Identifying and preventing degradation in flavin mononucleotide-based redox flow batteries via NMR and EPR spectroscopy

Abstract While aqueous organic redox flow batteries (RFBs) represent potential solutions to large-scale grid storage, their electrolytes suffer from short lifetimes due to rapid degradation. We show how an understanding of these degradation processes can be used to dramatically improve performance,...

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Main Authors: Dominic Hey, Rajesh B. Jethwa, Nadia L. Farag, Bernardine L. D. Rinkel, Evan Wenbo Zhao, Clare P. Grey
Format: Article
Language:English
Published: Nature Portfolio 2023-08-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-023-40649-4
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author Dominic Hey
Rajesh B. Jethwa
Nadia L. Farag
Bernardine L. D. Rinkel
Evan Wenbo Zhao
Clare P. Grey
author_facet Dominic Hey
Rajesh B. Jethwa
Nadia L. Farag
Bernardine L. D. Rinkel
Evan Wenbo Zhao
Clare P. Grey
author_sort Dominic Hey
collection DOAJ
description Abstract While aqueous organic redox flow batteries (RFBs) represent potential solutions to large-scale grid storage, their electrolytes suffer from short lifetimes due to rapid degradation. We show how an understanding of these degradation processes can be used to dramatically improve performance, as illustrated here via a detailed study of the redox-active biomolecule, flavin mononucleotide (FMN), a molecule readily derived from vitamin B2. Via in-situ nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) we identify FMN hydrolysis products and show that these give rise to the additional plateau seen during charging of an FMN-cyanoferrate battery. The redox reactions of the hydrolysis product are not reversible, but we demonstrate that capacity is still retained even after substantial hydrolysis, albeit with reduced voltaic efficiency, FMN acting as a redox mediator. Critically, we demonstrate that degradation is mitigated and battery efficiency is substantially improved by lowering the pH to 11. Furthermore, the addition of cheap electrolyte salts to tune the pH results in a dramatic increase in solubility (above 1 M), this systematic improvement of the flavin-based system bringing RFBs one step closer to commercial viability.
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spelling doaj.art-7329ab3954c3419ea83d11f62858737f2023-11-20T10:09:51ZengNature PortfolioNature Communications2041-17232023-08-0114111010.1038/s41467-023-40649-4Identifying and preventing degradation in flavin mononucleotide-based redox flow batteries via NMR and EPR spectroscopyDominic Hey0Rajesh B. Jethwa1Nadia L. Farag2Bernardine L. D. Rinkel3Evan Wenbo Zhao4Clare P. Grey5Yusuf Hamied Department of Chemistry, University of CambridgeYusuf Hamied Department of Chemistry, University of CambridgeYusuf Hamied Department of Chemistry, University of CambridgeYusuf Hamied Department of Chemistry, University of CambridgeYusuf Hamied Department of Chemistry, University of CambridgeYusuf Hamied Department of Chemistry, University of CambridgeAbstract While aqueous organic redox flow batteries (RFBs) represent potential solutions to large-scale grid storage, their electrolytes suffer from short lifetimes due to rapid degradation. We show how an understanding of these degradation processes can be used to dramatically improve performance, as illustrated here via a detailed study of the redox-active biomolecule, flavin mononucleotide (FMN), a molecule readily derived from vitamin B2. Via in-situ nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) we identify FMN hydrolysis products and show that these give rise to the additional plateau seen during charging of an FMN-cyanoferrate battery. The redox reactions of the hydrolysis product are not reversible, but we demonstrate that capacity is still retained even after substantial hydrolysis, albeit with reduced voltaic efficiency, FMN acting as a redox mediator. Critically, we demonstrate that degradation is mitigated and battery efficiency is substantially improved by lowering the pH to 11. Furthermore, the addition of cheap electrolyte salts to tune the pH results in a dramatic increase in solubility (above 1 M), this systematic improvement of the flavin-based system bringing RFBs one step closer to commercial viability.https://doi.org/10.1038/s41467-023-40649-4
spellingShingle Dominic Hey
Rajesh B. Jethwa
Nadia L. Farag
Bernardine L. D. Rinkel
Evan Wenbo Zhao
Clare P. Grey
Identifying and preventing degradation in flavin mononucleotide-based redox flow batteries via NMR and EPR spectroscopy
Nature Communications
title Identifying and preventing degradation in flavin mononucleotide-based redox flow batteries via NMR and EPR spectroscopy
title_full Identifying and preventing degradation in flavin mononucleotide-based redox flow batteries via NMR and EPR spectroscopy
title_fullStr Identifying and preventing degradation in flavin mononucleotide-based redox flow batteries via NMR and EPR spectroscopy
title_full_unstemmed Identifying and preventing degradation in flavin mononucleotide-based redox flow batteries via NMR and EPR spectroscopy
title_short Identifying and preventing degradation in flavin mononucleotide-based redox flow batteries via NMR and EPR spectroscopy
title_sort identifying and preventing degradation in flavin mononucleotide based redox flow batteries via nmr and epr spectroscopy
url https://doi.org/10.1038/s41467-023-40649-4
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