Bio-inspired self-healing materials hold great promise for applications in wearable electronics, artificial muscles and soft robots, etc. However, self-healing at subzero temperatures remains a great challenge because the reconstruction of interactions will experience resistance of the frozen segments. Here, we present an ultrarobust subzero healable glassy polymer by incorporating polyphenol nano-assemblies with a large number of end groups into polymerizable deep eutectic solvent elastomers. The combination of multiple dynamic bonds and rapid secondary relaxations with low activation energy barrier provides a promising method to overcome the limited self-healing ability of glassy polymers, which can rarely be achieved by conventional dynamic cross-linking. The resulted material exhibits remarkably improved adhesion force at low temperature (promotes 30 times), excellent mechanical properties (30.6 MPa) and desired subzero healing efficiencies (85.7% at −20 °C). We further demonstrated that the material also possesses reliable cryogenic strain-sensing and functional-healing ability. This work provides a viable approach to fabricate ultrarobust subzero healable glassy polymers that are applicable for winter sports wearable devices, subzero temperature-suitable robots and artificial muscles.

仿生自愈材料在可穿戴电子产品、人造肌肉和软体机器人等方面的应用前景广阔。然而，在零度以下的温度下自愈仍然是一个巨大的挑战，因为相互作用的重建将遇到冻结部分的阻力。在这里，我们通过将具有大量端基的多酚纳米组件结合到可聚合的低共熔溶剂弹性体中，展示了一种超坚固的零度以下可修复玻璃态聚合物。多个动态键和快速二次弛豫与低活化能垒的结合提供了一种有前途的方法来克服玻璃态聚合物有限的自愈能力，这很难通过传统的动态交联来实现。所得材料在低温下表现出显着改善的粘附力（提升 30 倍）、出色的机械性能（30.6 MPa）和理想的零下愈合效率（-20 °C 时为 85.7%）。我们进一步证明该材料还具有可靠的低温应变传感和功能修复能力。这项工作提供了一种可行的方法来制造适用于冬季运动可穿戴设备、适合零下温度的机器人和人造肌肉的超坚固的零下可修复玻璃态聚合物。