Novel Triple Tertiary Amine Polymer-Based Hydrogen Bond Network Inducing Highly Efficient Proton-Conducting Channels of Amphoteric Membranes for High-Performance Vanadium Redox Flow Battery.

A novel amphoteric membrane was designed by blending triple tertiary amine-grafted poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TTA) with sulfonated poly(ether ether ketone) (SPEEK) for vanadium redox flow batteries. An "acid-base pair" effect is formed by the combination of the tertiary amine group and sulfonic group, and extra nonbonding amine groups could be protonated. Both of them constitute a hydrogen bond network, which facilitates proton conduction and also hinders vanadium permeability because of the lowered swelling ratio and Donnan effect. All these contribute to improve the ion selectivity of the membrane while maintaining ionic conductivity. Compared with other amphoteric and SPEEK-based membranes, the membrane exhibits an excellent performance. The amphoteric membrane containing 15% PPO-TTA exhibits an ultralow vanadium permeability of 3.4 × 10-9 cm2 s-1 and a low area resistance of 0.39 Ω cm-2. Consequently, the cell assembled with this membrane shows excellent performances far superior to SPEEK and Nafion 212. The Coulombic efficiency and energy efficiency of the cell are 94.3-98.3 and 90.3-77.1% at 40-200 mA cm-2, respectively, and have no significant reductions after 200 cycles. This performance is at a high level among the amphoteric and SPEEK-based membranes reported in recent years. The cell's open circuit voltage is maintained for up to 165 h. In addition, the membrane's chemical stability is improved by the effective barrier to the vanadium ion.