Zinc-iodine batteries (ZIBs) face challenges, such as polyiodide shuttling, self-discharge, and temperature sensitivity. To overcome these issues, we developed a separator functionalized with an ionic covalent organic framework (COF@GF), which incorporates pyridine quaternary ammonium active sites. The COF@GF separator enhances ionic conductivity (13.9 mS cm^-1) and Zn²⁺ transference number (0.76), suppresses anode dendrite formation, and reduces self-discharge. In situ Raman spectroscopy and theoretical calculations show that COF's moderate electronic conductivity improves I₃^-/I₅^- conversion kinetics and enhances polyiodide adsorption through Lewis acid-base interactions, thus controlling redox chemistry and suppressing shuttle effects. COF@GF-modified ZIBs exhibit stable cycling for over 5000 cycles at 20 C and perform well across temperatures from -5 to 60 °C. At 0 °C, the battery retains 89.6% of its capacity over 10000 cycles, with a minimal decay rate of 0.001% per cycle, showcasing the potential of ionic COF materials for practical aqueous ZIB applications.

锌碘电池（ZIBs）面临多项挑战，如多碘化物穿梭、自放电和温度敏感性。为了解决这些问题，我们开发了一种功能性隔膜，该隔膜涂覆有离子共价有机框架（COF@GF），并集成了吡啶季铵活性位点。COF@GF隔膜可以增强离子导电性（13.9毫西门子每厘米）和Zn²⁺传递数（0.76），抑制阳极枝晶的形成，并减少自放电现象。原位拉曼光谱和理论计算表明，COF的中等电子传导性能可以改善I₃^-/I₅^-转化动力学，并通过路易斯酸碱相互作用增强多碘化物吸附，从而控制氧化还原化学反应并抑制穿梭效应。经过COF@GF改进的ZIBs在20C条件下可实现超过5000次稳定的循环，在-5至60°C温度范围内表现出良好的性能。在0°C时，电池在10,000次循环后仍能保持89.6%的容量，并且每周期衰减率仅为0.001%，展示了离子型COF材料在实际应用中的潜力。