Proton-conducting perovskites are among the most promising electrolytes for Proton Ceramic Fuel Cells (PCFCs), electrolysers and separation membranes. Particularly, yttrium-doped barium cerate, BaCe1-xYxO3-δ (BCY), shows one of the highest protonic conductivities at intermediate temperatures (σ ∼ 10−3 S cm−1 at 400°C); values that are typically achieved under humidified atmospheres (pH2O ∼ 10−2 atm). However, BCY has commonly been discarded for such applications due to its instability in the presence of water vapour and carbonaceous atmospheres. A recent discovery has shown that BCY10 exhibits pure protonic conductivity under very low humidity contents (∼10−5–10−4 atm), owing to its very high equilibrium constant for hydration. This peculiar characteristic allows this material to retain its functionally as a proton conductor in such conditions, while preventing its decomposition. Hence, this chapter explores the electrochemical properties of the BaCe0.9Y0.1O3-δ (BCY10) composition, comprehensively establishing its limiting operation conditions through defect chemistry and thermodynamic analyses. Moreover, the importance of such conditions is highlighted with respect to potential industrially relevant hydrogenation/de-hydrogenation reactions at low temperatures under low humidity.
Part of the book: Analytical Chemistry