Cycle behaviour of hydrogen bromine redox flow battery cells with bromine complexing agents

Küttinger, Michael; Brunetaud, Ruben; Włodarczyk, Jakub K.; Fischer, P.; Tübke, Jens

doi:10.1016/j.jpowsour.2021.229820

Cited by 21 publications

(16 citation statements)

References 56 publications

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“…Electrolytic conductivities of the aqueous electrolytes of 1-alkylpyridin-1-ium BCAs and 1-alkyl-3-methylimidazol-1-ium BCAs electrolyte at various SoC are determined at θ = 23 ± 1 °C in a conductivity cell by potentiostatic impedance spectroscopy. The cell constant is determined in a 1 M KCl aqueous solution at θ = 23 ± 1 °C with κ (1 M KCl at θ = 23 °C) = 103.9 mS cm − 1 (calculated from [ 85 ]). A detailed description can be found in the ESI.…”

Section: Methodsmentioning

confidence: 99%

Systematic Study of Quaternary Ammonium Cations for Bromine Sequestering Application in High Energy Density Electrolytes for Hydrogen Bromine Redox Flow Batteries

et al. 2021

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Bromine complexing agents (BCAs) are used to reduce the vapor pressure of bromine in the aqueous electrolytes of bromine flow batteries. BCAs bind hazardous, volatile bromine by forming a second, heavy liquid fused salt. The properties of BCAs in a strongly acidic bromine electrolyte are largely unexplored. A total of 38 different quaternary ammonium halides are investigated ex situ regarding their properties and applicability in bromine electrolytes as BCAs. The focus is on the development of safe and performant HBr/Br2/H2O electrolytes with a theoretical capacity of 180 Ah L−1 for hydrogen bromine redox flow batteries (H2/Br2-RFB). Stable liquid fused salts, moderate bromine complexation, large conductivities and large redox potentials in the aqueous phase of the electrolytes are investigated in order to determine the most applicable BCA for this kind of electrolyte. A detailed study on the properties of BCA cations in these parameters is provided for the first time, as well as for electrolyte mixtures at different states of charge of the electrolyte. 1-ethylpyridin-1-ium bromide [C2Py]Br is selected from 38 BCAs based on its properties as a BCA that should be focused on for application in electrolytes for H2/Br2-RFB in the future.

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Section: Methodsmentioning

confidence: 99%

Systematic Study of Quaternary Ammonium Cations for Bromine Sequestering Application in High Energy Density Electrolytes for Hydrogen Bromine Redox Flow Batteries

et al. 2021

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“…Real HBFB and other bromine-based RFB systems, operate at much different conditions from those commonly encountered in electroanalytical chemistry. Higher electrolyte concentration up to 7-8 M HBr is dictated by energy density requirements and capital cost reductions [6][7][8][9]. During operation (especially charging process), HBFB stacks warm up significantly, which necessitates a separate heat exchange system.…”

Section: State Of the Artmentioning

confidence: 99%

“…where 𝑐 B is the total molar concentration of bromine-containing species. Finally, from equilibrium relationships (5), (6), and (8), three additional equations can be formulated:…”

Section: Mass Balances At Equilibriummentioning

confidence: 99%

“…Owing to the generality of the developed model, a modification or addition of thermodynamic phenomena is manageable. The first example of such extension could be modelling of the bromine electrode OCP with additives, such as recently studied bromine complexing agents (BCAs) [6]. A systematic analysis similar to the one presented could be utilised to determine bromine complex stability constants and thus to compare bromine binding strength of different BCAs.…”

Section: Extension Of the Ocv Modelling Approach To Other Rfb Systemsmentioning

confidence: 99%

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Exploring the thermodynamics of the bromine electrode in concentrated solutions for improved parametrisation of hydrogen–bromine flow battery models

Włodarczyk

Küttinger

Friedrich

et al. 2021

Journal of Power Sources

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“…The organic liquid phase, formed by free bromine and the BCA, remains at the bottom of the electrolyte reservoir, immiscible in the aqueous liquid phase [14]. In this manner, different quaternary amines have been used as BCAs in commercial batteries, particularly complexes such as methylethylmorpholinium bromide (MEM) or methylethylpyrrolidinium bromide (MEP), or their mixture [5,13,[19][20][21]. Additional quaternary ammonium complexes which capture the electro-generated bromine but retain it in the aqueous phase have also been examined.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Performance of Zn/Br Flow Battery Using N-Methyl-N-Propylmorpholinium Bromide as Complexing Agent

Jiménez-Blasco¹,

Moreno²,

Cólera³

et al. 2021

IJMS

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Redox flow batteries (RFB) are one of the most interesting technologies in the field of energy storage, since they allow the decoupling of power and capacity. Zinc–bromine flow batteries (ZBFB) are a type of hybrid RFB, as the capacity depends on the effective area of the negative electrode (anode), on which metallic zinc is deposited during the charging process. Gaseous bromine is generated at the positive electrode (cathode) during the charging process, so the use of bromine complexing agents (BCA) is very important. These BCAs are quaternary amines capable of complexation with bromine and generating an organic phase, immiscible with the aqueous electrolyte. One of the most commonly used BCAs in RFB technology is 4-methylethylmorpholinium bromide (MEM-Br). In this work, an alternative quaternary amine 4-methylpropylmorpholinium bromide (MPM-Br) was studied. MPM-Br was integrated into the electrolyte, and 200 charge–discharge cycles were performed on the resulting ZBFBs. The obtained results were compared with those when MEM-Br was used, and it was observed that the electrolyte with MPM-Br displays a higher resistance in voltage and higher energy efficiency, making it a promising alternative to MEM-Br.

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Cycle behaviour of hydrogen bromine redox flow battery cells with bromine complexing agents

Cited by 21 publications

References 56 publications

Systematic Study of Quaternary Ammonium Cations for Bromine Sequestering Application in High Energy Density Electrolytes for Hydrogen Bromine Redox Flow Batteries

Systematic Study of Quaternary Ammonium Cations for Bromine Sequestering Application in High Energy Density Electrolytes for Hydrogen Bromine Redox Flow Batteries

Exploring the thermodynamics of the bromine electrode in concentrated solutions for improved parametrisation of hydrogen–bromine flow battery models

Enhanced Performance of Zn/Br Flow Battery Using N-Methyl-N-Propylmorpholinium Bromide as Complexing Agent

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