Asymmetry-induced electric current rectification in permselective systems

For a symmetric ion permselective system, in terms of geometry and bulk concentrations, the system response is also symmetric under opposite electric field polarity. In this work we derive an analytical solution for the concentration distribution, electric potential, and current-voltage response for a four-layered system comprised of two microchambers connected by two permselective regions of varying properties. It is shown that any additional asymmetry in the system, in terms of the geometry, bulk concentration, or surface charge property of the permselective regions, results in current rectification. Our work is divided into two parts: when both permselective regions have the same surface charge sign and the case of opposite signs. For the same sign case we are able to show that the system behaves as a dialytic battery while accounting for field-focusing effects. For the case of opposite signs (i.e., bipolar membrane), our system exhibits the behavior of a bipolar diode where the magnitude of the rectification can be of order 10(2)-10(3).