Huang Siming, Wang Mingshan, Feng Yuanlong, Li Qian, Yang Zhenliang, Chen Junchen, Guo Bingshu, Ma Zhiyuan, Yu Bo, Huang Yun, Li Xing
School of New Energy and Materials, Southwest Petroleum University, Chengdu, Sichuan 610500, P. R. China.
Institute of Materials, China Academy of Engineering Physics, Mianyang, Sichuan 621908, P. R. China.
ACS Appl Mater Interfaces. 2024 Oct 23;16(42):57228-57238. doi: 10.1021/acsami.4c13974. Epub 2024 Oct 8.
Tin sulfide (SnS) has emerged as a promising anode material for sodium ion batteries (SIBs) due to its high theoretical capacity and large interlayer spacing. However, several challenges, such as severe insufficient electrochemical reactivity, rapid capacity degradation, and poor rate performance, still hinder its application in SIBs. In this study, in situ introduction of copper ions and a carbon conductive framework to form SnS nanocrystals embedded in a CuSnS lamellar structure heterojunction composite (SnS/CuSnS/RGO) with graphene as the supporting material is proposed to achieve dual-driven sodium ion/electron migration during the continuous electrochemical process. The designed structure facilitates the preferential electrochemical reduction of copper ions into copper nanocrystals during the discharge process and functions as a catalytically active center to promote multivalence tin sodiation reaction. Furthermore, during the charging process, the presence of copper nanocrystals also facilitates efficient desodiation of NaSn and further activates to form higher valence state sulfides. As a result, the SnS/CuSnS/RGO composite demonstrates high cycling stability with a high reversible capacity of 395 mAh g at 5A g after 500 cycles with a capacity retention of 85.6%. In addition, the assembled NaV(PO)∥SnS/CuSnS/RGO sodium ion full cell achieves 93.7% capacity retention after 80 cycles at 0.5 A g.
硫化锡(SnS)因其高理论容量和大层间距,已成为一种有前景的钠离子电池(SIBs)负极材料。然而,一些挑战,如严重的电化学反应活性不足、快速的容量衰减和较差的倍率性能,仍然阻碍其在钠离子电池中的应用。在本研究中,提出原位引入铜离子和碳导电骨架,以形成嵌入以石墨烯为支撑材料的CuSnS层状结构异质结复合材料(SnS/CuSnS/RGO)中的SnS纳米晶体,从而在连续的电化学过程中实现双驱动的钠离子/电子迁移。所设计的结构有助于在放电过程中将铜离子优先电化学还原为铜纳米晶体,并作为催化活性中心促进多价锡的钠化反应。此外,在充电过程中,铜纳米晶体的存在也有助于NaSn的高效脱钠,并进一步活化形成更高价态的硫化物。结果,SnS/CuSnS/RGO复合材料表现出高循环稳定性,在5A g下500次循环后具有395 mAh g的高可逆容量,容量保持率为85.6%。此外,组装的NaV(PO)∥SnS/CuSnS/RGO钠离子全电池在0.5 A g下80次循环后容量保持率达到93.7%。