Multilayered films composed of alternating layers of graphene fluoride (GF) and silver nanowires (AgNWs) in an aramid nanofiber (ANF) matrix were fabricated. The films were prepared by sequential vacuum filtration of GF@ANF and AgNWs@ANF suspensions to obtain multilayered composite architectures. The multilayered GF@ANF/AgNWs@ANF films exhibited exceptional mechanical flexibility and strength, with tensile strength up to 130 MPa and 5000 bending cycles with negligible performance deterioration. The films displayed remarkably high electromagnetic interference (EMI) shielding effectiveness up to 54 dB in X-band frequencies, attributed to the multiple internal reflections in the multilayered structure. EMI shielding was dominated by absorption rather than reflection, enabling attenuation of incident microwaves without secondary pollution. The multilayered films also exhibited ultrahigh in-plane thermal conductivity of up to 45 W/mK, owing to the thermally conductive GF and AgNWs networks. The EMI shielding effectiveness and thermal conductivity were retained after temperature and bending cycling. The composite films also demonstrated excellent flame retardancy. This study provides an effective route toward concurrent enhancement of multi-functional properties through architectural engineering at the nanoscale. The combination of robust EMI shielding, mechanical flexibility, thermal management, and fire safety highlights the potential of rationally designed multilayered composites for practical applications in 5 G wearable electronics devices, communications systems, and radar technologies.
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