The microstructure of lithium cation hydration shell has been studied by means of molecular dynamics simulations. The aqueous LiCl solution has been analyzed in the temperature range from -30 to 120 °C using the SPC and ST2 water models for a set of model Lennard-Jones parameters of intermolecular potentials. The results of simulations have been compared to NMR-relaxation data and concern the reorganization of the lithium-cation hydration shell with temperature variations. The obtained results show that it is necessary to modify the water model.