BF3-promoted electrochemical properties of quinoxaline in propylene carbonate

Carino, Emily V.; Diesendruck, Charles E.; Moore, Jeffrey S.; Curtiss, Larry A.; Assary, Rajeev S.; Brushett, Fikile R.

doi:10.1039/C5RA00137D

BF₃-promoted electrochemical properties of quinoxaline in propylene carbonate

Journal Article · Wed Feb 04 00:00:00 EST 2015 · RSC Advances

DOI:https://doi.org/10.1039/C5RA00137D· OSTI ID:1214332

Carino, Emily V. ^[1]; Diesendruck, Charles E. ^[2]; Moore, Jeffrey S. ^[2]; Curtiss, Larry A. ^[3]; Assary, Rajeev S. ^[3]; Brushett, Fikile R. ^[4]

Joint Center for Energy Storage Research (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering
Joint Center for Energy Storage Research (United States); Univ. of Illinois at Urbana Champaign, IL (United States). Dept. of Chemistry
Joint Center for Energy Storage Research (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Joint Center for Energy Storage Research (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering

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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1214332

Alternate ID(s):: OSTI ID: 1392126

Journal Information:: RSC Advances, Journal Name: RSC Advances Journal Issue: 24 Vol. 5; ISSN 2046-2069; ISSN RSCACL

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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