Similar to graphene, few-layer black phosphorus possesses many excellent properties such as good thermal stability, mechanical properties and unique characteristic dimension effects, which is considered as promising nanoadditives. But the low yield and inferior interfacial adhesion with polymer matrix are unavoidable obstruction to fabricate high performance nanocomposites. Herein, we report a facile and environmentally friendly approach to simultaneously exfoliate and modify black phosphorus (BP) by electrochemical cathodic exfoliation, where BP crystal acted as the cathode and ethylene imine polymer (PEI) acted as electrolyte and modifier. The positively charged PEI would uniformly anchor on the surface of the newly peeled-off BP nanosheets through electrostatic attraction effect, resulting in preventing the agglomeration of BP nanosheets and improve the compatibility between BP and waterborne polyurethane (WPU) matrix. Significantly, with the addition of 2.0 wt% PEI modified BP in WPU matrix, the fire safety of WPU composites was enhanced. The peak heat-release rate, total heat release, total smoke production and total CO yield are decreased by 34.3%, 21.2%, 22.3% and 50.2% compared to pure WPU, respectively. Also, the tensile strength of WPU composites was increased by 71% (from 21.9 to 31.0 MPa) at the cost of the breaking elongation slightly decreased by 5.6%. This work provides the possibility for the scalable preparation and a real application of BP in polymer nanocomposites.

类似于石墨烯，很少层的黑磷具有许多优异的性能，例如良好的热稳定性，机械性能和独特的特征尺寸效应，被认为是有前途的纳米添加剂。但是低产率和与聚合物基体的不良界面粘合是不可避免的阻碍制备高性能纳米复合材料的障碍。本文中，我们报告了一种简便且环保的方法，可通过电化学阴极剥落同时剥落和修饰黑磷（BP），其中BP晶体充当阴极，乙烯亚胺聚合物（PEI）充当电解质和改性剂。带正电的PEI通过静电吸引作用均匀地锚定在新剥离的BP纳米片的表面，从而防止了BP纳米片的团聚，并改善了BP与水性聚氨酯（WPU）基质之间的相容性。值得注意的是，在WPU基体中添加2.0 wt％PEI改性的BP，可增强WPU复合材料的防火性。与纯WPU相比，峰值放热率，总放热，总烟雾产生和总CO产量分别降低了34.3％，21.2％，22.3％和50.2％。此外，WPU复合材料的拉伸强度提高了71％（从21.9 MPa增至31.0 MPa），而断裂伸长率的降低略微降低了5.6％。这项工作为可扩展的制备方法和将BP实际应用于聚合物纳米复合材料提供了可能性。在WPU基体中加入0 wt％PEI改性的BP，提高了WPU复合材料的防火性。与纯WPU相比，峰值放热率，总放热，总烟雾产生和总CO产量分别降低了34.3％，21.2％，22.3％和50.2％。此外，WPU复合材料的拉伸强度提高了71％（从21.9 MPa增至31.0 MPa），而断裂伸长率的降低略微降低了5.6％。这项工作为可扩展的制备方法和将BP实际应用于聚合物纳米复合材料提供了可能性。在WPU基体中加入0 wt％PEI改性的BP，增强了WPU复合材料的防火性。与纯WPU相比，峰值放热率，总放热，总烟雾产生和总CO产量分别降低了34.3％，21.2％，22.3％和50.2％。此外，WPU复合材料的拉伸强度提高了71％（从21.9 MPa增至31.0 MPa），而断裂伸长率的降低略微降低了5.6％。这项工作为可扩展的制备方法和将BP实际应用于聚合物纳米复合材料提供了可能性。0MPa）以断裂伸长率为代价略微降低了5.6％。这项工作为可扩展的制备方法和将BP实际应用于聚合物纳米复合材料提供了可能性。0MPa）以断裂伸长率为代价略微降低了5.6％。这项工作为可扩展的制备方法和将BP实际应用于聚合物纳米复合材料提供了可能性。