Concentration Polarization of Salt-Containing Liquid Electrolytes

Using the example of Li-battery electrolytes, the importance of the concept of conservative ensembles for polarization behavior and transference measurements of salt-containing liquid electrolytes is stressed. The conventional evaluation of the stationary values fails if the ion pair is mobile and can act as a vehicle of a single ion such as Li+. The necessary generalization is considered. While the analytical form of the time dependence of voltage or current is not affected provided the ion pairing is sufficiently fast, the diffusion coefficient contains nontrivial extra contributions. Finally, soggy-sand electrolytes are inspected, in which polarization occurs in the space-charge zones.