Active electron-conducting electrodes

This kind of source has the advantages of the fixed chemical potential of sodium, good contact between liquid sodium and the solid electrolyte, and no additional electronic conducting electrode is needed as the counter electrode (C) to connect with the external electric circuit. In practice, elemental sodium is too active, and a very tight seal is required to prevent sodium vapor from migrating and reacting chemically with CO and in the sink vapor phase. Consequently, the system setup becomes more complex. The choice of the source in the current study is a combination of Na COj, CO and O2 gas phase, and an inert Pt counter... 

Generally, the activation layer is a functionally graded porous structure made of the same composition as the membrane layer. A second case is when the two porous interfaces, acting as mixed ionic/electronic-conducting electrodes, are made of materials different from the membrane (a purely ion-conducting electrolyte), as shown in Figure 9.10c. In this case, the oxygen flux can be precisely controlled by the... 

Most battery electrodes are porous stmctures in which an interconnected matrix of soHd particles, consisting of both nonconductive and electronically conductive materials, is filled with electrolyte. When the active mass is nonconducting, conductive materials, usually carbon or metallic powders, are added to provide electronic contact to the active mass. The soHds occupy 50% to 70% of the volume of a typical porous battery electrode. Most battery electrode stmctures do not have a well defined planar surface but have a complex surface extending throughout the volume of the porous electrode. MacroscopicaHy, the porous electrode behaves as a homogeneous unit. 

Perhaps the first practical application of carbonaceous materials in batteries was demonstrated in 1868 by Georges Le-clanche in cells that bear his name [20]. Coarsely ground MnO, was mixed with an equal volume of retort carbon to form the positive electrode. Carbonaceous powdered materials such as acetylene black and graphite are commonly used to enhance the conductivity of electrodes in alkaline batteries. The particle morphology plays a significant role, particularly when carbon blacks are used in batteries as an electrode additive to enhance the electronic conductivity. One of the most common carbon blacks which is used as an additive to enhance the electronic conductivity of electrodes that contain metal oxides is acetylene black. A detailed discussion on the desirable properties of acetylene black in Leclanche cells is provided by Bregazzi [21], A suitable carbon for this application should have characteristics that include (i) low resistivity in the presence of the electrolyte and active electrode material, (ii) absorption and retention of a significant... 

From Eq. (18) the concentration of electrons, and according to Eq. (11) the concentration of holes also, depend on the lithium activity of the electrode phases with which the electrolyte is in contact. Since anode and cathode have quite different lithium activities, the electronic concentration may vary to a large extent and an ionically conducting material may readily turn into an electronic conductor. 

Although several metals, such as Pt and Ag, can also act as electrocatalysts for reaction (3.7) the most efficient electrocatalysts known so far are perovskites such as Lai-xSrxMn03. These materials are mixed conductors, i.e., they exhibit both anionic (O2 ) and electronic conductivity. This, in principle, can extend the electrocatalytically active zone to include not only the three-phase-boundaries but also the entire gas-exposed electrode surface. 

Due to its electronic conductivity, polypyrrole can be grown to considerable thickness. It also constitutes, by itself, as a film on platinum or gold, a new type of electrode surface that exhibits catalytic activity in the electrochemical oxidation of ascorbic acid and dopamine in the reversible redox reactions of hydroquinones and the reduction of molecular oxygen iV-substituted pyrroles are excellent... 

To reduce the formation of carbon deposited on the anode side [2], MgO and Ce02 were selected as a modification agent of Ni-YSZ anodic catalyst for the co-generation of syngas and electricity in the SOFC system. It was considered that Ni provides the catalytic activity for the catalytic reforming and electronic conductivity for electrode, and YSZ provides ionic conductivity and a thermal expansion matched with the YSZ electrolyte. 

But when the contents of Nafion ionomer was increased from 30 to 45 % to find out the better electrode structures, the Pt-Ru/SRaw, which had showed the lowest single cell performance, became the best electro-catalyst. By this result one can conclude that as long as the structure of the electrode can be optimized for the each of new electro-catalysts, the active metal size is a more important design parameter rather than inter-metal distances. Furthermore, when the electro-catalysts are designed, the principal parameters should be determined in the consideration of the electrode structures which affect on the electron conduction, gas permeability, proton conductivity, and so on. 

Another convenient way to disperse platinum-based electrocatalysts is to use electron-conducting polymers, such as polyaniline (PAni) or polypyrrole (PPy), which play the role of a three-dimensional electrode.In such a way very dispersed electrocatalysts are obtained, with particle sizes on the order of a few nanometers, leading to a very high activity for the oxidation of methanol (Fig. 10). 

Thus, the enhanced activity of the electrode can be attributed to the presence of both electrons and oxygen vacancies (mixed electronic and ionic conduction) in the electrode material. 

Nonmetal electrodes are most often fabricated by pressing or rolling of the solid in the form of fine powder. For mechanical integrity of the electrodes, binders are added to the active mass. For higher electronic conductivity of the electrode and a better current distribution, conducting fillers are added (carbon black, graphite, metal powders). Electrodes of this type are porous and have a relatively high specific surface area. The porosity facilitates access of dissolved reactants (H+ or OH ions and others) to the inner electrode layers. 

Metallophosphazenes are a new type of macromolecule designed to bridge the gap between polymers and metals. Although still at an exploratory stage of laboratory development, they may provide access to electronically-conducting polymers, magnetically-active polymers, macromolecular catalysts, electrode mediator systems, or polymers crosslinked by metal atoms. 

As our quantum-chemical calculations show, similar transformation and delocalization of bonds takes place in the conductive forms of some other types of CPs (polyaniline, polypyrolle, etc.). Delocalization of chemical bonds after activation leads to appearance of an electronic conductivity in such types of conducting polymers and creates prerequisites for their application as electrode materials of electrochemical power sources. Such activation can be stimulated by intercalation of ions, applying the potential, and by use of some other low energetic factors. 

Apart from electron promoters a large number of electron mediators have long been investigated to make redox enzymes electrochemically active on the electrode surface. In the line of this research electron mediators such as ferrocene and its derivatives have successfully been incorporated into an enzyme sensor for glucose [3]. The mediator was easily accessible to both glucose oxidase and an electron tunnelling pathway could be formed within the enzyme molecule [4]. The present authors [5,6] and Lowe and Foulds [7] used a conducting polymer as a molecular wire to connect a redox enzyme molecule to the electrode surface. 

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