Ammonia (NH3) is a fundamental chemical used in numerous applications, primarily as a fertilizer. The Haber-Bosch is currently the most widely used and efficient process for its production; unfortunately, it is energy intensive and significantly contributes to the global CO2 emissions. Consequently, alternative routes for green ammonia synthesis are being investigated to mitigate environmental impact and achieve independence from fossil fuels. Among the different alternative, the lithium-mediated electrochemical nitrogen reduction reaction (Li-NRR) is nowadays considered one of the most promising. This study focuses on the optimization of the electrochemical protocol for the Li-mediated system. A batch system was employed and two consecutive regimes of applied current were imposed: (i) a pulsed-current regime, during which a solid electrolyte interphase (SEI) layer is formed, followed by (ii) a steady-current regime, in which the nitrogen reduction reaction mainly occurs.