1,2-Dimethylimidazole based bromine complexing agents for vanadium bromine redox flow batteries

To stabilize bromine produced during a vanadium-bromine redox flow batteries (V[sbnd]Br RFBs) charging, a bromine complexing agent (BCA) should be effectively used as a supporting material in V[sbnd]Br electrolyte. However, there remains a problem of improving the unstable reversibility between V²⁺ and V³⁺ in electrolyte including halogen elements (Br and Cl). This paper describes two imidazole-based BCAs, which are 1,2-dimethyl-3-ethylimidazolium bromide (DMEIm: C₇H₁₃BrN₂) and 1,2-dimethyl-3-propylimidazolium bromide (DMPIm: C₈H₁₅BrN₂), for not only confirming the capture of bromine but also improving the redox reaction of vanadium ions in V[sbnd]Br electrolyte. The effectiveness of the proposed two imidazole-based BCAs is demonstrated through the following experiments: cyclic voltammetry (CV), nuclear magnetic resonance analysis (NMR), scanning electron microscopy (SEM) analysis and cyclic cell operation test. Experimental results show that both the diffusion coefficient and the peak currents of each electrolyte using the proposed imidazole-based BCAs increases linearly with the rise of scan rate on the recorded CV curves, providing improved reversible reaction of V²⁺/V³⁺ in negative electrolyte. It also exhibits that the electrolytes using the DMEIm and DMPIm provide significantly improved charge (discharge) capacities which are 9.38 (31.01) % and 11.8 (35.66) % higher than the pristine one, respectively, resulting in 13.27% and 14.36% higher current efficiencies. In addition, corrosion cracks on the separator surface due to bromine attack are not observed after the cyclic cell operation. Consequently, these results indicate that the proposed two imidazole-based BCAs can not only sequester bromine during the V[sbnd]Br RFB charging, but also enhance electrochemical reversibility caused by improving diffusion coefficient of vanadium.