Generalization of the Gouy-Chapman-Stern model of an electric double layer for a morphologically complex electrode: deterministic and stochastic morphologies.

We generalize the linearized Gouy-Chapman-Stern theory of an electric double layer for morphologically complex and disordered electrodes. An equation for capacitance is obtained using a linear Gouy-Chapman or Debye-Hückel equation for the potential near the complex-geometry electrode-electrolyte interface. The effect of the surface morphology of an electrode on an electric double layer is obtained using multiple scattering formalism in surface curvature. The result for capacitance is expressed in terms of the ratio of Gouy screening length to the local principal radii of curvatures of the surface. We also include a contribution of a compact layer, which is significant in the overall prediction of capacitance. Our general results are analyzed in detail for two special morphologies of electrodes, i.e., a nanoporous membrane and a forest of nanopillars. Variations of local shapes and global size variations due to residual randomness in morphology are accounted for as curvature fluctuations over a reference shape element. In particular, the theory shows that the presence of geometrical fluctuations in porous systems causes an enhanced dependence of capacitance on mean pore sizes and suppresses the magnitude of capacitance. This theory is further extended to include contributions to capacitance from adsorption of ions and electrode material due to electronic screening. Our predictions are in reasonable agreement with recent experimental measurements on supercapacitive microporous and mesoporous systems.