《工程科学学报》录用稿，htps:/doi.org/10.13374/i,issn2095-9389.2021.09.18.001©北京科技大学2020 红磷的纳米化及其在钠离子电池中的应用 张宇，白金，赵海雷区 北京科技大学材料科学与工程学院，北京100083 ☒通讯作者：hlzhao@ustb.edu.cn 摘要：钠离子电池(SBs)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SBs负极材料中，红磷拥 有超高的理论比容量(2596mAhg)、合适的氧化还原电位(0.4Vvs.NaNa.)以及丰富的资源储量， 是极具潜力的SBs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环磷的制备方法，本 文我们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。 关键词：电池：钠离子：负极：红磷：纳米化 分类号：TM912:TB332 Preparation of Nano Red Rhosphorus and its Application in Sodium-Ion Batteries Yu Zhang,Jin Bai,Hailei Zhao School of Materials Science and Engineering,University of Science and Technology Beijing,Beijing 100083 Corresponding author:hlzhao@ustb.edu. Abstract: Sodium-ion batteries(SIBsaehighly desirable energy storage devices because of their low-cost,high safety, environmentally friendly features and therefore have wide application prospects in the fields of large-scale energy storage and electric vehicles.SIBs share a similar energy storage mechanism to lithium-ion batteries (LIBs)and can be fabricated with presently existing lithium-ion battery production equipment,thus have been recognized as the most promising alternative to LIBs.However,the radius of Na'is around 34%larger than Li,which leads to many deyeloped eleetrode materials for LIBs unsuitable for SIBs.Therefore,the exploration of novel electrode materials for SIB has become a hot topic of this area in recent years.Among various candidate anode materials of SIBs,red phosphorus is a promising material due to its ultra-high theoretical specific capacity(2596 mAh g),a suitable oxidation-reduction potential(0.4 V vs.Na/Na),and abundant resource reserves.However,the extremely low intrinsic conductivity and huge volume effect upon sodium storage of red phosphorus greatly limit its capacity utilization,long-term cycle stability,and rate performance.At present,one of the effective approaches for modification of red phosphorus anode is to prepare nano-sized red phosphorus(NRP).Downsizing red phosphorus is helpful to prevent the red phosphorus from pulverization caused by large volume change during charge/discharge process,and meanwhile can shorten the Na'transmission distance,which together enable the high electrochemical activity and long-term cycling stability.In this review,the recent studies on NRP preparation for advanced SIBs are extensively reviewed.The preparation methods of NRP include mainly ball milling,红磷的纳米化及其在钠离子电池中的应用 张宇，白金，赵海雷 北京科技大学材料科学与工程学院，北京 100083  通讯作者：hlzhao@ustb.edu.cn 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 mAh 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 文我们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。 关键词：电池；钠离子；负极；红磷；纳米化 分类号：TM912；TB332 Preparation of Nano Red Phosphorus and its Application in Sodium-Ion Batteries Yu Zhang, Jin Bai, Hailei Zhao School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083  Corresponding author: hlzhao@ustb.edu.cn Abstract: Sodium-ion batteries (SIBs) are highly desirable energy storage devices because of their low-cost, high safety, environmentally friendly features, and therefore have wide application prospects in the fields of large-scale energy storage and electric vehicles. SIBs share a similar energy storage mechanism to lithium-ion batteries (LIBs) and can be fabricated with presently existing lithium-ion battery production equipment, thus have been recognized as the most promising alternative to LIBs. However, the radius of Na+ is around 34% larger than Li+ , which leads to many developed electrode materials for LIBs unsuitable for SIBs. Therefore, the exploration of novel electrode materials for SIB has become a hot topic of this area in recent years. Among various candidate anode materials of SIBs, red phosphorus is a promising material due to its ultra-high theoretical specific capacity (2596 mAh g-1), a suitable oxidation-reduction potential (0.4 V vs. Na/Na+ .), and abundant resource reserves. However, the extremely low intrinsic conductivity and huge volume effect upon sodium storage of red phosphorus greatly limit its capacity utilization, long-term cycle stability, and rate performance. At present, one of the effective approaches for modification of red phosphorus anode is to prepare nano-sized red phosphorus (NRP). Downsizing red phosphorus is helpful to prevent the red phosphorus from pulverization caused by large volume change during charge/discharge process, and meanwhile can shorten the Na+ transmission distance, which together enable the high electrochemical activity and long-term cycling stability. In this review, the recent studies on NRP preparation for advanced SIBs are extensively reviewed. The preparation methods of NRP include mainly ball milling, 1 《工程科学学报》录用稿，https://doi.org/10.13374/j.issn2095-9389.2021.09.18.001 ©北京科技大学 2020 录用稿件，非最终出版稿