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Title: An Investigation of the Ionic Conductivity and Species Crossover of Lithiated Nafion 117 in Nonaqueous Electrolytes

Abstract

Nonaqueous redox flow batteries are a fast-growing area of research and development motivated by the need to develop lowcost energy storage systems. The identification of a highly conductive, yet selective membrane, is of paramount importance to enabling such a technology. We report the swelling behavior, ionic conductivity, and species crossover of lithiated Nafion 117 membranes immersed in three nonaqueous electrolytes (PC, PC : EC, and DMSO). Our results show that solvent volume fraction within the membrane has the greatest effect on both conductivity and crossover. An approximate linear relationship between diffusive crossover of neutral redox species (ferrocene) and the ionic conductivity of membrane was observed. As a secondary effect, the charge on redox species modifies crossover rates in accordance with Donnan exclusion. The selectivity of membrane is derived mathematically and compared to experimental results reported here. The relatively low selectivity for lithiated Nafion 117 in nonaqueous conditions suggests that new membranes are required for competitive nonaqueous redox flow batteries to be realized. Potential design rules are suggested for the future membrane engineering work.

Authors:
 [1];  [2];  [3];  [2];  [4]; ORCiD logo [5];  [1];  [6];  [4];  [6];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Chemical Engineering
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); United Technologies Research Center (UTRC), Hartford, CT (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR) and Chemical Sciences and Engineering Division
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Univ. of California, Berkeley, CA (United States). Dept. of Chemical Engineering
  5. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Chemical Engineering
  6. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Univ. of Illinois at Urbana-Champaign, IL (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1474904
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 163; Journal Issue: 1; Related Information: © 2015 The Author(s). Published by ECS.; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ionic conductivity; Nafion; nonaqueous; redox flow battery; selectivity; species crossover

Citation Formats

Su, Liang, Darling, Robert M., Gallagher, Kevin G., Xie, Wei, Thelen, Jacob L., Badel, Andres F., Barton, John L., Cheng, Kevin J., Balsara, Nitash P., Moore, Jeffrey S., and Brushett, Fikile R. An Investigation of the Ionic Conductivity and Species Crossover of Lithiated Nafion 117 in Nonaqueous Electrolytes. United States: N. p., 2015. Web. doi:10.1149/2.03211601jes.
Su, Liang, Darling, Robert M., Gallagher, Kevin G., Xie, Wei, Thelen, Jacob L., Badel, Andres F., Barton, John L., Cheng, Kevin J., Balsara, Nitash P., Moore, Jeffrey S., & Brushett, Fikile R. An Investigation of the Ionic Conductivity and Species Crossover of Lithiated Nafion 117 in Nonaqueous Electrolytes. United States. doi:10.1149/2.03211601jes.
Su, Liang, Darling, Robert M., Gallagher, Kevin G., Xie, Wei, Thelen, Jacob L., Badel, Andres F., Barton, John L., Cheng, Kevin J., Balsara, Nitash P., Moore, Jeffrey S., and Brushett, Fikile R. Wed . "An Investigation of the Ionic Conductivity and Species Crossover of Lithiated Nafion 117 in Nonaqueous Electrolytes". United States. doi:10.1149/2.03211601jes. https://www.osti.gov/servlets/purl/1474904.
@article{osti_1474904,
title = {An Investigation of the Ionic Conductivity and Species Crossover of Lithiated Nafion 117 in Nonaqueous Electrolytes},
author = {Su, Liang and Darling, Robert M. and Gallagher, Kevin G. and Xie, Wei and Thelen, Jacob L. and Badel, Andres F. and Barton, John L. and Cheng, Kevin J. and Balsara, Nitash P. and Moore, Jeffrey S. and Brushett, Fikile R.},
abstractNote = {Nonaqueous redox flow batteries are a fast-growing area of research and development motivated by the need to develop lowcost energy storage systems. The identification of a highly conductive, yet selective membrane, is of paramount importance to enabling such a technology. We report the swelling behavior, ionic conductivity, and species crossover of lithiated Nafion 117 membranes immersed in three nonaqueous electrolytes (PC, PC : EC, and DMSO). Our results show that solvent volume fraction within the membrane has the greatest effect on both conductivity and crossover. An approximate linear relationship between diffusive crossover of neutral redox species (ferrocene) and the ionic conductivity of membrane was observed. As a secondary effect, the charge on redox species modifies crossover rates in accordance with Donnan exclusion. The selectivity of membrane is derived mathematically and compared to experimental results reported here. The relatively low selectivity for lithiated Nafion 117 in nonaqueous conditions suggests that new membranes are required for competitive nonaqueous redox flow batteries to be realized. Potential design rules are suggested for the future membrane engineering work.},
doi = {10.1149/2.03211601jes},
journal = {Journal of the Electrochemical Society},
number = 1,
volume = 163,
place = {United States},
year = {2015},
month = {12}
}

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