Rational Assembly of Hollow Microporous Carbon Spheres as P Hosts for Long‐Life Sodium‐Ion Batteries
Rational Assembly of Hollow Microporous Carbon Spheres as P Hosts for Long‐Life Sodium‐Ion Batteries
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DOI：
10.1002/aenm.201702267
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发表时间：
2018-03
影响因子：
27.8
通讯作者：
S. Yao;Jiang Cui;Jiaqiang Huang;Jian‐Qiu Huang;W. Chong;Lei Qin;Y. Mai;Jang‐Kyo Kim
中科院分区：
文献类型：
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作者：
S. Yao;Jiang Cui;Jiaqiang Huang;Jian‐Qiu Huang;W. Chong;Lei Qin;Y. Mai;Jang‐Kyo Kim
本文报道了新型中空多孔碳纳米球（HPCNS）作为高性能钠离子电池（SIB）磷（P）活性材料的主体的合理组装。采用蒸发冷凝法制备P/C复合材料，从理论和实验两方面进行了阐述，以达到优化设计。结合分子动力学模拟和密度泛函理论计算表明，聚合物P4的形态和P负载在P/C复合材料中主要取决于碳载体的孔径和表面状态。直径为1-2 nm的微孔和附着在碳表面的含氧官能团对于实现高P负载和优异的结构稳定性是必不可少的。根据这些发现，HPCNS/无定形赤磷复合材料与增强的结构/功能特性的合成，它呈现出一个非常低的体积膨胀率为67.3%，在循环过程中，远小于商业红P的理论值为300%。复合阳极具有出色的钠存储容量和卓越的长寿命循环稳定性，在1000次循环后容量保持率超过76%。这项工作表明了基于准确的理论预测合理设计电极材料的重要性，并揭示了未来开发具有成本效益的P/C复合阳极用于商业可行的SIB。
This paper reports the rational assembly of novel hollow porous carbon nanospheres (HPCNSs) as the hosts of phosphorous (P) active materials for high‐performance sodium‐ion batteries (SIBs). The vaporization‐condensation process is employed to synthesize P/C composites, which is elucidated by both theories and experiments to achieve optimized designs. The combined molecular dynamics simulations and density functional theory calculations indicate that the morphologies of polymeric P4 and the P loading in the P/C composites depend mainly on the pore size and surface condition of carbon supports. Micropores of 1–2 nm in diameter and oxygenated functional groups attached on carbon surface are essential for achieving high P loading and excellent structural stability. In light of these findings, HPCNS/amorphous red phosphorus composites with enhanced structural/functional features are synthesized, which present an extremely low volume expansion of ≈67.3% during cycles, much smaller than the commercial red P's theoretical value of ≈300%. The composite anodes deliver an exceptional sodium storage capacity and remarkable long‐life cyclic stability with capacity retention over 76% after 1000 cycles. This work signifies the importance of rational design of electrode materials based on accurate theoretical predictions and sheds light on future development of cost‐effective P/C composite anodes for commercially viable SIBs.