Reversibly Compressible, Highly Elastic, and Durable Graphene Aerogels for Energy Storage Devices under Limiting Conditions

High porosity combined with mechanical durability in conductive materials is in high demand for special applications in energy storage under limiting conditions, and it is fundamentally important for establishing a relationship between the structure/chemistry of these materials and their properties. Herein, polymer‐assisted self‐assembly and cross‐linking are combined for reduced graphene oxide (rGO)‐based aerogels with reversible compressibility, high elasticity, and extreme durability. The strong interplay of cross‐linked rGO (x‐rGO) aerogels results in high porosity and low density due to the re‐stacking inhibition and steric hinderance of the polymer chains, yet it makes mechanical durability and structural bicontinuity possible even under compressive strains because of the coupling of directional x‐rGO networks with polymer viscoelasticity. The x‐rGO aerogels retain >140% and >1400% increases in the gravimetric and volumetric capacitances, respectively, at 90% compressive strain, showing reversible change and stability of the volumetric capacitance under both static and dynamic compressions; this makes them applicable to energy storage devices whose volume and mass must be limited.