Owing to the growing heat removal issue of modern electronic devices, polymer composites with high thermal conductivity have drawn much attention in the past few years. However, a traditional method to enhance the thermal conductivity of the polymers by addition of inorganic fillers usually creates composite with not only limited thermal conductivity but also other detrimental effects due to large amount of fillers required. Here, novel polymer composites are reported by first constructing 3D boron nitride nanosheets (3D-BNNS) network using ice-templated approach and then infiltrating them with epoxy matrix. The obtained polymer composites exhibit a high thermal conductivity (2.85 W m(-1) K(-1)), a low thermal expansion coefficient (24-32 ppm K(-1)), and an increased glass transition temperature (T(g)) at relatively low BNNSs loading (9.29 vol%). These results demonstrate that this approach opens a new avenue for design and preparation of polymer composites with high thermal conductivity. The polymer composites are potentially useful in advanced electronic packaging techniques, namely, thermal interface materials, underfill materials, molding compounds, and organic substrates.

With the current development of modern electronics toward miniaturization, high-degree integration and multifunctionalization, considerable heat is accumulated, which results in the thermal failure or even explosion of modern electronics. The thermal conductivity of materials has thus attracted much attention in modern electronics. Although polymer composites with enhanced thermal conductivity are expected to address this issue, achieving higher thermal conductivity (above 10 W m K) at filler loadings below 50.0 wt % remains challenging. Here, we report a nanocomposite consisting of boron nitride nanotubes and cellulose nanofibers that exhibits high thermal conductivity (21.39 W m K) at 25.0 wt % boron nitride nanotubes. Such high thermal conductivity is attributed to the high intrinsic thermal conductivity of boron nitride nanotubes and cellulose nanofibers, the one-dimensional structure of boron nitride nanotubes, and the reduced interfacial thermal resistance due to the strong interaction between the boron nitride nanotubes and cellulose nanofibers. Using the as-prepared nanocomposite as a flexible printed circuit board, we demonstrate its potential usefulness in electronic device-cooling applications. This thermally conductive nanocomposite has promising applications in thermal interface materials, printed circuit boards or organic substrates in electronics and could supplement conventional polymer-based materials.