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Protonic ceramics have unique transport properties that make them suitable for applications in intermediate temperature fuel cells and steam electrolyzers, hydrogen separation membranes, and various membrane reactors for chemical synthesis. Since the discovery of ceramic proton conductors more than twenty years ago, and the ensuing enthusiasm, practical issues relating to ceramic fabrication have hampered advancement of the technology. The best ceramic proton conductors were thought to be acceptor-doped barium cerates, but these turned out not to be chemically stable in the typical use environments. The other leading candidates, acceptor-doped barium zirconates, proved too difficult to sinter. Most other protonic ceramics investigated either exhibited much lower conductivity or poor chemical stability. Two breakthroughs have recently taken place making it feasible, for the first time, to manufacture these ceramic proton conductors commercially and inexpensively with the prerequisite properties. First, the recognition that barium cerate and barium zirconate form a complete solid solution (BaCexZry-xY1-yO3, for all values of 1 > y > 0.8 and x between 0 and y), has made it possible to tailor the mechanical, chemical and transport properties for various applications. Second, the discovery of solid state reactive sintering has made it possible to prepare dense, phase-pure ceramics at reasonable temperatures. This chapter describes fabrication and characterization of BCZY proton conductors using 1-2 wt% NiO as a sintering additive for solid state reactive sintering.

Co-Ionic Conduction in Protonic Ceramics of the Solid Solution, BaCe(x)Zr(y-x)Y(1-y)O3- Part I: Fabrication and Microstructure