Way to a Library of Ti‐Series Oxide Nanofiber Sponges that are Highly Stretchable, Compressible, and Bendable

Abstract Ti‐series oxide ceramics in the form of aerogels, such as TiO₂, SrTiO₃, BaTiO₃, and CaCu₃Ti₄O₁₂, hold tremendous potential as functional materials owing to their excellent optical, dielectric, and catalytic properties. Unfortunately, these inorganic aerogels are usually brittle and prone to pulverization owing to weak inter‐particulate interactions, resulting in restricted application performance and serious health risks. Herein, a novel strategy is reported to synthesize an elastic form of an aerogel‐like, highly porous structure, in which activity‐switchable Ti‐series oxide sols transform from the metastable state to the active state during electrospinning, resulting in condensation and solidification at the whipping stage to obtain curled nanofibers. These curled nanofibers are further entangled when flying in the air to form a physically interlocked, elastic network mimicking the microstructure of high‐elasticity hydrogels. This strategy provides a library of Ti‐series oxide nanofiber sponges with unprecedented stretchability, compressibility, and bendability, possessing extensive opportunities for greener, safer, and broader applications as integrated or wearable functional devices. As a proof‐of‐concept demonstration, a new, elastic form of TiO₂, composed of both “white” and “black” TiO₂ nanofiber sponges, is constructed as spontaneous air‐conditioning textiles in smart clothing, buildings, and vehicles, with unique bidirectional regulation of radiative cooling in summer and solar heating in winter.