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Inverse problems have been becoming an important method for determination of materials properties, size and shape design, identification of the proper boundary and/or initial conditions. In this work we show the application of the inverse method to multi-component electrochemical systems. The basic process operating in these systems is electrodiffusion which can be described by the full form of the Nernst-Planck and Poisson equations for arbitrary initial conditions and Neumann-like boundary conditions. No simplifications like electroneutrality or constant electric field assumption are used. Results for several examples are demonstrated: determination of chloride diffusion coefficient in concrete, optimization of detection limit for ion selective electrodes and determination of EIS spectra using NPP model. [ABSTRACT FROM AUTHOR]

All-solid-state electrodes are increasingly being used in clinical, industrial and environmental analysis. This wide range of applications requires deep theoretical description of such electrodes. This work concentrates on the development of a numerical tool for the qualitative prediction of electrochemical behaviour for solid-contact ion-selective electrodes at low analyte concentrations. For this purpose, a general approach to the description of electro-diffusion processes, namely the Nernst-Planck-Poisson (NPP) model, was applied. The results obtained from this model are verified by experimental data of lead(II)-selective electrodes based on a polymeric PVC membrane with polybenzopyrene doped with Eriochrome Black T used as the solid contact. [ABSTRACT FROM AUTHOR]

A non-equilibrium diffusion–reaction model is proposed to describe chloride transport and binding in cementitious materials. A numerical solution for this non-linear transport with reaction problem is obtained using the finite element method. The effective chloride diffusion coefficients and parameters of the chloride binding are determined using the inverse method based on a diffusion–reaction model and experimentally measured chloride concentrations. The investigations are performed for two significantly different cements: ordinary Portland and blast furnace cements. The results are compared with the classical diffusion model and appropriate apparent diffusion coefficients. The role of chloride binding, with respect to the different binding isotherms applied, in the overall transport of chlorides is discussed, along with the applicability of the two models. The proposed work allows the determination of important parameters that influence the longevity of concrete structures. The developed methodology can be extended to include more ions, electrostatic interactions, and activity coefficients for even more accurate estimation of the longevity. [ABSTRACT FROM AUTHOR]

Understanding the oxidation/reduction dynamics of secondary microparticles formed from agglomerated nanoscale primary particles is crucial for advancing electrochemical energy storage technologies. In this study, the behavior of individual copper hexacyanoferrate (CuHCF) microparticles is explored at both global and local scales combining scanning electrochemical microscopy (SECM), for electrochemical interrogation of a single, but global-scale microparticle, and optical microscopy monitoring to obtain a higher resolution dynamic image of the local electrochemistry within the same particle. Chronoamperometric experiments unveil a multistep oxidation/reduction process with varying dynamics. On the one hand, the global SECM analysis enables quantifying the charge transfer as well as its dynamics at the single microparticle level during the oxidation/reduction cycles by a redox mediator in solution. These conditions allow mimicking the charge storage processes in these particles when they are used as solid boosters in redox flow batteries. On the other hand, optical imaging with sub-particle resolution allows the mapping of local conversion rates and state-of-charge within individual CuHCF particles. These maps reveal that regions of different material loadings exhibit varying charge storage capacities and conversion rates. The findings highlight the significance of porous nanostructures and provide valuable insights for designing more efficient energy storage materials., (© 2024 The Authors. Small published by Wiley‐VCH GmbH.)