Graphene-Doped Ammonium Oxalate-Derived Carbon Aerogel with Controllable Structure for Synergistic Endothermic-Insulating Efficient Thermal Protection

High-performance thermal protection materials are urgently required in harsh thermal environments, such as hypersonic vehicles, the thermal runaway of energy batteries and high-temperature equipment. Conventional aerogels only exhibit passive thermal insulation and fail to resist instantaneous high-temperature attack. Herein, a cooling material of ammonium oxalate (AO) was introduced to achieve efficient, active endothermic protection. A cellular isolation effect induced by graphene nanosheets combined with anti-solvent crystallization was adopted to significantly decrease the size of AO crystals by over 93%. Based on superfine morphology and the constructed conduction network, the decomposition rate and heat absorption capacity of obtained graphene-doped AO powders (GdAPs) are improved by 41.2% and 30.4%, respectively. The mechanisms of morphology regulation and enhanced heat absorption are explored specifically in this study. Furthermore, GdAPs are embedded in phenolic resin to prepare thermal protection composite materials. Benefiting from their nearly complete thermal decomposition, GdAPs serve as a sacrificial template to generate discrete micropores in pyrolyzed resin. So, the as-prepared carbon aerogels (CAs) with a regulable microstructure exhibit an extremely low thermal conductivity of 0.056 W/(m·K), which is lower than those of reported CAs with the same density. Based on the above advantages, a synergistic endothermic-insulating thermal protection material is reported for the first time, and its heating rate is only 28.6% of that of commercial silica aerogel under identical high-temperature shock. Therefore, a new accessible strategy is demonstrated to provide high-efficiency thermal protection for resisting both abrupt and prolonged high temperature.