Red phosphorus has received remarkable attention as a promising anode material for sodium ion batteries (NIBs) due to its high theoretical capacity. However, its practical application has been impeded by its intrinsic low electronic conductivity and large volume variations during sodiation/desodiation process. Here, we design a composite to confine nanosized red phosphorus into the hierarchically porous carbon (HPC) walls by a vaporization-condensation strategy. The mass loading of P in the HPC/P composite is optimized to deliver a reversible specific capacity of 2,202 mAh/g_p based on the mass of red P (836 mAh/g_composite based on the total composite mass), a high capacity retention over 77% after 100 cycles, and excellent rate performance of 929 mAh/g_p at 2 C. The hierarchical porous carbon serves as the conductive networks, downsize the red phosphorus to nanoscale, and provide free space to accommodate the large volume expansions. The suppressed mechanical failure of the red phosphorus also enhances the stability of solid-electrolyte interface (SEI) layer, which is confirmed by the microscopy and impedance spectroscopy after the cycling tests. Our studies provide a feasible approach for potentially viable high-capacity NIB anode.

由于其高理论容量，红磷作为钠离子电池（NIB）的有前途的负极材料受到了广泛关注。然而，其固有的低电子电导率和在钠化/脱钠过程中的大体积变化阻碍了它的实际应用。在这里，我们设计了一种复合材料，通过蒸发-冷凝策略将纳米级红磷限制在分级多孔碳 (HPC) 壁中。HPC/P 复合材料中 P 的质量负载经过优化，可提供基于红 P 质量的2,202 mAh/g _p的可逆比容量（基于总复合质量的836 mAh/g_复合材料），高容量保持100次循环后超过77%，929 mAh/g _{p的优异倍率性能}在 2 C。分层多孔碳充当导电网络，将红磷缩小到纳米级，并提供自由空间以适应大体积膨胀。抑制红磷的机械故障也增强了固体电解质界面（SEI）层的稳定性，循环测试后的显微镜和阻抗谱证实了这一点。我们的研究为潜在可行的高容量 NIB 阳极提供了一种可行的方法。