Spider Silk‐Like Nanodomain Spacings Enable Mechanically Robust and Healable Elastomers with Record‐High Puncture Resistance

ABSTRACT Spider silk is an exceptionally strong, extensible, and tough natural material, the outstanding mechanical properties of which arise from β ‐sheet nanocrystalline protein domains with an average lattice spacing of approximately 10 nm. Herein, inspired by the microstructure of spider silk, a mechanically robust, healable, and reprocessable fluorinated supramolecular poly(urethane‐urea) (F‐SPUU) elastomer with record‐high puncture energy (889 mJ), is reported. The high‐performance stems from the cross‐linking of polytetrahydrofuran chains with in situ‐formed phase‐separated nanodomains (lattice spacing: 10.02 nm), closely resembling that observed in spider silk. These nanodomains consist of dynamic hydrogen bonded arrays and fluorinated phenol–carbamate bonds. They not only serve as rigid nanofillers that reinforce elastomers, but deform and disintegrate under external forces, dissipating energy to improve puncture resistance and damage tolerance, while endowing elastomers with self‐healability and reprocessability due to their reversibility. As a result, the F‐SPUU elastomer exhibits high tensile strength (39.6 MPa), superior fracture energy (90.8 kJ m ^{− 2} ), excellent self‐healing efficiency (99.1%), and low surface energy (41.7 mJ m ^{− 2} ). The tough self‐healing elastomers enable the fabrication of multifunctional triboelectric nanogenerators, offering a molecular engineering strategy for high performance polymers toward cutting‐edge applications.