Ionic high-temperature

Studies in solid state ionics, high temperature electrochemistry and fuel cells have been financed at EPFL by the Swiss Federal Office of Energy, by the Federal Office of Education and Science for participation in European Union research projects, and by the National Priority Programme for Materials (now terminated). The work continues in the context of the International Energy Agency programme for research, development and demonstration of advanced fuel cells, and of the European Science Foundation consortium OSSEP. 

Allan N L, G D Barrera, J A Purton, C E Sims and M B Taylor 2000. Ionic Solids at High Temperatures and Pressures Ah initio, Lattice Dynamics and Monte Carlo Studies. Physical Chemistry Chemical Physics 2 1099-1111. 

Different types of other coal liquefaction processes have been also developed to convert coals to liqnid hydrocarbon fnels. These include high-temperature solvent extraction processes in which no catalyst is added. The solvent is usually a hydroaromatic hydrogen donor, whereas molecnlar hydrogen is added as a secondary source of hydrogen. Similar but catalytic liquefaction processes use zinc chloride and other catalysts, usually under forceful conditions (375-425°C, 100-200 atm). In our own research, superacidic HF-BFo-induced hydroliquefaction of coals, which involves depolymerization-ionic hydrogenation, was found to be highly effective at relatively modest temperatnres (150-170°C). 

Applications. Polymers with small alkyl substituents, particularly (13), are ideal candidates for elastomer formulation because of quite low temperature flexibiUty, hydrolytic and chemical stabiUty, and high temperature stabiUty. The abiUty to readily incorporate other substituents (ia addition to methyl), particularly vinyl groups, should provide for conventional cure sites. In light of the biocompatibiUty of polysdoxanes and P—O- and P—N-substituted polyphosphazenes, poly(alkyl/arylphosphazenes) are also likely to be biocompatible polymers. Therefore, biomedical appHcations can also be envisaged for (3). A third potential appHcation is ia the area of soHd-state batteries. The first steps toward ionic conductivity have been observed with polymers (13) and (15) using lithium and silver salts (78). 

Kinetic mles of oxidation of MDASA and TPASA by periodate ions in the weak-acidic medium at the presence of mthenium (VI), iridium (IV), rhodium (III) and their mixtures are investigated by spectrophotometric method. The influence of high temperature treatment with mineral acids of catalysts, concentration of reactants, interfering ions, temperature and ionic strength of solutions on the rate of reactions was investigated. Optimal conditions of indicator reactions, rate constants and energy of activation for arylamine oxidation reactions at the presence of individual catalysts are determined. 

None of the interesting materials just described are the direct ancestors of the present generation of ionic liquids. Most of the ionic liquids responsible for the burst of papers in the last several years evolved directly from high-temperature molten salts, and the quest to gain the advantages of molten salts without the disadvantages. It all started with a battery that was too hot to handle. 

It should also be noted that terms such as high temperature and low temperature are also subjective, and depend to a great extent on experimental context. If we exclusively consider ionic liquids to incorporate an organic cation, and further limit the selection of salts to those that are liquid below 100 °C, a large range of materials are still available for consideration. 

Neutron diffraction has been used extensively to study a range of ionic liquid systems however, many of these investigations have focussed on high-temperature materials such as NaCl, studied by Enderby and co-workers [3]. A number of liquid systems with relatively low melting points have been reported, and this section summarizes some of the flndings of these studies. Many of the salts studied melt above 100 °C, and so are not room-temperature ionic liquids, but the same principles apply to the study of these materials as to the lower melting point salts. 

Ionic liquid structure To date, EXAFS has only been used to examine the structure of high-temperature molten salts in detail. 

A wide range of structural techniques may be utilized for the study of ionic liquids and dissolved species. Overall, in both high-temperature and low-temperature ionic... 

It was quite recently reported that La can be electrodeposited from chloroaluminate ionic liquids [25]. Whereas only AlLa alloys can be obtained from the pure liquid, the addition of excess LiCl and small quantities of thionyl chloride (SOCI2) to a LaCl3-sat-urated melt allows the deposition of elemental La, but the electrodissolution seems to be somewhat Idnetically hindered. This result could perhaps be interesting for coating purposes, as elemental La can normally only be deposited in high-temperature molten salts, which require much more difficult experimental or technical conditions. Furthermore, La and Ce electrodeposition would be important, as their oxides have interesting catalytic activity as, for instance, oxidation catalysts. A controlled deposition of thin metal layers followed by selective oxidation could perhaps produce cat-alytically active thin layers interesting for fuel cells or waste gas treatment. 

One leading prototype of a high-temperature fuel cell is the solid oxide fuel cell, or SOFC. The basic principle of the SOFC, like the PEM, is to use an electrolyte layer with high ionic conductivity but very small electronic conductivity. Figure B shows a schematic illustration of a SOFC fuel cell using carbon monoxide as fuel. 

Unlike the PEM, the ionic conduction occurs for the oxygen ion instead of the hydrogen ion. SOFCs are made of ceramic materials like zirconium (Z = 40) stabilized by yttrium (Z = 39). High-temperature oxygen conductivity is achieved by creating oxygen vacancies in the lattice structure of the electrolyte material. The halfcell reactions in this case are... 

Since hydrofluoride synthesis is based on thermal treatment at relatively high temperatures, the possibility of obtaining certain fluorotantalates can be predicted according to thermal stability of the compounds. In the case of compounds whose crystal structure is made up of an octahedral complex of ions, the most important parameter is the anion-cation ratio. Therefore, it is very important to take in to account the ionic radius of the second cation in relation to the ionic radius of tantalum. Large cations, are not included in the... 

Fig. 44. IR absorption spectra of Li3Ta04 (1), Li4Ta04F (2), LiJJbOfr (3), Li3Ti03F (4)- rock-salt-type structures with disordered ionic arrangement and high-temperature modifications of Li3Ta04 (5), Li4Ta04F (6), Li3Nb04 (7), LiMO.F (8).

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