[Show abstract][Hide abstract] ABSTRACT: Dielectric characteristics of a molecular model of liquid propylene carbonate are evaluated for utilization in molecular scale simulation of electrochemical capacitors based on nanotube forests. The linear-response dielectric constant of the bulk liquid, and its temperature dependence, is in good agreement with experiment. Dielectric saturation is studied by simulations with static uniform electric fields as large as 4 V/nm. The observed polarization is well described by the Langevin equation with the low-field/high-field crossover parameter of 0.09 V/nm. Simulation of liquid propylene carbonate confined between charged parallel graphite electrodes yields a capacitance that depends on the electric potential difference across those thin films. An effective dielectric constant inferred from the capacitance is significantly less than the uniform liquid dielectric constant, but is consistent with the nonlinear dielectric response at the strong fields applied to the electrode film. Those saturation effects reduce the weak-field capacitance.
The Journal of Chemical Physics 01/2010; 132(4):044701. · 3.12 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Described here are the first simulations of electric double-layer capacitors based on carbon nanotube forests modeled fully at a molecular level. The computations determine single-electrode capacitances in the neighborhood of 80 F/g, in agreement with experimental capacitances of electric double-layer capacitors utilizing carbon nanotube forests or carbide-derived carbons as electrode material. The capacitance increases modestly with the decrease of the pore size through radii greater than 1 nm, which is consistent with recent experiments on carbide-derived carbon electrodes. Because the various factors included in these simulations are precisely defined, these simulation data will help to disentangle distinct physical chemical factors that contribute to the performance of these materials, e.g., pore geometry, variable filling of the pores, pseudocapacitance, and electronic characteristics of the nanotubes.
Journal of the American Chemical Society 09/2009; 131(34):12373-6. · 10.68 Impact Factor