Ionically conductive solid film

For this reason, other types of electrolytes are used in addition to aqueous solutions (i.e., nonaqueous solutions of salts (Section 8.1), salt melts (Section 8.2), and a variety of solid electrolytes (Section 8.3). More recently, a new type of solid electrolyte is being employed more often (i.e., water-impregnated ionically conducting polymer films more about them in Chapter 26). 

Hammond and DeLongchamp [255] reported the development of a highly ionic, conductive, solid polymer electrolyte film from hydrogen bonding LBL... 

Transport through surface films and coatings, including membranes, ionic and electronic conducting polymers, fast ionic conducting solids, and passive corrosion films... 

The possibility of plasma copolymerization and the production of composite materials allows to design at the molecular level thin films of very low electronic conductivity, but with very high ionic conductivity. Such films can be obtained in the polymer-like form (polymer electrolytes) and as ionic glasses (solid oxide electrolytes). These new solid electrolyte systems enable us to replace the conventional solid electrolytes by the much thinner elements, which in addition have all the other advantages of plasma fabricated materials, for example, selective permeability. Thin films of solid electrolytes produced by cold plasma deposition techniques have been of particular interest recently. 

Thin-film solid electrolytes in the range of lpm have the advantage that the material which is inactive for energy storage is minimized and the resistance of the solid electrolyte film is drastically decreased for geometrical reasons. This allows the application of a large variety of solid electrolytes which exhibit quite poor ionic conductivity but high thermodynamic stability. The most important thin-film preparation methods for solid electrolytes are briefly summarized below. 

The conductivity ofthe film was calculated for 30 monolayers. The film was deposited onto a Ag microelectrode array with a 1-mm distance between fingers. The thickness ofthe monolayer was taken to be 2 x 10"7 cm. For an air humidity value of 60% the conductivity equals 1.3 x 10"6 (Q/cm)-1 The current through the film has an ionic character, and there is apparently layered solid electrolyte... 

Intermediate Temperature Solid Oxide Fuel Cell (ITSOFC) The electrolyte and electrode materials in this fuel cell are basically the same as used in the TSOFC. The ITSOFC operates at a lower temperature, however, typically between 600 to 800°C. For this reason, thin film technology is being developed to promote ionic conduction alternative electrolyte materials are also being developed. 

Although the literature on electrodeposited electroactive and passivating polymers is vast, surprisingly few studies exist on the solid-state electrical properties of such films, with a focus on systems derived from phenolic monomers, - and apparently none exist on the use of such films as solid polymer electrolytes. To characterize the nature of ultrathin electrodeposited polymers as dielectrics and electrolytes, solid-state electrical measurements are made by electrodeposition of pofy(phenylene oxide) and related polymers onto planar ITO or Au substrates and then using a two-electrode configuration with a soft ohmic contact as the top electrode (see Figure 27). Both dc and ac measurements are taken to determine the electrical and ionic conductivities and the breakdown voltage of the film. 

Some transition metal complexes are excellent conductors. Thin films of cyto-chrome-C3, which contains four heme moieties coordinated by protein, exhibited a high conductivity with mixed valence state (Fe /Fe ) and showed an increase in conductivity as the temperature was decreased (2 x 10 S cm at 268 K) [68-70]. The temperature dependence of conductivity in the highly conductive region is the opposite of that of semiconductors and may preclude the ionic conduction as a dominant contribution. However, since the high conductivity is realized in the presence of hydrogenase and hydrogen, the system is not strictly a single but rather a multicomponent molecular solid. 

PEO and Related Systems. High ionic conductivities have been characteristically associated with polymer-alkali metal complexes, which are receiving great deal of research attention as electrolytes for solid state batteries. LiC104 dispersed homogeneously in cross-linked (P-cyanoethyl methylsiloxane) polyO-cyano-ethyl methylsiloxane-co-dimethylsiloxane) shows a network film conducting in the order of 10 s ohm-1 cm-1 at room temperature [106]. 

Why is it assumed that an amorphous film will be protecting, i.e., passive It is because depassivation—the breakdown of the film—is associated with die easy passage (by means of electrodiffusion) of Fe from die metal through the film to die solution. This is solid-state ionic conduction and depends on the presence of vacancies in a crystalline lattice. An amorphous lattice has no regular vacancies as does a solid crystal, and hence the rate of electrodiffusion of Fe through it is greatly diminished, as is the breakdown of die passive layer. 

The polymerized ionic liquid (IL) shows great promise for diverse applications. Some polymerization methods have already been oriented toward specific applications. Polymerized ILs are useful in polar environments or where there are ion species for transport in the matrix. Amphoteric polymers that contain no carrier ions are being considered for several porposes in polymer electrolytes. Zwitterionic liquids (ZBLs) were introduced in Chapter 20 as ILs in which component ions cannot move with the potential gradient. ZILs can provide ion conductive paths upon addition of salt to the matrix. It is therefore possible to realize selective ion transport in an IL matrix. If the resulting matrix can form solid film over a wide temperature range, many useful ionic devices can be realized. This chapter focuses on the preparation and characteristics of amphoteric IL polymers. 

Kosacki, I., Rouleau, C.M., Becher, P.F., Bentley, J., and Lowndes, D.H., Nanoscale effects on the ionic conductivity in highly textured YSZ thin films. Solid State Ionics, 2005, 176, 1319-1326. 

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