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.

Supercapacitors composed of slit-shaped micropores ranging in size from 0.67 to 1.8 nm in a room-temperature ionic liquid were studied to investigate the dependence of capacitance (C) on the pore size (d) using molecular dynamics simulations. The capacitance versus pore size (i.e., the C–d curve) was found to exhibit two peaks located at 0.7 and 1.4 nm, respectively. Specifically, as the pore shrinks from 1.0 to 0.7 nm, the capacitance of the micropore increases anomalously, in good agreement with experimental observations. We report herein that the second peak within 1.0 to 1.8 nm is a new feature of the C–d curve. Furthermore, by analogy to the wave interference, we demonstrate that the interference of two electrical double layers near each slit wall does not only explain the entire C–d curve, including the anomalous character, but also predicts the oscillatory behavior of C–d curve beyond 1.8 nm.

Thermogalvanic cells offer a cheap, flexible and scalable route for directly converting heat into electricity. However, achieving a high output voltage and power performance simultaneously from low-grade thermal energy remains challenging. Here, we introduce strong chaotropic cations (guanidinium) and highly soluble amide derivatives (urea) into aqueous ferri/ferrocyanide ([Fe(CN)6]4−/[Fe(CN)6]3−) electrolytes to significantly boost their thermopowers. The corresponding Seebeck coefficient and temperature-insensitive power density simultaneously increase from 1.4 to 4.2 mV K−1 and from 0.4 to 1.1 mW K−2 m−2, respectively. The results reveal that guanidinium and urea synergistically enlarge the entropy difference of the redox couple and significantly increase the Seebeck effect. As a demonstration, we design a prototype module that generates a high open-circuit voltage of 3.4 V at a small temperature difference of 18 K. This thermogalvanic cell system, which features high Seebeck coefficient and low cost, holds promise for the efficient harvest of low-grade thermal energy.

Converting body heat into electricity is a promising strategy for supplying power to wearable electronics. To avoid the limitations of traditional solid-state thermoelectric materials, such as frangibility and complex fabrication processes, we fabricated two types of thermogalvanic gel electrolytes with positive and negative thermo-electrochemical Seebeck coefficients, respectively, which correspond to the n-type and p-type elements of a conventional thermoelectric generator. Such gel electrolytes exhibit not only moderate thermoelectric performance but also good mechanical properties. Based on these electrolytes, a flexible and wearable thermocell was designed with an output voltage approaching 1 V by utilizing body heat. This work may offer a new train of thought for the development of self-powered wearable systems by harvesting low-grade body heat.

Here we report the bias-evolution of the electrical double layer structure of an ionic liquid on highly ordered pyrolytic graphite measured by atomic force microscopy. We observe reconfiguration under applied bias and the orientational transitions in the Stern layer. The synergy between molecular dynamics simulation and experiment provides a comprehensive picture of structural phenomena and long and short-range interactions, which improves our understanding of the mechanism of charge storage on a molecular level.