Lithium-sulfur (Li-S) batteries with high specific capacity are expected to play important roles in next-generation high-energy-storage systems. However, uncontrollable shuttle effect of Li polysulfide (LiPS) and safety concerns still hinder their applications. Herein, we report an in-situ formed asymmetric gel polymer electrolyte (AGPE) fabricated through a novel and low-cost strategy. In cases of modifying the separator with Lewis acid and inducing an in-situ polymerization reaction, an enclosed catholyte chamber is constructed between sulfur cathode and separator while liquid-state electrolytes still maintain in the anode side. Experimental characterizations indicate the as-prepared AGPE could effectively prevents the shuttle effect while allowing rapidly Li⁺ transport property. With such AGPE, the Li symmetric cells show stable cycle performance over 1400 h cycling, and Li-S batteries exhibit a high capacity of 1090 mAh g⁻¹ with a capacity decay rate of only ∼0.2% per cycle after 200 cycles. Besides, by combining the electrochemical measurements and the evolution of sulfur species upon cycling, the origin of enhanced cycle performance is demonstrated from the perspective of reaction kinetics in this work. Our research therefore provides a novel strategy for the electrolyte configuration and reveals a promising direction for the performance improvement of Li-S batteries.

具有高比容量的锂硫（Li-S）电池有望在下一代高能量存储系统中发挥重要作用。然而，锂多硫化物（LiPS）不可控的穿梭效应和安全问题仍然阻碍了它们的应用。在此，我们报告了一种原位形成的不对称凝胶聚合物电解质 (AGPE)，该电解质是通过一种新颖且低成本的策略制造的。在用路易斯酸改性隔膜并引发原位聚合反应的情况下，在硫阴极和隔膜之间构建一个封闭的阴极电解液室，而液态电解质仍然保持在阳极侧。实验表征表明，所制备的 AGPE 可以有效地防止穿梭效应，同时允许快速 Li ⁺运输财产。使用这种 AGPE，Li 对称电池在 1400 小时的循环中表现出稳定的循环性能，而 Li-S 电池表现出 1090 mAh g ^-1的高容量，在 200 次循环后容量衰减率仅为每次循环 ~ 0.2%。此外，通过结合电化学测量和循环时硫物种的演变，这项工作从反应动力学的角度证明了循环性能增强的起源。因此，我们的研究为电解质配置提供了一种新的策略，并揭示了提高锂硫电池性能的有前途的方向。