As a thermodynamically stable semiconductor material, black phosphorus (BP) has potential application in the field of energy storage and conversion. The preparation of black phosphorus is still limited to the laboratory, which is far from adequate to meet the requirements of future industrial applications. Here, the gram-scale black phosphorus is synthesized in the ethylenediamine medium using a 120-200 °C low-temperature recyclable liquid phase method directly from red phosphorus. A crystallization mechanism from red to black phosphorus based on FTIR, XPS, and DFT calculations is proposed. Black phosphorus as the anode material for lithium ion batteries is superior in discharge specific capacity, rate capability, and cycling stability in comparison with red phosphorus. The facile low-temperature synthesis of BP by the ethylenediamine-assisted liquid phase process will facilitate the extended application of BP in the field of energy storage and conversion.