Thermally cross-linked sulfonated poly(ether ether ketone) membranes containing a basic polymer-grafted graphene oxide for vanadium redox flow battery application

Abstract

Sulfonated poly(ether ether ketone) (SPEEK) with a very high degree of sulfonation (DS) and poly(2,5-benzimidazole)-grafted graphene oxide (ABPBI-GO) are prepared and used as a polymer matrix and a filler, respectively, to prepare thermally cross-linked membranes for vanadium redox flow battery (VRFB) application. The thermally cross-linked SPEEK membranes containing ABPBI-GO exhibit significantly enhanced physicochemical stabilities due to the formation of the well-developed cross-linked structures by the chemical bonds formed through the solvothermal process and the acid–base interactions between the benzimidazole groups in filler and sulfonic acid groups in polymer chain. In addition, ABPBI-GO in the polymer matrix is found to be effective in decreasing the vanadium ion permeability while retaining high proton conductivity producing a high-performance VRFB membrane. The ionic selectivity of the thermally cross-linked SPEEK membrane containing 0.5 wt% of ABPBI-GO (TC-SPEEK/0.5) is 13.15 × 107 mS min cm−3, which is approximately 8 times larger than that of Nafion 212 (1.57 × 107 mS min cm−3). Accordingly, the VRFB cell fabricated using TC-SPEEK/0.5 membrane exhibits higher coulombic efficiencies (CE: 98.1–99.4%), voltage efficiencies (VE: 92.5–85.2%), and energy efficiencies (EE: 90.7–84.7%) than that using Nafion 212 (CE: 89.2–93.3%, VE: 90.7–81.2%, EE: 80.9–75.7%) at current density of 40–100 mA cm−2. Furthermore, the long-term stability of the VRFB cell using TC-SPEEK/0.5 membrane evaluated by the cycle test under realistic VRFB operation conditions is also found to be much better than that using Nafion 212.