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To improve the electrochemical performance of Li-S rechargeable batteries, tunable porous carbon materials, which are known as carbide-derived carbons (CDCs), are employed as adsorbents and conductive matrices for the cathodic sulfur materials. A new assembly for Li-S cells was developed by introducing multi-layer membranes as separators. The use of the multi-layer membranes enables the minimization of the shuttle effect by expanding the distance between the separators and blocking the penetration of the polysulfide. The best discharge capacity and cycle life were obtained with ten layers of PP membrane in a sulfur-CDC@1200 composite cathode, resulting in a discharge capacity of 670 mA h g−1 and a minimal gap in the charge-discharge capacity during cell cycling.