Lithium–sulfur (Li–S) battery can satisfy the need of the future power battery market because of its high energy density, but the hidden dangers caused by lithium anode have seriously hindered their commercialization. Herein, an innovative gel polymer electrolyte (GPE) composed of polyvinylidene fluoride (PVDF) and organo-polysulfide polymer (PSPEG) is proposed, which could be used in semi-solid-state Li–S batteries for protection of Li anodes. Particularly, organo-polysulfide polymer could chemically/electrochemically generate both inorganic and organic components simultaneously in-situ once contacting fresh Li metal surface and/or during discharging processes. And these inorganic/organic components could participate in the formation of the SEI layer and finally constitute a stable and flexible hybrid SEI layer on the surface of Li metal anode. Moreover, the organic components were permselective to lithium ions against anions. Therefore, PVDF/PSPEG GPE ensures the ideal chemical and electrochemical properties for Li–S batteries. Our work demonstrates an effective solution to solve the problems about Li anodes and contributes to the development of the safe Li metal batteries.

锂硫（Li–S）电池具有高能量密度，可以满足未来动力电池市场的需求，但是锂阳极造成的隐患严重阻碍了其商业化。本文提出了一种由聚偏二氟乙烯（PVDF）和有机多硫化物聚合物（PSPEG）组成的创新型凝胶聚合物电解质（GPE），可用于半固态Li–S电池中以保护Li阳极。特别地，一旦接触新鲜的Li金属表面和/或在放电过程中，有机多硫化物聚合物就可以同时化学/电化学地原位同时产生无机和有机组分。这些无机/有机组分可以参与SEI层的形成，并最终在锂金属阳极的表面上构成稳定且柔性的杂化SEI层。此外，有机组分对锂离子对阴离子具有选择性。因此，PVDF / PSPEG GPE确保了Li-S电池的理想化学和电化学性能。我们的工作证明了解决锂阳极问题的有效解决方案，并为安全的锂金属电池的开发做出了贡献。