A structure of oxide melts dictates in many respects their physicochemical properties, interaction rate with metallic melts, service characteristics of enamels and glasses. A problem of creation of the models for studying and analysis of influence of the anionic polymerization on transport properties of the multicomponent oxide electrolytes is considered. The structure relaxation slowness of molten borosilicates above liquidus temperature is investigated. The temperature and time dependences of the diffusion coefficients of Ni ions in Na2O · B2O3 · SiO2 and 2Na2O · 3B2O3 · SiO2 melts are obtained depending on compositions and temperatures.