Zirconia ionic conductivity

Ionic conductivity is used in oxygen sensors and in batteries (qv). Stabilized zirconia, Zr Ca 02 has a very large number of oxygen vacancies and very high conductivity. P-Alurnina/72(9(9j5 -4< -(y, NaAl O y, is an excellent cation conductor because of the high mobiUty of Na" ions. Ceramics of P-alurnina are used as the electrolyte in sodium-sulfur batteries. 

Other refractory oxides that can be deposited by CVD have excellent thermal stability and oxidation resistance. Some, like alumina and yttria, are also good barriers to oxygen diffusion providing that they are free of pores and cracks. Many however are not, such as zirconia, hafnia, thoria, and ceria. These oxides have a fluorite structure, which is a simple open cubic structure and is particularly susceptible to oxygen diffusion through ionic conductivity. The diffusion rate of oxygen in these materials can be considerable. 

SOE cells utilize solid ceramic electrolytes (e.g. yttria stabilized zirconia) that are good oxygen ion (0 ) conductors at very high temperatures in the range of 1000°C [8]. The operating temperature is decided by the ionic conductivity of the electrolyte. The feed gas, steam mixed with hydrogen, is passed through the cathode compartment. At the cathode side, the reaction is... 

Figure 10. Ionic conductivity of jully and partially stabilized zirconia bodies...

As can be seen, the mechanical strength of the partially stabilized body is approximately twice that of the fully stabilized and the thermal expansion is approximately 30% lower. Because of this, the thermal shock resistance of the PSZ body is greatly improved. The ionic conductivity of the PSZ body is lower but is still adequate for automotive applications. Figure 10 compares the conductivity of a yttria partially stabilized zirconia body with several fully stabilized bodies. 

Other fairly common stabilizers for zirconia include MgO (low cost but poor ionic conductivity and stability) and Sc20 (good ionic conductivity but high cost). 

Solid electrolytes, which show ionic conductivity in the solid state, are considered to be potential materials for practical use, some are already used as mentioned below. Solid electrolytes have characteristic functions, such as electromotive force, ion selective transmission, and ion omnipresence. Here we describe the practical use of calcia stabilized zirconia (CSZ), (Zr02)o,85(CaO)o 15, the structure and basic properties of which are discussed in detail in Sections 1.4.5 1.4.8. 

It has been reported (4,5) that solid electrolyte sensors using stabilized zirconia can detect reducible gases in ambient atmosphere by making use of an anomalous EMF which is unusually larger than is expected from the Nernst equation. However, these sensors should be operated in a temperature range above ca. 300°C mainly because the ionic conductivity of stabilized zirconia is too small at lower temperatures. On the other hand, solid state proton conductors such as antimonic acid (6,1), zirconium phosphate (8), and dodecamolybdo-phosphoric acid (9) are known to exhibit relatively high protonic conductivities at room temperature. We recently found that the electrochemical cell using these proton conductors could detect... 

A controlled modification of the rate and selectivity of surface reactions on heterogeneous metal or metal oxide catalysts is a well-studied topic. Dopants and metal-support interactions have frequently been applied to improve catalytic performance. Studies on the electric control of catalytic activity, in which reactants were fed over a catalyst interfaced with O2--, Na+-, or H+-conducting solid electrolytes like yttrium-stabilized zirconia (or electronic-ionic conducting supports like Ti02 and Ce02), have led to the discovery of non-Faradaic electrochemical modification of catalytic activity (NEMCA, Stoukides and Vayenas, 1981), in which catalytic activity and selectivity were both found to depend strongly on the electric potential of the catalyst potential, with an increase in catalytic rate exceeding the rate expected on the basis of Faradaic ion flux by up to five orders of... 

One of the exceptions was the discovery of high ionic conductivity in appropriately doped FaGa03.128 129 As in the other oxide ion conductors, its ionic conductivity depends on both the dopant level as well as on the nature of the dopant. A major difference to ceria and zirconia is the presence of two cations that can be substituted the detailed defect chemistry of such solid solutions is far from being fully understood. Co-doping of Sr on A sites and Mg on B-sites leads to an ionic conductivity of ca. 0.12—0.17 S cm 1 at 800°C,130-133 which is similar to doped ceria but considerably exceeds the value of YSZ (ca. 0.03 S cm 1 at 800°C80 81). The activation energy also varies with composition and can be as low as ca. 0.6 eV.130 131 At about 600-700°C, the... 

For the HTE process, the electrochemical cell consists of a tri-layer ceramic, well known for its brittleness, which limits applied loads. In addition, the relatively low ionic conduction properties of the electrolyte materials (3% yttrium-stabilised zirconia) requires an operating temperature above 700°C to reduce ohmic losses. This creates difficulties for the involved metallic materials, including bipolar plates and seals. 

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