Electronic Structure Distortions in Chromium Chelates Impair Redox Kinetics in Flow Batteries

Thurston, Jonathan R.; White, Keith P.; Kudisch, Max; Iglesias, Luis Kitsu; Lorenzetti, Julia; Bernasconi, Francesco; Toney, Michael F.; Marshak, Michael P.; Reber, David

doi:10.1002/batt.202500250

Electronic Structure Distortions in Chromium Chelates Impair Redox Kinetics in Flow Batteries

Journal Article · Wed Apr 09 00:00:00 EDT 2025 · Batteries & Supercaps

DOI:https://doi.org/10.1002/batt.202500250· OSTI ID:2566773

Thurston, Jonathan R. ^[1]; White, Keith P. ^[1]; Kudisch, Max ^[2]; Iglesias, Luis Kitsu ^[1]; Lorenzetti, Julia ^[3]; Bernasconi, Francesco ^[4]; Toney, Michael F. ^[5]; Marshak, Michael P. ^[6]; ^[7]

Univ. of Colorado, Boulder, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Swiss Federal Laboratories for Materials Science and Technology (Empa), Dübendorf (Switzerland); Ecole Polytechnique Federale Lausanne (EPFL) (Switzerland)
Swiss Federal Laboratories for Materials Science and Technology (Empa), Dübendorf (Switzerland); Eidgenoessische Technische Hochschule (ETH), Zurich (Switzerland)
Univ. of Colorado, Boulder, CO (United States); Renewable and Sustainable Energy Inst. (RASEI), Boulder, CO (United States)
Univ. of Wyoming, Laramie, WY (United States)
Swiss Federal Laboratories for Materials Science and Technology (Empa), Dübendorf (Switzerland)

Aminopolycarboxylate chelates are emerging as a promising class of electrolyte materials for aqueous redox flow batteries, offering tunable redox potentials, solubility, and pH stability through careful selection of ligands and transition metal ions. Despite their potential, the impact of molecular structure modifications on the electronic and electrochemical properties of these chelates remains underexplored. Here, in this study, we examine how introducing a hydroxyl group, often employed for its solubilizing properties, to the backbone of CrPDTA, a reference chelate material, significantly changes the thermodynamics and kinetics of the chelate's redox process. We correlate changes in molecular and electronic structures to different electrochemical responses resulting from the hydroxyl addition and show that the introduction of this functional group leads to a distortion in the octahedral coordination of chromium. Furthermore, increased anisotropic spin density and nonintegral oxidation state changes in the Cr metal center result in a larger barrier for electron transfer in CrPDTA‐OH. It is demonstrated that preserving a hexacoordinate chelate structure across a broad pH range is crucial for efficient flow battery application and it is emphasized that ligand modifications must avoid distorting the octahedral coordination of the transition metal.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: National Science Foundation (NSF); Swiss National Science Foundation (SNSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC36-08GO28308; SC0012704; SC0019370

OSTI ID:: 2566773

Report Number(s):: NREL/JA--5900-91659

Journal Information:: Batteries & Supercaps, Journal Name: Batteries & Supercaps Journal Issue: 11 Vol. 8; ISSN 2566-6223

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Electronic Structure Distortions in Chromium Chelates Impair Redox Kinetics in Flow Batteries

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