Electric Field‐Induced Ordered‐Structural Aerogels Enable Superinsulation and Multifunctionality

1D flexible fibers assembled 3D porous networked ceramic fiber aerogels (CFAs) are developed to overcome the brittleness of traditional ceramic particle aerogels. However, existing CFAs with disordered and quasi-ordered structures fail to balance the relationship between flexibility, robustness, and thermal insulation. Creating novel architectural CFAs with an excellent combination of performances has proven extremely challenging. In this paper, a novel strategy is adopted to fabricate porous mullite fibrous aerogels (MFAs) with ordered structures by combining fiber sedimentation and electric field-induced fiber alignment techniques. For the first time, electric field-induced alignment of ceramic fibers is utilized to prepare bulk aerogels on a large scale. The resulting MFAs exhibit ultra-low high-temperature thermal conductivity of 0.0830 W m^-1 K^-1 at 1000 °C, anisotropic mechanical and sound absorption performances, and multifunctionality in terms of the combination of thermal insulation, sound absorption, and hydrophobicity. The successful synthesis of such fascinating materials may provide new insights into the design and development of multifunctional CFAs for various applications.