Effective Poisson-Nernst-Planck (PNP) equations are derived for macroscopic
ion transport in charged porous media under periodic fluid flow by an
asymptotic multi-scale expansion with drift. The microscopic setting is a
two-component periodic composite consisting of a dilute electrolyte continuum
(described by standard PNP equations) and a continuous dielectric matrix, which
is impermeable to the ions and carries a given surface charge. Four new
features arise in the upscaled equations: (i) the effective ionic diffusivities
and mobilities become tensors, related to the microstructure; (ii) the
effective permittivity is also a tensor, depending on the electrolyte/matrix
permittivity ratio and the ratio of the Debye screening length to the
macroscopic length of the porous medium; (iii) the microscopic fluidic
convection is replaced by a diffusion-dispersion correction in the effective
diffusion tensor; and (iv) the surface charge per volume appears as a
continuous "background charge density", as in classical membrane models. The
coefficient tensors in the upscaled PNP equations can be calculated from
periodic reference cell problems. For an insulating solid matrix, all gradients
are corrected by the same tensor, and the Einstein relation holds at the
macroscopic scale, which is not generally the case for a polarizable matrix,
unless the permittivity and electric field are suitably defined. In the limit
of thin double layers, Poisson's equation is replaced by macroscopic
electroneutrality (balancing ionic and surface charges). The general form of
the macroscopic PNP equations may also hold for concentrated solution theories,
based on the local-density and mean-field approximations. These results have
broad applicability to ion transport in porous electrodes, separators,
membranes, ion-exchange resins, soils, porous rocks, and biological tissues
