Abstract Elemental phosphorus, one of the most promising high-capacity anode materials for sodium-ion batteries (SIB), suffers from the low practical capacity and severe cycling degradation, due to its low conductivity and significant volume change (>300%) upon electrochemical sodiation/desodiation. Here, we report a ball-milled phosphorus/reduced graphene oxide (rGO) nanocomposite for high-performance anode in SIBs. The reduction level of the rGO is tuned to simultaneously achieve highly conductive pathways and tight chemical bonding between P and rGO in the composite electrode. Allotrope transformation from red to black phosphorus nanocrystalline is observed in the milled nanocomposites. The optimized P/rGO1000 composite, containing rGO reduced by hydrothermal reaction and heat-treatment, achieves high specific capacity (2032.4 mAh g−1 at 100 mA g−1), excellent rate capability (1306.6 mAh g−1 at 1C rate), and stable cyclability (98.7% capacity retention after 300 cycles at 780 mA g−1). These excellent electrochemical performances are ascribed to the synergistic effects of nanostructuring by ball milling, existence of black phosphorus nanocrystallines, and tight chemical bonding at interfaces between P and rGO. Considering the facile synthesis of ball milling process, our approach can be highly promising for high-capacity anode in practical SIB.

中文翻译：

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用于稳定钠离子存储的红磷/还原氧化石墨烯复合材料的合理设计

摘要 元素磷是钠离子电池（SIB）最有前途的高容量负极材料之一，由于其电导率低和电化学反应后体积变化显着（>300%），存在实际容量低和循环退化严重的问题。钠化/去钠化。在这里，我们报告了一种球磨的磷/还原氧化石墨烯 (rGO) 纳米复合材料，用于 SIB 中的高性能阳极。调整 rGO 的还原水平以同时实现复合电极中 P 和 rGO 之间的高导电通路和紧密的化学键合。在研磨的纳米复合材料中观察到从红磷纳米晶体到黑磷纳米晶体的同素异形体转变。优化的 P/rGO1000 复合材料含有通过水热反应和热处理还原的 rGO，实现了高比容量（2032. 4 mAh g-1 at 100 mA g-1)、优异的倍率性能（1C 倍率下 1306.6 mAh g-1）和稳定的循环性能（780 mA g-1 下 300 次循环后容量保持率为 98.7%）。这些优异的电化学性能归因于球磨形成的纳米结构、黑磷纳米晶体的存在以及 P 和 rGO 之间界面上的紧密化学键的协同作用。考虑到球磨过程的简便合成，我们的方法在实际 SIB 中对于高容量阳极非常有希望。P 和 rGO 之间的界面处有紧密的化学键。考虑到球磨过程的简便合成，我们的方法在实际 SIB 中对于高容量阳极非常有希望。P 和 rGO 之间的界面处有紧密的化学键。考虑到球磨过程的简便合成，我们的方法在实际 SIB 中对于高容量阳极非常有希望。