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Hydrogen bromine redox flow batteries (RFB) are considered to be one of the most promising storage alternatives, as this technology offers both high energy and high-power density. In this work a printed circuit board type of segmented current collector for the measurement of locally resolved current density was developed. This analytical tool was inserted as hydrogen anode current collector in a hydrogen-bromine test cell. Charging and discharging operation was monitored under different stoichiometric flow conditions and the impact on current distribution is presented. This technique offers the possibility to prove cell limiting conditions with spatial resolution, improving our understanding and determining optimal operating conditions for a given design. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Hydrogen bromine redox flow batteries utilize bromine electrolytes in their positive half cell, offering capacities larger than 100 Ah L−1. Addition of quaternary ammonium compounds, so-called bromine complexing agents (BCA), may increase safety as they reduce the vapour pressure of bromine in the posolyte. However, they have not been applied so far. They (a) interact with perfluorosulfonic acid membranes leading to significant reduction of membrane conductivity and (b) they form a low conductive ionic liquid with polybromides, leading to high overvoltage if the formation happens at the electrode. In this work a solution to this problem is proposed by an excess addition of Br 2 to these electrolytes. The excess bromine leads to a permanent bromine fused salt phase in the tank. Bromine formed in the cell stays in the aqueous phase and bromine transfer between the two phases happens in the tank. Transfer of Br 2 without the transfer of [BCA]+ cations exists between the phases, while [C2Py]+ cations remain in the fused salt and do not influence cell performance. For the first time a posolyte capacity of 179.6 Ah L−1 based on 7.7 M hydrobromic acid with BCA is achieved compared to previous investigations with e.g. 53.9 Ah L−1. • Evaluation of bromine posolytes with complexing agents (BCA) for energy storage. • Investigation of Br 2 transfer mechanism between aqueous electrolyte and fused salt. • Successful development of electrolyte by intervention in complexation reaction. • Reduced influence of BCA cation on PFSA membrane performance and cell performance. • Increase of the useable electrolyte capacity from 53.9 Ah L−1 to 179.6 Ah L−1. [ABSTRACT FROM AUTHOR]

Bromine complexing agents (BCA) are used to improve the safety of aqueous bromine electrolytes versus bromine outgassing in bromine electrolytes. In this work, cycling performance of hydrogen-bromine redox flow battery cells with 1-ethylpyridin-1-ium bromide ([C2Py]Br) as BCA in a bromine electrolyte with a theoretical capacity of 179.6 A h L−1 is investigated for the first time. The BCA leads to increased ohmic overvoltages. One cause of the ohmic drop can be attributed to [C2Py]+ cation interaction with the perfluorosulfonic acid (PFSA) membrane, which results in a drop of its conductivity. The BCA also interacts with bromine in the cell, by forming a non-aqueous fused salt second phase which exhibits a ten times lower conductivity compared to the aqueous electrolyte. A steep rise in cell voltage at the beginning of the charge curve followed by a regeneration of the cell voltage is attributed to this effect. Electrolyte crossover leads to an accumulation of [C2Py]+ in the electrolyte solution and intensifies both adverse processes. Under this condition only 30% of the theoretical electrolyte capacity of 179.6 A h L−1 is available under long term cycle conditions. However, electrolyte capacity is high enough to compete with other flow battery technologies. [Display omitted] • [C2Py]Br as bromine complexing agent in safe posolytes for H 2 /Br 2 -RFB. • Two-phase electrolyte: bromine-poor aqueous phase and bromine-rich fused salt. • Bromine half cell performance limitation due to formation of [C2Py]-fused salt. • Membrane performance limitation due to interaction with [C2Py]+ cations. • Br 2 crossover intensifies both effects due to release of BCA from fused salt. [ABSTRACT FROM AUTHOR]