Core–Shell Composite Nanofibers with High Temperature Resistance, Hydrophobicity and Breathability for Efficient Daytime Passive Radiative Cooling

Abstract Radiative cooling technology, which is renowned for its ability to dissipate heat without energy consumption, has garnered immense interest. However, achieving high performance, multifunctionality, and smart integration while addressing challenges such as film thickness and enhancing anisotropic light reflection remains challenging. In this study, a core–shell composite nanofiber, PVDF@PEI, is introduced and designed primarily from a symmetry‐breaking perspective to develop highly efficient radiative cooling materials. Using a combination of solvent‐induced phase separation (EIPS) inverse spinning and (aggregation) self‐assembly methods (EISA or EIAA) and coaxial electrostatic spinning (ES), superconformal surface anisotropic porous nanofiber membranes are fabricated. These membranes exhibit exceptional thermal stability (up to 210 °C), high hydrophobicity (contact angle of 126°), robust UV protection (exceeding 99%), a fluorescence multiplication effect (with a 0.6% increase in fluorescence quantum efficiency), and good breathability. These properties enable the material to excel in a wide range of application scenarios. Moreover, this material achieved a remarkable daytime cooling temperature of 8 °C. The development of this fiber membrane offers significant advancements in the field of wearables and the multifunctionality of materials, paving new paths for future research and innovation.