Ion States Impact Charge Transport and Dielectric Constant for Poly(ethylene oxide)-Based Sulfonylimide Lithium Ionomers

Understanding dielectric response and charge transport in ion-containing polymers is essential for the design and implementation of these materials in energy-related applications. Our previous study identified the significant impacts of anion chemical composition on ion conduction for poly(ethylene oxide)-based lithium ionomers with polymer-fixed sulfonylimide (MTLi) and sulfonate anions (J. Mater. Chem. C, 2022, 10, 14569). In this study, we further explore the dielectric response and Li+ conduction in the context of different ion states using DFT. The most relevant ion states impacting the dielectric response and Li+ conduction are represented with a four-state model. DFT calculation using the cluster-continuum solvation model captures the local solvation effects of poly(ethylene oxide) and reveals low cluster dissociation energy between neutral and charged states. Low cluster dissociation energy explains the weakly aggregated morphology with low aggregation number based on X-ray scattering and implies that Li+ rapidly exchanges between different ion states. Consequently, Li+ can hop along aggregates for high ion content MTLi, which results in its significant dielectric response, comparable conductivity, and lower Haven ratio despite stronger aggregation than the low ion content counterparts. Different from typical ionomers where raising ion content is detrimental to the ion transport and dielectric response, the understandings based on different ion states for MTLi offer new insights to promote ion conduction and dielectric response for single-ion conducting ionomers.

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Work Title Ion States Impact Charge Transport and Dielectric Constant for Poly(ethylene oxide)-Based Sulfonylimide Lithium Ionomers
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Open Access
Creators
  1. Wenwen Mei
  2. Deyang Yu
  3. Louis A. Madsen
  4. Robert Hickey
  5. Ralph H. Colby
Keyword
  1. Actions
  2. Cluster Ions
  3. Insulators
  4. Ionomers
  5. Ions
License CC BY 4.0 (Attribution)
Work Type Article
Publisher
  1. Macromolecules
Publication Date June 28, 2023
Publisher Identifier (DOI)
  1. 10.1021/acs.macromol.3c00294
Deposited October 22, 2024

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Version 1
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  • Created
  • Updated
  • Added Creator Wenwen Mei
  • Added Creator Deyang Yu
  • Added Creator Louis A. Madsen
  • Added Creator Robert Hickey
  • Added Creator Ralph H. Colby
  • Updated Work Title, Publisher, Publisher Identifier (DOI), and 2 more Show Changes
    Work Title
    • Ion States Impact Charge Transport and Dielectric Constant for Poly(ethylene oxide)- based Sulfonylimide Lithium Ionomers
    • Ion States Impact Charge Transport and Dielectric Constant for Poly(ethylene oxide)-Based Sulfonylimide Lithium Ionomers
    Publisher
    • Macromolecules
    Publisher Identifier (DOI)
    • 10.1021/acs.macromol.3c00294
    Description
    • <p>Understanding dielectric response and charge transport in ion-containing polymers is essential for the design and implementation of these materials in energy-related applications. Our previous study identified the significant impacts of anion chemical composition on ion conduction for poly(ethylene oxide)-based lithium ionomers with polymer-fixed sulfonylimide (MTLi) and sulfonate anions (J. Mater. Chem. C, 2022, 10, 14569). In this study, we further explore the dielectric response and Li<sup>+</sup> conduction in the context of different ion states using DFT. The most relevant ion states impacting the dielectric response and Li<sup>+</sup> conduction are represented with a four-state model. DFT calculation using the cluster-continuum solvation model captures the local solvation effects of poly(ethylene oxide) and reveals low cluster dissociation energy between neutral and charged states. Low cluster dissociation energy explains the weakly aggregated morphology with low aggregation number based on X-ray scattering and implies that Li<sup>+</sup> rapidly exchanges between different ion states. Consequently, Li<sup>+</sup> can hop along aggregates for high ion content MTLi, which results in its significant dielectric response, comparable conductivity, and lower Haven ratio despite stronger aggregation than the low ion content counterparts. Different from typical ionomers where raising ion content is detrimental to the ion transport and dielectric response, the understandings based on different ion states for MTLi offer new insights to promote ion conduction and dielectric response for single-ion conducting ionomers.</p>
    Publication Date
    • 2023-06-28
  • Updated
  • Updated
  • Updated Creator Wenwen Mei
  • Updated Creator Deyang Yu
  • Updated Creator Louis A. Madsen
  • Updated Creator Robert Hickey
  • Updated Creator Ralph H. Colby
  • Added SulfonylimideMacro2023.pdf
  • Updated License Show Changes
    License
    • https://creativecommons.org/licenses/by/4.0/
  • Published
  • Updated
  • Updated Keyword Show Changes
    Keyword
    • Actions, Cluster Ions, Insulators, Ionomers, Ions