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

Title: BF 3-promoted electrochemical properties of quinoxaline in propylene carbonate

Abstract

Electrochemical and density functional studies demonstrate that coordination of electrolyte constituents to quinoxalines modulates their electrochemical properties. Quinoxalines are shown to be electrochemically inactive in most electrolytes in propylene carbonate, yet the predicted reduction potential is shown to match computational estimates in acetonitrile. We find that in the presence of LiBF 4 and trace water, an adduct is formed between quinoxaline and the Lewis acid BF3, which then displays electrochemical activity at 1–1.5 V higher than prior observations of quinoxaline electrochemistry in non-aqueous media. Direct synthesis and testing of a bis-BF 3 quinoxaline complex further validates the assignment of the electrochemically active species, presenting up to a ~26-fold improvement in charging capacity, demonstrating the advantages of this adduct over unmodified quinoxaline in LiBF 4-based electrolyte. The use of Lewis acids to effectively “turn on” the electrochemical activity of organic molecules may lead to the development of new active material classes for energy storage applications.

Authors:
 [1];  [2];  [2];  [3];  [3];  [4]
  1. Joint Center for Energy Storage Research (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering
  2. Joint Center for Energy Storage Research (United States); Univ. of Illinois at Urbana Champaign, IL (United States). Dept. of Chemistry
  3. Joint Center for Energy Storage Research (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  4. Joint Center for Energy Storage Research (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1214332
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
RSC Advances
Additional Journal Information:
Journal Volume: 5; Journal Issue: 24; Journal ID: ISSN 2046-2069
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Carino, Emily V., Diesendruck, Charles E., Moore, Jeffrey S., Curtiss, Larry A., Assary, Rajeev S., and Brushett, Fikile R. BF3-promoted electrochemical properties of quinoxaline in propylene carbonate. United States: N. p., 2015. Web. doi:10.1039/C5RA00137D.
Carino, Emily V., Diesendruck, Charles E., Moore, Jeffrey S., Curtiss, Larry A., Assary, Rajeev S., & Brushett, Fikile R. BF3-promoted electrochemical properties of quinoxaline in propylene carbonate. United States. doi:10.1039/C5RA00137D.
Carino, Emily V., Diesendruck, Charles E., Moore, Jeffrey S., Curtiss, Larry A., Assary, Rajeev S., and Brushett, Fikile R. Wed . "BF3-promoted electrochemical properties of quinoxaline in propylene carbonate". United States. doi:10.1039/C5RA00137D. https://www.osti.gov/servlets/purl/1214332.
@article{osti_1214332,
title = {BF3-promoted electrochemical properties of quinoxaline in propylene carbonate},
author = {Carino, Emily V. and Diesendruck, Charles E. and Moore, Jeffrey S. and Curtiss, Larry A. and Assary, Rajeev S. and Brushett, Fikile R.},
abstractNote = {Electrochemical and density functional studies demonstrate that coordination of electrolyte constituents to quinoxalines modulates their electrochemical properties. Quinoxalines are shown to be electrochemically inactive in most electrolytes in propylene carbonate, yet the predicted reduction potential is shown to match computational estimates in acetonitrile. We find that in the presence of LiBF4 and trace water, an adduct is formed between quinoxaline and the Lewis acid BF3, which then displays electrochemical activity at 1–1.5 V higher than prior observations of quinoxaline electrochemistry in non-aqueous media. Direct synthesis and testing of a bis-BF3 quinoxaline complex further validates the assignment of the electrochemically active species, presenting up to a ~26-fold improvement in charging capacity, demonstrating the advantages of this adduct over unmodified quinoxaline in LiBF4-based electrolyte. The use of Lewis acids to effectively “turn on” the electrochemical activity of organic molecules may lead to the development of new active material classes for energy storage applications.},
doi = {10.1039/C5RA00137D},
journal = {RSC Advances},
number = 24,
volume = 5,
place = {United States},
year = {2015},
month = {2}
}

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

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Progress in Flow Battery Research and Development
journal, June 2011

  • Skyllas-Kazacos, M.; Chakrabarti, M. H.; Hajimolana, S. A.
  • Journal of The Electrochemical Society, Vol. 158, Issue 8, p. R55-R79
  • DOI: 10.1149/1.3599565

Electrochemical Energy Storage for Green Grid
journal, May 2011

  • Yang, Zhenguo; Zhang, Jianlu; Kintner-Meyer, Michael C. W.
  • Chemical Reviews, Vol. 111, Issue 5, p. 3577-3613
  • DOI: 10.1021/cr100290v

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
journal, May 2009

  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396
  • DOI: 10.1021/jp810292n

Electrochemical Properties of an All-Organic Redox Flow Battery Using 2,2,6,6-Tetramethyl-1-Piperidinyloxy and N-Methylphthalimide
journal, January 2011

  • Li, Zhen; Li, Sha; Liu, Suqin
  • Electrochemical and Solid-State Letters, Vol. 14, Issue 12, p. A171-A173
  • DOI: 10.1149/2.012112esl

Redox flow batteries a review
journal, September 2011

  • Weber, Adam Z.; Mench, Matthew M.; Meyers, Jeremy P.
  • Journal of Applied Electrochemistry, Vol. 41, Issue 10, p. 1137-1164
  • DOI: 10.1007/s10800-011-0348-2

Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004


Non-aqueous vanadium acetylacetonate electrolyte for redox flow batteries
journal, December 2009

  • Liu, Qinghua; Sleightholme, Alice E. S.; Shinkle, Aaron A.
  • Electrochemistry Communications, Vol. 11, Issue 12, p. 2312-2315
  • DOI: 10.1016/j.elecom.2009.10.006

An All-Organic Non-aqueous Lithium-Ion Redox Flow Battery
journal, June 2012

  • Brushett, Fikile R.; Vaughey, John T.; Jansen, Andrew N.
  • Advanced Energy Materials, Vol. 2, Issue 11, p. 1390-1396
  • DOI: 10.1002/aenm.201200322