Anode-surface layer

It is well known that in contact with both liquid and polymer electrolytes, lithium is thermodynamically unstable toward the solvents and salts and becomes covered by a passivating fdm that slows the corrosion of the lithium. It is now generally accepted that the existence and successful operation of most lithium battery systems, as primary and secondary power sources, are due solely to this anode-surface layer. 

Aluminum has a low density it is a strong metal and an excellent electrical conductor. Although it is strongly reducing and therefore easily oxidized, aluminum is resistant to corrosion because its surface is passivated in air by a stable oxide film. The thickness of the oxide layer can be increased by making aluminum the anode of an electrolytic cell the result is called anodized aluminum. Dyes may be added to the dilute sulfuric acid electrolyte used in the anodizing process to produce surface layers with different colors. 

The addition of various Kolbe radicals generated from acetic acid, monochloro-acetic acid, trichloroacetic acid, oxalic acid, methyl adipate and methyl glutarate to acceptors such as ethylene, propylene, fluoroolefins and dimethyl maleate is reported in ref. [213]. Also the influence of reaction conditions (current density, olefin-type, olefin concentration) on the product yield and product ratios is individually discussed therein. The mechanism of the addition to ethylene is deduced from the results of adsorption and rotating ring disc studies. The findings demonstrate that the Kolbe radicals react in the surface layer with adsorbed ethylene [229]. In the oxidation of acetate in the presence of 1-octene at platinum and graphite anodes, products that originate from intermediate radicals and cations are observed [230]. 

The chemical mechanism rests on the effect of intervening redox systems (see Section 13.6). Here intermediate reactants such as species on a cathode surface, species on an anode surface, or reducing and oxidizing agents in the solution layer next to the electrode are first produced electrochemicaUy from solution components. The further interaction of these reactants with the organic substance is purely chemical in character, for example, following a reaction... 

Each of these reactions occurs in its own typical potential range. Several reactions may occur in parallel. The oxidation of solution components and the evolution of oxygen and chlorine are discussed in Chapter 15, the formation of surface layers in Section 16.3. In the present section we discuss anodic metal dissolution. 

In the anodic polarization of metals, surface layers of adsorbed oxygen are almost always formed by reactions of the type of (10.18) occurring in parallel with anodic dissolution, and sometimes, phase layers (films) of tfie metal s oxides or salts are also formed. Oxygen-containing layers often simply are produced upon contact of the metal with the solution (without anodic polarization) or with air (the air-oxidized surface state). 

A wide variety of in situ techniques are available for the study of anodic hhns. These include reflectance, eUipsometry, X-ray reflectivity, and SXRD. X-ray reflectivity can be used to study thick surface layers up to 1000 A. The reflectance technique has been used to study oxide growth on metals, and it yields information on oxide thickness, roughness, and stoichiometry. It the only technique that can give information on buried metal-oxide interfaces. It is also possible to get information on duplex or multiple-layer oxide hhns or oxide hhns consisting of layers with different porosity. Films with thicknesses of anywhere from 10 to 1000 A can be studied. XAS can be used to study the chemistry of dilute components such as Cr in passive oxide hhns. 

In the late 1960s it was discovered (Entina, 1968 Binder et al., 1972) that a strong synergy effect exists in the platinum-ruthenium system. Alloys of these two metals are two to three orders of magnitude more active catalytically for the anodic oxidation of methanol than pure platinum, whereas pure ruthenium is altogether inactive for this reaction. Prolonged exploitation of such anodes is attended by a gradual decrease in catalytic activity of the alloys because of slow anodic dissolution of ruthenium from the surface layer. A similar simation is seen for platinum-tin alloys, which... 

During the anodic polarization of platinum to potentials of about 3.0 V (RHE), one or several layers (but no more than three) of chemisorbed oxygen are formed, which sometimes are called the a-oxide of platinum. The limiting thickness of these layers is about 1.3 nm. They can be studied both by electrochemical methods and by ellipsometry. At more positive potentials phase-oxide surface layers, the p-oxides are formed. The quantitative composition and structure of these layers and the exact limits of potential for their formation depend on many factors composition of the electrolyte solution, time of polarization, surface history, and often remain unknown. 

The character of the oxide layers influences the kinetics and mechanism of the electrochemical reactions occurring on the platinum anode surface. The relation between the rate of oxygen evolution and oxide layer thickness is complex. In the region where the a-oxides exist, the reaction rate decreases with increasing oxide layer thickness. In the region where the P-oxides exist, the reaction rate depends little on oxide layer thickness or, according to some data, increases with increasing oxide layer thickness. 

Radiotracer techniques involving lsO in the anodization process are used with subsequent neutron activation analysis84 or SIMS.85 Another method involves implantation of inert ion markers into the surface layer of the sample prior to anodization and examination of the position of the markers after the oxide film has grown to a certain thickness.86 Assuming immobility of the inert species, the ratio of the cation to the anion transport number, t+/, should be equal to the ratio of the outer to the inner layer thickness. Numerous experimental determinations72,87 suggest t+ and f to be 0.4 and 0.6, respectively. 

SOFC electrodes are commonly produced in two layers an anode or cathode functional layer (AFL or CFL), and a current collector layer that can also serve as a mechanical or structural support layer or gas diffusion layer. The support layer is often an anode composite plate for planar SOFCs and a cathode composite tube for tubular SOFCs. Typically the functional layers are produced with a higher surface area and finer microstructure to maximize the electrochemical activity of the layer nearest the electrolyte where the reaction takes place. A coarser structure is generally used near the electrode surface in contact with the current collector or interconnect to allow more rapid diffusion of reactant gases to, and product gases from, the reaction sites. A typical microstructure of an SOFC cross-section showing both an anode support layer and an AFL is shown in Figure 6.4 [24],... 

The HIL acts as an interface connection layer between the anode and the HTL so as to improve the film forming property of the subsequent organic layer and to facilitate efficient hole injection. Hole injection materials (HIMs) should have good adhesion to the anode and should serve to smooth the anode surface. The most common HIMs are... 

The formation of etch pits and tunnels on n-Si during anodization in HF solutions was reported in the early 1970 s. It was found that the solid surface layer is the remaining substrate silicon left after anodic dissolution. The large current observed on n-Si at an anodic potential was postulated to be due to barrier breakdown.5,6 By early 80 s7"11 it was established that the brown films formed by anodization on silicon substrate of all types are a porous material with the same single crystalline structure as the substrate. 

The changes in reorientation of surface atoms were explained using the dynamic model of the crystal space lattice. It was assumed that during anodic polarization, when the oxidation of adsorbed water is taking place, atoms oscillate mainly in a direction perpendicular to the electrode surface. This process leads to periodic separation of atoms in the first surface layer. Thus, the location of atoms in different orientations is possible. It was stated that various techniques of electrode pretreatment used for... 

Metal foams have been used in the past in the development of FF plates. However, Gamburzev and Appleby [53] used Ni foams as both a DL and a flow field plate with an MPL layer on one of its surfaces. They observed that such a design had high contact resistance between the nickel foam and the MPL and also increased gas diffusion resistance due to the required MPL thickness. Arisetty, Prasad, and Advani [54] were able to demonstrate that these materials can also be used as potential anode diffusion layers in DMFCs (see Figure 4.10). In fact, the nickel foam used in this study performed better than a carbon cloth (Avcarb 1071HCB) and a stainless steel mesh. However, it was recognized that a major drawback for these foams is their susceptibility to corrosion. 

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