Precise control of versatile microstructure and properties of graphene aerogel via freezing manipulation.

A deep understanding of the shaping technique is urgently required to precisely tailor the pore structure of a graphene aerogel (GA) in order to fit versatile application backgrounds. In the present study, the microstructure and properties of GA were regulated by freeze-casting using an ice crystal template frozen from -10 °C to -196 °C. The phase field simulation method was applied to probe the microstructural evolution of the graphene-H2O system during freezing. Both the experimental and simulation results suggested that the undercooling degree was fundamental to the nucleation and growth of ice crystals and dominated the derived morphology of GA. The pore size of GA was largely regulated from 240 to 6 μm via decreasing the freezing temperature from -10 °C to -196 °C but with a constant density of 8.3 mg cm-3. Rapid freeze casting endowed GA with a refined pore structure and therefore better thermal, electrical, and compressive properties, whereas the GA frozen slowly had superior absorption properties owing to the continuous and tube-like graphene lamellae. The GA frozen at -196 °C exhibited the highest Young's modulus of 327 kPa with similar densities to those reported in the literature. These findings demonstrate the diverse potential applications of GA with regulated pore morphologies and also contribute to cryogenic-induced phase separation methods.