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membranes Article A Hydrogen-Bromate Flow Battery as a Rechargeable Chemical Power Source Natalia V. Kartashova 1,2,* , Dmitry V. Konev 3,4,* , Pavel A. Loktionov 2,3 , Artem T. Glazkov 2,4 , Olga A. Goncharova 3,4, Mikhail M. Petrov 2 , Anatoly E. Antipov 2 and Mikhail A. Vorotyntsev 4 1 2 3 4 * Correspondence: kartashova9natali@gmail.com (N.V.K.); dkfrvzh@yandex.ru (D.V.K.) Abstract: The hydrogen-bromate flow battery represents one of the promising variants for hybrid power sources. Its membrane-electrode assembly (MEA) combines a hydrogen gas diffusion anode and a porous flow-through cathode where bromate reduction takes place from its acidized aqueous solution: BrO3− + 6 H+ + 6 e− = Br− + 3 H2O (*). The process of electric current generation occurs on the basis of the overall reaction: 3 H2 + BrO3− = Br− + 3 H2O (**), which has been studied in previous publications. Until this work, it has been unknown whether this device is able to function as a rechargeable power source. This means that the bromide anion, Br−, should be electrooxidized into the bromate anion, BrO3−, in the course of the charging stage inside the same cell under strongly acidic conditions, while until now this process has only been carried out in neutral or alkaline solutions with specially designed anode materials. In this study, we have demonstrated that processes (*) and (**) can be performed in a cyclic manner, i.e., as a series of charge and discharge stages with the use of MEA: H2, Freidenberg H23C8 Pt-C/GP-IEM 103/Sigracet 39AA, HBr + H2SO4; square cross-section of 4 cm2 surface area, under an alternating galvanostatic mode at a current density of 75 mA/cm2. The coulombic, voltaic and energy efficiencies of the flow battery under a cyclic regime, as well as the absorption spectra of the catholyte, were measured during its operation. The total amount of Br-containing compounds penetrating through the membrane into the anode space was also determined. Keywords: crossover; flow battery; fuel cell; bromate anions reduction; bromide anions oxidation; redox mediator cycle 1. Introduction Rechargeable power sources operating on the principle of redox flow batteries (RFBs) are an object of unrelenting interest for the scientific community, as they represent one of the principal ways to reduce the cost of each unit of electric energy, 1 kWh, of large-scale energy storage [1–3]. Among most well-known systems of this type one can point to those based on iron [4,5], vanadium [6–10], zinc-halide [11,12] and lithium-iodide redox-mediator RFBs [13], sodium-sulfur (Na-S) [14], hybrid lithium-TEMPO [15] and hydrogen-bromine RFBs [1,15–17]. A specific feature of the H2-Br2 system is the hydrogen reaction which requires a platinum catalyst at the anode [1,15–17], which is poisoned by transmembrane crossover of Br-containing species from the cathode space [18–20] where the electrode reaction takes place: Br2 + 2 e− = 2 Br−. The transition from the bromine- to bromate-based power sources [20–22] provides a chance to reduce this danger. Owing to the cation-exchange type of separating membranes Faculty of Fundamental Physical and Chemical Engineering, Lomonosov Moscow State University, 119991 Moscow, Russia EMCPS Department, Mendeleev University of Chemical Technology of Russia, 125047 Moscow, Russia Federal Research Center of Problem of Chemical Physics and Medicinal Chemistry RAS, 142432 Chernogolovka, Russia Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 119071 Moscow, Russia Citation: Kartashova, N.V.; Konev, D.V.; Loktionov, P.A.; Glazkov, A.T.; Goncharova, O.A.; Petrov, M.M.; Antipov, A.E.; Vorotyntsev, M.A. A Hydrogen-Bromate Flow Battery as a Rechargeable Chemical Power Source. Membranes 2022, 12, 1228. https://doi.org/10.3390/ membranes12121228 Academic Editor: Byungchan Bae Received: 7 October 2022 Accepted: 1 December 2022 Published: 5 December 2022 Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affil- iations. Copyright: © 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/). Membranes 2022, 12, 1228. https://doi.org/10.3390/membranes12121228 https://www.mdpi.com/journal/membranesPDF Image | Hydrogen-Bromate Flow Battery
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