Low intrinsic thermal conductivity (TC) of polymer materials has severely limited their further applicability in electronic and electrical products. To enhance the TC, a strategy for constructing nanofiller-based thermal conductive networks by patterned self-assembly of electrospun nanofibers was first proposed in this paper. By selecting a regular metal mesh as the collector, the electrostatic field-induced directional deposition of nanofibers was achieved, thereby constructing interconnected heat transfer paths aligned in at least four directions. The in-plane TC of heat-pressed electrospun polyvinylidene fluoride (PVDF) nanofibers with 20 wt% loading of boron nitride nanosheets (BNNSs) can reach 7.27 W/(m·K). Electrical insulation of the PVDF/BNNS composites has also been confirmed, showing high volume resistivity and breakdown strength, which have increased by 460.0 % and 26.6 %, respectively, compared to pure PVDF. Finally, a double-layer composite film with waterproof and easy-cleaning characteristics was prepared for electronic device packaging. This simple and efficient preparation strategy for thermal conductive networks may bring new perspectives to thermal management applications.
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