Asymmetric rectified electric fields: nonlinearities and equivalent circuits

Recent experiments [S. H. Hashemi et al., Phys. Rev. Lett., 2018, 121, 185504] have shown that a long-ranged steady electric field emerges when applying an oscillating voltage over an electrolyte with unequal mobilities of cations and anions confined between two planar blocking electrodes. To explain this effect we analyse full numerical calculations based on the Poisson-Nernst-Planck equations by means of analytically constructed equivalent electric circuits. Surprisingly, the resulting equivalent circuit has two capacitive elements, rather than one, which introduces a new timescale for electrolyte dynamics. We find a good qualitative agreement between the numerical results and our simple analytic model, which shows that the long-range steady electric field emerges from the different charging rates of cations and anions in the electric double layers. By solving transport equations and using equivalent circuits, we analyse the asymmetric rectified electric fields that develop in aqueous electrolytes under the influence of AC voltage in the case that cationic and anionic diffusivities are different.