Artificial charged membranes, similar to the biological membranes, are self-assembled nanostructured materials constructed from macromolecules. The mutual interactions of parts of macromolecules leads to phase separation and appearance of microheterogeneities within the membrane bulk. On the other hand, these interactions also cause spontaneous microheterogeneity on the membrane surface, to which macroheterogeneous structures can be added at the stage of membrane fabrication. Membrane bulk and surface heterogeneity affect essentially the properties and membrane performance in the applications in the field of separation (water desalination, salt concentration, food processing and other), energy production (fuel cells, reverse electrodialysis), chlorine-alkaline electrolysis, medicine and other. We review the models describing ion transport in ion-exchange membranes and electromembrane systems with an emphasis on the role of micro- and macroheterogeneities in and on the membranes. Irreversible thermodynamics approach, “solution-diffusion” and “pore-flow” models, the multiphase models built within the effective-medium approach are examined as the tools for describing ion transport in the membranes. 2D and 3D models involving or not convective transport in electrodialysis cells are presented and analysed. Some examples are given when specially designed surface heterogeneity on the membrane surface results in enhancement of ion transport in intensive current electrodialysis.

Water splitting (WS) and electroconvection (EC) are the main phenomena affecting ion transfer through ion-exchange membranes in intensive current regimes of electrodialysis. While EC enhances ion transport, WS, in most cases, is an undesirable effect reducing current efficiency and causing precipitation of sparingly soluble compounds. A mathematical description of the transfer of salt ions and H⁺ (OH⁻) ions generated in WS is presented. The model is based on the Nernst–Planck and Poisson equations; it takes into account deviation from local electroneutrality in the depleted diffusion boundary layer (DBL). The current transported by water ions is given as a parameter. Numerical and semi-analytical solutions are developed. The analytical solution is found by dividing the depleted DBL into three zones: the electroneutral region, the extended space charge region (SCR), and the quasi-equilibrium zone near the membrane surface. There is an excellent agreement between two solutions when calculating the concentration of all four ions, electric field, and potential drop across the depleted DBL. The treatment of experimental partial current–voltage curves shows that under the same current density, the surface space charge density at the anion-exchange membrane is lower than that at the cation-exchange membrane. This explains the negative effect of WS, which partially suppresses EC and reduces salt ion transfer. The restrictions of the analytical solution, namely, the local chemical equilibrium assumption, are discussed.

The use of the Nernst–Planck and Poisson (NPP) equations allows computation of the space charge density near solution/electrode or solution/ion-exchange membrane interface. This is important in modelling ion transfer, especially when taking into account electroconvective transport. The most solutions in literature use the condition setting a potential difference in the system (potentiostatic or potentiodynamic mode). However, very often in practice and experiment (such as chronopotentiometry and voltammetry), the galvanostatic/galvanodynamic mode is applied. In this study, a depleted stagnant diffusion layer adjacent to an ion-exchange membrane is considered. In this article, a new boundary condition is proposed, which sets a total current density, i, via an equation expressing the potential gradient as an explicit function of i. The numerical solution of the problem is compared with an approximate solution, which is obtained by a combination of numerical solution in one part of the diffusion layer (including the electroneutral region and the extended space charge region, zone (I) with an analytical solution in the other part (the quasi-equilibrium electric double layer (EDL), zone (II). It is shown that this approach (called the “zonal” model) allows reducing the computational complexity of the problem tens of times without significant loss of accuracy. An additional simplification is introduced by neglecting the thickness of the quasi-equilibrium EDL in comparison to the diffusion layer thickness (the “simplified” model). For the first time, the distributions of concentrations, space charge density and current density along the distance to an ion-exchange membrane surface are computed as functions of time in galvanostatic mode. The calculation of the transition time, τ, for an ion-exchange membrane agree with an experiment from literature. It is suggested that rapid changes of space charge density, and current density with time and distance, could lead to lateral electroosmotic flows delaying depletion of near-surface solution and increasing τ.

Electromembrane devices are usually operated in two electrical regimes: potentiodynamic (PD), when a potential drop in the system is set, and galvanodynamic (GD), when the current density is set. This article theoretically investigates the current-voltage curves (CVCs) of flow-through electrodialysis membrane systems calculated in the PD and GD regimes and compares the parameters of the electroconvective vortex layer for these regimes. The study is based on numerical modelling using a basic model of overlimiting transfer enhanced by electroconvection with a modification of the boundary conditions. The Dankwerts’ boundary condition is used for the ion concentration at the inlet boundary of the membrane channel. The Dankwerts’ condition allows one to increase the accuracy of the numerical implementation of the boundary condition at the channel inlet. On the CVCs calculated for PD and DG regimes, four main current modes can be distinguished: underlimiting, limiting, overlimiting, and chaotic overlimiting. The effect of the electric field regime is manifested in overlimiting current modes, when a significant electroconvection vortex layer develops in the channel.

Overlimiting current modes are of considerable interest for the practice of electrodialysis (ED). However, the economical expedience of such ED modes is evident only for desalination of dilute...

This article considers a theoretical analysis of the influence of the main coupled effects and spacers on the transfer of salt ions in electromembrane systems (EMS) using a 2D mathematical model of the transfer process in a desalting channel with spacers based on boundary value problems for the coupled system of Nernst–Planck–Poisson and Navier–Stokes equations. The basic patterns of salt ion transport have been established, taking into account diffusion, electromigration, forced convection, electroconvection, dissociation/recombination reactions of water molecules, as well as spacers located inside the desalting channel. It has been shown that spacers and taking into account the dissociation/recombination reaction of water molecules significantly change both the formation and development of electroconvection. This article confirms the fact of the exaltation of the limiting current studied by Harkatz, where it is shown that the current (flux) of salt ions increases when the dissociation reaction begins by a certain value called the exaltation current, which is proportional to the flow of water dissociation products. A significant combined effect of electroconvection and dissociation/recombination reactions as well as the spacer system in the desalting channel on the transport of salt ions are shown. The complex, nonlinear, and non-stationary interaction of all the main effects of concentration polarization and spacers in the desalting channel are also considered in the work.