Abstract: Intelligent shape memory aerogels show great potential for thermal protection and electromagnetic devices. However, achieving wide-span multiple shape memory effects alongside high electrical conductivity remains challenging. Existing systems suffer from narrow transition windows, while rigid conductive fillers severely restrict polymer chain mobility, thereby degrading shape memory performance. To overcome this, we developed a polyimide-liquid metal bicontinuous aerogel (PLBA) via in-situ shape memory activation and molecular interfacial engineering. 4-aminothiophenol anchors onto gallium-indium nanoparticles via Ga–S bonds and forms hydrogen bonds with the polyimide matrix, ensuring uniform dispersion. Upon compressive deformation above the glass transition temperature, dispersed liquid metal nanoparticles break through their native oxide layers and polymer confinement. They coalesce into an interconnected continuous network, simultaneously fixing the temporary shape and activating electrical conductivity. The resulting PLBA exhibits excellent triple shape memory behavior with response temperatures of 16 ℃ and 291 ℃, delivering an ultra-large temperature span of 275 ℃. Both shape fixity and recovery ratios exceed 95% over multiple cycles. Additionally, the activated bicontinuous structure achieves a high electrical conductivity of 0.13 ±0.02 S cm^-1 and an electromagnetic interference shielding effectiveness of 32 dB in the X-band. This study successfully resolves the trade-off between wide-temperature multiple shape memory and high electrical conductivity, offering a promising material for multi-temperature alarm systems and large-deployable electromagnetic shielding applications.

Key words: Liquid metal, Polyimide aerogel, Bicontinuous structure, Triple shape memory, Electromagnetic interference shielding