As the anodes for Li-ion batteries, the metal phosphides exhibit lower voltage range than those of sulfides and oxides, thus leading to a higher power/energy density for the full cells. Among the metal phosphides, Sn₄P₃ is a promising choice due to its relatively high specific capacity. However, the lithiation process of Sn₄P₃ has not been well understood by the existing literature. To verify this issue, experimental program and calculational analysis are conducted in this study. Firstly, the Sn₄P₃ nanosheets are produced with a facile two-step method of direct current arc plasma and phosphating. The test results confirm the excellent cycling stability of the prepared Sn₄P₃. Moreover, cyclic voltammetry analysis and first-principles calculations reveal that Sn₄P₃ experiences a progressive lithiation process, i.e., Li⁺ is firstly inserted into Sn₄P₃ to form the main intermediate products of amorphous Li_xSn₄P₃, followed by a conversion to the amorphous Li₃P (a-Li₃P) and the crystalline Li_4.4Sn (c-Li_4.4Sn). The formation of a-Li₃P is earlier than c-Li_4.4Sn, which is verified by the radial distribution functions of Sn and P, the numbers of Sn_n and P_n clusters, and the Bader populations of Sn and P in a-Li_xSn₄P₃.

作为锂离子电池的阳极，金属磷化物的电压范围比硫化物和氧化物的电压范围低，因此导致整个电池的功率/能量密度更高。在金属磷化物中，Sn ₄ P ₃由于其相对较高的比容量而成为有前途的选择。但是，现有文献对Sn ₄ P ₃的锂化过程还没有很好的理解。为了验证这个问题，本研究进行了实验程序和计算分析。首先，通过简便的直流电弧等离子体和磷化两步法生产Sn ₄ P ₃纳米片。测试结果证实了所制备的锡具有出色的循环稳定性₄ P ₃。此外，循环伏安法和第一性原理计算表明，Sn ₄ P ₃经历了渐进的锂化过程，即首先将Li ⁺插入Sn ₄ P _3中以形成非晶态Li _x Sn ₄ P ₃的主要中间产物，然后通过转化为无定形的Li ₃ P（a-Li ₃ P）和结晶的Li _4.4 Sn（c-Li _4.4 Sn）。a-Li ₃ P的形成早于c-Li _4.4Sn由a-Li _x Sn ₄ P _3中的Sn和P的径向分布函数，Sn _n和P _n簇的数目以及Sn和P的Bader种群所验证。