Membrane development in organic redox flow batteries (ORFBs) is of significant importance. Herein, we designed a series of anion exchange membranes made from poly(p-phenylene oxide) (PPO) with different degrees of functionalization, cationic moieties and crosslinking degrees. We tested them in a N,N,N-2,2,6,6-heptamethylpiperidinyl oxy-4-ammonium chloride/1,1′-dimethyl-4,4′-bipyridinium dichloride (TMA-TEMPO/MV) based ORFB single cell to investigate the structure-property-performance relationship. The common problem of active species crossover is solved by controlling the membrane water uptake below 70 wt.%, resulting in stable systems with coulombic efficiency of over 99.3%. The cell employing a membrane prepared from PPO and trimethylamine moiety attached via a C6-spacer achieved the best overall cell performance. It delivered high capacity retention (94% after over 100 consecutive cycles) and higher peak power density (293 mW•cm⁻² at 16 mL•min⁻¹) and energy efficiency (80%) than the commercial reference memane FAA-3-50.

有机氧化还原液流电池 (ORFB) 的膜开发具有重要意义。在此，我们设计了一系列由具有不同功能化程度、阳离子部分和交联度的聚（对苯醚）（PPO）制成的阴离子交换膜。我们在 N,N,N中测试了它们基于-2,2,6,6-七甲基哌啶基氧-4-氯化铵/1,1'-二甲基-4,4'-联吡啶二氯化物 (TMA-TEMPO/MV) 的 ORFB 单电池研究结构-性能-性能关系。通过将膜吸水量控制在 70 wt.% 以下，解决了活性物种交叉的常见问题，从而使系统稳定，库仑效率超过 99.3%。采用由 PPO 制备的膜和通过 C6 间隔基连接的三甲胺部分的电池实现了最佳的整体电池性能。它提供了高容量保持率（超过 100 个连续循环后为 94%）和比商业参考 memane FAA-3-更高的峰值功率密度（293 mW•cm ^-2 在 16 mL•min ^-1时）和能量效率（80%） 50。