In this work, we report on a comparative analysis of the bromine permeability for three separator groups under the operating conditions of a non-flow zinc–bromine battery. A new method for the synthesis of porous heterogeneous membranes based on a cation-exchange resin followed by treatment with tetrabutylammonium bromide is proposed. It was shown that the modified membrane significantly reduced the bromine permeability (crossover) with an acceptable increase in the ionic conductivity of the separator group. Leakage currents not exceeding 10–20 µA/cm² were achieved, and the Coulomb efficiency was over 90%. The ionic conductivity (at AC) of a membrane soaked with water was compared for different pretreatment conditions. The frequency dependence of the membrane resistance is shown. The features of the conduction mechanism of the modified membrane are discussed.