Polymer transition metal chalcogenides

Pt-based catalysts are two necessary approaches at the current technology stage. It is believed that non-noble metal electrocatalysts is probably the sustainable solution for PEM fuel cell commercialization. In the past several decades, various nonnoble metal catalysts for ORR have been explored, including non-pyrolyzed and pyrolyzed transition metal nitrogen-containing complexes, transition metal chalcogenides, conductive polymer-based catalysts, metal oxides/carbides/nitrides/ oxynitrides/carbonitrides, and enzymatic compoimds. The major effort in non-noble metal electrocatalysts for ORR is to increase both the catalytic activity and stability. 

Non-precious metal catalyst research covers a broad range of materials. The most promising catalysts investigated thus far are carbon-supported M-N /C materials (M = Co, Fe, Ni, Mn, etc.) formed by pyrolysis of a variety of metal, nitrogen, and carbon precursor materials [106]. Other non-precious metal electrocatalyst materials investigated include non-pyrolyzed transition metal macrocycles [107-122], coti-ductive polymer-based complexes (pyrolyzed and non-pyrolyzed) [123-140], transition metal chalcogenides [141-148], metal oxide/carbide/nitride materials [149-166], as well as carbon-based materials [167-179]. The advances of these types of materials can be found in Chaps. 7-10 and 12-15 of this book. 

The polymer electrolyte lithium batteries contain aU solid-state components lithium as the anode material, a thin polymer film as a solid electrolyte and separator, and a transition metal chalcogenide or oxide, or a sulfur-based polymer as tbe cathode material. These features offer the potential for improved safety because of tbe reduced activity of lithium with the solid electrolyte, flexibility in design as tbe cell can be fabricated in various sizes and shapes, and high energy density. 

Table 10.1 summarizes the characteristics of common ISEs and a number of new sensors in this field. We have not included in this table the liquid or polymer membrane-based electrodes which are selective, but rather fragile (for more details on such membranes see References 58,59). ISEs of the first kind are not very numerous, e.g., F -ISE (monocrystalhne membrane based on LaFj), Ag" -ISE (silver salts), or Na" -ISE (Na alumino-silicate glass or polyciystalline NASICON [Na super ionic conductor] membranes). Most of the ISEs are of the second kind and are based on insoluble silver salts for example, halide ISEs (CE, Br, I"), Cd ", Pb ", Cu ", etc. Such ISEs use mixtures of insoluble salts based on silver sulfide or silver selenide. Recently, Vlasov etal. and Neshkova have proposed several glasses sensitive to transition metals. Typical ISE devices are shown in Figure 10.5. Thin-layer chemical sensors based on chalcogenide glasses have also been developed. ... 

A nonactive electrode may include noble metals such as gold, silver, and platinum, the so-called sp-metals such as In, Ga, Cd, Bi, as well as transition (or d) metals such as nickel or cobalt. Carbon electrodes and semiconductors such as indium tin oxide [1], diamond [2], and conducting polymers may fall into the category of nonactive electrodes in appropriate solutions, as do composite materials that contain metal oxides or chalcogenides. The behavior of active electrodes in nonaqueous solution is discussed separately in the next chapter. 

For all other oxide, fluoride, chalcogenide, metallic, polymer and molecular glasses, for which viscosity data is available in wide temperature ranges, log(77) vs 1/T plots have a negative curvature and thus the apparent values of decrease with temperature. The activation enthalphy for flow can vary by almost an order of magnitude between the melting point and the glass transition, as shown in Table 2 [1]. 

---