The exceptional lightweight, highly porous, and insulating properties of aerogel fibers make them ideal for thermal insulation. However, current aerogel fibers face limitations due to their low resistance to harsh environments and a lack of intelligent responses. Herein, a universal strategy for creating polymer aerogel fibers using crosslinked nanofiber building blocks is proposed. This approach combines controlled proton absorption gelation spinning with a heat-induced crosslinking process. As a proof-of-concept, Zylon aerogel fibers that exhibited robust thermal stability (up to 650 °C), high flame retardancy (limiting oxygen index of 54.2%), and extreme chemical resistance are designed and synthesized. These fibers possess high porosity (98.6%), high breaking strength (8.6 MPa), and low thermal conductivity (0.036 W m−1 K−1). These aerogel fibers can be knotted or woven into textiles, utilized in harsh environments (−196–400 °C), and demonstrate sensitive self-powered sensing capabilities. This method of developing aerogel fibers expands the applications of high-performance polymer fibers and holds great potential for future applications in wearable smart protective fabrics.
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