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.
A simple theory of electromechanical transduction for single-charge-carrier double-layer electroactuators is developed, in which the ion distribution and curvature are mutually coupled. The obtained expressions for the dependence of curvature and cha
rge accumulation on the applied voltage, as well as the electroactuation dynamics, are compared with literature data. The mechanical- or sensor- performance of such electroactuators appears to be determined by just three cumulative parameters, with all of their constituents measurable, permitting a scaling approach to their design.
In the recent experiments [Chmiola et al, Science 313, 1760 (2006); Largeot et al, J. Am. Chem. Soc. 130, 2730 (2008)] an anomalous increase of the capacitance with a decrease of the pore size of a carbon-based porous electric double-layer capacitor
has been observed. We explain this effect by the image forces which exponentially screen out the electrostatic interactions of ions in the interior of a pore. Packing of ions of the same sign becomes easier and is mainly limited by steric interactions. We call this state `superionic and suggest a simple model to describe it. The model reveals a possibility of a voltage-induced first-order transition between a cation(anion)-deficient phase and a cation(anion)-rich phase which manifests itself in a jump of capacitance as a function of voltage.
Based on renormalization group concepts and explicit mean field calculations we study the universal contribution to the effective force and torque acting on an ellipsoidal colloidal particle which is dissolved in a critical fluid and is close to a ho
mogeneous planar substrate. At the same closest distance between the substrate and the surface of the particle, the ellipsoidal particle prefers an orientation parallel to the substrate and the magnitude of the fluctuation induced force is larger than if the orientation of the particle is perpendicular to the substrate. The sign of the critical torque acting on the ellipsoidal particle depends on the type of boundary conditions for the order parameter at the particle and substrate surfaces, and on the pivot with respect to which the particle rotates.
