One Stone, Two Birds: Using High Electric Fields to Enhance the Mobility and the Concentration of Point Defects in Ion-Conducting Solids.

Improving the ionic conductivity of outstanding, composition-optimized crystalline electrolytes is a major challenge. Achieving increases of orders of magnitude requires, conceivably, highly nonlinear effects. One known possibility is the use of high electric fields to increase point-defect mobility. In this study, we investigate quantitatively a second possibility that high electric fields can increase substantially point-defect concentrations. As a model system, we take a pyrochlore oxide (La2Zr2O7) for its combination of structural vacancies and dominant anti-Frenkel disorder; we perform molecular-dynamics simulations with many-body potentials as a function of temperature and applied electric field. Results within the linear regime yield the activation enthalpies and entropies of oxygen-vacancy and oxygen-interstitial migration, and from three independent methods, the enthalpy and entropy of anti-Frenkel disorder. Transport data for the nonlinear regime are consistent with field-enhanced defect concentrations and defect mobilities. A route for separating the two effects is shown, and an analytical expression for the quantitative prediction of the field-dependent anti-Frenkel equilibrium constant is derived. In summary, we demonstrate that the one stone of a nonlinear driving force can be used to hit two birds of defect behavior.

A Single Model for the Thermodynamics and Kinetics of Metal Exsolution from Perovskite Oxides.

Exsolution has emerged as an outstanding route for producing oxide-supported metal nanoparticles. For ABO3-perovskite oxides, various late transition-metal cations can be substituted into the lattice under oxidizing conditions and exsolved as metal nanoparticles after reduction. A consistent and comprehensive description of the point-defect thermodynamics and kinetics of this phenomenon is lacking, however. Herein, supported by hybrid density-functional-theory calculations, we propose a single model that explains diverse experimental observations, such as why substituent transition-metal cations (but not host cations) exsolve from perovskite oxides upon reduction; why different substituent transition-metal cations exsolve under different conditions; why the metal nanoparticles are embedded in the surface; why exsolution occurs surprisingly rapidly at relatively low temperatures; and why the reincorporation of exsolved species involves far longer times and much higher temperatures. Our model's foundation is that the substituent transition-metal cations are reduced to neutral species within the perovskite lattice as the Fermi level is shifted upward within the bandgap upon sample reduction. The calculations also indicate unconventional influences of oxygen vacancies and A-site vacancies. Our model thus provides a fundamental basis for improving existing, and creating new, exsolution-generated catalysts.