The capacity of electrochemical interfaces is an important characteristic of the adjacent electrode and electrolyte materials [5,2]. In order to interpret experimental results of capacity measurements, mathematical models resolving the space charge layer are necessary [3,4,6]. These are usually based on Poisson-Nernst-Planck-type equations, which – together with equilibrium conditions – allow for a numerical computation of the differential capacity. In recent research, progress has been made in the modeling of space charge layers, most notably with taking the solvation effect into account [1,3], which leads to a coupled Poisson-momentum equation system [2,3,4]∇(ε0(1+χ)∇φ) = -q(φ,p)∇p = -q(φ,p)∇φwhere φ is the electrostatic potential, p the (local) material pressure, and q the charge density.The electrolyte is mainly considered as ideal mixture, which yields for the chemical potential μα ∼ log (yα), where yα is the mole fraction of constituent Xα (α = 0, 1, ..., N), which in turn yields in thermodynamic equilibrium an analytic expression yα = yα(φ,p) and thus q = q(φ,p) via the incompressibility constraint.Non-idealities, for example Debye-Hückel-like activity coefficients [7,8], yield more complex representations μα = μα(yα) or even μα = μα(y1, ..., yN), whereby the equilibrium condition ∇μα + e0zα∇φ = 0 cannot be employed anymore to derive an explicit expression for yα. Instead, it remains an implicit (differential) equation, which has to be solved (numerically) together with the Poisson and the momentum equation.For different examples of non-ideal chemical potential functions, e.g. Debye-Hückel-like acitivity coefficients [7,8], we derive the corresponding boundary value problems. Some remarks on mathematical issues of the derivation are given throughout the presentation and we describe the general strategy how to solve the corresponding coupled, non-linear differential equation system. Subsequently we provide numerical results for the differential capacity and the corresponding space charge layers and investigate the impact of the non-ideality by comparison to ideal, incompressible solvation mixtures.[1] M. Landstorfer. Electrochemistry Communications, 92:56–59 (2018).[2] M. Landstorfer, C. Guhlke, and W. Dreyer. Electrochimica Acta, 201:187–219 (2016).[3] W. Dreyer, C. Guhlke, and M. Landstorfer. Electrochemistry Communications, 43(0):75–78 (2014).[4] W. Dreyer, C. Guhlke, and R. Muller. Phys. Chem. Chem. Phys., 15:7075–7086 (2013).[5] G. Valette. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 122(0):285–297 (1981).[6] C.-L. Li and J.-L. Liu. SIAM Journal on Applied Mathematics, 80(5):2003–2023 (2020).[7] P. Debye and E. Hückel. Physikalische Zeitschrift, 24:185–206 (1923).[8] K. S. Pitzer. Activity coefficients in electrolyte solutions. CRC press, 2018.
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