Electrolytic expansion applications

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. 

An alternative to the Co-rich perovskites is the Sr-doped LaFe03 which has a lower thermal expansion coefficient and a superior chemical compatibility with doped Ce02 electrolyte. LaFe03 is expected to be more stable than Ni- and Co-based perovskites because the Fe3+ ion has the stable electronic configuration 3d5. It is, therefore, expected that compositions in the system (La,Sr)(Co,Fe)03 will have desirable properties for intermediate temperature SOFC cathode applications. 

The issue of mismatch of thermal expansion coefficients similar to that for a composite membrane is also very critical for fuel cells. In the fuel cells, electrodes are attached to solid electrolyte membranes. Significant temperature variations during applications, pretreatments or regeneration of the membranes (e.g., decoking) can cause serious mechanical problems associated with incompatible thermal expansions of different components. A possible partial solution to the above problem is to use partially stabilized instead of fully stabilized zirconia. The former has a significantly lower thermal expansion coefficient than the latter. 

Furthermore, the electrode material must be reasonably stable and not change its volume as a result of reduction or oxidation because such a volume change may cause the electrode to peel off the electrolyte. Also, the thermal expansion coefficient (TEC) of the electrode material must be close to the electrolyte material. Thus, in order to select a proper composition of the doped ceria for a specific electrode application, it is necessary to have knowledge of the ceria chemistry and its relation to the thermal, crystallograhical and electrical properties of the doped ceria. Therefore, the next sections briefly describe the ceria chemistry and the related properties. 

Another feature of AGM separators is their compressibility. With compression of the plate and separator stack, this AGM property guarantees good plate-separator contact, even if the plates are not perfectly smooth. Also, battery assembly is facilitated since the stack can be easily inserted into the cell after compression to a thickness lower than the cell dimension. An undesirable result of the compressibility is that the AGM separator does not exert sufficient resistance against expansion of the positive plate during battery cycle-life. This expansion is particularly prevalent in deep-cycle applications and can cause the battery to suffer premature capacity loss (PCL) via reduced inter-particle conductivity — a phenomenon known as PCL-2 [7]. In the literature, two additional characteristics, which are related to the PCL-2 failure mode, are discussed, namely, AGM separators shrink when first wetted with electrolyte and their fibres can be crushed at high pressure levels [8-10]. These features result in a loss of separator resilience, i.e., a lessening of the ability to display a reversible spring effect. 

If batteries are to be operated at elevated temperatures for extended periods, the relative density of the electrolyte should be decreased appropriately (generally to between 1.260 and 1.240). For low-temperature applications, batteries should have a large volume of electrolyte of high relative density to minimize the likelihood of freezing, and compressible separators and/or spacers that can absorb expansion should freezing and related expansion occur. The gel battery is considered to be the most appropriate VRLA technology for this task, as it can be constructed with an excess of acid. It also uses microporous separators, which should reduce the likelihood of short-circuits if the electrolyte were to freeze and expand. 

The purpose of this paper is to review two thermodynamic models for calculating aqueous electrolyte properties and give examples of parameter evaluations to high temperatures and pressures as well as applications to solubility calculations. The first model [the ion-interaction model of Pitzer (1) and coworkers] has been discussed extensively elsewhere (1-4) and will be reviewed only briefly here, while more detail will be given for an alternate model using a Margules expansion as proposed by Pitzer and Simonson (5). 

Aqueous solutions can be modeled by writing a virial equation such as (17.37) in which osmotic pressure replaces pressure. Friedman (1962) describes applications of cluster expansion theory, which include long-range Coulombic potentials as well as short-range square-well potentials that operate when unlike ions approach within the diameter of a water molecule. These models are mathematically quite cumbersome and are not easily used for routine calculations. They do predict the non-ideal behavior of simple electrolytes such as NaCl quite admirably at moderate concentrations however, they use the square-well potential as an adjustable parameter and so retain some of the properties of the D-H equation with an added adjustable term. For this reason these are not truly a priori models. 

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