Surface Segregation Entropy of Protons and Oxygen Vacancies in BaZrO3

The perovskite BaZrO3 has attracted considerable attention in the recent decade due to its high temperature proton conducting properties, and possible application as electrolyte in intermediate temperature fuel cells and electrolyzers. In this contribution, we performed, for the first time, first-principles calculations of the phonon contribution to the defect thermodynamics of the ZrO2 terminated (001) surface of BaZrO3. The approach allows us to determine both the segregation enthalpy and entropy of defects, which we apply to two fundamental defects in BaZrO3; fully charged oxygen vacancies (vO••) and protonic defects (OHO•). The calculations show that both defects exhibit favorable segre…