Lithium metal batteries are considered a promising technology to implement high energy density rechargeable systems beyond lithium-ion batteries. However, the development of dendritic morphology is the basis of safety and performance issues and represents the main limiting factor for using lithium anodes in commercial rechargeable batteries. In this study, the electrochemical behaviour of Li metal has been investigated in organic carbonate-based electrolytes by electrochemical impedance spectroscopy measurements and deposition/stripping galvanostatic cycling. Low amounts of tetraalkylammonium hexafluorophosphate salts have been added to the electrolytes with the aim of regulating the lithium deposition/stripping process through the electrostatic shielding effect that improves the lithium deposition. The use of NH₄PF₆ also determined good lithium deposition/stripping performance due to the chemical modification of the native solid electrolyte interphase via direct reaction with lithium.