Copper Diffusion in Copper Sulfide: a Systematic Study

Copper sulfide Cu(2-x)S is a model mineral for chalcogenides because of the existence of a non-stoichiometric compounds series in the range Cu(2)S - CuS in which properties change with x. For this reason, we have studied the influence of the mineral composition on the diffusion in this solid. Electrochemical Impedance Spectroscopy (EIS) applied to CU(2-x)S/cupric sulfate electrolyte was the main investigation technique. It enabled us to work at the equilibrium potential at which the composition is fixed and known. Changing the composition by electrochemically removing (or adding) a known amount of Cu, we were able to determine the chemical diffusion coefficient of copper in the composition range (from x = 0 to 0.066). In this work, we present the results obtained in the chalcocite and djurleite phases. These results were compared to other values reported in the literature. From this systematic study we discuss various diffusion mechanisms. Our observations support that in chalcocite and djurleite Cu diffuses via a vacancy mechanism.