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Pliant and versatile polymeric films engineered for electromagnetic interference (EMI) shielding play a pivotal role in driving the evolution of telecommunications, wearable electronics, and next-generation AI platforms. In this work, poly(p-phenylene benzobisthiazole) (PBO) fibers are subjected to sequential acid treatment with MSA/TFA mixture and subsequent deprotonation to afford well-defined PBO nanofibers (PNF). Water-dispersible silver nanowire (M-AgNWs) is synthesized via a controlled polyol reduction process coupled with Ag–S coordination surface functionalization. Then, M-AgNWs/PNF composite films are fabricated through vacuum-assisted filtration followed by thermal compression. The synthesized M-AgNWs/PNF composite films demonstrate remarkable multifunctional performance at a 50 wt.% M-AgNWs loading, which deliver an electrical conductivity (σ) of 4545 S/cm, superior X-band EMI shielding (81 dB), a thermal conductivity (λ) of 21.7 W/(m·K), and the tensile strength can be flexibly tuned within the range of 101.3 to 181.1 MPa. First-principles density functional theory (DFT) simulation results confirm that HEDS adsorbs onto AgNWs through Ag–S coordination, and the functionalized M-AgNWs can form efficient electrically and thermally conductive networks within PNF, thereby improving the EMI shielding and mechanical properties of the M-AgNWs/PNF composite films. Furthermore, M-AgNWs/PNF composite films demonstrate rapid, reversible photothermal and electrothermal responses. Under simulated sunlight irradiation with a power density of 120 mW/cm2, the surface temperature of M-AgNWs/PNF composite films rapidly rise from room temperature to 74.8 °C. Concurrently, under a voltage of 3.5 V, the surface temperature quickly escalates to 79.4 °C. This work offers an effective approach to fabricating lightweight, high-performance EMI shielding composites suitable for aerospace and integrated electronic devices.

This is an open access article under the terms of the Creative Commons Attribution 4.0 International License (CC BY 4.0, https://creativecommons.org/licenses/by/4.0/).
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