We investigated herein the morphological, structural, and electrochemical features of electrodes using a sulfur (S)-super P carbon (SPC) composite (i.e., S@SPC-73), and including few-layer graphene (FLG), multiwalled carbon nanotubes (MWCNTs), or a mixture of them within the current collector design. Furthermore, we studied the effect of two different electron-conducting agents, that is, SPC and FLG, used in the slurry for the electrode preparation. The supports have high structural crystallinity, while their morphologies are dependent on the type of material used. Cyclic voltammetry (CV) shows a reversible and stable conversion reaction between Li and S with an activation process upon the first cycle leading to the decrease of cell polarization. This activation process is verified by electrochemical impedance spectroscopy (EIS) with a decrease of the resistance after the first CV scan. Furthermore, CV at increasing scan rates indicates a Li+ diffusion coefficient (D) ranging between 10−9 and 10−7 cm2·s−1 in the various states of charge of the cell, and the highest D value for the electrodes using FLG as electron-conducting agent. Galvanostatic tests performed at constant current of C/5 (1 C = 1675 mA·gS−1) show high initial specific capacity values, which decrease during the initial cycles due to a partial loss of the active material, and subsequently increase due to the activation process. All the electrodes show a Coulombic efficiency higher than 97% upon the initial cycles, and a retention strongly dependent on the electrode formulation. Therefore, this study suggests a careful control of the electrode in terms of current collector design and slurry composition to achieve good electrode morphology, mechanical stability, and promising electrochemical performance in practical Li-S cells.

A solid polymer electrolyte has been developed and employed in lithium‐metal batteries of relevant interest. The material includes crystalline poly(ethylene glycol)dimethyl ether (PEGDME), LiTFSI and LiNO3 salts, and a SiO2 ceramic filler. The electrolyte shows ionic conductivity more than 10−4 S cm−1 at room temperature and approaching 10−3 S cm−1 at 60 °C, a Li+‐transference number exceeding 0.3, electrochemical stability from 0 to 4.4 V vs. Li+/Li, lithium stripping/deposition overvoltage below 0.08 V, and electrode/electrolyte interphase resistance of 400 Ω. Thermogravimetry indicates that the electrolyte stands up to 200 °C without significant weight loss, while FTIR spectroscopy suggests that the LiTFSI conducting salt dissolves in the polymer. The electrolyte is used in solid‐state cells with various cathodes, including LiFePO4 olivine exploiting the Li‐insertion, sulfur–carbon composite operating through Li conversion, and an oxygen electrode in which reduction and evolution reactions (i. e., ORR/OER) evolve on a carbon‐coated gas diffusion layer (GDL). The cells operate reversibly at room temperature with a capacity of 140 mA h g−1 at 3.4 V for LiFePO4, 400 mA h g−1 at 2 V for sulfur electrode, and 500 mA h g−1 at 2.5 V for oxygen. The results suggest that the electrolyte could be applied in room‐temperature solid polymer cells.