Phosphorus-based LIBs anode have attracted much attention for its high theoretical capacity. Much work so far has focused on the anode such as commercial red phosphorus and black phosphorus. However, little is known about the other phases of phosphorus. Here, we proposed a promising LIBs anode based on fibrous phosphorus and Hittorf's phosphorus. An Iodine-assisted CVD method was used to synthesize urchin-like fibrous phosphorus crystals and flower-like Hittorf's phosphorus crystals and the morphology of the twin phases was investigated systematically. Hittorf's Phosphorus exhibited an initial capacity of 2113.8 mA h g⁻¹ and a capacity of 558.0 mA h g⁻¹ after 40 cycles, whereas the fibrous phosphorus delivered a slightly lower initial discharge capacity of 1783.0 mA h g⁻¹ but a higher capacity of 817.0 mA h g⁻¹ after 40 cycles. It is concluded that fibrous phosphorus exhibited a best performance comparing with other single phases such as commercial red phosphorus (irreversible) and black phosphorus (the capacity fades from 1800.0 mA h g⁻¹ to 200.0 mA h g⁻¹ after 30 cycles). The Li-ion storage mechanism of fibrous phosphorus was investigated deeply. The uniform rod-like morphology and high conductivity of fibrous phosphorus improved the performance. Besides, the presence of Li₃P and LiP phases contributed to the cyclability.

磷基LIB阳极由于其高理论容量而备受关注。迄今为止，许多工作都集中在阳极上，例如商用红磷和黑磷。但是，对磷的其他相知之甚少。在这里，我们提出了一种有前途的基于纤维磷和希托夫磷的LIBs阳极。用碘辅助化学气相沉积法合成了海胆样的纤维状磷晶体和花状的希托夫磷晶体，并系统地研究了双相的形貌。Hittorf的磷的初始容量为2113.8 mA h g ^-1，在40个循环后的容量为558.0 mA h g ^-1，而纤维状磷的初始放电容量为1783.0 mA h g ^-1略低但40个循环后，容量更高，为817.0 mA h g ^-1。结论是，与其他单相，例如商业红磷（不可逆）和黑磷相比，纤维磷表现出最好的性能（30个循环后容量从1800.0 mA h g ^-1降低到200.0 mA h g ^-1）。深入研究了纤维状磷的锂离子存储机理。纤维磷的均匀棒状形态和高电导率改善了性能。此外，Li ₃ P和LiP相的存在有助于循环性。