Abstract
The electron transfer for fluorine evolution reaction on carbon anodes takes place through a nonuniform film of solid graphite fluoride. The carbon‐rich deep layers are characterized by a good electrical conductivity whereas the outer perfluorinated layers constitute a thin insulating film. Very low values of the β transfer coefficient arise because the probability of electron tunneling through the insulating film decreases with increase of its thickness. Chronopotentiometry experiments confirm the existence of two kinds of , depending on the potential of the working electrode. The reversibility of the redox system is discussed; then, the behavior of the formed on graphite and carbon anodes in the melt is interpreted by an electrochemical formation reaction coupled with both diffusion and thermal decomposition processes.
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