红磷的纳米化及其在钠离子电池中的应用

Preparation of nanosized red phosphorus and its application in sodium-ion batteries

  • 摘要: 钠离子电池(SIBs)具有成本低廉、安全性高、环境友好等优点,且可以兼容现有的锂离子电池生产设备,在大规模储能以及电动汽车领域都有着广泛的应用前景。在众多的SIBs负极材料中,红磷拥有超高的理论比容量(2596 mA·h·g–1)、合适的氧化还原电位(0.4 V vs Na/Na+)以及丰富的资源储量,是极具潜力的SIBs负极材料。然而红磷极低的本征电导率和在储钠过程中巨大的体积效应极大的限制了其容量利用率、长期循环稳定性和倍率性能。目前对红磷基负极材料改性的最有效方法之一是红磷的纳米化,纳米化可以改善红磷的电化学活性和长期循环稳定性。为了便于研究者了解纳米红磷的制备方法,本文系统总结了纳米红磷的制备方法,包括球磨、升华冷凝、热还原、气相生长、溶剂热、化学沉淀等,并对各种方法的优缺点进行了分析比较,最后对未来的研究方向进行了展望。希望能以此促进红磷负极的发展及其在钠离子电池中的实际应用。

     

    Abstract: Sodium-ion batteries (SIBs) are highly desirable energy storage devices because of their low cost, high safety, and environmental compatibility. Therefore, SIBs have wide application prospects in the fields of large-scale energy storage and electric vehicles. SIBs have a similar energy storage mechanism as that of lithium-ion batteries (LIBs) and can be fabricated using existing LIB production equipment. Thus, SIBs are the most promising alternative to LIBs. However, the radius of Na+ is ~34% larger than that of Li+; therefore, many electrode materials developed for LIBs are unsuitable for SIBs. The exploration of novel electrode materials for SIBs has garnered significant interest in recent years. Among various candidate anode materials for SIBs, red phosphorus is a promising material owing to its ultrahigh theoretical specific capacity (2596 mA·h·g–1), suitable oxidation–reduction potential (0.4 V vs Na/Na+), and abundance. However, the capacity utilization, long-term cycle stability, and rate performance of red phosphorous are limited due to its low intrinsic conductivity and a large volume effect upon sodium storage. At present, an effective approach for the modification of red phosphorus anodes is to prepare nanosized red phosphorus (NRP). Miniaturizing red phosphorus prevents structural damage via large volume changes during charge/discharge processes and also shortens Na+ transmission distances, which enables high electrochemical activity and long-term cycling stability. Herein, recent studies on NRP preparation for advanced SIBs are extensively reviewed. NRP preparation methods typically include ball milling, vaporization condensation, and chemical deposition. Other novel approaches such as thermal reduction, vapor growth, and solvothermal synthesis have also been reported. Ball milling is straightforward and scalable; however, strict guidelines are required to prevent the red phosphorus from burning and exploding, and slight oxidation and particle aggregation are unavoidable. Vaporization-condensation strategies are suitable for the uniform deposition of NRP onto a matrix but are limited by low phosphorus loading and residual white phosphorus. Chemical deposition methods are promising due to their simplicity, control over particle size, and scalability. There are two main chemical deposition strategies, i.e., the reduction of phosphorus-containing compounds and the dissolution and deposition of phosphorus amines. The former method is facile and compatible with ambient temperatures, while the latter method is safe, cost effective, and has high yields. Further studies should focus on morphology design, increasing phosphorus loading, and developing novel chemical reduction methods. We hope that this review promotes the development of red phosphorous anodes for application in SIBs.

     

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