Hyperbranched TEMPO-based polymers as catholytes for redox flow battery applications.

Autor:	Ehtiati K; Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena Humboldtstrasse 10 Jena 07743 Germany ulrich.schubert@uni-jena.de.; Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller University Jena Philosophenweg 7a Jena 07743 Germany., Anufriev I; Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena Humboldtstrasse 10 Jena 07743 Germany ulrich.schubert@uni-jena.de.; Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena Philosophenweg 7 Jena 07743 Germany., Friebe C; Helmholtz Institute for Polymers in Energy Applications Jena (HIPOLE Jena) Lessingstr. 12 - 14 07743 Jena Germany., Volodin IA; Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena Humboldtstrasse 10 Jena 07743 Germany ulrich.schubert@uni-jena.de.; Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller University Jena Philosophenweg 7a Jena 07743 Germany., Stolze C; Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena Humboldtstrasse 10 Jena 07743 Germany ulrich.schubert@uni-jena.de.; Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller University Jena Philosophenweg 7a Jena 07743 Germany., Muench S; Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena Humboldtstrasse 10 Jena 07743 Germany ulrich.schubert@uni-jena.de.; Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller University Jena Philosophenweg 7a Jena 07743 Germany., Festag G; Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena Humboldtstrasse 10 Jena 07743 Germany ulrich.schubert@uni-jena.de.; Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena Philosophenweg 7 Jena 07743 Germany., Nischang I; Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena Humboldtstrasse 10 Jena 07743 Germany ulrich.schubert@uni-jena.de.; Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller University Jena Philosophenweg 7a Jena 07743 Germany.; Helmholtz Institute for Polymers in Energy Applications Jena (HIPOLE Jena) Lessingstr. 12 - 14 07743 Jena Germany.; Helmholtz-Zentrum Berlin für Materialien und Energie GmbH (HZB) Hahn-Meitner-Platz 1 14109 Berlin Germany., Hager MD; Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena Humboldtstrasse 10 Jena 07743 Germany ulrich.schubert@uni-jena.de.; Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller University Jena Philosophenweg 7a Jena 07743 Germany.; Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena Philosophenweg 7 Jena 07743 Germany.; Helmholtz Institute for Polymers in Energy Applications Jena (HIPOLE Jena) Lessingstr. 12 - 14 07743 Jena Germany., Schubert US; Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena Humboldtstrasse 10 Jena 07743 Germany ulrich.schubert@uni-jena.de.; Center for Energy and Environmental Chemistry Jena (CEEC Jena), Friedrich Schiller University Jena Philosophenweg 7a Jena 07743 Germany.; Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena Philosophenweg 7 Jena 07743 Germany.; Helmholtz Institute for Polymers in Energy Applications Jena (HIPOLE Jena) Lessingstr. 12 - 14 07743 Jena Germany.
Jazyk:	angličtina
Zdroj:	RSC advances [RSC Adv] 2024 Oct 18; Vol. 14 (45), pp. 32893-32910. Date of Electronic Publication: 2024 Oct 18 (Print Publication: 2024).
DOI:	10.1039/d4ra03925d
Abstrakt:	Application of redox-active polymers (RAPs) in redox flow batteries (RFBs) can potentially reduce the stack cost through substitution of costly ion-exchange membranes by cheap size-exclusion membranes. However, intermolecular interactions of polymer molecules, i.e. , entanglements, particularly in concentrated solutions, result in relatively high electrolyte viscosities. Furthermore, the large size and limited mobility of polymers lead to slow diffusion and more sluggish heterogeneous electron transfer rates compared to quickly diffusing small molecules. Although a number of RAPs with varying electrolyte viscosities have been reported in the literature, the relation between the RAP structure and the hydrodynamic properties has not been thoroughly investigated. Herein, hyperbranched 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO)-based polymers intended for application as low-viscosity catholytes for RFBs are presented and the influence of the structure and the molar mass distribution on the hydrodynamic properties is investigated. A new synthesis approach for TEMPO-based polymers is established based on step-growth polymerization of a TEMPO-containing monomer using an aza-Michael addition followed by a postpolymerization modification to improve solubility in aqueous solutions. The compact structure of hyperbranched polymers was demonstrated using size-exclusion chromatography (SEC) with viscometric detection and the optimum molar mass was found based on the results of viscometric and crossover investigations. The resulting RAP revealed a viscosity of around 21 mPas at a concentration corresponding to around 1 M TEMPO-containing units, according to the calculated mass of the repeating unit, showing potential for high capacity polymer-based catholytes for RFBs. Nevertheless, possible partial deactivation of TEMPO units lowered the active TEMPO concentration of the hyperbranched RAPs. A faster diffusion and higher charge transfer rate were observed for the hyperbranched polymer compared to the previously reported linear polymers. However, in RFB tests, a poor performance was observed, which is attributed to the side reactions of the oxidized TEMPO moieties. Finally, pathways for overcoming the main remaining challenges, i.e. , high loss of material during dialysis as an indication of being prone to crossover, the partial deactivation of TEMPO moieties, and the subsequent side reactions under battery conditions, are suggested. Competing Interests: There are no conflicts to declare. (This journal is © The Royal Society of Chemistry.)
Databáze:	MEDLINE
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