Mechanochemical processing of BaZr1−yYyO3−δ (y = 0.15, 0.20) protonic ceramic electrolytes: Phase purity,microstructure, electrical properties and comparison with other preparation routes

BaZrO₃-based materials have been intensively researched due to their potential application as high-temperature proton conductors in devices such as proton ceramic fuel cells (PCFCs), separation membranes and electrolysers. Nonetheless, their implementation in these devices has often been constrained due to their processing difficulties, namely the formation of Ba-deficient compositions, coexistence of separate perovskite phases or the formation of segregated phases of the acceptor dopant. In this context, the current article shows mechanosynthesis to be an efficient preparation method for Ba(Zr,Y)O_3-δ materials, producing pure powders, containing nanometric crystallites, that offer good densification and grain growth. The phase formation, microstructure and electrical properties of the most promising BaZr_1-yY_yO_3-δ compositions, with yttrium contents of y = 0.15 (BZY15) and y = 0.20 (BZY20) are investigated and compared with literature data of materials made by other processing routes. Such a comparison highlights that phase separation of such compositions, commonly reported in the literature, does not occur for these mechanosynthesised materials of high homogeneity. Furthermore, high electrical performances can be obtained by this technique that can compete with some of the best reported in the literature. Electrical conductivity as a function of both oxygen and water partial pressure, in the temperature range of 550 °C ? 850 °C, are measured for both compositions and the partial conductivities of protons, oxygen vacancies and electron holes are determined from the defect model. The electron-hole conductivity of BZY20 is observed to be higher than that of BZY15 under all conditions, while proton and oxide-ion conductivities are shown to be higher for the composition BZY15.