We performed constant-potential molecular dynamics simulations to analyse the double-layer structure and capacitive performance of supercapacitors composed of conductive metal–organic framework (MOF) electrodes and ionic liquids. The molecular modelling clarifies how ions transport and reside inside polarized porous MOFs, and then predicts the corresponding potential-dependent capacitance in characteristic shapes. The transmission line model was adopted to characterize the charging dynamics, which further allowed evaluation of the capacitive performance of this class of supercapacitors at the macroscale from the simulation-obtained data at the nanoscale. These ‘computational microscopy’ results were supported by macroscopic electrochemical measurements. Such a combined nanoscale-to-macroscale investigation demonstrates the potential of MOF supercapacitors for achieving unprecedentedly high volumetric energy and power densities. It gives molecular insights into preferred structures of MOFs for accomplishing consistent performance with optimal energy–power balance, providing a blueprint for future characterization and design of these new supercapacitor systems.

我们进行了恒电位分子动力学模拟，以分析由导电金属有机框架（MOF）电极和离子液体组成的超级电容器的双层结构和电容性能。分子模型阐明了离子如何在极化多孔 MOF 内传输和驻留，然后预测特征形状中相应的电位依赖性电容。采用传输线模型来表征充电动力学，这进一步允许从模拟获得的纳米级数据评估此类超级电容器在宏观级的电容性能。这些“计算显微镜”结果得到宏观电化学测量的支持。这种结合纳米尺度到宏观尺度的研究证明了 MOF 超级电容器在实现前所未有的高体积能量和功率密度方面的潜力。它为 MOF 的首选结构提供了分子见解，以实现具有最佳能量-功率平衡的一致性能，为这些新超级电容器系统的未来表征和设计提供了蓝图。