Nanostructured metal phosphides are very attractive materials in energy storage and conversion, but their applications are severely limited by complicated preparation steps, harsh conditions and large excess of highly toxic phosphorus source. Here we develop a highly efficient one-step method to synthesize Sn₄P₃ nanostructure based on simultaneous reduction of SnCl4 and PCl₃ on mechanically activated Na surface and in situ phosphorization. The low-toxic PCl₃ displays a very high phosphorizing efficiency (100%). Furthermore, this simple method is powerful to control phosphide size. Ultrafine Sn₄P₃ nanocrystals (< 5 nm) supported on carbon sheets (Sn₄P₃/C) are obtained, which is due to the unique bottom-up surface-limited reaction. As the anode material for sodium/lithium ion batteries (SIBs/LIBs), the Sn₄P₃/C shows profound sodiation/lithiation extents, good phase-conversion reversibility, excellent rate performance and long cycling stability, retaining high capacities of 420 mAh/g for SIBs and 760 mAh/g for LIBs even after 400 cycles at 1.0 A/g. Combining simple and efficient preparation, low-toxic and high-efficiency phosphorus source and good control of nanosize, this method is very promising for low-cost and scalable preparation of high-performance Sn₄P₃ anode.

纳米结构的金属磷化物在能量存储和转换中是非常有吸引力的材料，但是由于复杂的制备步骤，苛刻的条件和大量过量的剧毒磷源，其应用受到了严重限制。在这里，我们基于在机械活化的Na表面上同时还原SnCl4和PCl ₃并原位磷化，开发了一种高效的一步法来合成Sn ₄ P ₃纳米结构。低毒的PCl ₃具有很高的磷化效率（100％）。此外，这种简单的方法可有效控制磷化物的尺寸。碳片（Sn）上负载的超细Sn ₄ P ₃纳米晶体（<5 nm）_获得4 P ₃ / C），这是由于独特的自下而上的表面受限反应。作为钠/锂离子电池（SIBs / LIBs ）的负极材料，Sn ₄ P ₃ / C表现出深厚的绝缘/锂化程度，良好的相变可逆性，优异的倍率性能和长循环稳定性，并保持了420 mAh的高容量即使在1.0 A / g的条件下经过400次循环，SIB仍为/ g，LIB为760 mAh / g。该方法结合了简单高效的制备方法，低毒高效的磷源以及良好的纳米尺寸控制，对于低成本，可扩展地制备高性能Sn ₄ P ₃阳极非常有希望。