Cathodes, aluminum carbon

Zinc electrowinning Zinc in a sulfuric acid/ aqueous solution, lead-silver alloy anodes, aluminum cathodes, barium carbonate, or strontium, colloidal additives... 

Numerous methods for the synthesis of salicyl alcohol exist. These involve the reduction of salicylaldehyde or of salicylic acid and its derivatives. The alcohol can be prepared in almost theoretical yield by the reduction of salicylaldehyde with sodium amalgam, sodium borohydride, or lithium aluminum hydride by catalytic hydrogenation over platinum black or Raney nickel or by hydrogenation over platinum and ferrous chloride in alcohol. The electrolytic reduction of salicylaldehyde in sodium bicarbonate solution at a mercury cathode with carbon dioxide passed into the mixture also yields saligenin. It is formed by the electrolytic reduction at lead electrodes of salicylic acids in aqueous alcoholic solution or sodium salicylate in the presence of boric acid and sodium sulfate. Salicylamide in aqueous alcohol solution acidified with acetic acid is reduced to salicyl alcohol by sodium amalgam in 63% yield. Salicyl alcohol forms along with -hydroxybenzyl alcohol by the action of formaldehyde on phenol in the presence of sodium hydroxide or calcium oxide. High yields of salicyl alcohol from phenol and formaldehyde in the presence of a molar equivalent of ether additives have been reported (60). Phenyl metaborate prepared from phenol and boric acid yields salicyl alcohol after treatment with formaldehyde and hydrolysis (61). 

At the cathode, aluminum ions pick up electrons to form elemental aluminum (Eq. 12.10), which being denser than the molten cryolite, gradually accumulates as a pool beneath the electrolyte melt layer and rests on the carbon lining. 

FIGURE 10.8 Aluminum production by electrolysis. At the cathode, aluminum ions are reduced to aluminum metal. The anode reaction is production of oxygen gas, which reacts with the carbon anodes. (The cell reaction is 2 AI Oj + 3 C... 

The liquid (sulfur-based compounds) and sohd sulfur cathodes (items 6 and 7) do not develop surface chemistry that can be separated from their main electrochemical redox reactions. Hence, when the reduction of sulfur SO2 or SOCI2 produces insoluble species such as LiCl, LijS, and LijO, they precipitate on the current collector [9]. When formed, LijS can be reoxidized, up to elemental sulfur, via various LLS intermediate compounds [10]. Hence, the current collector, which may be aluminum (Al) plus carbon in the case of sulfur cathodes or carbon in the case of SOCI2 cathodes, does not develop intrinsic surface chemistry beyond the precipitation of the reduction products of the active mass. 

The cell for this process is unlike the cell for the electrolysis of aluminum which is made of carbon and also acts as the cathode. The cell for the fused-salt electrolysis is made of high temperature refractory oxide material because molten manganese readily dissolves carbon. The anode, like that for aluminum, is made of carbon. Cathode contact is made by water-cooled iron bars that are buried in the wall near the hearth of the refractory oxide cell. 

According to Faraday s law, one Faraday (26.80 Ah) should deposit one gram equivalent (8.994 g) of aluminum. In practice only 85—95% of this amount is obtained. Loss of Faraday efficiency is caused mainly by reduced species ( Al, Na, or A1F) dissolving or dispersing in the electrolyte (bath) at the cathode and being transported toward the anode where these species are reoxidized by carbon dioxide forming carbon monoxide and metal oxide, which then dissolves in the electrolyte. Certain bath additives, particularly aluminum fluoride, lower the content of reduced species in the electrolyte and thereby improve current efficiency. 

Aluminum is best detected quaUtatively by optical emission spectroscopy. SoHds can be vaporized direcdy in a d-c arc and solutions can be dried on a carbon electrode. Alternatively, aluminum can be detected by plasma emission spectroscopy using an inductively coupled argon plasma or a d-c plasma. Atomic absorption using an aluminum hoUow cathode lamp is also an unambiguous and sensitive quaUtative method for determining alurninum. 

Anthracite. Anthracite is preferred to other forms of coal (qv) in the manufacture of carbon products because of its high carbon-to-hydrogen ratio, its low volatile content, and its more ordered stmcture. It is commonly added to carbon mixes used for fabricating metallurgical carbon products to improve specific properties and reduce cost. Anthracite is used in mix compositions for producing carbon electrodes, stmctural brick, blocks for cathodes in aluminum manufacture, and in carbon blocks and brick used for blast furnace linings. 

Refractories in the Aluminum Industry. Carbon materials are used in the HaH-Heroult primary aluminum cell as anodes, cathodes, and sidewalls because of the need to withstand the corrosive action of the molten fluorides used in the process (see Aluminumand aluminum alloys). 

Production of one metric ton of molten aluminum requites about 500 kg of anode carbon and 7.5—10 kg of cathode blocks which is the largest industry usage of carbon materials. Aluminum smelters generally have an on-site carbon plant for anode production. Anode technology is focused on taw materials (petroleum coke and coal-tar pitch), processing techniques, and todding practices (74). 

The cathodic protection of plain carbon and low-alloy steels can be achieved with galvanic anodes of zinc, aluminum or magnesium. For materials with relatively more positive protection potentials (e.g., stainless steels, copper, nickel or tin alloys), galvanic anodes of iron or of activated lead can be used. 

FIGURE 14.24 In the Hall process, aluminum oxide is dissolved in molten cryolite and the mixture is electrolyzed in a cell with carbon anodes and a steel cathode. The molten aluminum flows out of the bottom ot the cell. 

Fignre 27.3 shows a typical spectroelectrochemical cell for in sitn XRD on battery electrode materials. The interior of the cell has a construction similar to a coin cell. It consists of a thin Al203-coated LiCo02 cathode on an aluminum foil current collector, a lithium foil anode, a microporous polypropylene separator, and a nonaqueous electrolyte (IMLiPFg in a 1 1 ethylene carbonate/dimethylcarbonate solvent). The cell had Mylar windows, an aluminum housing, and was hermetically sealed in a glove box. 

In Moscow Power Engineering Institute (TU) portable air aluminum batteries with saline electrolyte were developed [7, 18, and 20], In our devices, the air electrodes consist of two layers. Diffusion layer contains PTFE, carbon black and metal screen active layer consists of activated carbon and PTFE. At 293 K and the range of current density 2-25 mA/ cm2 dependence of cathode potential E (in H-scale) upon current density J (Figure 2) may by written by the Tafel equation (12). 

There is no question that the development and commercialization of lithium ion batteries in recent years is one of the most important successes of modem electrochemistiy. Recent commercial systems for power sources show high energy density, improved rate capabilities and extended cycle life. The major components in most of the commercial Li-ion batteries are graphite electrodes, LiCo02 cathodes and electrolyte solutions based on mixtures of alkyl carbonate solvents, and LiPF6 as the salt.1 The electrodes for these batteries always have a composite structure that includes a metallic current collector (usually copper or aluminum foil/grid for the anode and cathode, respectively), the active mass comprises micrometric size particles and a polymeric binder. 

Aluminum is produced according to the Hall-Heroult process [42-44]. At the cathode, AlxFy species are reduced and lead to liquid aluminum. As the electrolysis proceeds, the metal from the aluminum oxide precipitates at the bottom of the cell. At the anode, oxygen evolution takes place producing carbon dioxide/monoxide and hence resulting in current and performance losses [42-44]. 

Molten Carbonate Fuel Cell The electrolyte in the MCFC is a mixture of lithium/potassium or lithium/sodium carbonates, retained in a ceramic matrix of lithium aluminate. The carbonate salts melt at about 773 K (932°F), allowing the cell to be operated in the 873 to 973 K (1112 to 1292°F) range. Platinum is no longer needed as an electrocatalyst because the reactions are fast at these temperatures. The anode in MCFCs is porous nickel metal with a few percent of chromium or aluminum to improve the mechanical properties. The cathode material is hthium-doped nickel oxide. 

Also, supernatant solution in the Bayer liquor still contains an appreciable amount of soluble aluminum salt that needs to be removed by electrolysis prior to gallium recovery. This may be done either by treating the solution with lime to precipitate out calcium aluminate or by neutralizing the solution with carbon dioxide to precipitate alumina hydrate (Hudson, L.K. 1965. J. Metals, 17, pp. 948-51). Removal of most aluminum by these processes enhances the concentration of gallium in the solution to a level of approximately 0.1% whereupon the solution may be electrolyzed using an anode, cathode, and cell made of stainless steel. 

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