium-Air Batteries; American Chemical Society; ACS Omega; 3; 9; 9-2018; 11205-112152470-1343CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/full/10.1021/acsomega.8b01443info:eu-repo/semantics/altIdentifier/doi/10.1021/acsomega.8b01443info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:53:44Zoai:ri.conicet.gov.ar:11336/89329instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 09:53:44.518CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Ionic Transport and Speciation of Lithium Salts in Glymes: Experimental and Theoretical Results for Electrolytes of Interest for Lithium-Air Batteries
title Ionic Transport and Speciation of Lithium Salts in Glymes: Experimental and Theoretical Results for Electrolytes of Interest for Lithium-Air Batteries
spellingShingle Ionic Transport and Speciation of Lithium Salts in Glymes: Experimental and Theoretical Results for Electrolytes of Interest for Lithium-Air Batteries
Horwitz, Gabriela
Litio
Diglimas
Conductividad Ionica
Dinamica Molecular
title_short Ionic Transport and Speciation of Lithium Salts in Glymes: Experimental and Theoretical Results for Electrolytes of Interest for Lithium-Air Batteries
title_full Ionic Transport and Speciation of Lithium Salts in Glymes: Experimental and Theoretical Results for Electrolytes of Interest for Lithium-Air Batteries
title_fullStr Ionic Transport and Speciation of Lithium Salts in Glymes: Experimental and Theoretical Results for Electrolytes of Interest for Lithium-Air Batteries
title_full_unstemmed Ionic Transport and Speciation of Lithium Salts in Glymes: Experimental and Theoretical Results for Electrolytes of Interest for Lithium-Air Batteries
title_sort Ionic Transport and Speciation of Lithium Salts in Glymes: Experimental and Theoretical Results for Electrolytes of Interest for Lithium-Air Batteries
dc.creator.none.fl_str_mv Horwitz, Gabriela
Factorovich, Matias Hector
Rodriguez, Javier
Laria, Daniel Hector
Corti, Horacio Roberto
author Horwitz, Gabriela
author_facet Horwitz, Gabriela
Factorovich, Matias Hector
Rodriguez, Javier
Laria, Daniel Hector
Corti, Horacio Roberto
author_role author
author2 Factorovich, Matias Hector
Rodriguez, Javier
Laria, Daniel Hector
Corti, Horacio Roberto
author2_role author
author
author
author
dc.subject.none.fl_str_mv Litio
Diglimas
Conductividad Ionica
Dinamica Molecular
topic Litio
Diglimas
Conductividad Ionica
Dinamica Molecular
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Glycol ethers, or glymes, have been recognized as good candidates as solvents for lithium-air batteries because they exhibit relatively good stability in the presence of superoxide radicals. Diglyme (bis(2-methoxy-ethyl)ether), in spite of its low donor number, has been found to promote the solution mechanism for the formation of Li2O2 during the discharge reaction, leading to large deposits, that is, high capacities. It has been suggested that lithium salt association in these types of solvents could be responsible for this behavior. Thus, the knowledge of the speciation and transport behavior of lithium salts in these types of solvents is relevant for the optimization of the lithium-air battery performance. In this work, a comprehensive study of lithium trifluoromethanesulfonate (LiTf) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in 1,2-di-methoxyethane (DME) and diglyme, over a wide range of concentrations, have been performed. Consistent ion pairs and triplet ions formation constants have been obtained by resorting to well-known equations that describe the concentration dependence of the molar conductivities in highly associated electrolytes, and we found that the system LiTf/DME would be the best to promote bulky Li2O2 deposits. Unexpected differences are observed for the association constants of LiTf and, to a lesser extent, for LiTFSI, in DME and diglyme, whose dielectric constants are similar. Molecular dynamics (MD) simulations allowed us to rationalize these differences in terms of the competing interactions of the O-sites of the ethers and the SOx groups of the corresponding anions with Li+ ion. The limiting Li+ diffusivity derived from the fractional Walden rule agrees quite well with those obtained from MD simulations, when solvent viscosity is conveniently rescaled.
Fil: Horwitz, Gabriela. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Factorovich, Matias Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Rodriguez, Javier. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina
Fil: Laria, Daniel Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Comisión Nacional de Energía Atómica; Argentina
Fil: Corti, Horacio Roberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Comisión Nacional de Energía Atómica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
description Glycol ethers, or glymes, have been recognized as good candidates as solvents for lithium-air batteries because they exhibit relatively good stability in the presence of superoxide radicals. Diglyme (bis(2-methoxy-ethyl)ether), in spite of its low donor number, has been found to promote the solution mechanism for the formation of Li2O2 during the discharge reaction, leading to large deposits, that is, high capacities. It has been suggested that lithium salt association in these types of solvents could be responsible for this behavior. Thus, the knowledge of the speciation and transport behavior of lithium salts in these types of solvents is relevant for the optimization of the lithium-air battery performance. In this work, a comprehensive study of lithium trifluoromethanesulfonate (LiTf) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in 1,2-di-methoxyethane (DME) and diglyme, over a wide range of concentrations, have been performed. Consistent ion pairs and triplet ions formation constants have been obtained by resorting to well-known equations that describe the concentration dependence of the molar conductivities in highly associated electrolytes, and we found that the system LiTf/DME would be the best to promote bulky Li2O2 deposits. Unexpected differences are observed for the association constants of LiTf and, to a lesser extent, for LiTFSI, in DME and diglyme, whose dielectric constants are similar. Molecular dynamics (MD) simulations allowed us to rationalize these differences in terms of the competing interactions of the O-sites of the ethers and the SOx groups of the corresponding anions with Li+ ion. The limiting Li+ diffusivity derived from the fractional Walden rule agrees quite well with those obtained from MD simulations, when solvent viscosity is conveniently rescaled.
publishDate 2018
dc.date.none.fl_str_mv 2018-09
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/89329
Horwitz, Gabriela; Factorovich, Matias Hector; Rodriguez, Javier; Laria, Daniel Hector; Corti, Horacio Roberto; Ionic Transport and Speciation of Lithium Salts in Glymes: Experimental and Theoretical Results for Electrolytes of Interest for Lithium-Air Batteries; American Chemical Society; ACS Omega; 3; 9; 9-2018; 11205-11215
2470-1343
CONICET Digital
CONICET
url http://hdl.handle.net/11336/89329
identifier_str_mv Horwitz, Gabriela; Factorovich, Matias Hector; Rodriguez, Javier; Laria, Daniel Hector; Corti, Horacio Roberto; Ionic Transport and Speciation of Lithium Salts in Glymes: Experimental and Theoretical Results for Electrolytes of Interest for Lithium-Air Batteries; American Chemical Society; ACS Omega; 3; 9; 9-2018; 11205-11215
2470-1343
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/full/10.1021/acsomega.8b01443
info:eu-repo/semantics/altIdentifier/doi/10.1021/acsomega.8b01443
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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