Nonlinear Ionic Transport through Microstructured Solid Electrolytes : Homogenization Estimates

The most promising solid electrolytes available to date consist of poly-ethylene-oxide (PEO) complexes doped with a lithium salt such as lithium perchlorate (LiClO4) or lithium iodide (LiI). At room temperature, the transport of lithium ions through these electrolytes is believed to occur by a hoppi...

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Detalles Bibliográficos
Autores principales:	Curto Sillamoni, Ignacio José, Idiart, Martín Ignacio
Formato:	Articulo
Lenguaje:	Español
Publicado:	2016
Materias:	Ingeniería Aeronáutica diffusion migration heterogeneous solids periodic homogenization nonlinearity
Acceso en línea:	http://sedici.unlp.edu.ar/handle/10915/127289 http://venus.ceride.gov.ar/ojs/index.php/mc/article/view/5112/5044
Aporte de:	SEDICI (UNLP) de Universidad Nacional de La Plata

id	I19-R120-10915-127289
record_format	dspace
institution	Universidad Nacional de La Plata
institution_str	I-19
repository_str	R-120
collection	SEDICI (UNLP)
language	Español
topic	Ingeniería Aeronáutica diffusion migration heterogeneous solids periodic homogenization nonlinearity
spellingShingle	Ingeniería Aeronáutica diffusion migration heterogeneous solids periodic homogenization nonlinearity Curto Sillamoni, Ignacio José Idiart, Martín Ignacio Nonlinear Ionic Transport through Microstructured Solid Electrolytes : Homogenization Estimates
topic_facet	Ingeniería Aeronáutica diffusion migration heterogeneous solids periodic homogenization nonlinearity
description	The most promising solid electrolytes available to date consist of poly-ethylene-oxide (PEO) complexes doped with a lithium salt such as lithium perchlorate (LiClO4) or lithium iodide (LiI). At room temperature, the transport of lithium ions through these electrolytes is believed to occur by a hopping mechanism whereby, under the action of an electric ﬁeld, ions jump along coordination sites available throughout the polymeric chains. Under moderate electric ﬁeld intensities this mechanism results in a weakly nonlinear relation between the current density of electric charge and the electric ﬁeld intensity which for most practical purposes can be approximated by a linear relation. Above a certain ﬁeld intensity, however, a sudden increase of electric current is observed and the response becomes strongly nonlinear. The range of electric ﬁeld intensities delimited by this threshold is known as the electrochemical stability window of the electrolyte and bears relevance to battery design for it dictates the electrochemical compatibility between electrodes and the electrolyte. Now, this window can vary consirably with microstructural properties such as crystallinity and second-phase inclusions. The purpose of this work is to put forward a multi-scale approach to estimate such variations. To that end, we consider the transport of multiple ionic species by diffusion and migration through microstructured solid electrolytes in the presence of strong electric ﬁelds. The assumed constitutive relations for the constituent phases follow from convex energy and dissipation potentials which guarantee thermodynamic consistency. The effective response is heuristically deduced from a multi-scale convergence analysis of the relevant ﬁeld equations. The resulting homogenized response involves an effective dissipation potential per species. Each potential is mathematically akin to that of a standard nonlinear heterogeneous conductor. A ‘linearcomparison’ homogenization technique is then used to generate multi-scale estimates for these nonlinear potentials in terms of available estimates for corresponding linear conductors. By way of example, use is made of the Maxwell-Garnett and Effective-Medium linear approximations to generate estimates for two-phase systems with power-law dissipation. Explicit formulas are given for some limiting cases. In the case of threshold-type behavior, the estimates exhibit non-analytical dilute limits and seem to be consistent with ﬁelds localized in low energy paths. The estimates should be relevant for assessing the electrochemical stability of microstructured solid electrolytes.
format	Articulo Articulo
author	Curto Sillamoni, Ignacio José Idiart, Martín Ignacio
author_facet	Curto Sillamoni, Ignacio José Idiart, Martín Ignacio
author_sort	Curto Sillamoni, Ignacio José
title	Nonlinear Ionic Transport through Microstructured Solid Electrolytes : Homogenization Estimates
title_short	Nonlinear Ionic Transport through Microstructured Solid Electrolytes : Homogenization Estimates
title_full	Nonlinear Ionic Transport through Microstructured Solid Electrolytes : Homogenization Estimates
title_fullStr	Nonlinear Ionic Transport through Microstructured Solid Electrolytes : Homogenization Estimates
title_full_unstemmed	Nonlinear Ionic Transport through Microstructured Solid Electrolytes : Homogenization Estimates
title_sort	nonlinear ionic transport through microstructured solid electrolytes : homogenization estimates
publishDate	2016
url	http://sedici.unlp.edu.ar/handle/10915/127289 http://venus.ceride.gov.ar/ojs/index.php/mc/article/view/5112/5044
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bdutipo_str	Repositorios
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Nonlinear Ionic Transport through Microstructured Solid Electrolytes : Homogenization Estimates

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