Hexagonal boron nitride nanosheets (BNNSs) exhibit remarkable thermal and dielectric properties. However, their self-assembly and alignment in macroscopic forms remain challenging due to the chemical inertness of boron nitride, thereby limiting their performance in applications such as thermal management. In this study, we present a coaxial wet spinning approach for the fabrication of BNNSs/polymer composite fibers with high nanosheet orientation. The composite fibers were prepared using a superacid-based solvent system and showed a layered structure comprising an aramid core and an aramid/BNNSs sheath. Notably, the coaxial fibers exhibited significantly higher BNNSs alignment compared to uniaxial aramid/BNNSs fibers, primarily due to the additional compressive forces exerted at the core-sheath interface during the hot drawing process. With a BNNSs loading of 60 wt%, the resulting coaxial fibers showed exceptional properties, including an ultrahigh Herman orientation parameter of 0.81, thermal conductivity of 17.2 W m -1 K -1 , and tensile strength of 192.5 MPa. These results surpassed those of uniaxial fibers and previously reported BNNSs composite fibers, making them highly suitable for applications such as wearable thermal management textiles. Our findings present a promising strategy for fabricating high-performance composite fibers based on BNNSs.
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