LAUSR

Polymer‐based thermal interface materials (TIMs) with excellent thermal conductivity and electrical resistivity are in high demand in the electronics industry. In the past decade, thermally conductive fillers, such as boron nitride nanosheets (BNNS), were usually incorporated into the polymer‐based TIMs to improve their thermal conductivity for efficient heat management. However, the thermal performance of those composites means that they are still far from practical applications, mainly because of poor control over the 3D conductive network. In the present work, a high thermally conductive BNNS/epoxy composite is fabricated by building a nacre‐mimetic 3D conductive network within an epoxy resin matrix, realized by a unique bidirectional freezing technique. The as‐prepared composite exhibits a high thermal conductivity (6.07 W m−1 K−1) at 15 vol% BNNS loading, outstanding electrical resistivity, and thermal stability, making it attractive to electronic packaging applications. In addition, this research provides a promising strategy to achieve high thermal conductive polymer‐based TIMs by building efficient 3D conductive networks.