Abstract
Vanadium redox flow batteries (VRFBs) depend on the separator membrane for their efficiency and cycle life. Herein, two amphoteric ion exchange membranes are synthesized, based on sulfonic acid group-grafted poly(p-terphenyl piperidinium), for VRFBs. Using ether-free poly(p-terphenyl piperidine) (PTP) as the polymer matrix, and sodium 2-bromoethanesulphonate (ES) and 1,4-butane sultone (BS) as grafting agents, We achieve quaternization of PTP through an environmentally friendly process without alkaline catalysts. PTP-ES and PTP-BS membranes exhibit low area resistance, high H+ permeability, and significantly reduced vanadium ion permeability, leading to exceptional ion selectivity, which is 3.06×106Smincm-3 and 4.34×106Smincm-3, respectively,three orders of magnitude higher than that of Nafion115 (0.27×104Smincm-3). The VRFB with PTP-BS achieves a self-discharge duration of 190h, compared to 86h for Nafion 115. Additionally, under current densities of 40-160mAcm-2, PTP-BS shows coulombic efficiencies of 98.1-99.1% and energy efficiencies of 92.0-82.1%, outperforming Nafion 115. The VRFB with PTP-BS also demonstrates excellent cycle stability and discharge capacity retention over 300 cycles at 100mAcm-2. Therefore, the amphoteric PTP-BS membrane shows remarkable performance, offering significant potential for VRFB applications.
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