Thermal management has become a critical challenge in electronics and portable devices. To address this issue, polymer composites with high thermal conductivity (TC) and low dielectric property are urgently needed. In this work, we fabricated perfluoroalkoxy (PFA) composite with high anisotropic TC and low dielectric constant by aligning boron nitride nanosheets (BNNs) via hot pressing. We characterized the thermal stability, microstructure, in-plane and through-plane TCs, heat dissipation capability, and dielectric property of the composites. The results indicate that the BNNs–PFA composites possessed good thermal stability. When the BNNs content was higher than 10 wt %, the BNNs were well layer aligned in the PFA matrix, and the composites showed obvious anisotropic TC. The in-plane TC and through-plane TCs of 30 wt % BNNs–PFA composite were 4.65 and 1.94 W m⁻¹ K⁻¹, respectively. By using the composite in thermal management of high-power LED, we found that alignment of BNNs in composite significantly improves the heat dissipation capability of composite. In addition, the composites exhibited a low dielectric property. This study shows that hot pressing is a facile and low-cost method to fabricate bulk composite with anisotropic TC, which has wide applications in electronic packaging.

With the rapid development of electronics and portable devices, polymer nanocomposites with high through-plane thermal conductivity (TC) are urgently needed. In this work, we fabricated graphene nanosheets−perfluoroalkoxy (GNs−PFA) composite sheets with high through-plane TCs via hot-pressing followed by mechanical machining. When the GNs content exceeded 10 wt%, GNs were vertically aligned in the PFA matrix, and the through-plane TCs of nanocomposites were 10–15 times higher than their in-plane TCs. In particular, the composite with 30 wt% GNs exhibited a through-plane TC of 25.57 W/(m·K), which was 9700% higher than that of pure PFA. The composite with 30 wt% GNs was attached to the surface of a high-power light-emitting diode (LED) to assess its heat-dissipation capability. The composite with vertically aligned GNs lowered the LED surface temperature by approximately 16 °C compared with pure PFA. Our facile, low-cost method allows for the large-scale production of GNs–PFA nanocomposites with high through-plane TCs, which can be used in various thermal-management applications.