Gadolinium-Vacancy Clusters in the (111) Surface of Gadolinium-Doped Ceria: A Density Functional Theory Study

High Resolution Image Download MS PowerPoint Slide Solid-oxide fuel cells are promising devices for sustainable power generation. Electrolyte materials play an important role in connecting the anode and cathode, and they influence the performance of the device. In this context, gadolinium-doped ceria (GDC) has proven to be an efficient electrolyte material, although the presence of dopant clusters can lower its efficiency. After usage, dopant clusters start appearing at dislocations, translocations, grain boundaries, or surfaces. Hence, the study of dopant clustering at the atomic level near these regions becomes of vital importance, as it allows us to understand the reasons for the occurrence of this phenomenon and its impact on the oxygen conduction. In this context, the present paper studies the impact of dopant clustering near the (111) GDC surface. We have studied two different gadolinium concentrations in the material, of approximately 7% and 14%, which are close to the optimum concentration of 10%. Our results indicate that surface relaxation is a key factor in determining the preference of defect clusters to be found in the surface. We have also calculated the relative abundance of different defect clusters at different temperatures, including the configurational entropy term. It was revealed that working temperatures (650–1100 K) show the relative abundance of different cluster structures, displaying that, at high concentrations, preferred dopant clusters resemble the structure of Gd 2 O 3, showing the formation of gadolinia domains. Finally, we show that oxygen diffusion will be affected by the formation of these domains. After evaluating the oxygen mobility, we conclude that oxygen vacancies will be trapped by the gadolinium clusters at the surface. These vacancy traps prevent oxygen diffusion, thereby affecting negatively the performance of the material and the fuel cell in general.