Current-driven solvent segregation in lithium-ion electrolytes

Wang, A. A., Greenbank, S., Li, G. , Howey, D. A. and Monroe, C. W. (2022) Current-driven solvent segregation in lithium-ion electrolytes. Cell Reports Physical Science, 3(9), 101047. (doi: 10.1016/j.xcrp.2022.101047)

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Liquid lithium-battery electrolytes universally incorporate at least two solvents to balance conductivity and viscosity. Almost all continuum models treat cosolvent systems such as ethylene carbonate:ethyl-methyl carbonate (EC:EMC) as single entities whose constituents travel with identical velocities. We test this “single-solvent approximation” by subjecting LiPF6:EC:EMC blends to constant-current polarization in Hittorf experiments. A Gaussian process regression model trained on physicochemical properties quantifies changes in composition across the Hittorf cell. EC and EMC are found to migrate at noticeably different rates under applied current, demonstrating conclusively that the single-solvent approximation is violated and that polarization of salt concentration is anticorrelated with that of EC. Simulations show extreme solvent segregation near electrode/liquid interfaces: a 5% change in EC:EMC ratio, post-Hittorf polarization, implies more than a 50% change adjacent to the interface during the current pulse. Understanding how lithium-ion flux induces local cosolvent or additive imbalances suggests new approaches to electrolyte design.

Item Type:Articles
Additional Information:This work was supported by the Faraday Institution Multiscale Modelling Project , subaward FIRG025 under EPSRC grant number EP/S003053/1.
Glasgow Author(s) Enlighten ID:Li, Dr Guanchen
Creator Roles:
Li, G.Conceptualization
Authors: Wang, A. A., Greenbank, S., Li, G., Howey, D. A., and Monroe, C. W.
College/School:College of Science and Engineering > School of Engineering > Systems Power and Energy
Journal Name:Cell Reports Physical Science
Publisher:Elsevier (Cell Press)
ISSN (Online):2666-3864
Published Online:08 September 2022
Copyright Holders:Copyright © 2022 The Author(s)
First Published:First published in Cell Reports Physical Science 3(9): 101047
Publisher Policy:Reproduced under a Creative Commons license

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