Thermally Insulating Polyimide Aerogel Skeletons Constructed by Hybridizing the Al–O Network Phase

Polyimide aerogels have garnered considerable attention due to their high-performance combination of a lightweight nature, low thermal conductivity, and high mechanical strength, which renders them ideal candidates for thermal insulators in aerospace. However, the inherent conflict in achieving multifunctional (dimensional stability and mechanical stiffness at high temperatures, and highly efficient thermal insulation) integration presents a great challenge. Here, we present an aerogel skeleton construction strategy based on hybridizing an Al–O network phase to create multifunctional polyimide aerogels. The resulting aerogels partially constructed by Al–O network phase exhibit an outstanding resistance to high temperatures (shrinkage of 0.56% after experiencing 200 °C for 2400 s), which is markedly superior to that of conventional polyimide aerogels. The excellent insulation capability of the aerogel is reflected in its low thermal conductivity (0.0214 W m−1 K−1) and its ability to maintain a cold-side temperature of just 59.7 °C under a 150 °C heat source. Furthermore, remarkable enhancements in mechanical properties are found at high-temperature conditions, providing evidence for the compressive stresses of 0.329 and 0.394 MPa under 3% strain at the respective temperatures of 200 and 250 °C, showing a clear trend of enhanced compressive stress with rising temperature. These advancements in high-temperature stability and mechanical properties substantially broaden the scope for their potential applications in aerospace thermal protection systems.