  The recently developed modified Donnan (mD) model provides a simple and
useful description of the electrical double layer in microporous carbon
electrodes, suitable for incorporation in porous electrode theory. By
postulating an attractive excess chemical potential for each ion in the
micropores that is inversely proportional to the total ion concentration, we
show that experimental data for capacitive deionization (CDI) can be accurately
predicted over a wide range of applied voltages and salt concentrations. Since
the ion spacing and Bjerrum length are each comparable to the micropore size
(few nm), we postulate that the attraction results from fluctuating bare
Coulomb interactions between individual ions and the metallic pore surfaces
(image forces) that are not captured by meanfield theories, such as the
Poisson-Boltzmann-Stern model or its mathematical limit for overlapping double
layers, the Donnan model. Using reasonable estimates of the micropore
permittivity and mean size (and no other fitting parameters), we propose a
simple theory that predicts the attractive chemical potential inferred from
experiments. As additional evidence for attractive forces, we present data for
salt adsorption in uncharged microporous carbons, also predicted by the theory.
