Owing to its distinctive structure and properties, 2D silicon (2DSi) has been widely applied in hydrogen storage, sensors, electronic device, catalysis, electrochemical energy storage, etc. However, scalable and low-cost fabrication of high-quality 2DSi remains a great challenge. In this work, a physical vacuum distillation method is designed to obtain high-quality 2DSi from a bulk layered calcium-silicon alloy. With this method, the lower boiling point calcium metal is evaporated to construct 2DSi and can be further recycled. The effect of vacuum conditions on morphology, components, and electrochemical properties is further explored. As an anode for lithium-ion batteries, the 2DSi delivers a stable cyclability of 835 mAh g-1 after 3000 cycles at 5000 mA g-1 (0.003025% capacity decay per cycle). The electrochemical performance enhancing mechanism is also probed. In addition, a 2D/2D flexible and binder-free paper by combining 2DSi with 2D MXene is constructed. As a lithiophilic nuclear agent for lithium metal anodes, the 2DSi can efficiently suppress the Li dendrite growth and reduce nucleation barriers, achieving a high Coulombic efficiency (98% at 1 mA cm-2, 97% at 2 mA cm-2) around 600 cycles and a long lifespan of 1000 h. The crystal growth difference of lithium metal on Cu foil and 2DSi is studied. This work may provide a pathway for green, low-cost, and scalable synthesis of 2D materials.