Millefeuille-inspired highly conducting polymer nanocomposites based on controllable layer-by-layer assembly strategy for durable and stable electromagnetic interference shielding.

High-performance conductive polymer nanocomposites containing two-dimensional (2D) MXene are garnering substantial interest for electromagnetic shielding interference (EMI) in flexible electronics. However, owing to the non-sticky nature and undesirable mechanical performances of freestanding MXene film, it remains a formidable challenge to make the trade-off between outstanding EMI shielding capability and high stability. In this study, inspired by the structure and manufacturing process of millefeuille cakes, we propose a controllably layer-by-layer assembling strategy for fabricating flexible multilayered EMI shielding composite films based on MXene and an inherently conductive polymer (ICP). The multilayer films bearing alternating aramid nanofibers/polypyrrole nanowires (AFPy) and TiCT reinforced by waterborne polyurethane (TiCT@WPU) layers are orderly constructed by a facile alternating vacuum filtration method. Benefiting from the special architectures, the AFPy-70/TiCT@WPU-4 film exhibits a high electrical conductivity of 1.74 S cm and superior EMI shielding effectiveness of 40.9 dB at lower TiCT loading content (32 wt%). Moreover, synergistic integration of hydrogen bonding and π-π stacks in multilayered films is achieved, especially in tandem with controlled crack generation within the whole film. Excellent EMI shielding performance remains well maintained even after being suffered to back-and-forth bending test (over 10,000 cycles), ultrasonication, and cryogenic temperature, validating great potential as high-performance EMI shielding film resisting extreme conditions.