A Nitroxide Containing Organic Molecule in a Deep Eutectic Solvent for Flow Battery Applications

Sinclair, Nicholas S.; Poe, Derrick; Savinell, Robert F.; Maginn, Edward J.; Wainright, Jesse S.

doi:10.1149/1945-7111/abe28a

Title: A Nitroxide Containing Organic Molecule in a Deep Eutectic Solvent for Flow Battery Applications

Journal Article · Fri Feb 12 00:00:00 EST 2021 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/1945-7111/abe28a· OSTI ID:1832966

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The nitroxide radical redox organic molecule, 2-phenyl-4,4,5,5-tetrame- thylimidazoline-1-oxyl-3-oxide (PTIO), was investigated for the first time in a deep eutectic solvent (DES)-like system consisting of a 1:4 molar ratio of choline chloride and ethylene glycol (Ch1EG4) as a redox flow battery electrolyte. PTIO is a single molecule with three oxidation states, and can provide both positive and negative redox couples for a flow battery. A flow battery using the PTIO/Ch1EG4 electrolyte demonstrated nearly 50% round trip efficiency with an approximately 1 V open circuit potential. Inefficiencies were primarily due to membrane resistance which can be significantly lowered with increased temperature. While PTIO appears stable over short periods (hours), the oxidized form is not stable in the DES-like electrolyte over longer times. Molecular modeling was performed to investigate the relative stability of PTIO in DES as compared to the previously studied 4-hydroxy-TEMPO (4HT). It was found that the oxoammonium cation 4HT ⁺ exhibits a noticeably larger nucleophilic reactive cloud as compared to PTIO ⁺ , indicating a higher reactivity. This method to predict stability of the oxoammonium cation shows promise to inform the design and synthesis of promising redox systems based on nitroxide radicals in DES electrolytes to identify new chemistries for large scale energy storage.

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Research Organization:: Case Western Reserve Univ., Cleveland, OH (United States)

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

Grant/Contract Number:: SC0019409

OSTI ID:: 1832966

Alternate ID(s):: OSTI ID: 1808449

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Vol. 168 Journal Issue: 2; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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