Intrinsic Dipole Moments and Electron Transfer at the MIEC-Gas Interfaces

Abstract

The catalytic and transport properties of mixed ionic-electronic conducting (MIEC) electrodes for solid oxide fuel cells (SOCs) are well documented and utilised, yet poorly understood. In the current study, a novel kinetic framework for the electrochemical behaviour of hydrogen at the MIEC-gas interface will be discussed for three parallel treatments: as an ideal gas, as an adsorbate on the electrode surface and as a charge carrier dissolved in the oxide lattice. This model gives a physically meaningful reason for the enhancement in electrochemical activity of a MIEC electrode as the steam pressure is increased in both fuel cell and electrolysis modes, and is ubiquitous for any electrochemical system where the electric double layer is described as a Heaviside step function.The process of charge transfer at the MIEC electrode/gas interface comprises of ambipolar exchange of ions and electronic species. The result of such a process causes charge separation and an associated dipole moment at the electrode surface. By applying an overpotential η to the MIEC electrode, an electrostatic surface potential shift away from equilibrium may be established where an effective double layer is formed between the electrode surface and the adsorbed species. Although no net charge transfer occurs, this surface potential shift modifies the surface chemistry and is the driving force for the ambipolar exchange of ions and electronic species.Density Functional Theory (DFT) calculations were used to study the electrostatic potential at the ceria [111] surface, where we were able to calculate the dipole moment and adsorption energy as a function of hydroxyl coverage. The theory of the electrostatic potential at the MIEC-gas interface was then applied to predict the surface electrochemical properties as a function of local overpotential. The mechanistic understanding gained from this model is widely applicable to a range of MIEC systems and provides a basis upon which the operating conditions can be tailored.