skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Enhanced Stability of the Carba- closo-dodecaborate Anion for High-Voltage Battery Electrolytes through Rational Design

Abstract

Future energy applications rely on our ability to tune liquid intermolecular interactions and achieve designer electrolytes with highly optimized properties. Here, we demonstrate rational, combined experimental–computational design of a new carba- closo-dodecaborate-based salt with enhanced anodic stability for Mg energy storage applications. We first establish, through a careful examination using a range of solvents, the anodic oxidation of a parent anion, the carba-closo-dodecaborate anion at 4.6 V vs Mg 0/2+ (2.0 vs Fc 0/+), a value lower than that projected for this anion in organic solvent-based electrolytes and lower than weakly associating bis(trifluoromethylsulfonyl)imide and tetrafluoroborate anions. Solvents such as acetonitrile, 3-methylsulfolane, and 1,1,1,3,3,3-hexafluoroisopropanol are shown to enable the direct measurement of carba- closo-dodecaborate oxidation, where the resultant neutral radical drives passive film formation on the electrode. Second, we employ computational screening to evaluate the impact of functionalization of the parent anion on its stability and find that replacement of the carbon-vertex proton with a more electronegative fluorine or trifluoromethyl ligand increases the oxidative stability and decreases the contact-ion pair formation energy while maintaining reductive stability. This predicted expansion of the electrochemical window for fluorocarba- closo-dodecaborate is experimentally validated. Future work includes evaluation of the viability of these derivative anions asmore » efficient and stable carriers for energy storage as a function of the ionic transport through the resulting surface films formed on candidate cathodes.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [3];  [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Materials, Physical and Chemical Sciences Center
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Technologies Division
  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); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Technologies Division; Univ. of California, Berkeley, CA (United States). Dept. of Materials Science
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1466987
Report Number(s):
SAND-2018-6418J
Journal ID: ISSN 0002-7863; 664406
Grant/Contract Number:  
AC04-94AL85000; NA0003525
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 35; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE; Magnesium; Multivalent; Electrochemistry; Weakly Coordinating; Electrochemical Window; Carborane, Sulfone; Glyme

Citation Formats

Hahn, Nathan T., Seguin, Trevor J., Lau, Ka-Cheong, Liao, Chen, Ingram, Brian J., Persson, Kristin A., and Zavadil, Kevin R. Enhanced Stability of the Carba-closo-dodecaborate Anion for High-Voltage Battery Electrolytes through Rational Design. United States: N. p., 2018. Web. doi:10.1021/jacs.8b05967.
Hahn, Nathan T., Seguin, Trevor J., Lau, Ka-Cheong, Liao, Chen, Ingram, Brian J., Persson, Kristin A., & Zavadil, Kevin R. Enhanced Stability of the Carba-closo-dodecaborate Anion for High-Voltage Battery Electrolytes through Rational Design. United States. doi:10.1021/jacs.8b05967.
Hahn, Nathan T., Seguin, Trevor J., Lau, Ka-Cheong, Liao, Chen, Ingram, Brian J., Persson, Kristin A., and Zavadil, Kevin R. Mon . "Enhanced Stability of the Carba-closo-dodecaborate Anion for High-Voltage Battery Electrolytes through Rational Design". United States. doi:10.1021/jacs.8b05967. https://www.osti.gov/servlets/purl/1466987.
@article{osti_1466987,
title = {Enhanced Stability of the Carba-closo-dodecaborate Anion for High-Voltage Battery Electrolytes through Rational Design},
author = {Hahn, Nathan T. and Seguin, Trevor J. and Lau, Ka-Cheong and Liao, Chen and Ingram, Brian J. and Persson, Kristin A. and Zavadil, Kevin R.},
abstractNote = {Future energy applications rely on our ability to tune liquid intermolecular interactions and achieve designer electrolytes with highly optimized properties. Here, we demonstrate rational, combined experimental–computational design of a new carba-closo-dodecaborate-based salt with enhanced anodic stability for Mg energy storage applications. We first establish, through a careful examination using a range of solvents, the anodic oxidation of a parent anion, the carba-closo-dodecaborate anion at 4.6 V vs Mg0/2+ (2.0 vs Fc0/+), a value lower than that projected for this anion in organic solvent-based electrolytes and lower than weakly associating bis(trifluoromethylsulfonyl)imide and tetrafluoroborate anions. Solvents such as acetonitrile, 3-methylsulfolane, and 1,1,1,3,3,3-hexafluoroisopropanol are shown to enable the direct measurement of carba-closo-dodecaborate oxidation, where the resultant neutral radical drives passive film formation on the electrode. Second, we employ computational screening to evaluate the impact of functionalization of the parent anion on its stability and find that replacement of the carbon-vertex proton with a more electronegative fluorine or trifluoromethyl ligand increases the oxidative stability and decreases the contact-ion pair formation energy while maintaining reductive stability. This predicted expansion of the electrochemical window for fluorocarba-closo-dodecaborate is experimentally validated. Future work includes evaluation of the viability of these derivative anions as efficient and stable carriers for energy storage as a function of the ionic transport through the resulting surface films formed on candidate cathodes.},
doi = {10.1021/jacs.8b05967},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 35,
volume = 140,
place = {United States},
year = {2018},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Save / Share: