Si has been extensively investigated as an anode material for lithium-ion batteries because of its superior theoretical capacity. However, a scalable fabrication method for a Si-based anode with high initial coulombic efficiency (ICE) and large volumetric capacity remains a critical challenge. Herein, we proposed a novel porous Si/Cu anode in which planar Si islands were embedded in the porous Cu matrix through combined laser additive manufacturing and chemical dealloying. The compositions and dimensions of the structure were controlled by metallurgical and chemical reactions during comprehensive interaction. Such a structure has the advantages of micro-sized Si and porous architecture. The planar Si islands decreased the surface area and thus increased ICE. The porous Cu matrix, which acted as both an adhesive-free binder and a conductive network, provided enough access for electrolyte and accommodated volume expansion. The anode structure was well maintained without observable mechanical damage after cycling, demonstrating the high structure stability and integrity. The porous Si/Cu anode showed a high ICE of 93.4% and an initial volumetric capacity of 2131 mAh cm–3, which retained 1697 mAh cm–3 after 100 cycles at 0.20 mA cm–2. Furthermore, the full-cell configuration (porous Si/Cu //LiFePO4) exhibited a high energy density of 464.9 Wh kg–1 and a capacity retention of 84.2% after 100 cycles.
