The present document describes an electrolytic cell comprising a protective layer comprising elemental copper covering at least in part or all of a refractory material assembly covering an interior surface thereof. Also described is a copper oxide containing composition comprising copper oxide and any one of a reducing agent and a binder. Also described is a method of protecting a refractory material assembly covering an interior surface of an electrolytic cell, comprising covering at least in part, or all of the refractory material assembly with a copper sheet, a structure comprising elemental copper, a copper oxide, an elemental copper comprising composite material, a copper oxide containing composition and combinations thereof, to provide a protective layer comprising elemental copper.