Statistical description of electro-diffusion processes of ions intercalation in "electrolyte – electrode" system

Abstract

We propose a statistical theory of classical-quantum description of electro-diffusion processes of intercalation in "electrolyte – electrode" system. Using the nonequilibrium statistical operator method the generalized transport equations of Nernst-Planck type for ions and electrons in the "electrolyte – electrode" system are obtained. These equations take into account time memory effects and spatial heterogeneity. Within a classical description an analytical calculation of spatially inhomogeneous diffusion coefficients for ions is carried out.

Kinetic description of ion transport in the system "ionic solution – porous environment"

“…Another aspect of research is related to the ionic conductivity of ionic solutions in porous and layered structures, which is important in connection with the anomalous behavior of ion diffusion and polarization effects [2,14,[20][21][22][23]. In particular, theoretical studies of electrodiffusion processes of ion transfer in systems are relevant "electrolyte -electrode" [4,5,14,[24][25][26][27][28][29][30][31] and associated with the need to describe nonequilibrium processes of intercalation-deintercalation of ions, and with the need for a theory suitable for practical application for forecasting and management these processes. Problems in the description of electrode processes are connected, first of all, as with the superficial phenomena at the interface "electrolyte -electrode", where complex processes of adsorption, desorption, diffusion, and in the middle of the electrodes (porous, layered in structure), where complex processes of association, dissociation between ions, their anomalous (sub or super) diffusion due to complex interaction with the structure of the electrode, which in turn are associated with problems of charge accumulation on electrodes in batteries.…”

“…It should be noted that some way of calculating the diffusion coefficients of ions depending on the coordinates for the systems "electrolyte solution -membrane", "electrolyte solution -vitreous fuel-containing materials", "electrolyte solution -soil" was proposed in [34][35][36]. In [14,27], a statistical theory was proposed to describe electrodiffusion ion transfer processes in the system "electrolyte -electrode " taking into account the spatial inhomogeneities and memory effects using the nonequilibrium method statistical operator (NSO). In [14,28,29,31], experimental and theoretical study of subdiffusion impedance for multilayer system GaSe with encapsulated βcyclodextrin having a porous fractal structure was carried out.…”

Kinetic description of ion transport in the system "ionic solution -- porous environment"

“…Another aspect of research is related to the ionic conductivity of ionic solutions in porous and layered structures, which is important in connection with the anomalous behavior of ion diffusion and polarization effects. 2,14,[20][21][22][23] In particular, theoretical studies of electrodiffusion processes of ion transfer in systems are relevant "electrolyte -electrode" 4,5,14,[24][25][26][27][28][29][30][31] and associated with the need to describe nonequilibrium processes of intercalation-deintercalation of ions, and with the need for a theory suitable for practical application for forecasting and management these processes. Problems in the description of electrode processes are connected, first of all, as with the superficial phenomena at the interface "electrolyte -electrode", where complex processes of adsorption, desorption, diffusion, and in the middle of the electrodes (porous, layered in structure), where complex processes of association, dissociation between ions, their anomalous (sub or super) diffusion due to complex interaction with the structure of the electrode, which in turn are associated with problems of charge accumulation on electrodes in batteries.…”

“…It should be noted that some way of calculating the diffusion coefficients of ions depending on the coordinates for the systems "electrolyte solution -membrane", "electrolyte solutionvitreous fuel-containing materials", "electrolyte solution -soil" was proposed in. [34][35][36] In, 14,27 a statistical theory was proposed to describe electrodiffusion ion transfer processes in the system "electrolyte -electrode " taking into account the spatial inhomogeneities and memory effects using the nonequilibrium method statistical operator (NSO). In, 14,28,29,31 experimental and theoretical study of subdiffusion impedance for multilayer system GaSe with encapsulated β-cyclodextrin having a porous fractal structure was carried out.…”