Vapor bromine/ammonium salts

Figure 2. Vapor pressures of bromine/quaternary ammonium salt complexes elemental Br2, Me4N+ Br, MEMBr, Oct,MeN Cl. From Ref. [59J.

Violent reactions with ammonium salts, chlorate salts, beryllium fluoride, boron diiodophosphide, carbon tetrachloride + methanol, 1,1,1-trichloroethane, 1,2-dibromoethane, halogens or interhalogens (e.g., fluorine, chlorine, bromine, iodine vapor, chlorine trifluoride, iodine heptafluoride), hydrogen iodide, metal oxides + heat (e.g., beryllium oxide, cadmium oxide, copper oxide, mercury oxide, molybdenum oxide, tin oxide, zinc oxide), nitrogen (when ignited), silicon dioxide powder + heat, polytetrafluoroethylene powder + heat. 

The chemical species present in the electrolyte are actually more complex than that described. In solution, elemental bromine exists in equilibrium with bromide ions to form polybromide ions, Br, where = 3, 5, 7. Aqueous zinc bromide is ionized, and zinc ions exist as various complex ions and ion pairs. The electrolyte also contains complexing agents which associate with polybromide ions to form a low-solubility second liquid phase. The complex reduces the amount of bromine contained in the aqueous phase 10 to 100-fold, which, in addition to the separator, also reduces the amount of bromine available in the eeU for the self-discharge reaction. The complex also provides a way to store bromine at a site remote from the zinc deposits and is discussed further in the next section. Salts with organic cations such as iV-methyl-iV-ethylmorpholinium bromide (MEMBr) are commonly used as the complexing agents. One researcher has proposed a mixture of four quaternary ammonium salts for use in zinc/bromine batteries. The proposed electrolyte has favorable properties with regard to aqueous bromine concentration, resistivity, and bromine diffusion and does not form solid complexes at low temperatures (5°C and above). Complexes with quaternary ammonium ions are reversible and also have an added safety benefit due to a much reduced bromine vapor pressure (see Sec. 35.6). 

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