Fundamental parameters governing ion conductivity in polymer electrolytes

A. Kisliuk; V. Bocharova; I. Popov; C. Gainaru; A. P. Sokolov

doi:10.1016/j.electacta.2018.12.143

Fundamental parameters governing ion conductivity in polymer electrolytes

A. Kisliuk, V. Bocharova, I. Popov, C. Gainaru, A. P. Sokolov

Soft Materials and Membranes

Research output: Contribution to journal › Article › peer-review

63 Scopus citations

Abstract

We analyze conductivity of polymerized ionic liquids with focus on fundamental limitations hindering faster charge transport in polymer electrolytes. We emphasize that to achieve the required ionic conductivity ∼10 ⁻³ S/cm in dry polymer electrolytes, a decoupling of ion transport from segmental dynamics is required. We demonstrate that two competing mechanisms control decoupling of ion transport: electrostatic interactions that dominates for small ions such Li, and elastic force that dominates for large ions. Our experimental results indeed confirm significant contribution of the elastic force to the energy barrier controlling transport of large ions. We also emphasize importance of ion-ion correlations that strongly affect charge transport (conductivity) even at the same ion diffusivity. Our analysis suggests that these correlations suppress ion conductivity in polymer electrolytes by about ten times. At the end, we formulate some ideas on design of polymer electrolytes with high ion conductivity.

Original language	English
Pages (from-to)	191-196
Number of pages	6
Journal	Electrochimica Acta
Volume	299
DOIs	https://doi.org/10.1016/j.electacta.2018.12.143
State	Published - Mar 10 2019

Funding

This manuscript has been authored by UT-Battelle, LLC under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan).Authors thank K. D. Kreuer and C. A. Angell for helpful discussions and suggestions. This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Science and Engineering Division.

Funders	Funder number
U.S. Department of Energy

Keywords

Haven ratio
Ion conductivity
Polymer electrolytes
Shear modulus

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10.1016/j.electacta.2018.12.143

Cite this

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title = "Fundamental parameters governing ion conductivity in polymer electrolytes",

abstract = " We analyze conductivity of polymerized ionic liquids with focus on fundamental limitations hindering faster charge transport in polymer electrolytes. We emphasize that to achieve the required ionic conductivity ∼10 −3 S/cm in dry polymer electrolytes, a decoupling of ion transport from segmental dynamics is required. We demonstrate that two competing mechanisms control decoupling of ion transport: electrostatic interactions that dominates for small ions such Li, and elastic force that dominates for large ions. Our experimental results indeed confirm significant contribution of the elastic force to the energy barrier controlling transport of large ions. We also emphasize importance of ion-ion correlations that strongly affect charge transport (conductivity) even at the same ion diffusivity. Our analysis suggests that these correlations suppress ion conductivity in polymer electrolytes by about ten times. At the end, we formulate some ideas on design of polymer electrolytes with high ion conductivity.",

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T1 - Fundamental parameters governing ion conductivity in polymer electrolytes

AU - Kisliuk, A.

AU - Bocharova, V.

AU - Popov, I.

AU - Gainaru, C.

AU - Sokolov, A. P.

PY - 2019/3/10

Y1 - 2019/3/10

N2 - We analyze conductivity of polymerized ionic liquids with focus on fundamental limitations hindering faster charge transport in polymer electrolytes. We emphasize that to achieve the required ionic conductivity ∼10 −3 S/cm in dry polymer electrolytes, a decoupling of ion transport from segmental dynamics is required. We demonstrate that two competing mechanisms control decoupling of ion transport: electrostatic interactions that dominates for small ions such Li, and elastic force that dominates for large ions. Our experimental results indeed confirm significant contribution of the elastic force to the energy barrier controlling transport of large ions. We also emphasize importance of ion-ion correlations that strongly affect charge transport (conductivity) even at the same ion diffusivity. Our analysis suggests that these correlations suppress ion conductivity in polymer electrolytes by about ten times. At the end, we formulate some ideas on design of polymer electrolytes with high ion conductivity.

AB - We analyze conductivity of polymerized ionic liquids with focus on fundamental limitations hindering faster charge transport in polymer electrolytes. We emphasize that to achieve the required ionic conductivity ∼10 −3 S/cm in dry polymer electrolytes, a decoupling of ion transport from segmental dynamics is required. We demonstrate that two competing mechanisms control decoupling of ion transport: electrostatic interactions that dominates for small ions such Li, and elastic force that dominates for large ions. Our experimental results indeed confirm significant contribution of the elastic force to the energy barrier controlling transport of large ions. We also emphasize importance of ion-ion correlations that strongly affect charge transport (conductivity) even at the same ion diffusivity. Our analysis suggests that these correlations suppress ion conductivity in polymer electrolytes by about ten times. At the end, we formulate some ideas on design of polymer electrolytes with high ion conductivity.

KW - Haven ratio

KW - Ion conductivity

KW - Polymer electrolytes

KW - Shear modulus

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JO - Electrochimica Acta

JF - Electrochimica Acta

ER -

Fundamental parameters governing ion conductivity in polymer electrolytes

Abstract

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Keywords

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