On the interfacial lithium dynamics in Li 7 La 3 Zr 2 O 12 :poly(ethylene oxide) (LiTFSI) composite polymer-ceramic solid electrolytes under strong polymer phase confinement.

Autor: Bonilla MR; BCAM - Basque Center for Applied Mathematics, Alameda de Mazarredo 14, E-48009 Bilbao, Spain. Electronic address: mrincon@bcamath.org., García Daza FA; Department of Chemical Engineering, The University of Manchester, Manchester M13 9PL, United Kingdom., Cortés HA; BCAM - Basque Center for Applied Mathematics, Alameda de Mazarredo 14, E-48009 Bilbao, Spain., Carrasco J; Centre for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Alava Technology Park, Albert Einstein 48, 01510 Vitoria-Gasteiz, Spain., Akhmatskaya E; BCAM - Basque Center for Applied Mathematics, Alameda de Mazarredo 14, E-48009 Bilbao, Spain; IKERBASQUE, Basque Foundation for Science, Plaza Euskadi 5, 48009 Bilbao, Spain.
Jazyk: angličtina
Zdroj: Journal of colloid and interface science [J Colloid Interface Sci] 2022 Oct; Vol. 623, pp. 870-882. Date of Electronic Publication: 2022 May 16.
DOI: 10.1016/j.jcis.2022.05.069
Abstrakt: A better molecular-level understanding of Li + diffusion through ceramic/polymer interfaces is key to design high-performance composite solid-state electrolytes for all-solid-state batteries. By considering as a case study a composite electrolyte constituted by Li + conductive Ga 3+ doped-Li 7 La 3 Zr 2 O 12 (LLZO) garnet fillers embedded within a poly(ethylene oxide) and lithium bis(trifluoromethanesulfonyl) imide polymer matrix (PEO(LiTFSI)), we investigate Li + interfacial dynamics at conditions of high polymer confinement, with large filler particles in a fully amorphous polymer phase. Such confinement scenario is aimed to capture the conditions near the percolation threshold, at which conductivity enhancement is often reported. Using molecular dynamics simulations combined with the generalized shadow hybrid Monte Carlo method and umbrella sampling calculations, we explain why the hopping towards the polymer phase of the Li + sitting on the LLZO surface is thermodynamically hindered, while hopping of Li + from the polymer to the LLZO is kinetically slowed-down by rigidified polymer near the interface. In addition, we demonstrate how the overlap of LLZO-bound polymer chains at high confinement leads to a decrease of Li + diffusivity within the interstitial space. We put forward that these insights are relevant to interpret the variation of ionic conductivity as a function of volume fraction and filler particle sizes also below the glass transition temperature of the polymer, at the typical operating conditions of lithium ion batteries.
Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
(Copyright © 2022 Elsevier Inc. All rights reserved.)
Databáze: MEDLINE
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