Redox flow batteries (RFBs) are among the most investigated technologies for large scale energy storage applications. Since the first commercialization of all-vanadium RFB (in the early 90’s), the technology has evolved towards the development of new systems. This review focuses on three innovative concepts including aqueous organic RFB (AO-RFB), dual-circuit RFB and redox solid booster-based RFB. We will highlight the recent advances in the last five years and discuss the main challenges encountered. Particularly, we focused on the utilization of redox-mediated process to reach higher energy density than conventional RFB.

All redox flow batteries suffer from low energy storage density in comparison with conventional Li-ion batteries. However, this issue can be mitigated by utilization of solid energy storage materials to enhance the energy storage capacity. In this paper we demonstrate the utilization of copper hexacyanoferrate (CuHCF) Prussian blue analogue for this purpose, coupled with N,N,N-2,2,6,6-heptamethylpiperidinyl oxy-4-ammonium chloride (TEMPTMA) as a soluble redox mediator to target the redox transitions of the solid material. In this case, indirect charging and discharging of CuHCF suspended in the electrolyte by electrochemically oxidized/reduced TEMPTMA was observed by chronoamperometry. Secondly, electrochemistry of different CuHCF composites with carbon black and multi-walled carbon nanotubes were investigated, highlighting that the high conductivity of the solid energy storage materials is crucial to access the maximal charge storage capacity. Finally, a CuHCF-TEMPTMA/Zn aqueous redox flow battery achieved stable cycling performances with high coulombic efficiency of 95% and volumetric capacity of 350 C mL−1.