Theory of Cation Solvation and Ionic Association in Nonaqueous Solvent Mixtures

Conventional lithium-ion batteries, and many next-generation technologies, rely on organic electrolytes with multiple solvents to achieve the desired physicochemical and interfacial properties. The complex interplay between these properties can often be elucidated via the coordination environment of...

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Main Authors: Zachary A.H. Goodwin, Michael McEldrew, Boris Kozinsky, Martin Z. Bazant
Format: Article
Language:English
Published: American Physical Society 2023-03-01
Series:PRX Energy
Online Access:http://doi.org/10.1103/PRXEnergy.2.013007
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author Zachary A.H. Goodwin
Michael McEldrew
Boris Kozinsky
Martin Z. Bazant
author_facet Zachary A.H. Goodwin
Michael McEldrew
Boris Kozinsky
Martin Z. Bazant
author_sort Zachary A.H. Goodwin
collection DOAJ
description Conventional lithium-ion batteries, and many next-generation technologies, rely on organic electrolytes with multiple solvents to achieve the desired physicochemical and interfacial properties. The complex interplay between these properties can often be elucidated via the coordination environment of the cation. We develop a theory for the coordination shell of cations in nonaqueous solvent mixtures that can be applied with high fidelity, up to extremely high salt concentrations. Our theory can naturally explain simulation and experimental values of cation solvation in “classical” nonaqueous electrolytes. Moreover, we utilize our theory to understand general design principles of emerging classes of nonaqueous electrolyte mixtures, such as high entropy electrolytes. It is hoped that this theory provides a systematic framework to understand simulations and experiments that engineer the solvation structure and ionic associations of concentrated nonaqueous electrolytes.
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spelling doaj-art-e7e84754c43e478ba889477ddf639a732025-08-20T01:55:15ZengAmerican Physical SocietyPRX Energy2768-56082023-03-012101300710.1103/PRXEnergy.2.013007Theory of Cation Solvation and Ionic Association in Nonaqueous Solvent MixturesZachary A.H. GoodwinMichael McEldrewBoris KozinskyMartin Z. BazantConventional lithium-ion batteries, and many next-generation technologies, rely on organic electrolytes with multiple solvents to achieve the desired physicochemical and interfacial properties. The complex interplay between these properties can often be elucidated via the coordination environment of the cation. We develop a theory for the coordination shell of cations in nonaqueous solvent mixtures that can be applied with high fidelity, up to extremely high salt concentrations. Our theory can naturally explain simulation and experimental values of cation solvation in “classical” nonaqueous electrolytes. Moreover, we utilize our theory to understand general design principles of emerging classes of nonaqueous electrolyte mixtures, such as high entropy electrolytes. It is hoped that this theory provides a systematic framework to understand simulations and experiments that engineer the solvation structure and ionic associations of concentrated nonaqueous electrolytes.http://doi.org/10.1103/PRXEnergy.2.013007
spellingShingle Zachary A.H. Goodwin
Michael McEldrew
Boris Kozinsky
Martin Z. Bazant
Theory of Cation Solvation and Ionic Association in Nonaqueous Solvent Mixtures
PRX Energy
title Theory of Cation Solvation and Ionic Association in Nonaqueous Solvent Mixtures
title_full Theory of Cation Solvation and Ionic Association in Nonaqueous Solvent Mixtures
title_fullStr Theory of Cation Solvation and Ionic Association in Nonaqueous Solvent Mixtures
title_full_unstemmed Theory of Cation Solvation and Ionic Association in Nonaqueous Solvent Mixtures
title_short Theory of Cation Solvation and Ionic Association in Nonaqueous Solvent Mixtures
title_sort theory of cation solvation and ionic association in nonaqueous solvent mixtures
url http://doi.org/10.1103/PRXEnergy.2.013007
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AT boriskozinsky theoryofcationsolvationandionicassociationinnonaqueoussolventmixtures
AT martinzbazant theoryofcationsolvationandionicassociationinnonaqueoussolventmixtures