Flexible and wearable electronics represent an emerging frontier, but realizing their potential requires addressing challenges like electromagnetic interference (EMI) shielding, electrical insulating thermal management, and mechanical flexibility. Layer-by-layer structure with alternating conductive and insulating layers offers a promising solution. In this work, we fabricated layer-by-layer structured papers combining boron arsenide (BA) as insulating layers and two-dimensional copper nanoflake (CuF) as conductive layers based on aramid nanofiber (ANF) film via alternating vacuum filtration. The resultant paper (BA4/CuF3) consists of 3 layers of CuF (50 wt%) based ANF (CuF@ANF) conductive layers sandwiched between 4 layers of BA (50 wt%) based ANF (BA/ANF) insulating layers providing exceptional EMI shielding effectiveness (SE) up to 52 dB in the X-band frequency, and in-plane thermal conductivity up to 32.8 W/mK. Meanwhile, the composite papers also demonstrate excellent mechanical flexibility, with the BA4/CuF3 papers exhibiting a tensile strength of 92.38 MPa and EMI SE above 50 dB. Moreover, the composites impart thermal stability up to 500 °C and reduce flammability. The concurrent enhancement of EMI shielding, thermal conductivity, and mechanical properties confirms the potential of layer-by-layer BA/CuF papers for next-generation flexible electronics demanding electromagnetic protection and thermal management.
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