Carbon‐Microcuboid‐Supported Phosphorus‐Coordinated Single Atomic Copper with Ultrahigh Content and Its Abnormal Modification to Na Storage Behaviors
Carbon‐Microcuboid‐Supported Phosphorus‐Coordinated Single Atomic Copper with Ultrahigh Content and Its Abnormal Modification to Na Storage Behaviors
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DOI：
10.1002/aenm.202000400
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发表时间：
2020-04
影响因子：
27.8
通讯作者：
Yifan Li;Minhong Kong;Junping Hu;Jisheng Zhou
中科院分区：
文献类型：
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作者：
Yifan Li;Minhong Kong;Junping Hu;Jisheng Zhou
碳支撑单原子金属在能量转换和储能领域引起了极大的兴趣。然而，到目前为止，金属含量远远低于预期。此外，理论计算表明，自组装膜是碱金属离子存储的优良锚固位，但实验研究仍未触及。本文提出了一种金属-有机膦骨架衍生策略来制备高含量(26.3wt%)的碳微方体单原子铜。原子铜主要由P部分稳定，即使在浓的HCl和HNO3中也表现出很强的稳定性。有趣的是，实验研究和第一性原理计算表明，铜原子可以改变钠的存储行为，使钠在完全放电状态下保持离子状态，这可能是缓解树枝晶形成安全问题的一条新途径。铜原子还促进了电子转移和扩散动力学。结果表明，碳立方体在5A g−1下可以提供107.7 mAhg−1的高容量，并表现出1000次循环的长寿命。这一策略为制备用于能量转换和存储的高含量P配位原子金属提供了新的可能性。
Carbon‐supported single atomic metals (SAMs) have aroused great interest in energy conversion and storage fields. However, metal content has to date, been far below expectation. Additionally, theoretical calculations show that SAMs are superb anchoring sites for alkali metal‐ion storage, but the experimental research remains untouched. Herein, a metal–organophosphine framework derived strategy is proposed to prepare carbon microcuboids‐supported single atomic Cu with a high content of 26.3 wt%. Atomic Cu is stabilized mainly by P moieties, exhibiting robust stability even in concentrated HCl and HNO3. Interestingly, experimental investigations and first‐principle calculations indicate that Cu atoms can alter the Na storage behavior and enable Na to maintain an ionic state at a fully discharging state for sodium‐ion batteries, which may be a new pathway to mitigate safety concerns of dendrite formation. The Cu atoms also enhance electron transfer and diffusion kinetics. As a result, the carbon cuboids can deliver a high capacity of 107.7 mAh g−1 at 5 A g−1 and show a long life of 1000 cycles for Na storage. This strategy offers a new possibility for fabricating high‐content P‐coordinated atomic metals for energy conversion and storage.