Non-linear effects in electrolytes at large applied voltage

TL;DR

This paper derives an exact, voltage-independent solution for ion diffusion in polymer electrolytes using Nernst-Planck-Poisson equations, revealing limits of the model at high voltages where non-linear effects dominate.

Contribution

It provides an exact analytical solution for ion concentration profiles at arbitrary voltages without assuming low ion concentration, highlighting the model's limitations at high voltages.

Findings

Exact solution for ion concentration independent of kinetic properties

Identification of voltage threshold where NPP validity breaks down

Estimation of upper voltage bound for model applicability

Abstract

The steady state of ions diffusion in polymer electrolytes at arbitrary applied voltage is analyzed in the framework of the Nernst-Planck-Poisson equation (NPP). The exact solution of the set of equations is found without the assumption of low ions concentration. The solution is independent of the kinetic properties of the system. At constant voltage there is a master curve for concentration in terms of the initial concentration. Enhancing the voltage causes an increase of the ion concentration gradient and consequently the applicability of the NPP is violated for high voltages. The analytical finding is estimated by using experimental data from recent measurements (P. Kohn et al Phys. Rev. Left. 99, 086104 (2007)). As the result we find an upper bound for the validity of the NPP. Above this voltage higher order gradient terms become relevant.