Key Laboratory of Precision and Intelligent Chemistry, Department of Applied Chemistry, School of Chemistry and Material Science, University of Science and Technology of China, Hefei, P. R. China.
EastCHEM School of Chemistry, University of Edinburgh, Edinburgh, UK.
Nature. 2023 May;617(7960):299-305. doi: 10.1038/s41586-023-05888-x. Epub 2023 Apr 26.
The enhancement of separation processes and electrochemical technologies such as water electrolysers, fuel cells, redox flow batteries and ion-capture electrodialysis depends on the development of low-resistance and high-selectivity ion-transport membranes. The transport of ions through these membranes depends on the overall energy barriers imposed by the collective interplay of pore architecture and pore-analyte interaction. However, it remains challenging to design efficient, scaleable and low-cost selective ion-transport membranes that provide ion channels for low-energy-barrier transport. Here we pursue a strategy that allows the diffusion limit of ions in water to be approached for large-area, free-standing, synthetic membranes using covalently bonded polymer frameworks with rigidity-confined ion channels. The near-frictionless ion flow is synergistically fulfilled by robust micropore confinement and multi-interaction between ion and membrane, which afford, for instance, a Na diffusion coefficient of 1.18 × 10 m s, close to the value in pure water at infinite dilution, and an area-specific membrane resistance as low as 0.17 Ω cm. We demonstrate highly efficient membranes in rapidly charging aqueous organic redox flow batteries that deliver both high energy efficiency and high-capacity utilization at extremely high current densities (up to 500 mA cm), and also that avoid crossover-induced capacity decay. This membrane design concept may be broadly applicable to membranes for a wide range of electrochemical devices and for precise molecular separation.
增强分离过程和电化学技术(如水电解槽、燃料电池、氧化还原液流电池和离子捕获电渗析)依赖于开发低电阻和高选择性的离子传输膜。离子通过这些膜的传输取决于孔结构和孔-分析物相互作用的集体相互作用施加的总能量障碍。然而,设计高效、可扩展和低成本的选择性离子传输膜,为低能量障碍传输提供离子通道仍然具有挑战性。在这里,我们采用了一种策略,使用具有刚性限制离子通道的共价键合聚合物框架,为大面积、独立的合成膜接近水中离子的扩散极限。强大的微孔限制和离子与膜之间的多相互作用协同实现了几乎无摩擦的离子流动,例如,Na 扩散系数为 1.18×10-9 m2 s-1,接近无限稀释时纯水中的值,且面电阻低至 0.17 Ω cm2。我们在快速充电的水性有机氧化还原液流电池中展示了高效的膜,在极高的电流密度(高达 500 mA cm-2)下实现了高能量效率和高容量利用率,并且避免了交叉引起的容量衰减。这种膜设计概念可能广泛适用于各种电化学设备的膜以及精确的分子分离。