Theory of electrochemical phase formation in galvanostatic electrodeposition conditions

Theoretical investigation of nucleation process and growth of new phased crystals in galvanostatic electrodeposition conditions was carried out. A general model of the process which includes time overvoltage dependencies and crystals numbers formed at electrode was evaluated. The nucleation period and distribution of crystals according their sizes were established.  The size impact on phase formation which occurs in the nanosized area of crystals was studied.

The modeling of galvanostatic phase formation considering the double electric layer charging, adatoms accumulating on the electrode surface, deposited ions concentration changing near electrode, dependencies of overvoltage for as nucleation rate as  new phase growth rate was developed. It was demonstrated that for crystals with sizes close to critical the size effects appear, that is dependence of discharge and diffusion on nanocrystall surface curvature. The influence of electrodeposition parameters (current density, electrolyte concentration) on phase formation kinetics is determined. The theoretical and experimental regularities are in a good agreement.

Publications:

  1. Isaev V.A., Grishenkova O.V., Semerikova O.L. Three-dimensional nucleation and growth under galvanostatic condition. Journal of Solid State Electrochemistry, 2013, vol. 17, pp. 361-363.
  2. Isaev V.A., Grishenkova O.V. Galvanostatic nucleation and growth under diffusion control. Journal of Solid State Electrochemistry, 2013, vol. 17, pp. 1505-1508.

Authors: Isaev V.A., DSc (Chemistry), principle researcher; Grishenkova O.V., PhD (Chemistry), researcher; Semerikova O.L., PhD (Chemistry), researcher.