With the rapid advancements in 5G and communication technology, electromagnetic wave (EMW) absorption materials play a crucial role in reducing interference, enhancing the efficiency and stability of communication equipment, and minimizing maintenance requirements. However, the challenge remains in effectively utilizing cost-effective raw materials with simple synthesis conditions to achieve highly consistent product quality and superior EWM absorption performance. This study employs carbon nanofibers (CNFs) derived from polyacrylonitrile (PAN) as substrates and utilizes electrodeposition technology to create a composite material that exhibits both magnetic and dielectric properties. The results show that the petal-like porous Co composite CNFs (Co/CNFs) demonstrates excellent impedance matching and significant EMW absorption capabilities, which can be attributed to synergistic microstructural effects and multiple loss mechanisms. At a filling ratio of 20 wt% and a thickness of 1.8 mm, the Co/CNFs achieves a minimum reflection loss of −45 dB, extending the effective absorption bandwidth to 4.6 GHz. Performance assessment through power loss density (PLD) and radar cross-section (RCS) simulations evaluates the material’s capabilities, confirming the enhanced performance of Co/CNFs compared to the perfect electrical conductor (PEC). This efficient preparation method holds substantial potential for practical applications and serves as a comprehensive guide for achieving a balance between high performance, efficiency, and cost-advantages.
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