3D Hierarchically Porous High‐Mass Loading SiOx Anodes Enabled by Consecutive Multi‐Layer Printing and Mid‐Infrared Laser Annealing

Developing high‐energy‐density SiO x anodes for lithium‐ion batteries requires the strategy to address critical issues related to poor electron/ion transport kinetics and large volumetric changes during cycling. In this study, a novel approach is presented that combines digitally programmable 3D printing and mid‐infrared laser annealing techniques. The chemical scheme is designed for synthesizing carbon‐SiO x nanocomposites using a soft‐templated sol–gel method, in which molecularly incorporated carbon nanodomains are capable of efficiently absorbing mid‐infrared wavelength photons. During laser annealing, the carbon nanodomains serving as photothermal agents enable not only a highly efficient, localized carbothermal reduction to produce electrochemically active SiO x but also trigger the carbonization/graphitization of the polyacrylic acid binder for forming an electrically conductive framework. Consequently, this results in the formation of dual‐porous SiO x anode, featuring mesopores (≈8 nm in diameter) and macropores (100–600 nm in diameter). In parallel, the digitally programmable 3D printing process defines a grid‐pore channel architecture (with a spacing of ≈200 µm). It comprehensively enhances electron/ion transport and structural integrity in ultrathick electrodes. The resulting 3D anode achieves a high areal capacity of 9.5 mAh cm −2 at a mass loading as high as 6.6 mg cm −2 . Combinatorial analyses reveal that the 3D‐printed and laser‐annealed SiO x anode achieves a significantly enhanced electrochemical performance, attributed to a substantial increase in electrical conductivity and Li‐ion diffusion coefficient, along with the formation of a LiF‐rich thin SEI layer.