Electronic conductivity metallic perovskites

In this chapter the focus is upon electronic conductivity in perovskites. The electrons in perovskites are believed to be strongly correlated that is, they do not behave as a classical electron gas, but are the subject to electron-electron interactions. This leads to considerable modification of the collective electron behaviour of the conduction electrons, resulting in metal-insulator transitions, high-temperature superconductivity, half-metals and colossal magnetoresistance (CMR). The effects of strong correlation are important for the 3d, 4d and4f elements. In many ways the topics described here are thus a continuation of the previous chapter on magnetic perovskites, and in truth the two subject areas cannot be separated in a hard and fast maimer. 

At the other end of the conduction spectrum, many oxides have conductivities dominated by electron and positive hole contributions to the extent that some, such as Re03, SnOa and tire perovskite LaCrOs have conductivities at the level of metallic conduction. High levels of p-type semiconduction are found in some transition metal perovskites especially those containing alio-valent ions. Thus the lanthairum-based perovskites containing transition metal ions, e.g. LaMOs (M-Cr, Mn, Fe, Co, Ni) have eirlranced p-type semiconduction due to the dependence of the transition metal ion valencies on the ambient... 

Although several metals, such as Pt and Ag, can also act as electrocatalysts for reaction (3.7) the most efficient electrocatalysts known so far are perovskites such as Lai-xSrxMn03. These materials are mixed conductors, i.e., they exhibit both anionic (O2 ) and electronic conductivity. This, in principle, can extend the electrocatalytically active zone to include not only the three-phase-boundaries but also the entire gas-exposed electrode surface. 

In this chapter the technological development in cathode materials, particularly the advances being made in the material s composition, fabrication, microstructure optimization, electrocatalytic activity, and stability of perovskite-based cathodes will be reviewed. The emphasis will be on the defect structure, conductivity, thermal expansion coefficient, and electrocatalytic activity of the extensively studied man-ganite-, cobaltite-, and ferrite-based perovskites. Alterative mixed ionic and electronic conducting perovskite-related oxides are discussed in relation to their potential application as cathodes for ITSOFCs. The interfacial reaction and compatibility of the perovskite-based cathode materials with electrolyte and metallic interconnect is also examined. Finally the degradation and performance stability of cathodes under SOFC operating conditions are described. 

To meet the requirements for electronic conductivity in both the SOFC anode and cathode, a metallic electronic conductor, usually nickel, is typically used in the anode, and a conductive perovskite, such as lanthanum strontium manganite (LSM), is typically used in the cathode. Because the electrochemical reactions in fuel cell electrodes can only occur at surfaces where electronic and ionically conductive phases and the gas phase are in contact with each other (Figure 6.1), it is common... 

In addition to being able to catalyze the dissociation of O2. the material used for the cathode must be electronically conductive in the presence of air at high temperature, a property found primarily in noble metals and electronically conductive oxides. Ionic conductivity is also desirable for extending the reaction zone well into the electrode since the ions must ultimately be transferred to the electrolyte. Since precious metals are prohibitively expensive when used in quantities sufficient for providing electronic conductivity, essentially all SOFC prototypes use perovskite-based cathodes, with the most common material being a Sr-doped LaMnOs (LSM). In most cases, the cathode is a composite of the electronically conductive ceramic and an ionically conductive oxide, often the same material used in the electrolyte. 

In contrast, in most ion-selective membranes the charge conduction is done by ions. Thus, a mismatch between the charge-transfer carriers can exist at the noble metal/membrane interface. This is particularly true for polymer-based membranes, which are invariably ionic conductors. On the other hand, solid-state membranes that exhibit mixed ionic and electronic conductivity such as chalcogenide glasses, perovskites, and silver halides and conducting polymers (Lewenstam and Hulanicky, 1990) form good contact with noble metals. 

In the case of oxygen transport the best prospects at this moment are the use of metal-oxide composites with high electronic conductivity, or separation with perovskite-derived membranes as reported by Balachandral et al. [22]. These latter membranes are thick (0.5-1.0 mm) and have long-term stability at high temperature. 

The late transition metal-containing perovskites exhibit high electronic conductivities. In the materials which receive prime interest for oxygen delivery applications, the electronic contribution at high temperature of operation is usually predominant. The values for e.g., Lai rxCoi.yFey03 at 800°C in air... 

The comparison of mixed-potential emf from perovskite, fluorite, and spinel metal-oxide electrodes used in the mixed-potential HC sensors was presented [95] for justification of using the precatalyst to mitigate cross-reference. The thermodynamic, chemical and mechanical stability in the exhaust gases, sufficient electron conductivity to control device impedance, as well as the ability to generate stable... 

The other approach to increase the electronic conductivity of these perovskite-based membranes is to add a metal phase (10-40 vol%). The metal phases studied include palladium, niobium, tantalum, vanadium and zirconium or their binary mixtures [69-72]. In order to nrmirtiize the stress at internal interfaces that can lead to the formation of dislocations and initiation of cracks, the ceramic support materials were chosen so as to be lattice matched to the metals and metal alloys [73]. 

There are several advantages to using a dual-phase membrane over a singlephase mixed electronic ionic conductor. These include the fact that the ionic conductors such as YSZ are much more chemically and thermally stable compared to most perovskites. Thus, dual-phase membranes are Ukely to be able to tolerate the harsh conditions of an oxygen separation device. They also show good tolerance to both CO2 and steam. The difficulty comes in the selection of an electronically conducting material. The cost of noble metals makes their incorporation into commercial devices unlikely. Therefore, the electron-conducting phase is Umited to a... 

The perovskite materials which are considered suitable for the electron-conducting phase are based around the generic composition (Ln,Ae)Tm03, where Ln is a lanthanide, most commonly lanthanum, Ae is an alkaline earth, most commonly calcium, strontium or barium, and Tm is a transition metal, most commonly Ti,... 

---