Sulfonated component-incorporated quaternized poly(phthalazinone ether ketone) membranes with improved ion selectivity, stability and water transport resistance in a vanadium redox flow battery

Abstract

Novel poly(phthalazinone ether ketone)-based amphoteric ion exchange membranes with improved ion selectivity, stability and water transport resistance were prepared for vanadium redox flow battery (VRB) applications. The preparation method ensured the absence of electrostatic interaction. A small amount of sulfonated poly(phthalazinone ether ketone) (SPPEK) with different ion exchange capacity (IEC) values was mixed with brominated poly(phthalazinone ether ketone) (BPPEK) to prepare base membranes with the solution casting method, and they were aminated in trimethylamine to obtain the resulting membranes (Q/S-x, x represents the IEC value of SPPEK). Compared with the AEM counterpart (QBPPEK) prepared from the amination of the BPPEK membrane, Q/S-1.37 showed lower swelling ratio and area resistance (R). The R value of Q/S-1.37 (0.58 Ω cm²) was close to that of Nafion115. The VO²⁺ and V³⁺ permeability values of Q/S-x were 96.7–97.6% and 98.5–99.2% less than those of Nafion115, respectively, demonstrating the excellent ion selectivity of Q/S-x. Compared with Nafion115 and QBPPEK, Q/S-1.37 displayed 90.0% and 92.1% decrease in the static water transport volume and 93.2% and 66.7% decrease in the cycling transport rate, respectively, revealing good water transport resistance. Compared with Nafion115, Q/S-1.37 exhibited an increase of 1.0–5.7% in the coulombic efficiency (CE) and an increase of 2.5–8.7% in the energy efficiency (EE) at 20–200 mA cm⁻². Q/S-x showed better chemical stability in VO₂⁺ solutions than QBPPEK. VRB with Q/S-1.37 could be steadily operated for 400 h without sudden capacity and efficiency drop, while VRB with QBPPEK could hold for only around 250 h. Q/S-1.37 retained higher CE, EE and capacity retention than Nafion115, displaying good long-term stability. Thus, the Q/S-x are promising for use in commercial VRBs.