Having smaller energy density than batteries, supercapacitors have exceptional power density and cyclability. Their energy density can be increased using ionic liquids and electrodes with sub-nanometer pores, but this tends to reduce their power dens
ity and compromise the key advantage of supercapacitors. To help address this issue through material optimization, here we unravel the mechanisms of charging sub-nanometer pores with ionic liquids using molecular simulations, navigated by a phenomenological model. We show that charging of ionophilic pores is a diffusive process, often accompanied by overfilling followed by de-filling. In sharp contrast to conventional expectations, charging is fast because ion diffusion during charging can be an order of magnitude faster than in bulk, and charging itself is accelerated by the onset of collective modes. Further acceleration can be achieved using ionophobic pores by eliminating overfilling/de-filling and thus leading to charging behavior qualitatively different from that in conventional, ionophilic pores.
Dissipative particle dynamics (DPD) is a novel particle method for mesoscale modeling of complex fluids. DPD particles are often thought to represent packets of real atoms, and the physical scale probed in DPD models are determined by the mapping of
DPD variables to the corresponding physical quantities. However, the non-uniqueness of such mapping has led to difficulties in setting up simulations to mimic real systems and in interpreting results. For modeling transport phenomena where thermal fluctuations are important (e.g., fluctuating hydrodynamics), an area particularly suited for DPD method, we propose that DPD fluid particles should be viewed as only 1) to provide a medium in which the momentum and energy are transferred according to the hydrodynamic laws and 2) to provide objects immersed in the DPD fluids the proper random kicks such that these objects exhibit correct fluctuation behaviors at the macroscopic scale. We show that, in such a case, the choice of system temperature and mapping of DPD scales to physical scales are uniquely determined by the level of coarse-graining and properties of DPD fluids. We also verified that DPD simulation can reproduce the macroscopic effects of thermal fluctuation in particulate suspension by showing that the Brownian diffusion of solid particles can be computed in DPD simulations with good accuracy.
