Mixed-conducting solid oxide membrane

Lin, Y. S., Wang, W., and Han, J. (1994). Oxygen permeation through thin mixed-conducting solid oxide membranes, AIChE J. 40(5), 786. 

Oxygen separation through thick mixed-conducting solid oxide membrane... 

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... 

Solid mixed ionic-electronic conductors (MIECs) exhibit both ionic and electronic (electron-hole) conductivity. Naturally, in any material there are in principle nonzero electronic and ionic conductivities (a i, a,). It is customary to limit the use of the term MIEC to those materials in which a, and 0, 1 do not differ by more than two orders of magnitude. It is also customary to use the term MIEC if a, and Ogi are not too low (o, a i 10 S/cm). Obviously, there are no strict rules. There are processes where the minority carriers play an important role despite the fact that 0,70 1 exceeds those limits and a, aj,i< 10 S/cm. In MIECs, ion transport normally occurs via interstitial sites or by hopping into a vacant site or a more complex combination based on interstitial and vacant sites, and electronic (electron/hole) conductivity occurs via delocalized states in the conduction/valence band or via localized states by a thermally assisted hopping mechanism. With respect to their properties, MIECs have found wide applications in solid oxide fuel cells, batteries, smart windows, selective membranes, sensors, catalysis, and so on. 

Fig. 3. Oxygen transport in solids. 02 is dissociated and ionized at the reduction interface to give O2 ions, which are transferred across the solid to the oxidation interface, at which they lose the electrons to return back to 02 molecules that are released to the stream, (a) In the solid electrolyte cell based on a classical solid electrolyte, the ionic oxygen transport requires electrodes and external circuitry to transfer the electrons from the oxidation interface to the reduction interface (b) in the mixed conducting oxide membrane, the ionic oxygen transport does not require electrodes and external circuitry to transfer the electrons to the reduction interface from the oxidation interface, because the mixed conductor oxide provides high conductivities for both oxygen ions and electrons.

Strontium ferrite perovskite. The nonstoiehiometric strontium ion oxide SrFeOx (2.5solid state electrolyte itself, doped with rare earths or transition metals, it forms materials, whieh exhibit even greater ionie conductivity. These oxides are used as materials for self-supported oxygen conduetivity membranes. 

Fig. 10.1. Different membrane concepts incorporating an oxygen ion conductor (a) mixed conducting oxide, (b) solid electrolyte cell (oxygen pump), and (c) dual-phase membrane. Also shown is the schematics of an asymmetric porous membrane (d), consisting of a support, an intermediate and a barrier layer having a graded porosity across the membrane.

Decreasing operation temperature of solid oxide fuel cells (SOFCs) and electrocatalytic reactors down to 800-1100 K requires developments of novel materials for electrodes and catalytic layers, applied onto the surface of solid electrolyte or mixed conducting membranes, with a high performance at reduced temperatures. Highly-dispersed active oxide powders can be prepared and deposited using various techniques, such as spray pyrolysis, sol-gel method, co-precipitation, electron beam deposition etc. However, most of these methods are relatively expensive or based on the use of complex equipment. This makes it necessary to search for alternative synthesis and porous-layer processing routes, enabling to decrease the costs of electrochemical cells. Recently, one synthesis technique based on the use... 

As in the case of the previous family of iron perovskites, this new series of compounds are of interest for their use as mixed ionic electronic conducting materials, mainly from the point of view of cathodes for Solid Oxide Fuel Cells (SOFC), although they could also be used as ceramic membranes for oxygen separation. In the ptresent case, the degree of lanthanide substitution was fixed to x=0.5 given that previous studies have shown that it is precisely at this degree of substitution when electronic and ionic conductivity are maximised (Hansen, 2010 Vidal et al., 2007). 

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