Evaporation-condensation of red phosphorous to prepare phosphorous-based anodes inevitably generates white P residual, severely limiting its practical application due to the serious safety concern. Rather than removing the white P residual by complicated post-treatments, essentially prohibiting the generation of white P is a more meaningful alternative, but unfortunately it has been rarely studied so far. Herein, we demonstrate that the generation of white P can be substantially suppressed via sulfur-mediated phosphorous activation. Moreover, the prepared sulfur-doped P also exhibits the ever-reported fastest redox kinetics for sodium-ion storage. Electron spin resonance spectra and density functional theory calculations reveal that the introduced sulfur lives in the high-spin state during the evaporation-condensation process, which could activate P₄ for polymerization. Meanwhile, sulfur-induced electron delocalization can also accelerate the Na-P redox kinetics. The capability to modulate phosphorus polymerization via the high-spin mediator could revolutionize the application of phosphorous for batteries and beyond.

红色磷的蒸发冷凝以制备磷基阳极不可避免地会产生白色P残留物，由于对安全性的严重关注，严重限制了其实际应用。除了通过复杂的后处理去除白色P残留物以外，基本上禁止生成白色P是更有意义的选择，但是不幸的是，到目前为止，尚未对其进行研究。在本文中，我们证明可以通过硫介导的磷活化基本上抑制白色P的产生。此外，制备的硫掺杂的P还表现出前所未有的钠离子存储最快的氧化还原动力学。电子自旋共振谱和密度泛函理论计算表明，在蒸发-冷凝过程中，引入的硫以高自旋状态存在，₄用于聚合。同时，硫诱导的电子离域也可以加速Na-P氧化还原动力学。通过高旋转介体调节磷聚合的能力可能会彻底改变磷在电池及其他方面的应用。