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Title: Correlations from Ion Pairing and the Nernst-Einstein Equation

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.

Authors:
 [1];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials and Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE
OSTI Identifier:
1529913
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 122; Journal Issue: 13; Journal ID: ISSN 0031-9007
Country of Publication:
United States
Language:
English

Citation Formats

France-Lanord, Arthur, and Grossman, Jeffrey C. Correlations from Ion Pairing and the Nernst-Einstein Equation. United States: N. p., 2019. Web. doi:10.1103/PhysRevLett.122.136001.
France-Lanord, Arthur, & Grossman, Jeffrey C. Correlations from Ion Pairing and the Nernst-Einstein Equation. United States. doi:10.1103/PhysRevLett.122.136001.
France-Lanord, Arthur, and Grossman, Jeffrey C. Mon . "Correlations from Ion Pairing and the Nernst-Einstein Equation". United States. doi:10.1103/PhysRevLett.122.136001.
@article{osti_1529913,
title = {Correlations from Ion Pairing and the Nernst-Einstein Equation},
author = {France-Lanord, Arthur and Grossman, Jeffrey C.},
abstractNote = {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.},
doi = {10.1103/PhysRevLett.122.136001},
journal = {Physical Review Letters},
issn = {0031-9007},
number = 13,
volume = 122,
place = {United States},
year = {2019},
month = {4}
}