The aim of this work is to identify the theoretical limitations of molten salts electrolysis using solid electrodes to overcome these limitations in practice. We applied the theory of electric field distribution on the electrodes in aqueous solutions to predict the distribution of current density and potential on the polycrystalline surface of electrodes in molten salts. By combining the theoretical background of the current density distribution with the basic laws of potential formation on the surface of the electrodes, we determined and validated the sequence of numerical studies of electrolytic processes in the pole gap. The application of the method allowed the characteristics of the current concentration edge effect at the periphery of smooth electrodes and the distribution of current density and potential on the heterogeneous electrode surface to be determined. The functional relationship and development of the electrolysis parameters on the smooth and rough surfaces of electrodes were established by the different scenario simulations of their interaction. It was shown that it is possible to reduce the nonuniformity of the current and potential distribution on the initially rough surface of electrodes with an increase in the cathode polarisation, alumina concentration optimisation and melt circulation. It is, nonetheless, evident that with prolonged electrolysis, physical and chemical inhomogeneity can develop, nullifying all attempts to stabilise the process. We theoretically established a relationship between the edge effect and roughness and the distribution of the current density and potential on solid electrodes, which can act as a primary and generalising reason for their increased consumption, passivation and electrolytic process destabilisation in standard and low-melting electrolytes. This functional relationship can form a basis for developing the methods of flattening the electric field distribution over the anodes and cathodes area and, therefore, stabilising the electrolytic process. Literature overview, laboratory tests and theoretical calculations allowed the organising principle of a stable electrolytic process to be formulated -the combined application of elliptical electrodes and the electrochemical micro-borating of the cathodes. Practical verification of this assumption is one direction for further theoretical and laboratory research.
