We present a 'computational microscopy' analysis (targeted molecular dynamics simulations) of the structure and performance of conductive metal organic framework (MOF) electrodes in supercapacitors with room temperature ionic liquids. The molecular modeling predicts the characteristic shapes of the potential dependence of electrode capacitance, relying on the structure of MOF electrodes and particularly how ions transport and reside in MOFs under polarization. Transmission line model was adopted to characterize the charging dynamics process and build up a bridge to evaluate the capacitive performance of practical supercapacitor devices at macroscale from the simulation-obtained data at nanoscale. Such nanoscale-to-macroscale analysis demonstrates the potential of MOF supercapacitors for achieving unprecedentedly high volumetric energy and power densities. The investigation gives molecular insights into the preferred structures of MOF for achieving these results, which could provide a blueprint for future experimental characterization of these new systems.

As a class of porous materials with crystal lattices, metal–organic frameworks (MOFs), featuring outstanding specific surface area, tunable functionality, and versatile structures, have attracted huge attention in the past two decades. Since the first conductive MOF is successfully synthesized in 2009, considerable progress has been achieved for the development of conductive MOFs, allowing their use in diverse applications for electrochemical energy storage. Among those applications, supercapacitors have received great interest because of their high power density, fast charging ability, and excellent cycling stability. Here, the efforts hitherto devoted to the synthesis and design of conductive MOFs and their auspicious capacitive performance are summarized. Using conductive MOFs as a unique platform medium, the electronic and molecular aspects of the energy storage mechanism in supercapacitors with MOF electrodes are discussed, highlighting the advantages and limitations to inspire new ideas for the development of conductive MOFs for supercapacitors.

Molecular modeling has been considered indispensable in studying the energy storage of supercapacitors at the atomistic level. The constant potential method (CPM) allows the electric potential to be kept uniform in the electrode, which is essential for a realistic description of the charge repartition and dynamics process in supercapacitors. However, previous CPM studies have been limited to the potentiostatic mode. Although widely adopted in experiments, the galvanostatic mode has rarely been investigated in CPM simulations because of a lack of effective methods. Here we develop a modeling approach to simulating the galvanostatic charge–discharge process of supercapacitors under constant potential. We show that, for nanoporous electrodes, this modeling approach can capture experimentally consistent dynamics in supercapacitors. It can also delineate, at the molecular scale, the hysteresis in ion adsorption–desorption dynamics during charging and discharging. This approach thus enables the further accurate modeling of the physics and electrochemistry in supercapacitor dynamics.

Molecular modeling can study the energy storage of supercapacitors at the atomistic level and has become indispensable in this research. The constant potential method (CPM) allows keeping the electric potential uniform on the electrode, which is essential for a realistic description of the charge repartition and dynamics process in supercapacitors. Prior CPM studies have been limited to the potentiostatic mode. Though widely adopted in the experiment, the galvanostatic mode has been rarely investigated in CPM simulations due to a lack of effective methods. In this work, we developed a modeling approach to simulating the galvanostatic charge-discharge of supercapacitors under constant potential (GCD-CPM). We show that, for nanoporous electrodes, GCD-CPM can capture supercapacitor dynamics in excellent agreement with experimental measurements and delineate the ion adsorption-desorption dynamics underlying the hysteresis with molecular resolutions during charging and discharging. Therefore, this GCD-CPM modeling could open up new avenues for exploring the rich physics and electrochemistry of supercapacitor dynamics.