Perovskite-type mixed-conducting materials

Since the membrane conducts oxygen ions, in the great majority of the cases through a mechanism involving anion vacancy diffusion, an equivalent counterflux of electrons should take place for charge neutrality membrane materials should be mked conductors. Perovskite-type mixed-conducting materials are considered suitable candidates for use in dense membrane reactor chemical looping processes, since they fulfill most of the required characteristics. 

Some of the many different types of catalysts which have good catalytic properties for the OCM reaction qualify as membrane materials. Membrane reactors for OCM were designed and tested by Nozaki et al. (1992). Three kinds of reactors were developed the first one consisted of a porous membrane covered with a thin film of catalyst (type I) the second one, a dense ionic-conducting membrane (non porous) with catalytic layer (type II) and the third one was a membrane made of perovskite-type mixed oxides which was active for OCM (type III). Figure 11 presents the diagram for the membrane reactor system and table 13 shows the different materials used for supports and coated catalysts. 

Acceptor doping in perovskite oxides gives materials with a vacancy population that can act as proton conductors in moist atmospheres (Section 6.9). In addition, the doped materials are generally p-type semiconductors. This means that in moist atmospheres there is the possibility of mixed conductivity involving three charge carriers (H+, O2-, and h ) or four if electrons, e, are included. 

As described in Section 8.2.6, along with YSZ, mixed oxygen-ion, and electron-conducting oxides with a perovskite-type structure, the so-called Aurivillius phase and pyrochlore materials are fundamentally used for the production of a variety of high-temperature electrochemical devices [50-58],... 

The limits of integration are the oxygen partial pressures maintained at the gas phase boundaries. Equation (10.10) has general validity for mixed conductors. To carry the derivation further, one needs to consider the defect chemistry of a specific material system. When electronic conductivity prevails, Eqs. (10.9) and (10.10) can be recast through the use of the Nemst-Einstein equation in a form that includes the oxygen self-diffusion coefficient Dg, which is accessible from ionic conductivity measurements. This is further exemplified for perovskite-type oxides in Section 10.6.4, assuming a vacancy diffusion mechcinism to hold in these materials. 

Additional attempts have been presented to render hosts with the fluorite and the related pyrochlore structure electronically conductive by doping with mixed-valence and/or shallow dopants. The list of dopant materials examined includes oxides of elements of, for example, Ti, Cr, Mn, Fe, Zn, Fe, Sn, Ce, Pr, Gd, Tb and U. In general, however, the extent of mixed conductivity that can be obtained in fluorite-type ceramics is rather limited, by comparison with the corresponding values found in some of the perovskite and perovskite-related oxides considered in the next section. 

The considerations in this chapter were mainly prompted by the potential application of mixed-conducting perovskite-type oxides to be used as dense ceramic membranes for oxygen delivery applications, and lead to the following general criteria for the selection of materials... 

Teraoka, Y., Zhang, H. M., Okrunoto, K. Yattrazoe, N. Mixed ionic-electronic conductivity of Lal-xSrxCol-yFey03-8 perovskite-type oxides. Materials Research Bulletin 23, 51-58, doi Doi 10.1016/0025-5408(88)90224-3 (1988). 

Zhang, K., Sunarso, J., Shao, Z., Zhou, W Sun, C., Wang, S., and Liu, S. (2011) Research progress and materials selection guidelines on mixed conducting perovskite-type ceramic membranes for oxygen production. RSC Adv., 1, 1661-1676. 

Continuous air separation by an oxygen-conducting membrane which constitutes the wall of a CPO reactor is another approach which has received much interest, also from industry. Two types of membrane materials have been studied zirkonia-based membranes, which are efficient oxygen ion conductors but require electrodes to transfer electrons to the reduction interface, and perovskites (of general formula ABO3, with dopants in the A and/or B site), which are mixed ionic/electronic conductors (MIEC). ... 

Some perovskite-type oxides having transition elements at B sites exhibit mixed conduction at elevated temperatures. A typical example is doped lanthanum cobaltite, in which oxide ions and holes are charge carriers. The electronic conductivity is a few orders of magnitudes higher than that of the oxide-ionic although the ionic conductivity itself is sufficiently high (>10 S cm at several 100°Q. This kind of mixed conductor is a promising candidate for the electrode materials of SOFCs and ceramic membrane reactors and is described in Chapters 7 and 8 in detail. 

---