Complexing Additives to Reduce the Immiscible Phase Formed in the Hybrid ZnBr₂Flow Battery

The zinc-bromine redox flow battery (RFB) is one of a very few commercially viable RFB energy storage systems capable of integration with intermittent renewable energy sources to deliver improved energy management. However, due to the volatility of the electrogenerated bromine and potential for its crossover from positive to negative electrolytes, this system requires the use of quaternary ammonium complexes ( N -methyl- N -ethylpyrrolidinium, (MEP)) to capture this bromine. This produces an immiscible phase with the Br 2 which requires a complex network of pipes, pumps and automated controls to ensure access to the electroactive material during discharge. In this work, the use of novel quaternary ammonium complexes to capture the electrogenerated bromine but to keep it in the aqueous phase is examined. Three compounds, 1-(carboxymethyl) pyridine-1-ium, 1-(2-carboxymethyl)-1-methylmorpholin-1-ium and 1-(2-carboxymethyl)-1-methylpyrrolidin-1-ium, were found to successfully reduce the volume of the immiscible phase formed on complexing with the polybromide (Br x − ) whilst displaying similar enthalpy of vaporization values as that of MEP . Electrochemical analysis also revealed that these compounds did not impact on the electrode kinetics of the Br − /Br x − reaction indicating that the resulting surface film formed with these compounds behaved as a chemically modified electrode, in contrast to the surface film formed with MEP.