In Situ Synthesis of SiO2/Polyimide Aerogels with Improved Thermal Safety via Introducing Methyltrimethoxysilane

Polyimide aerogels (PIAs) possess enormous application potential in high-temperature thermal insulation scenarios. As high-efficiency thermal insulation materials, their thermal safety and thermal insulation performance are of crucial importance. Currently, poor dimensional stability, high-temperature pyrolysis, and severe shrinkage remain the key factors restricting their development and practical application. In this work, we employ an in situ co-gelation synthesis strategy, where methyltrimethoxysilane (MTMS) is introduced as the silica precursor to fabricate SiO2/polyimide aerogels (Si@PIAs). This strategy enhances the interfacial bonding strength between the organic and inorganic phases, enabling their complementation of strengths. Experimental results demonstrate that the incorporation of the inorganic SiO2phase endows Si@PIAs with higher thermal safety, superior thermal insulation performance, lower density, and reduced shrinkage. Among them, Si10@PIA performs best with a density of 85 mg/cm3, a thermal conductivity of 23.28 mW/(m·K), and a heat flow peak temperature of 720.7 °C. More importantly, pyrolysis analysis reveals that the pyrolysis process of Si@PIAs shifts to a randomized nucleation and growth model (n= 2/5) with the mechanism functiong(α) = [−ln(1 −α)]5/2. Compared with pure PIAs, Si@PIAs possess stronger resistance to pyrolysis, lower gross calorific value, and improved thermal safety. This study provides theoretical and practical guidance for the development of high-performance aerogel materials, promoting their application in lithium-ion battery separators, high-temperature insulation, and fire-resistant materials.