Highly Stable and Controllable Self‐Assembled Conductive Networks Enabled by Stereocomplex Crystallite Frameworks for Enhanced Electromagnetic Shielding

ABSTRACT The advancement of lightweight and miniaturized electronic devices has exacerbated the demand for high‐efficiency electromagnetic interference (EMI) shielding materials. However, traditional polymer composites typically suffer from limited EMI shielding effectiveness and poor mechanical strength, primarily attributed to the disordered distribution of conductive nanofillers and flawed structural design. Here, a high‐stability self‐assembled conductive network encapsulated by stereocomplex crystallites was designed using the Pickering emulsion method, and conductive fillers were secondarily filled into the skeleton to prepare green degradable electromagnetic shielding materials with both high electrical conductivity and good mechanical properties at low filler contents. The unique SC‐encapsulated skeleton structure endows the composite with an electromagnetic interference shielding effectiveness of 51 dB, while its electrical conductivity is enhanced to 339 S/m. Owing to the good dispersion of fillers and the improvement in matrix crystallinity, the composites demonstrate excellent mechanical properties, with a tensile strength of 51.93 MPa and a storage modulus of 119.37 MPa at 120°C, significantly enhancing high‐temperature structural stability. Moreover, due to the formation of an efficient continuous conductive network, the composites also exhibit ultrafast Joule heating performance. This work provides valuable insights into the design of high‐performance degradable CPCs with multifunctional EMI shielding applications.