Theoretical and Experimental Investigation of Functionalized Cyanopyridines Yield an Anolyte with an Extremely Low Reduction Potential for Nonaqueous Redox Flow Batteries

Vaid, Thomas P.; Cook, Monique E.; Scott, Jessica D.; Borjesson Carazo, Marino; Ruchti, Jonathan; Minteer, Shelley D.; Sigman, Matthew S.; McNeil, Anne J.; Sanford, Melanie S.

doi:10.1002/chem.202202147

Theoretical and Experimental Investigation of Functionalized Cyanopyridines Yield an Anolyte with an Extremely Low Reduction Potential for Nonaqueous Redox Flow Batteries

Journal Article · Thu Oct 27 00:00:00 EDT 2022 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.202202147· OSTI ID:1894972

^[1]; Cook, Monique E. ^[1]; Scott, Jessica D. ^[1]; Borjesson Carazo, Marino ^[2]; Ruchti, Jonathan ^[3]; Minteer, Shelley D. ^[3]; Sigman, Matthew S. ^[3]; McNeil, Anne J. ^[4]; ^[1]

Joint Center for Energy Storage Research 9700 S. Cass Avenue Argonne, Illinois 60439 USA, Department of Chemistry University of Michigan 930 North University Avenue Ann Arbor, Michigan 48109 USA
Joint Center for Energy Storage Research 9700 S. Cass Avenue Argonne, Illinois 60439 USA, Institute of Chemical Research of Catalonia (ICIQ) The Barcelona Institute of Science and Technology Av. Països Catalans 16 43007 Tarragona Spain
Joint Center for Energy Storage Research 9700 S. Cass Avenue Argonne, Illinois 60439 USA, Department of Chemistry University of Utah 315 South 1400 East Salt Lake City, Utah 84112 USA
Joint Center for Energy Storage Research 9700 S. Cass Avenue Argonne, Illinois 60439 USA, Department of Chemistry University of Michigan 930 North University Avenue Ann Arbor, Michigan 48109 USA, Macromolecular Science and Engineering Program University of Michigan Ann Arbor, Michigan 48109 USA

Abstract

Cyanopyridines and cyanophenylpyridines were investigated as anolytes for nonaqueous redox flow batteries (RFBs). The three isomers of cyanopyridine are reduced at potentials of −2.2 V or lower vs. ferrocene ^+/0 (Fc ^+/0 ), but the 3‐CNPy⋅ ⁻ radical anion forms a sigma‐dimer that is re‐oxidized at E ≈−1.1 V, which would lead to poor voltaic efficiency in a RFB. Bulk electrochemical charge‐discharge cycling of the cyanopyridines in acetonitrile and 0.50 M [NBu ₄ ][PF ₆ ] shows that 2‐CNPy and 4‐CNPy lose capacity quickly under these conditions, due to irreversible chemical reaction/decomposition of the radical anions. Density‐functional theory (DFT) calculations indicated that adding a phenyl group to the cyanopyridines would, for some isomers, limit dimerization and improve the stability of the radical anions, while shifting their E _1/2 only about +0.10 V relative to the parent cyanopyridines. Among the cyanophenylpyridines, 3‐CN‐6‐PhPy and 3‐CN‐4‐PhPy are the most promising as anolytes. They exhibit reversible reductions at E _1/2 =−2.19 and −2.22 V vs. ferrocene ^+/0 , respectively, and retain about half of their capacity after 30 bulk charge‐discharge cycles. An improved version of 3‐CN‐6‐PhPy with three methyl groups (3‐cyano‐4‐methyl‐6‐(3,5‐dimethylphenyl)pyridine) has an extremely low reduction potential of −2.50 V vs. Fc ^+/0 (the lowest reported for a nonaqueous RFB anolyte) and loses only 0.21 % of capacity per cycle during charge‐discharge cycling in acetonitrile.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)

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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1894972

Alternate ID(s):: OSTI ID: 2423769
OSTI ID: 1905661

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 70 Vol. 28; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (30)

Die Chemie der Redox-Flow-Batterien Noack, Jens; Roznyatovskaya, Nataliya; Herr, Tatjana Angewandte Chemie, Vol. 127, Issue 34 https://doi.org/10.1002/ange.201410823	journal	June 2015
Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery Wei, Xiaoliang; Xu, Wu; Huang, Jinhua Angewandte Chemie, Vol. 127, Issue 30 https://doi.org/10.1002/ange.201501443	journal	April 2015
Redox-Flow-Batterien: von metallbasierten zu organischen Aktivmaterialien Winsberg, Jan; Hagemann, Tino; Janoschka, Tobias Angewandte Chemie, Vol. 129, Issue 3 https://doi.org/10.1002/ange.201604925	journal	November 2016
The Chemistry of Redox-Flow Batteries Noack, Jens; Roznyatovskaya, Nataliya; Herr, Tatjana Angewandte Chemie International Edition, Vol. 54, Issue 34 https://doi.org/10.1002/anie.201410823	journal	June 2015
Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery Wei, Xiaoliang; Xu, Wu; Huang, Jinhua Angewandte Chemie International Edition, Vol. 54, Issue 30 https://doi.org/10.1002/anie.201501443	journal	April 2015
Redox-Flow Batteries: From Metals to Organic Redox-Active Materials Winsberg, Jan; Hagemann, Tino; Janoschka, Tobias Angewandte Chemie International Edition, Vol. 56, Issue 3 https://doi.org/10.1002/anie.201604925	journal	November 2016
Cathodic reductions of cyanopyridines in liquid ammonia Brown, O. R.; Butterfield, R. J. Electrochimica Acta, Vol. 27, Issue 11 https://doi.org/10.1016/0013-4686(82)80093-5	journal	November 1982
Heterogeneous electron transfer kinetics for a variety of organic electrode reactions at the mercury-acetonitrile interface using either tetraethylammonium perchlorate or tetraheptylammonium perchlorate electrolyte Petersen, Ralph A.; Evans, Dennis H. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 222, Issue 1-2 https://doi.org/10.1016/0022-0728(87)80282-6	journal	May 1987
Conversion constants for redox potentials measured versus different reference electrodes in acetonitrile solutions at 25°C Pavlishchuk, Vitaly V.; Addison, Anthony W. Inorganica Chimica Acta, Vol. 298, Issue 1 https://doi.org/10.1016/S0020-1693(99)00407-7	journal	January 2000
The electrochemical reduction of cyanopyridines—A general mechanism Volke, J.; Skála, V. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 36, Issue 2 https://doi.org/10.1016/S0022-0728(72)80260-2	journal	May 1972
Highly Concentrated Phthalimide-Based Anolytes for Organic Redox Flow Batteries with Enhanced Reversibility Zhang, Changkun; Niu, Zhihui; Ding, Yu Chem, Vol. 4, Issue 12 https://doi.org/10.1016/j.chempr.2018.08.024	journal	December 2018
Recent advances in molecular engineering of redox active organic molecules for nonaqueous flow batteries Kowalski, Jeffrey A.; Su, Liang; Milshtein, Jarrod D. Current Opinion in Chemical Engineering, Vol. 13 https://doi.org/10.1016/j.coche.2016.08.002	journal	August 2016
Reversible dimerization of anion radicals: Studies of two cyanopyridines Macías-Ruvalcaba, Norma A.; Evans, Dennis H. Journal of Electroanalytical Chemistry, Vol. 660, Issue 2 https://doi.org/10.1016/j.jelechem.2010.07.019	journal	September 2011
Recent developments in organic redox flow batteries: A critical review Leung, P.; Shah, A. A.; Sanz, L. Journal of Power Sources, Vol. 360 https://doi.org/10.1016/j.jpowsour.2017.05.057	journal	August 2017
Tailoring Two-Electron-Donating Phenothiazines To Enable High-Concentration Redox Electrolytes for Use in Nonaqueous Redox Flow Batteries Attanayake, N. Harsha; Kowalski, Jeffrey A.; Greco, Katharine V. Chemistry of Materials, Vol. 31, Issue 12 https://doi.org/10.1021/acs.chemmater.8b04770	journal	May 2019
All-Liquid Electroactive Materials for High Energy Density Organic Flow Battery Xing, Xueqi; Liu, Qinghua; Xu, Wenqiang ACS Applied Energy Materials, Vol. 2, Issue 4 https://doi.org/10.1021/acsaem.8b01874	journal	February 2019
High-Performance Oligomeric Catholytes for Effective Macromolecular Separation in Nonaqueous Redox Flow Batteries Hendriks, Koen H.; Robinson, Sophia G.; Braten, Miles N. ACS Central Science, Vol. 4, Issue 2 https://doi.org/10.1021/acscentsci.7b00544	journal	January 2018
“Wine-Dark Sea” in an Organic Flow Battery: Storing Negative Charge in 2,1,3-Benzothiadiazole Radicals Leads to Improved Cyclability Duan, Wentao; Huang, Jinhua; Kowalski, Jeffrey A. ACS Energy Letters, Vol. 2, Issue 5 https://doi.org/10.1021/acsenergylett.7b00261	journal	April 2017
Flow Batteries: Current Status and Trends Soloveichik, Grigorii L. Chemical Reviews, Vol. 115, Issue 20 https://doi.org/10.1021/cr500720t	journal	September 2015
Electrochemistry of organic redox liquids. Reduction of 4-cyanopyridine Morris, Rael B.; Fischer, Kurt F.; White, Henry S. The Journal of Physical Chemistry, Vol. 92, Issue 18 https://doi.org/10.1021/j100329a048	journal	September 1988
Electron Spin Resonance of Electrolytically Generated Nitrile Radicals Rieger, Philip H.; Bernal, Ivan.; Reinmuth, William H. Journal of the American Chemical Society, Vol. 85, Issue 6 https://doi.org/10.1021/ja00889a010	journal	March 1963
Physical Organic Approach to Persistent, Cyclable, Low-Potential Electrolytes for Flow Battery Applications Sevov, Christo S.; Hickey, David P.; Cook, Monique E. Journal of the American Chemical Society, Vol. 139, Issue 8 https://doi.org/10.1021/jacs.7b00147	journal	February 2017
Developing a Predictive Solubility Model for Monomeric and Oligomeric Cyclopropenium-Based Flow Battery Catholytes Robinson, Sophia G.; Yan, Yichao; Hendriks, Koen H. Journal of the American Chemical Society, Vol. 141, Issue 26 https://doi.org/10.1021/jacs.9b04270	journal	May 2019
Mechanism-Based Design of a High-Potential Catholyte Enables a 3.2 V All-Organic Nonaqueous Redox Flow Battery Yan, Yichao; Robinson, Sophia G.; Sigman, Matthew S. Journal of the American Chemical Society, Vol. 141, Issue 38 https://doi.org/10.1021/jacs.9b07345	journal	September 2019
Static Dielectric Constants of Acetonitrile/Water Mixtures at Different Temperatures and Debye−Hückel A and a ₀ B Parameters for Activity Coefficients Gagliardi, Leonardo G.; Castells, Cecilia B.; Ràfols, Clara Journal of Chemical & Engineering Data, Vol. 52, Issue 3 https://doi.org/10.1021/je700055p	journal	May 2007
Expanding and Testing a Computational Method for Predicting the Ground State Reduction Potentials of Organic Molecules on the Basis of Empirical Correlation to Experiment Lynch, Eugene J.; Speelman, Amy L.; Curry, Bryce A. The Journal of Organic Chemistry, Vol. 77, Issue 15 https://doi.org/10.1021/jo300853k	journal	July 2012
Efficient Computational Methods for Accurately Predicting Reduction Potentials of Organic Molecules Speelman, Amy L.; Gillmore, Jason G. The Journal of Physical Chemistry A, Vol. 112, Issue 25 https://doi.org/10.1021/jp800782e	journal	June 2008
Pathways to low-cost electrochemical energy storage: a comparison of aqueous and nonaqueous flow batteries Darling, Robert M.; Gallagher, Kevin G.; Kowalski, Jeffrey A. Energy & Environmental Science, Vol. 7, Issue 11, p. 3459-3477 https://doi.org/10.1039/C4EE02158D	journal	January 2014
Advances in flow batteries promise cheap backup power Service, Robert F. Science, Vol. 362, Issue 6414 https://doi.org/10.1126/science.362.6414.508	journal	November 2018
Electrochemical Properties of Organic Liquid Electrolytes Based on Quaternary Onium Salts for Electrical Double-Layer Capacitors Ue, Makoto Journal of The Electrochemical Society, Vol. 141, Issue 11 https://doi.org/10.1149/1.2059270	journal	January 1994

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