Homogenization of the Poisson-Nernst-Planck Equations for Ion Transport in Charged Porous Media

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

Transient electrohydrodynamic flow with concentration dependent fluid properties: modelling and energy-stable numerical schemes

Transport of electrolytic solutions under influence of electric fields occurs in phenomena ranging from biology to geophysics. Here, we present a continuum model for single-phase electrohydrodynamic flow, which can be derived from fundamental thermodynamic principles. This results in a generalized Navier-Stokes-Poisson-Nernst-Planck system, where fluid properties such as density and permittivity depend on the ion concentration fields. We propose strategies for constructing numerical schemes for this set of equations, where solving the electrochemical and the hydrodynamic subproblems are decoupled at each time step. We provide time discretizations of the model that suffice to satisfy the same energy dissipation law as the continuous model. In particular, we propose both linear and non-linear discretizations of the electrochemical subproblem, along with a projection scheme for the fluid flow. The efficiency of the approach is demonstrated by numerical simulations using several of the proposed schemes

Unconditionally positivity preserving and energy dissipative schemes for Poisson--Nernst--Planck equations

We develop a set of numerical schemes for the Poisson--Nernst--Planck equations. We prove that our schemes are mass conservative, uniquely solvable and keep positivity unconditionally. Furthermore, the first-order scheme is proven to be unconditionally energy dissipative. These properties hold for various spatial discretizations. Numerical results are presented to validate these properties. Moreover, numerical results indicate that the second-order scheme is also energy dissipative, and both the first- and second-order schemes preserve the maximum principle for cases where the equation satisfies the maximum principle.Comment: 24 pages, 10 figure

Models and numerical methods for electrolyte flows

The most common mathematical models for electrolyte flows are based on the dilute solution assumption, leading to a coupled system of the Nernst--Planck--Poisson drift-diffusion equations for ion transport and the Stokes resp. Navier--Stokes equations for fluid flow. This contribution discusses historical and recent model developments beyond the dilute solution assumption and focuses on the effects of finite ion sizes and solvation. A novel numerical solution approach is presented and verified here which aims at preserving on the discrete level consistency with basic thermodynamic principles and structural properties like independence of flow velocities from gradient contributions to external forces

Existence of solution to a system of PDEs modeling the crystal growth inside lithium batteries

The life-cycle of electric batteries depends on a complex system of interacting electrochemical and growth phenomena that produce dendritic structures during the discharge cycle. We study herein a system of 3 partial differential equations combining an Allen--Cahn phase-field model (simulating the dendrite-electrolyte interface) with the Poisson--Nernst--Planck systems simulating the electrodynamics and leading to the formation of such dendritic structures. We prove novel existence, uniqueness and stability results for this system and use it to produce simulations based on a finite element code.Comment: 27 pages, 22 figures, free software and open source code availabl