Additive Manufacturing of Energy Materials Using Self‐Assembled Graphene Oxide and Printable Resin

Abstract A strategy is reported for fabricating 3D‐printed electrodes using self‐assembled graphene oxide (GO) core–shell microspheres as tunable microreactors. This approach enables control over microsphere size and shell thickness via pH adjustment and sonication parameters, yielding either individual conductive particles or interconnected networks suitable for Direct Ink Writing. Following pyrolysis, the resulting hierarchically porous, rigid constructs exhibit surface area of 1000 m ² g ⁻¹ and compressive strengths up to 9.5 MPa – outperforming most 3D‐printed carbon supercapacitor structures in mechanical robustness. Electrochemically, the optimized architecture delivers 125 F g ⁻¹ , 1.4 F and 4.7 F cm ⁻³ in 1 m H ₂ SO ₄ , and maintains >95% of its capacity after 30 000 cycles while preserving structural integrity. This method combines bottom‐up GO self‐assembly with top‐down additive manufacturing to produce mechanically resilient, high‐performance supercapacitor electrodes – bridging nanoscale material design with macroscale energy storage systems engineering.