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Title: BF3-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 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.

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 Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1214332
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: 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. https://doi.org/10.1039/C5RA00137D
Carino, Emily V., Diesendruck, Charles E., Moore, Jeffrey S., Curtiss, Larry A., Assary, Rajeev S., and Brushett, Fikile R. 2015. "BF3-promoted electrochemical properties of quinoxaline in propylene carbonate". United States. https://doi.org/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},
url = {https://www.osti.gov/biblio/1214332}, journal = {RSC Advances},
issn = {2046-2069},
number = 24,
volume = 5,
place = {United States},
year = {Wed Feb 04 00:00:00 EST 2015},
month = {Wed Feb 04 00:00:00 EST 2015}
}

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Cited by: 29 works
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Works referencing / citing this record:

Rechargeable organic–air redox flow batteries
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Crystal structure of 1,3-bis(2,3-dimethylquinoxalin-6-yl)benzene
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