Electrolyte: The electrolyte is a molten bath of cryolite (NaAlF) and dissolved alumina. Cryolite is a good solvent for alumina with low melting point, satisfactory viscosity, and low vapour pressure. Its density is also lower than that of liquid aluminium (2 vs 2.3 g/cm), which allows natural separation of the product from the salt at the bottom of the cell. The cryolite ratio (NaF/AlF) in pure cryolite is 3, with a melting temperature of 1010 °C, and it forms a eutectic with 11% alumina at 960 °C. In industrial cells the cryolite ratio is kept between 2 and 3 to decrease its melting temperature to 940–980 °C.
Cathode: Carbon cathodes are essentially made of anthracite, graphite and petroleum coke, which are calcined at around 1200 °C and crushed and sieved prior to being used in cathode manufacturing. Aggregates are mixed with coal-tar pitch, formed, and baked. Carbon purity is not as stringent as for anode, because metal contamination from cathode is not significant. Carbon cathode must have adequate strength, good electrical conductivity and high resistance to wear and sodium penetration. Anthracite cathodes have higher wear resistance and slower creep with lower amplitude [15] than graphitic and graphitized petroleum coke cathodes. Instead, dense cathodes with more graphitic order have higher electrical conductivity, lower energy consumption [14], and lower swelling due to sodium penetration. Swelling results in early and non-uniform deterioration of cathode blocks.
Anode: Carbon anodes have a specific situation in aluminium smelting and depending on the type of anode, aluminium smelting is divided in two different technologies; “Soderberg” and “prebaked” anodes. Anodes are also made of petroleum coke, mixed with coal-tar-pitch, followed by forming and baking at elevated temperatures. The quality of anode affects technological, economical and environmental aspects of aluminium production. Energy efficiency is related to the nature of anode materials, as well as the porosity of baked anodes. Around 10% of cell power is consumed to overcome the electrical resistance of prebaked anode (50–60 μΩm). Carbon is consumed more than theoretical value due to a low current efficiency and non-electrolytic consumption. Inhomogeneous anode quality due to the variation in raw materials and production parameters also affects its performance and the cell stability.
Prebaked consumable carbon anodes are divided into graphitized and coke types. For manufacturing of the graphitized anodes, anthracite and petroleum coke are calcined and classified. They are then mixed with coal-tar pitch and pressed. The pressed green anode is then baked at 1200 °C and graphitized. Coke anodes are made of calcined petroleum coke, recycled anode butts, and coal-tar pitch (binder). The anodes are manufactured by mixing aggregates with coal tar pitch to form a paste with a doughy consistency. This material is most often vibro-compacted but in some plants pressed. The green anode is then sintered at 1100–1200 °C for 300–400 hours, without graphitization, to increase its strength through decomposition and carbonization of the binder. Higher baking temperatures increase the mechanical properties and thermal conductivity, and decrease the air and CO reactivity. The specific electrical resistance of the coke-type anodes is higher than that of the graphitized ones, but they have higher compressive strength and lower porosity.
Soderberg electrodes (in-situ baking), used for the first time in 1923 in Norway, are composed of a steel shell and a carbonaceous mass which is baked by the heat being escaped from the electrolysis cell. Soderberg Carbon-based materials such as coke and anthracite are crushed, heat-treated, and classified. These aggregates are mixed with pitch or oil as binder, briquetted and loaded into the shell. Temperature increases bottom to the top of the column and in-situ baking takes place as the anode is lowered into the bath. Significant amount of hydrocarbons are emitted during baking which is a disadvantage of this type of electrodes. Most of the modern smelters use prebaked anodes since the process control is easier and a slightly better energy efficiency is achieved, compared to Soderberg anodes.