Simultaneous enhancement in thermal conductivity and flame retardancy of flexible film by introducing covalent bond connection

Owing to the high interface thermal resistance and aggregation in polymer-based materials, the thermal conductivity of multi-walled carbon nanotubes (MWCNTs) has been severely decreased in practical applications. In this work, an amino-functionalized black phosphorene (BP–NH2) fabricated by ball milling has been employed to react with carboxylated multi-wall carbon nanotubes (MWCNTs–COOH) via covalent bonds to prepare a nanofiller (BP–MWCNTs) with high thermal conductivity and excellent flame retardancy. When incorporating 20.0 wt% BP–MWCNTs into cellulose nanofiber (CNF), the CNF/BP–MWCNTs 20.0 shows an in-plane thermal conductivity of 22.38 ± 0.39 W m−1 K−1 and a cross-plane thermal conductivity of 0.36 ± 0.03 W m−1 K−1, resulting in an anisotropy index of 62.17. The effective medium theory (EMT) calculation demonstrates the interface thermal resistance is reduced to 1/39 that of pure MWCNTs, which is ascribed to the covalent bond between BP–NH2 and MWCNTs–COOH. Simultaneously, the CNF/BP–MWCNTs 20.0 can pass the testing of UL-94 V-0 grade and the limiting oxygen index (LOI) value can be increased from 18.1% to 29.9%. Its peak of heat release rate (PHRR), total heat release (THR), smoke production rate (SPR), total smoke production (TSP), CO generated per second (COP) and CO2 generated per second (CO2P) are decreased by 37.47%, 43.51%, 50.00%, 35.29%, 50.00% and 19.70%, respectively, which is due to the formation of an intumescent flame-retardant system rich in carbon source (MWCNTs), acid source (BP) and gas source (amino groups). This covalent linkage strategy offers a new thought for the preparation of flexible materials to enhance the thermal conductivity and fire resistance.