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Title: Iron-iminopyridine complexes as charge carriers for non-aqueous redox flow battery applications

Abstract

Non-aqueous redox flow batteries (RFBs) have been gaining increased attention in the energy storage arena. Some of their attractive features include the promise for high energy densities, wider voltage windows compared to aqueous systems, as well as wider operating temperature ranges. One of the major challenges in the development of these systems is the lack of electroactive materials that can undergo reversible redox events within the larger potential window of organic solvents. In this paper, we present the design, synthesis, and measurement of electrochemical properties of some iron-based imine- and iminopyridine complexes as promising candidates for RFB applications. Synthesized complexes afforded three reversible redox couples over a ~3 V range. The redox events were also computationally explored and are in good agreement with experimental data. Theoretical calculations show that the redox event at the positive potential can be characterized as metal-centered event corresponding to Fe3+ → Fe2+ reduction, while the two redox events at negative potentials are associated with the consecutive reductions of iminopyridine or diimine moieties. This work has led to the identification of a promising anolyte material, [tris(imino)pyridine)Fe][OTf]2 (1), which is soluble in acetonitrile and is synthesized in two simple steps. This species shows outstanding performance when cycledmore » between 1.0 V and 2.35 V, with 93% coulombic efficiency, 84% energy efficiency, and a capacity decay rate of 0.61% per cycle at 5 mA cm–2. Further modifications to this kind of charge carrier may lead to the development of high energy density materials for grid scale energy storage applications.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Electricity (OE); USDOE Office of Science (SC)
OSTI Identifier:
1765877
Alternate Identifier(s):
OSTI ID: 1809848
Report Number(s):
LA-UR-20-28348
Journal ID: ISSN 2405-8297
Grant/Contract Number:  
89233218CNA000001; 20170046DR; 2018BU0048; 89233218NCA000001; 2022547; 2022548; 2022549; 2022550
Resource Type:
Accepted Manuscript
Journal Name:
Energy Storage Materials
Additional Journal Information:
Journal Volume: 37; Journal Issue: C; Journal ID: ISSN 2405-8297
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; inorganic and physical chemistry; organic chemistry; non-aqueous redox flow batteries; iron-imine complexes; charge carriers; renewable energy; energy storage

Citation Formats

Gordon, John Cameron, Sharma, Shikha, Andrade, Gabriel A., Maurya, Sandipkumar, Popov, Ivan Aleksandrovich, Batista, Enrique Ricardo, Davis, Benjamin L., Mukundan, Rangachary, Smythe, Nathan C., Tondreau, Aaron M., and Yang, Ping. Iron-iminopyridine complexes as charge carriers for non-aqueous redox flow battery applications. United States: N. p., 2021. Web. doi:10.1016/j.ensm.2021.01.035.
Gordon, John Cameron, Sharma, Shikha, Andrade, Gabriel A., Maurya, Sandipkumar, Popov, Ivan Aleksandrovich, Batista, Enrique Ricardo, Davis, Benjamin L., Mukundan, Rangachary, Smythe, Nathan C., Tondreau, Aaron M., & Yang, Ping. Iron-iminopyridine complexes as charge carriers for non-aqueous redox flow battery applications. United States. https://doi.org/10.1016/j.ensm.2021.01.035
Gordon, John Cameron, Sharma, Shikha, Andrade, Gabriel A., Maurya, Sandipkumar, Popov, Ivan Aleksandrovich, Batista, Enrique Ricardo, Davis, Benjamin L., Mukundan, Rangachary, Smythe, Nathan C., Tondreau, Aaron M., and Yang, Ping. Mon . "Iron-iminopyridine complexes as charge carriers for non-aqueous redox flow battery applications". United States. https://doi.org/10.1016/j.ensm.2021.01.035. https://www.osti.gov/servlets/purl/1765877.
@article{osti_1765877,
title = {Iron-iminopyridine complexes as charge carriers for non-aqueous redox flow battery applications},
author = {Gordon, John Cameron and Sharma, Shikha and Andrade, Gabriel A. and Maurya, Sandipkumar and Popov, Ivan Aleksandrovich and Batista, Enrique Ricardo and Davis, Benjamin L. and Mukundan, Rangachary and Smythe, Nathan C. and Tondreau, Aaron M. and Yang, Ping},
abstractNote = {Non-aqueous redox flow batteries (RFBs) have been gaining increased attention in the energy storage arena. Some of their attractive features include the promise for high energy densities, wider voltage windows compared to aqueous systems, as well as wider operating temperature ranges. One of the major challenges in the development of these systems is the lack of electroactive materials that can undergo reversible redox events within the larger potential window of organic solvents. In this paper, we present the design, synthesis, and measurement of electrochemical properties of some iron-based imine- and iminopyridine complexes as promising candidates for RFB applications. Synthesized complexes afforded three reversible redox couples over a ~3 V range. The redox events were also computationally explored and are in good agreement with experimental data. Theoretical calculations show that the redox event at the positive potential can be characterized as metal-centered event corresponding to Fe3+ → Fe2+ reduction, while the two redox events at negative potentials are associated with the consecutive reductions of iminopyridine or diimine moieties. This work has led to the identification of a promising anolyte material, [tris(imino)pyridine)Fe][OTf]2 (1), which is soluble in acetonitrile and is synthesized in two simple steps. This species shows outstanding performance when cycled between 1.0 V and 2.35 V, with 93% coulombic efficiency, 84% energy efficiency, and a capacity decay rate of 0.61% per cycle at 5 mA cm–2. Further modifications to this kind of charge carrier may lead to the development of high energy density materials for grid scale energy storage applications.},
doi = {10.1016/j.ensm.2021.01.035},
journal = {Energy Storage Materials},
number = C,
volume = 37,
place = {United States},
year = {Mon Feb 01 00:00:00 EST 2021},
month = {Mon Feb 01 00:00:00 EST 2021}
}

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