Upscaling scheme for long-term ion diffusion in charged porous media.

Abstract

Description of long-term (over years) ion diffusion at the pore scale is a huge challenge since the characteristic time of diffusion in a typical representative elementary volume is around microseconds, generally ten orders of magnitude lower than the time we were concerned with. This paper presents a numerical upscaling scheme for ion diffusion with electrical double-layer effects (electrodiffusion) considered in charged porous media. After a scaling analysis for the nondimensional governing equations of ion transport at the pore scale, we identify the conditions for decoupling of electrical effect and diffusion, and therefore are able to choose apposite temporal and spatial scales for corresponding directions of the electrodiffusion process. The upscaling scheme is therefore proposed based on a numerical framework for governing equations using a lattice Boltzmann method. The electrical potential or concentration profiles from steady- or unsteady-state electrodiffusion in the long, straight channel, calculated by this upscaling scheme, are compared with the well-meshed full-sized simulations with good agreement. Furthermore, this scheme is used to predict tracer-ion throughdiffusion and outdiffusion in hardened cement pastes. All numerical results show good agreement with the full-sized simulations or experiment data without any fitting parameters. This upscaling scheme bridges the ion diffusion behaviors in different time scales, and may help to improve the understanding of long-term ion transport mechanisms in charged porous media.