Facile Exfoliation and Noncovalent Superacid Functionalization of Boron Nitride Nanosheets and Their Use for Highly Thermally Conductive and Electrically Insulating Polymer Nanocomposites.

There is an increasing demand for highly thermally conductive and electrically insulating polymer materials for next-generation electronic devices, power systems, and communication equipment. Boron nitride nanosheets (BNNSs) are insulating materials with extremely high thermal conductivity. However, BNNSs suffer from the lack of facile and low-cost methods for producing large volumes of BNNSs, and extremely low through-plane thermal conductivities of BNNS/polymer composites as compared to the in-plane thermal conductivities. Herein, highly soluble, noncovalently functionalized boron nitride nanosheets (NF-BNNSs) with chlorosulfonic acid (CSA) were prepared by extremely facile and low-cost direct exfoliation of hexagonal boron nitrides (h-BNs), and acted as excellent nanofillers for dramatically improving both in- and through-plane thermal conductivities of insulating polymers. CSA is a cheap and versatile superacid with a large production volume. CSA showed strong physical adsorption on h-BN surfaces, giving few-layered NF-BNNSs in high yields (up to ∼25%). The crystallinity of the NF-BNNS was perfectly maintained even after CSA treatment. The physical adsorption of CSAs imparted high solubility for BNNSs in various organic solvents, yielding NF-BNNS uniformly dispersed-thermoplastic polymer composite films through a simple wet-process using predispersed NF-BNNS solutions. Random dispersion of NF-BNNSs in thermoplastic polymer films dramatically enhanced both the in- and through-plane thermal conductivities (>10 W m-1 K-1). The through-plane thermal conductivity of the NF-BNNS/polybutylene terephthalate (PBT) composite films was much greater (up to 11.0 W m-1 K-1) than those previously reported for BNNS/thermoplastic polymer composites (≤2.6 W m-1 K-1). These results are also due to an increase of interactions between the BNNS and polymer matrices, caused by physical adsorption of CSAs on BNNS surfaces. Moreover, the volume resistivity of the NF-BNNS/PBT composite films was significantly improved compared with pristine PBT. The NF-BNNS/polymer composites are very promising as highly thermally conductive and electrically insulating materials in various applications.