Short- and long-range contributions to equilibrium and transport properties of solid electrolytes

TL;DR

This paper develops a combined theoretical approach to describe ionic systems, incorporating both short-range and long-range interactions, to better understand the properties and phase behavior of solid electrolytes.

Contribution

It introduces a novel integral equation framework that accounts for Coulomb interactions and employs a lattice approximation with an improved pair distribution function calculation.

Findings

The model accurately predicts chemical potentials and diffusion coefficients.

The approach indicates possible phase transitions in solid ionic conductors.

Extended applicability to a wide range of thermodynamic conditions.

Abstract

Condensed ionic systems are described in the framework of a combined approach that takes into account both long-range and short-range interactions. Short-range interaction is expressed in terms of mean potentials and long-range interaction is considered in terms of screening potentials. A system of integral equations for these potentials is constructed based on the condition of the best agreement of the system of study with the reference system. In contrast to the description of media with short-range interactions, in this text the reference distribution includes not only the field of mean potentials but also Coulomb interaction between particles. A one-component system made of ions in a neutralizing background of fixed counterions is considered. The model can be used to describe solid ionic conductors. In order to study the movement of cations on the sites of their sub-lattice, the lattice approximation of the theory is employed based on the calculation of the pair distribution function. Using the collective variables approach, a technique improving the starting expression for this function is proposed. Notably, the neglected terms in the expansion of this function are approximated by single-particle terms ensuring that the normalization condition is satisfied. As a result, the applicability of the theory is extended to a wide region of thermodynamic parameters. The chemical potential and the diffusion coefficient are calculated showing the possibility of phase transitions characteristic of the system.