Thermodynamics of Electromechanically-Coupled Mixed Ionic-Electronic Conductors: Deformation potential, Vegard strains and Flexoelectric effect

TL;DR

This paper develops a thermodynamic framework to analyze the complex electromechanical coupling in mixed ionic-electronic conductors, incorporating effects like deformation potential, Vegard strains, and flexoelectricity, relevant for various electrochemical devices.

Contribution

It introduces generalized equations for bias, concentration, and strain in MIECs, including novel considerations of flexoelectric effects and local surface displacements caused by electric fields.

Findings

Derived new bias-concentration-strain equations for MIECs.

Extended analysis to scanning probe microscopy geometries.

Identified the role of flexoelectric coupling in surface displacement.

Abstract

Strong coupling among external voltage, electrochemical potentials, concentrations of electronic and ionic species, and strains is a ubiquitous feature of solid state mixed ionic-electronic conductors (MIECs), the materials of choice in devices ranging from electroresistive and memristive elements to ion batteries and fuel cells. Here, we analyze in detail the electromechanical coupling mechanisms and derive generalized bias-concentration-strain equations for MIECs including effects of concentration-driven chemical expansion, deformation potential, and flexoelectric effect contributions. This analysis is extended towards the bias-induced strains in the uniform and scanning probe microscopy-like geometries. Notably, the contribution of the electron-phonon and flexoelectric coupling to the local surface displacement of the mixed ionic-electronic conductor caused by the electric field scanning probe microscope tip has not been considered previously. The developed thermodynamic approach allows evolving theoretical description of mechanical phenomena induced by the electric fields (electro-mechanical response) in solid state ionics towards analytical theory and phase-field modeling of the MIECs in different geometries and under varying electrical, chemical, and mechanical boundary conditions.