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We suggest polyacrylonitrile-based materials as membranes for redox-flow batteries. Bulk polyacrylonitrile is not ion-conductive, therefore we have applied two different procedures to enhance its hydrophilicity and porosity, namely solvent-induced phase separation and localized hydrolysis. By testing in a model allvanadium redox-flow battery, we have demonstrated that the proposed approaches allow preparation of the membranes with the operating parameters comparable to these of commercial Nafion membrane used as the benchmark.