Elucidating the Molecular Origins of the Transference Number in Battery Electrolytes Using Computer Simulations.

Content Provider	Europe PMC
Author	Fang, Chao Mistry, Aashutosh Srinivasan, Venkat Balsara, Nitash P. Wang, Rui
Copyright Year	2023
Abstract	The rate at which rechargeable batteries can be chargedand dischargedis governed by the selective transport of the working ions throughthe electrolyte. Conductivity, the parameter commonly used to characterizeion transport in electrolytes, reflects the mobility of both cationsand anions. The transference number, a parameter introduced over acentury ago, sheds light on the relative rates of cation and aniontransport. This parameter is, not surprisingly, affected by cation–cation,anion–anion, and cation–anion correlations. In addition,it is affected by correlations between the ions and neutral solventmolecules. Computer simulations have the potential to provide insightsinto the nature of these correlations. We review the dominant theoreticalapproaches used to predict the transference number from simulationsby using a model univalent lithium electrolyte. In electrolytes oflow concentration, one can obtain a quantitative model by assumingthat the solution is made up of discrete ion-containing clusters–neutralion pairs, negatively and positively charged triplets, neutral quadruplets,and so on. These clusters can be identified in simulations using simplealgorithms, provided their lifetimes are sufficiently long. In concentratedelectrolytes, more clusters are short-lived and more rigorous approachesthat account for all correlations are necessary to quantify transference.Elucidating the molecular origin of the transference number in thislimit remains an unmet challenge.
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Journal	JACS Au
Volume Number	3
DOI	10.1021/jacsau.2c00590
PubMed Central reference number	PMC9975840
Issue Number	2
PubMed reference number	36873702
e-ISSN	26913704
Language	English
Publisher	American Chemical Society
Publisher Date	2023-02-02
Access Restriction	Open
Rights License	Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). © 2023 The Authors. Published by American Chemical Society
Subject Keyword	batteries electrolytes ion transport transference number computer simulation
Content Type	Text
Resource Type	Article
Subject	Chemistry Physical and Theoretical Chemistry Analytical Chemistry Organic Chemistry