The construction of 3D filler networks is an effective strategy to improve the thermal conductivity of epoxy resins, yet it is still severely limited by the disconnection of conduction channels. In this contribution, an original interlocking hybrid skeleton with continuous conduction channels was developed by assembling BNNS into an in situ-formed interlocking Al2O3 platelet skeleton using commercial polyurethane as a template, where large intergranular contact areas of Al2O3 platelets were established by sintering to greatly decrease the contact thermal resistance. Besides, the interlocking Al2O3 skeleton coupled with BNNS under hydrogen bonding endowed further improvement of its thermal conductivity. The optimized Al2O3/BNNS/EP composite displayed an excellent thermal conductivity of 5.01 W/mK at 15.3 vol% of Al2O3 and 11.4 vol% of BNNS loading, far higher than that of neat epoxy resin by 1904.0 %. Meanwhile, the interlocking hybrid skeleton provided the epoxy resin with low dielectric loss, satisfactory thermal stability and flame retardancy.
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