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Influence of the anion on diffusivity and mobility of ionic liquids composite polybenzimidazol membranes

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Influence of the anion on diffusivity and mobility of ionic liquids composite polybenzimidazol membranes

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dc.contributor.author Compañ Moreno, Vicente es_ES
dc.contributor.author Escorihuela Fuentes, Jorge es_ES
dc.contributor.author Olvera, Jessica es_ES
dc.contributor.author Garcia-Bernabe, Abel es_ES
dc.contributor.author ANDRIO, ANDREU es_ES
dc.date.accessioned 2021-03-17T04:31:39Z
dc.date.available 2021-03-17T04:31:39Z
dc.date.issued 2020-09-10 es_ES
dc.identifier.issn 0013-4686 es_ES
dc.identifier.uri http://hdl.handle.net/10251/163975
dc.description.abstract [EN] The study of proton conductivity processes has received increasing attention in the past decades due to their potential applications in fields such as electrochemical devices and fuel cells. Despite the high number of composite membranes which have been described for this purpose, fundamental studies of the conduction phenomena in polymeric membranes are scarce. In this article, we study on the effect of the anion on ionic conductivity of ionic liquid composite polybenzimidazole (PBI) membranes. These membranes, which contain 1-butyl-3-methylimidazolium (BMIM) with different counterions ([Cl]-, [NCS]-, [NTf2]- and [BF4]-) were analyzed by electrochemical impedance spectroscopy (EIS) in order to study the influence of the anion on the ionic conductivity, but also mobility and charge carrier density at different temperatures. The methodology for this analysis is based on the Coelho model of electrode polarization (EP), where the dependence of the complex dielectric permittivity on frequency is represented in terms of a Cole-Cole function, contrarily to the generally used simple Debye relaxation. The calculated activation energies associated to the conductivity showed a dependence on the anion and is around 65-84 kJ mol-1, which suggests that the ionic conductivity mainly occurs through the vehicle-type mechanism. The calculated diffusivity values followed the trend D NTf2 > D Cl > D BF4> D SCN, with an associated activation energy (in kJ·mol¿1) following the trend Eact(NTf2) = 10.9 < Eact(Cl) = 12.6 < Eact(BF4) = 18.5 < Eact(SCN) = 25.1. The comparison between these values reveals that a decrease in the ion binding energies (Eb) and stabilization energies (Es) could be responsible for the growth of the diffusion coefficient around one or two orders of magnitude depending on temperature and anion. The low stabilization energy observed for the NTF2- and Cl- anions in comparison with NCS- and BF4, can be attributed to the poor stabilization of separated ion pairs by coordination with the PBI segments, which is reflected in the values of the dielectric permittivity (es) calculated by EIS. es_ES
dc.description.sponsorship This work was financially supported by the Ministerio de Economia y Competitividad (MINECO) under project ENE2015-69203-R. es_ES
dc.language Inglés es_ES
dc.publisher Elsevier es_ES
dc.relation.ispartof Electrochimica Acta es_ES
dc.rights Reconocimiento - No comercial - Sin obra derivada (by-nc-nd) es_ES
dc.subject Polymer electrolytes es_ES
dc.subject Polybenzimidazole es_ES
dc.subject Ionic liquids es_ES
dc.subject Conductivity es_ES
dc.subject Ionic transport es_ES
dc.subject Mobility es_ES
dc.subject Electrochemical impedance spectroscopy es_ES
dc.subject.classification MAQUINAS Y MOTORES TERMICOS es_ES
dc.title Influence of the anion on diffusivity and mobility of ionic liquids composite polybenzimidazol membranes es_ES
dc.type Artículo es_ES
dc.identifier.doi 10.1016/j.electacta.2020.136666 es_ES
dc.relation.projectID info:eu-repo/grantAgreement/MINECO//ENE2015-69203-R/ES/DESARROLLO Y EVALUACION DE NUEVAS MEMBRANAS POLIMERICAS REFORZADAS CON NANOFIBRAS PARA SU APLICACION EN PILAS DE COMBUSTIBLE CON ELEVADA ESTABILIDAD TERMICA/ es_ES
dc.rights.accessRights Abierto es_ES
dc.contributor.affiliation Universitat Politècnica de València. Departamento de Termodinámica Aplicada - Departament de Termodinàmica Aplicada es_ES
dc.description.bibliographicCitation Compañ Moreno, V.; Escorihuela Fuentes, J.; Olvera, J.; Garcia-Bernabe, A.; Andrio, A. (2020). Influence of the anion on diffusivity and mobility of ionic liquids composite polybenzimidazol membranes. Electrochimica Acta. 354:1-12. https://doi.org/10.1016/j.electacta.2020.136666 es_ES
dc.description.accrualMethod S es_ES
dc.relation.publisherversion https://doi.org/10.1016/j.electacta.2020.136666 es_ES
dc.description.upvformatpinicio 1 es_ES
dc.description.upvformatpfin 12 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 354 es_ES
dc.relation.pasarela S\423669 es_ES
dc.contributor.funder Ministerio de Economía y Competitividad es_ES
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