The separator, an ionic permeable and electronic insulating membrane between cathode and anode, plays a crucial role in the electrochemical and safety performance of batteries. However, commercial polyolefin separators not only suffer from inevitable thermal shrinkage at elevated temperature, but also fail to inhibit the hidden chemical crosstalk of reactive gases such as O , leading to often reported thermal runaway (TR) and hence preventing large-scale implementation of high-energy-density lithium-ion batteries. Herein, a nanoporous non-shrinkage separator (GS-PI) is fabricated via a novel gel-stretching orientation approach to eliminate TR. In situ synchrotron small angle X-ray scattering during heating clearly shows that the as-prepared thin GS-PI separator exhibits superior mechanical tolerance at high temperature, thus effectively preventing internal short circuit. Meanwhile, the unique nanoporous structure design further blocks chemical crosstalk and the associated exothermic reactions. Accelerating rate calorimetry tests reveal that the practical 1 Ah LiNi Co Mn O (NCM622)/graphite pouch cell using GS-PI nanoporous separator show a maximum temperature rise (dT/dt ) of only 3.7 °C s compared to 131.6 °C s in the case of Al O @PE macroporous separator. Moreover, despite the reduced pore size, the GS-PI separator demonstrates better cycling stability than conventional Al O @PE separator at high temperature without sacrificing specific capacity and rate capability.

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