9 research outputs found
Diffuse-Charge Dynamics in Electrochemical Systems
The response of a model micro-electrochemical system to a time-dependent
applied voltage is analyzed. The article begins with a fresh historical review
including electrochemistry, colloidal science, and microfluidics. The model
problem consists of a symmetric binary electrolyte between parallel-plate,
blocking electrodes which suddenly apply a voltage. Compact Stern layers on the
electrodes are also taken into account. The Nernst-Planck-Poisson equations are
first linearized and solved by Laplace transforms for small voltages, and
numerical solutions are obtained for large voltages. The ``weakly nonlinear''
limit of thin double layers is then analyzed by matched asymptotic expansions
in the small parameter , where is the
screening length and the electrode separation. At leading order, the system
initially behaves like an RC circuit with a response time of
(not ), where is the ionic diffusivity, but nonlinearity
violates this common picture and introduce multiple time scales. The charging
process slows down, and neutral-salt adsorption by the diffuse part of the
double layer couples to bulk diffusion at the time scale, . In the
``strongly nonlinear'' regime (controlled by a dimensionless parameter
resembling the Dukhin number), this effect produces bulk concentration
gradients, and, at very large voltages, transient space charge. The article
concludes with an overview of more general situations involving surface
conduction, multi-component electrolytes, and Faradaic processes.Comment: 10 figs, 26 pages (double-column), 141 reference