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Lithium-sulfur (Li-S) batteries are being considered as one of the most promising candidates for the development of next-generation energy storage technologies. Although much progress has been made over the past decade, the development of Li-S batteries is still scourged by a crucial polysulfideshuttle problem. To address such a critical issue, we present here an approach to reduce the pore size of the separator to prevent the penetration of soluble polysulfide species. A polymer with intrinsic nanoporosity (PIN) is developed within the micron-scale pores of a polypropylene separator. The framework of polypropylene acts as a skeleton to sustain reliable mechanical properties with the thin membrane. Upon the formation of PIN in the pores, the polypropylene separator maintains its thickness. With the thin PIN-polypropylene membrane, the Li-S cells could be operated with relatively high sulfur loading. The PIN allows the transport of Li +-ions, but suppresses the penetration of the polysulfide species. The Li-S batteries with the PIN modified polypropylene separator exhibit enhanced cycling performance.

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