In this review, the state of the art of modified membranes developed and applied for the improved performance of redox flow batteries (RFBs) is presented and critically discussed. The review begins with an introduction to the energy-storing chemical principles and the potential of using RFBs in the energy transition in industrial and transport-related sectors. Commonly used membrane modification techniques are briefly presented and compared next. The recent progress in applying modified membranes in different RFB chemistries is then critically discussed. The relationship between a given membrane modification strategy, corresponding ex situ properties and their impact on battery performance are outlined. It has been demonstrated that further dedicated studies are necessary in order to develop an optimal modification technique, since a modification generally reduces the crossover of redox-active species but, at the same time, leads to an increase in membrane electrical resistance. The feasibility of using alternative advanced modification methods, similar to those employed in water purification applications, needs yet to be evaluated. Additionally, the long-term stability and durability of the modified membranes during cycling in RFBs still must be investigated. The remaining challenges and potential solutions, as well as promising future perspectives, are finally highlighted.
Keywords: active species crossover; capacity fade; energy efficiency; improved performance; long-term stability/durability; membrane; pore filling; redox flow battery; surface modification.