Zirconia electronic conduction

The anode material in SOF(7s is a cermet (rnetal/cerarnic composite material) of 30 to 40 percent nickel in zirconia, and the cathode is lanthanum rnanganite doped with calcium oxide or strontium oxide. Both of these materials are porous and mixed ionic/electronic conductors. The bipolar separator typically is doped lanthanum chromite, but a metal can be used in cells operating below 1073 K (1472°F). The bipolar plate materials are dense and electronically conductive. 

In general Zr02 oxygen sensors consist of a tube-like solid-state Zr02 electrolyte where the electronic conductivity is based on oxygen ion charge carrier transport. The inner and outer surface of the yttrium-doped and stabilized zirconia tube is covered by porous platinum electrodes. 

A number of oxides with the fluorite structure are used in solid-state electrochemical systems. They have formulas A02 xCaO or A02 xM203, where A is typically Zr, Hf, and Th, and M is usually La, Sm, Y, Yb, or Sc. Calcia-stabilized zirconia, ZrC)2.xCaO, typifies the group. The technological importance of these materials lies in the fact that they are fast ion conductors for oxygen ions at moderate temperatures and are stable to high temperatures. This property is enhanced by the fact that there is negligible cation diffusion or electronic conductivity in these materials, which makes them ideal for use in a diverse variety of batteries and sensors. 

The solid oxide electrolyte must be free of porosity that permits gas to permeate from one side of the electrolyte layer to the other, and it should be thin to minimize ohmic loss. In addition, the electrolyte must have a transport number for O as close to unity as possible, and a transport and a transport number for electronic conduction as close to zero as possible. Zirconia-based electrolytes are suitable for SOFCs because they exhibit pure anionic conductivity over a wide... 

Yttria stabilized zirconia formed by this reaction fills the air electrode pores. The dynamics of this CVD stage has been modeled by Carolan and Michaels [120], who observed that films produced in this manner penetrate the substrate no more than 2-3 pore diameters from the chloride face of the substrate. It has also been shown that the penetration depth is independent of water concentration. The second step of this method is the EVD step. Once pore closure is achieved, the reactants are not longer in contact. Electrochemical semipermeability related to the existence of small electronic conductivity and large gradient of oxygen partial pressure leads to oxygen transport from the steam side to the chloride side through the deposited electrolyte. The electrochemical reactions involved are ... 

Electrolyte-cubic stabilized zironia Almost without exception cubic stabilized zirconia is the chosen ceramic for the electrolyte in SOFCs. This is because of its adequate conductivity and almost total absence of electronic conductivity, and because it is stable against the wide range of oxygen partial pressures ( 1 atm. to 10 20 atm.) encountered in a fuel cell. Also, because of a combination of availability and cost the favoured compound is yttria-stabilized zirconia, ZrO2+8-10mol.% Y203 (YSZ). 

A third path, namely the ionization of the oxygen on the electrolyte surface followed by a direct incorporation into the electrolyte, can also not be excluded. In this case the electronic charge carriers, which are required in the oxygen reduction reaction, have to be supplied from the electrolyte. In solid electrolytes with very low electronic conductivity (e.g. zirconia), it can therefore be expected that the active zone is restricted to a region very close to the three-phase boundary. Hence, this path is, from a geometrical point of view, similar to the surface path discussed above. 

---