Electrochemical exfoliation and functionalization of black phosphorene to enhance mechanical properties and flame retardancy of waterborne polyurethane

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.