Mixed proton—electron conducting oxide

Defect-structure-wise there are two main routes to a mixed proton-electron conducting oxide. The simplest would be to dissolve protons compensated by electrons originating directly from hydrogen gas ... 

Ceramic electrochemical reactors are currently undergoing intense investigation, the aim being not only to generate electricity but also to produce chemicals. Typically, ceramic dense membranes are either pure ionic (solid electrolyte SE) conductors or mixed ionic-electronic conductors (MIECs). In this chapter we review the developments of cells that involve a dense solid electrolyte (oxide-ion or proton conductor), where the electrical transfer of matter requires an external circuitry. When a dense ceramic membrane exhibits a mixed ionic-electronic conduction, the driving force for mass transport is a differential partial pressure applied across the membrane (this point is not considered in this chapter, although relevant information is available in specific reviews). 

As the mixed proton and electron conductive oxide membrane becomes sufficiently thin, surface kinetics will become important, and difiusion of protons across the membrane will no longer be rate deterrriining for the overall hydrogen flux. Bouwmeester et al. [10] defined a characteristic thickness, L, for membranes where surface kinetics and bulk kinetics are equally important to the flux. Decreasing a membrane s thickness below gives essentially no increase in the flux. 

With the requirement of electronic conductivity, oxides containing cations with mixed valence and, in particular, reducible cations are preferable. Oxides containing transition metals are therefore appropriate alternatives. There are indications based on conductivity measurements that Ti02 could be a possible candidate [83], but no direct measurements of hydrogen permeability have been reported. Tita-nates, in general, however, are interesting because there are a number of materials classes that accommodate oxygen vacancies and may dissolve protons. 

Today, the term solid electrolyte or fast ionic conductor or, sometimes, superionic conductor is used to describe solid materials whose conductivity is wholly due to ionic displacement. Mixed conductors exhibit both ionic and electronic conductivity. Solid electrolytes range from hard, refractory materials, such as 8 mol% Y2C>3-stabilized Zr02(YSZ) or sodium fT-AbCb (NaAluOn), to soft proton-exchange polymeric membranes such as Du Pont s Nafion and include compounds that are stoichiometric (Agl), non-stoichiometric (sodium J3"-A12C>3) or doped (YSZ). The preparation, properties, and some applications of solid electrolytes have been discussed in a number of books2 5 and reviews.6,7 The main commercial application of solid electrolytes is in gas sensors.8,9 Another emerging application is in solid oxide fuel cells.4,5,1, n... 

A series of perovskite compositions were synthesized using oxides and carbonates of the cations by conventional ceramic process. The synthesized powders were characterized using powder x-ray diffraction technique to ensure phase purity. Conductivity measurements were made in H2-H2O atmosphere to determine proton conductity. As the perovskite compositions are inherently mixed conducting, the transference numbers for proton and electron conduction were also determined by varying the partial pressures of hydrogen and steam across the membrane. 

Acceptor-doped SrCe03 is, without doubt, the mixed electron-proton conducting oxide system most studied, both with respect to actual measurements of... 

Key words membrane reactor, perovskite, proton conducting membrane, mixed ionic-electronic conductor (MIEC), partial oxidation of methane... 

---