Comparison and numerical treatment of generalised Nernst-Planck models

In its most widespread, classical formulation, the Nernst-Planck-Poisson system for ion transport in electrolytes fails to take into account finite ion sizes. As a consequence, it predicts unphysically high ion concentrations near electrode surfaces. Historical and recent approaches to an approriate modification of the model are able to fix this problem. Several appropriate formulations are compared in this paper. The resulting equations are reformulated using absolute activities as basic variables describing the species amounts. This reformulation allows to introduce a straightforward generalisation of the Scharfetter-Gummel finite volume discretization scheme for drift-diffusion equations. It is shown that it is thermodynamically consistent in the sense that the solution of the corresponding discretized generalized Poisson-Boltzmann system describing the thermodynamical equilibrium is a stationary state of the discretized time-dependent generalized Nerns-Planck system. Numerical examples demonstrate the improved physical correctness of the generalised models and the feasibility of the numerical approach

Comparison of thermodynamically consistent charge carrier flux discretizations for Fermi-Dirac and Gauss-Fermi statistics

We compare three thermodynamically consistent ScharfetterGummel schemes for different distribution functions for the carrier densities, including the FermiDirac integral of order 1/2 and the GaussFermi integral. The most accurate (but unfortunately also most costly) generalized ScharfetterGummel scheme requires the solution of an integral equation. We propose a new method to solve this integral equation numerically based on Gauss quadrature and Newtons method. We discuss the quality of this approximation and plot the resulting currents for FermiDirac and GaussFermi statistics. Finally, by comparing two modified (diffusion-enhanced and inverse activity based) ScharfetterGummel schemes with the more accurate generalized scheme, we show that the diffusion-enhanced ansatz leads to considerably lower flux errors, confirming previous results (J. Comp. Phys. 346:497-513, 2017)

Comparison of thermodynamically consistent charge carrier flux discretizations for Fermi--Dirac and Gauss--Fermi statistics

We compare three thermodynamically consistent Scharfetter--Gummel schemes for different distribution functions for the carrier densities, including the Fermi--Dirac integral of order 1/2 and the Gauss--Fermi integral. The most accurate (but unfortunately also most costly) generalized Scharfetter--Gummel scheme requires the solution of an integral equation. We propose a new method to solve this integral equation numerically based on Gauss quadrature and Newton's method. We discuss the quality of this approximation and plot the resulting currents for Fermi--Dirac and Gauss--Fermi statistics. Finally, by comparing two modified (diffusion-enhanced and inverse activity based) Scharfetter--Gummel schemes with the more accurate generalized scheme, we show that the diffusion-enhanced ansatz leads to considerably lower flux errors, confirming previous results (J. Comp. Phys. 346:497-513, 2017)

Unipolar drift-diffusion simulation of S-shaped current-voltage relations for organic semiconductor devices

We discretize a unipolar electrothermal drift-diffusion model for organic semiconductor devices with Gauss--Fermi statistics and charge carrier mobilities having positive temperature feedback. We apply temperature dependent Ohmic contact boundary conditions for the electrostatic potential and use a finite volume based generalized Scharfetter-Gummel scheme. Applying path-following techniques we demonstrate that the model exhibits S-shaped current-voltage curves with regions of negative differential resistance, only recently observed experimentally

Highly accurate quadrature-based Scharfetter-Gummel schemes for charge transport in degenerate semiconductors

We introduce a family of two point flux expressions for charge carrier transport described by drift-diffusion problems in degenerate semiconductors with non-Boltzmann statistics which can be used in Voronoi finite volume discretizations. In the case of Boltzmann statistics, Scharfetter and Gummel derived such fluxes by solving a linear two point boundary value problem yielding a closed form expression for the flux. Instead, a generalization of this approach to the nonlinear case yields a flux value given implicitly as the solution of a nonlinear integral equation. We examine the solution of this integral equation numerically via quadrature rules to approximate the integral as well as Newtons method to solve the resulting approximate integral equation. This approach results into a family of quadrature-based Scharfetter-Gummel flux approximations. We focus on four quadrature rules and compare the resulting schemes with respect to execution time and accuracy. A convergence study reveals that the solution of the approximate integral equation converges exponentially in terms of the number of quadrature points. With very few integration nodes they are already more accurate than a state-of-the-art reference flux, especially in the challenging physical scenario of high nonlinear diffusion. Finally, we show that thermodynamic consistency is practically guaranteed

Highly accurate quadrature-based Scharfetter--Gummel schemes for charge transport in degenerate semiconductors

We introduce a family of two point flux expressions for charge carrier transport described by drift-diffusion problems in degenerate semiconductors with non-Boltzmann statistics which can be used in Vorono"i finite volume discretizations. In the case of Boltzmann statistics, Scharfetter and Gummel derived such fluxes by solving a linear two point boundary value problem yielding a closed form expression for the flux. Instead, a generalization of this approach to the nonlinear case yields a flux value given implicitly as the solution of a nonlinear integral equation. We examine the solution of this integral equation numerically via quadrature rules to approximate the integral as well as Newton's method to solve the resulting approximate integral equation. This approach results into a family of quadrature-based Scharfetter-Gummel flux approximations. We focus on four quadrature rules and compare the resulting schemes with respect to execution time and accuracy. A convergence study reveals that the solution of the approximate integral equation converges exponentially in terms of the number of quadrature points. With very few integration nodes they are already more accurate than a state-of-the-art reference flux, especially in the challenging physical scenario of high nonlinear diffusion. Finally, we show that thermodynamic consistency is practically guaranteed

Transport of solvated ions in nanopores: Asymptotic models and numerical study

Improved Poisson--Nernst--Planck systems taking into account finite ion size and solvation effects provide a more accurate model of electric double layers compared to the classical setting. We introduce and discuss several variants of such improved models. %Based on spatially fully resolved numerical models We study the effect of improved modeling in large aspect ratio nanopores. Moreover, we derive approximate asymptotic models for the improved Poisson--Nernst--Planck systems which can be reduced to one-dimensional systems. In a numerical study, we compare simulation results obtained from solution of the asymptotic 1D-models with those obtained by discretization of the full resolution models

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

Comparison and numerical treatment of generalized Nernst--Planck models

In its most widespread, classical formulation, the Nernst-Planck-Poisson system for ion transport in electrolytes fails to take into account finite ion sizes. As a consequence, it predicts unphysically high ion concentrations near electrode surfaces. Historical and recent approaches to an approriate modification of the model are able to fix this problem. Several appropriate formulations are compared in this paper. The resulting equations are reformulated using absolute activities as basic variables describing the species amounts. This reformulation allows to introduce a straightforward generalisation of the Scharfetter-Gummel finite volume discretization scheme for drift-diffusion equations. It is shown that it is thermodynamically consistent in the sense that the solution of the corresponding discretized generalized Poisson-Boltzmann system describing the thermodynamic equilibrium is a stationary state of the discretized time-dependent generalized Nernst-Planck system. Numerical examples demonstrate the improved physical correctness of the generalised models and the feasibility of the numerical approach