Correlations from Ion Pairing and the Nernst-Einstein Equation
Name
PhysRevLett.122.136001.pdf
Description
Published version
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417.17 KB
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Adobe PDF
Checksum (MD5)
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Author(s)
France-Lanord, Arthur
Grossman, Jeffrey C.
Date Issued
April 2019
Journal
Physical Review Letters
Publisher
American Physical Society (APS)
Citation
France-Lanord, Arthur, and Jeffrey C. Grossman. “Correlations from Ion Pairing and the Nernst-Einstein Equation.” Physical Review Letters 122, 13 (April 2019): 136001. © 2019 American Physical Society
Version
Final published version
Abstract
We present a new approximation to ionic conductivity well suited to dynamical atomic-scale simulations, based on the Nernst-Einstein equation. In our approximation, ionic aggregates constitute the elementary charge carriers, and are considered as noninteracting species. This approach conveniently captures the dominant effect of ion-ion correlations on conductivity, short range interactions in the form of clustering. In addition to providing better estimates to the conductivity at a lower computational cost than exact approaches, this new method allows us to understand the physical mechanisms driving ion conduction in concentrated electrolytes. As an example, we consider Li+ conduction in poly(ethylene oxide), a standard solid-state polymer electrolyte. Using our newly developed approach, we are able to reproduce recent experimental results reporting negative cation transference numbers at high salt concentrations, and to confirm that this effect can be caused by a large population of negatively charged clusters involving cations.
MIT Department
Massachusetts Institute of Technology. Research Laboratory of Electronics
Massachusetts Institute of Technology. Department of Materials Science and Engineering
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DOI of Published Version
https://doi.org/10.1103/PhysRevLett.122.136001
