context: LLZO pellets were sputter-coated (LEICA EM ACE600) with Au on both sides to form contacts that acted as Li ion quasi-blocking electrodes. In order to fabricate Li symmetric cells, LLZO pellets were sandwiched between two Li metal discs (Sigma Aldrich) either with or without interposition of IL interlayers. 5 μL of the gel electrolytes were introduced at each interface. Cells without the interlayer were heated till 180 °C (melting temperature of Li) to promote Li–SE mutual contact. Both Au|LLZO|Au and Li|LLZO|Li were assembled in Swagelok©-type cell holders. Electrochemical impedance spectroscopy (EIS) was performed using an electrochemical workstation (ZAHNER-Elektrik GmbH) with an applied sinusoidal excitation voltage of 10 mV in the frequency range from 5 MHz to 0.01 Hz. EIS data were fitted with ZView software. A Bio-Logic VMP-3 potentiostat was used to conduct the Li stripping and plating tests at current densities ranging from 0.05 to 0.4 mA cm−2. The cathode slurry was prepared by mixing S/NC powders (90 wt%) and the PVDF binder (10 wt%, Kynar) by magnetic stirring using NMP as solvent. The obtained slurry was cast onto aluminum foil by doctor blade techniques and thereafter dried at 60 °C for 24 h. The sulfur loading at the electrode was ∼0.5 mgsulfur cm−2. The electrochemical performance of the full cells was tested by galvanostatic cycling with 0.1C (1C = 1672 mA gsulfur−1) in the voltage range between 3 and 1.5 V, using an Arbin BT-2000 battery tester at room temperature. The preparation of the cells and all electrochemical tests were performed in an argon-filled glove-box.