Competing anode materials

The SEI is formed by parallel and competing reduction reactions and its composition thus depends on i0, t], and the concentrations of each of the electroactive materials. For carbon anodes, (0 also depends on the surface properties of the electrode (ash content, surface chemistry, and surface morphology). Thus, SEI composition on the basal plane is different from that on the cross—section planes. 

Surface layers of silicon oxide are important in semiconductor device fabrication as interlayer dielectrics for capacitors, isolation of conducting layers, or as masking materials. However, anodic oxides, due to their relatively poor electrical properties, breakdown voltage, and leakage current, have not yet found much use in device technology, and cannot compete with thermal oxides obtained at high temperatures of 700 to 900 °C. 

Anodic treatment of 1,2- or 1,4-dihydroxy-substituted benzenes to form the corresponding quinones or masked congeners is well known, since they represent valuable synthetic intermediates [64]. Benzoquinone ketals of electron rich arenes like 18 can be challenging since the oxidative aryl-aryl coupling reaction usually competes. When using BDD anodes the benzoquinone ketal 19 is obtained in an almost quantitative manner, demonstrating the superior properties of this electrode material. Despite the basic conditions, no deblocking of the silyl-protected phenol moiety is observed [65] (Scheme 9). 

Another approach to reducing the EOF as well as wall adsorption is to add a compound to the running buffer that will compete with the solute for the silanol sites on the surface. These materials must have some affinity for the charged or polar sites on the inner wall and so they must, themselves, be hydrophilic or charged. Nonionic surfactants are hydrophilic to prevent solute adsorption on the wall and block the silanols in order to reduce the EOF. The use of cationic polymers in the buffer results in a reversal of EOF to the anodic direc-... 

Silicon is highly unstable in aqueous electrolytes due to the formation of an insulating oxide film which prevents the use of n-Si as photoanode. On the other hand, the silicon electrode has poor kinetics for hydrogen evolution which is not desirable for its use as a photocathode. Many methods have been explored to stabilize Si electrodes in aqueous solutions for possible applications as photochemical cells. They include coating the surface with noble metals, metal oxides, metal silicides, or organic materials as shown in Table 6.6. Also, some redox species, the reduction of which can favorably compete with the oxidation of silicon, can be used to stabilize silicon anodes... 

Dark current-potential curves representing a majority carrier transfer to a redox system have been measured by many research groups. Mostly cathodic currents at n-type electrodes have been studied rather than anodic currents at p-type semiconductors. This is because anodic hole consumption from p-type electrodes usually results in corrosion of the material. At least it is difficult to find a redox system where the oxidation of the redox couple competes sufficiently quickly with the corrosion. 

This phenomenon degrades the Coulombic efficiency of the anode, then it has to be minimized for practical applications where high capacity is required. This could be overcome by particular aluminum alloys more resistant to corrosion, but the competing requirement of fast anodic dissolution makes very difficult the research of the suitable material [36, 37]. Another possibility to improve the anode performance is to modify the electrolyte composition by adding corrosion inhibitors [38]. The difficulties met up today in this field leave the possibility to use the aluminum-air batteries only as mechanically rechargeable systems, with practical performance (300-500 Wh/kg) very far from the theoretical values (Table 1.8 Fig. 5.14). 

The main obstacle to creating liquid junction solar cells is photocorrosion of semiconductor electrodes, which reduces considerably their lifetime. In order to prevent, for example, anodic photocorrosion, a well-reversible redox couple is introduced into an electrolyte solution, so that the reaction of oxidation of the red component competes for photoholes with the reaction of photodecomposition of the electrode material (see Section IV.2). With the aid of this method, photocorrosion has been practically prevented in certain types of photocells and the duration of their continuous operation has been increased up to about one year. Yet, there are other, more subtle mechanisms of electrode degra-dation, which has hitherto prevented the lifetime of photoelectrochemical cells from becoming comparable with the 20-year lifetime of solid-state solar cells. 

---