Extrusion‐Based 3D Printing of Hierarchically Porous Advanced Battery Electrodes

: A highly porous 2D nanomaterial, holey graphene oxide (hGO), is synthesized directly from holey graphene powder and employed to create an aqueous 3D printable ink without the use of additives or binders. Stable dispersions of hydrophilic hGO sheets in water (≈100 mg mL-1 ) can be readily achieved. The shear-thinning behavior of the aqueous hGO ink enables extrusion-based printing of fine filaments into complex 3D architectures, such as stacked mesh structures, on arbitrary substrates. The freestanding 3D printed hGO meshes exhibit trimodal porosity: nanoscale (4-25 nm through-holes on hGO sheets), microscale (tens of micrometer-sized pores introduced by lyophilization), and macroscale (<500 µm square pores of the mesh design), which are advantageous for high-performance energy storage devices that rely on interfacial reactions to promote full active-site utilization. To elucidate the benefit of (nano)porosity and structurally conscious designs, the additive-free architectures are demonstrated as the first 3D printed lithium-oxygen (Li-O2 ) cathodes and characterized alongside 3D printed GO-based materials without nanoporosity as well as nanoporous 2D vacuum filtrated films. The results indicate the synergistic effect between 2D nanomaterials, hierarchical porosity, and overall structural design, as well as the promise of a freeform generation of high-energy-density battery systems.