Kinetic and morphological properties of surface layers formed on the Li anode during storage in SOCl2/LiAlCl4 solution have been investigated. The synergetic effect of SO2 and LiAl(SO3Cl)4, used for voltage delay alleviation, changes the shape and size of the microcrystals of LiCl constituting the surface layer. It also leads to separate and modify the conduction and charge transfer processes involved in the kinetic properties of the surface layer at the equilibrium potential. These properties appear to be similar to those of a polycrystalline solid electrolyte where the grain boundaries induce an intergranular conduction process.