TECHNOLOGY FOCUS - ELECTRICAL POWER AND ENERGY - Preferred Method: The start-up layer(s) is/are eliminated by washing away the start-up layer(s) and/or permanently integrating portion(s) of start-up layer(s) in to the cathode surface by normal steady state operation of the cell. The start-up layer(s) is preferably applied on coating of an aluminum-wettable refractory material (2) formed at the cathode surface. Additional start-up layer(s) of a boron-containing solution comprising boron oxide, boric acid or tetraboric acid dissolved in methanol, ethylene glycol, glycerine and/or water, is applied on the cathode surface to form a glassy layer. The aluminum-wettable refractory coating protected by the start-up layer(s), is covered with a halide-based electrolyte having fusion point of 660degreesC-760degreesC. The halide-based electrolyte is mixed with or covered with a layer conductive material such as coke. The fluoride-based melt is added to the cell when the temperature of the cell exceeds the fusion point of the halide-based electrolyte. Oxygen is evolved on a non-carbon anode (6) during electrowinning of aluminum. The fluoride-based melt is operated at 700-970degreesC, preferably at 750-850degreesC during electrowinning of aluminum. Aluminum is produced on an aluminum-wettable drained cathode.    TECHNOLOGY FOCUS - INORGANIC CHEMISTRY - Preferred Material: The cathode is made of carbonaceous material, electro conductive carbon-free material and/or electrically non-conductive carbon-free material. The aluminum-wettable refractory coating comprises a refractory hard metal boride, preferably particulate refractory hard metal boride in a colloidal carrier. The metallization aluminum or alloy or intermetallic compound comprises aluminum and nickel, iron, titanium, cobalt, chromium, vanadium, zirconium, hafnium, niobium, tantalum, molybdenum, cerium and/or copper. The metallization is preferably an intermetallic compound comprising aluminum and nickel, iron, titanium, cobalt, chromium and/or zirconium. The intermetallic compound preferably nickel-aluminum (NiAl or Ni3Al). Preferred Method: The intermetallic compound is obtained aluminum in the form of powder, sheet, porous structure or mesh onto sheet, porous structure or mesh of a metal, or a vice-versa. The intermetallic compound is obtained by heating aluminum and the other metal on top of the cathode surface to a sufficient temperature to initiate a reaction for formation of intermetallic compound, before or during preheating of the cell. A thick sheet of aluminum having thickness of 1-5 mm is applied on the top of the start-up layer(s). An electric current is passed via anodes, through the conductive material and the conductive start-up layer(s)into the cell bottom, to heat the cell by Joule effect. A relatively thick sheet(s) of aluminum (4) having thickness of 1-5 mm is placed between is each anode and the temporary protection (3), preferably on the temporary protection. The cell bottom is preheated using burners or infrared radiation. One of the start-up layers is applied on the cathode surface using painting methods, such as brushes, toner, or spraying. At least one of the start-up layers is applied by hot-spraying molted metal. At least one of the start-up layers is applied by chemical vapor deposition, plasma deposition, plasma spraying, electro deposition, chemical deposition, adhesive application or hot pressing. At least one the start-up layer is applied with an automated or partly automated system. Preferred Properties: The pliable aluminum foil has thickness less than 0.1 mm, preferably 0.03-0.05 mm. The pliable aluminum foil is at least partly oxidized and partly incorporated into the cathode surface as alumina. The applied start-up layers are electrically conducted. At least one of the start-up layers extends up the cell side wall (8). At least one of the start-up layers extends above the level of the fluoride-based melt during normal use of the cell. Preferred Layer: One of the additional start-up layer is obtained from a solution containing aluminum phosphate selected from monoaluminum phosphate, aluminum phosphate, aluminum polyphosphate and/or aluminum metaphosphate. One of the additional layers is obtained from a colloidal solution that gel during preheating. The colloid is colloidal alumina, silica, yttria, ceria, thoria, zirconia, magnesia, lithia, monoaluminum phosphate and/or cerium acetate. The colloid is at least partly integrated into the cathode surface or aluminum-wettable refractory coating. The colloidal comprises particulate conductive selected from aluminum, nickel, iron, titanium, cobalt, chromium, zirconium and/or copper. At least one of the start-up layers contains carbides and/or borides of aluminum, titanium, chromium, vanadium, zirconium, hafnium, niobium, tantalum, molybdenum and/or cerium. At least on the start-up layer contains particulate aluminum.    TECHNOLOGY FOCUS - ORGANIC CHEMISTRY - Preferred Metallization: The metallization is obtained from metallic powder(s) applied in an aqueous or non-aqueous liquid, or in aqueous liquid containing organics. The liquid is polymer such as polyurethane, ethylene glycol, polyethylene glycol, resins, esters or waxes. POLYMER - One of the additional start-up layers is at least partly obtained from a polymer or polymer precursor. The polymer is polyurethane ethylene glycol, resins, esters or waxes.