[4]Helicenium Ion as Bipolar Redox Material for Symmetrical Fully Organic Pole-less Redox Flow Battery

07 November 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Long duration storage batteries such as Redox Flow Batteries (RFBs) are promising storage system to address the energy storage requirement that our society will require in the years to come. Recent effort has been focused on the development of metal free and high energy density system such as all-organic non-aqueous redox flow batteries (NAORFBs). However high-voltage NAORFBs currently use distinct anolytes and catholytes, which are separated by a membrane sensitive to osmotic pressure. This configuration results in permanent capacity and energy density fading rapidly with time. As an elegant solution, symmetric organic redox flow batteries (SORFB) have been proposed to address this issue. We recently reported the use of dimethoxyquinacridiniums (DMQA+) ions as efficient bipolar redox molecule (BRM) in static H-cell conditions. Herein, we are reporting the use of dimethoxyquinacridinium (DMQA+) ion, with a Egap of 2.1V and a theoretical energy density (Ed) to 14.9 Wh/L in CH3CN, as a bipolar redox molecule (BRM) in a full in flow RFB prototype and its ability to operate under polarity reversal. Essential kinetic properties of this molecule were assessed by cyclic voltammetry and correlated to DFT calculation. Its stability has been evaluated in static H-cell at two different concentration and then in full SORFB prototype. Although the coulombic and energy efficiency metrics were moderate, this pegylated DMQA+ exhibited a capacity retention of over 99.99%, and the property of operating under polarity inversion making it highly attractive for grid-scale long lifespan energy storage applications.

Keywords

Bipolar molecules
Symmetrical organic RFB
Helical carbocations
poleless RFB
organic electrolyte

Supplementary materials

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Supporting Information
Description
Experimental details; NMR spectra; Single X-ray diffraction; Electrochemical Investigations details; cell architectures; UV-Visible plot and max concentration; DFT SOMO-LUMO and calculated solvation free energy; and SORFBs cycling data.
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