Li Yunyong, Ou Changzhi, Zhu Junlu, Liu Zhonggang, Yu Jianlin, Li Wenwu, Zhang Haiyan, Zhang Qiaobao, Guo Zaiping
Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, School of Materials and Energy, Guangdong University of Technology, No. 100 Waihuan Xi Road, Guangzhou Higher Education Mega Center, Guangzhou, 510006, China.
Department of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen, Fujian 361005, China.
Nano Lett. 2020 Mar 11;20(3):2034-2046. doi: 10.1021/acs.nanolett.9b05349. Epub 2020 Feb 6.
Tin-based composites hold promise as anodes for high-capacity lithium/sodium-ion batteries (LIBs/SIBs); however, it is necessary to use carbon coated nanosized tin to solve the issues related to large volume changes during electrochemical cycling, thus leading to the low volumetric capacity for tin-based composites due to their low packing density. Herein, we design a highly dense graphene-encapsulated nitrogen-doped carbon@Sn (HD N-C@Sn/G) compact monolith with Sn nanoparticles double-encapsulated by N-C and graphene, which exhibits a high density of 2.6 g cm and a high conductivity of 212 S m. The as-obtained HD N-C@Sn/G monolith anode exhibits ultrahigh and durable volumetric lithium/sodium storage. Specifically, it delivers a high volumetric capacity of 2692 mAh cm after 100 cycles at 0.1 A g and an ultralong cycling stability exceeding 1500 cycles at 1.0 A g with only 0.019% capacity decay per cycle in lithium-ion batteries. Besides, TEM and SEM have revealed that the unique double-encapsulated structure effectively mitigates drastic volume variation of the tin nanoparticles during electrode cycling. Furthermore, the full cell using HD N-C@Sn/G as an anode and LiCoO as a cathode displays a superior cycling stability. This work provides a new avenue and deep insight into the design of high-volumetric-capacity alloy-based anodes with ultralong cycle life.
锡基复合材料有望成为高容量锂/钠离子电池(LIBs/SIBs)的阳极;然而,有必要使用碳包覆的纳米级锡来解决与电化学循环过程中体积变化大相关的问题,因此由于其低堆积密度,导致锡基复合材料的体积容量较低。在此,我们设计了一种高密度的石墨烯包裹的氮掺杂碳@Sn(HD N-C@Sn/G)紧凑整体材料,其中Sn纳米颗粒被N-C和石墨烯双重包裹,其密度高达2.6 g/cm³,电导率为212 S/m。所制备的HD N-C@Sn/G整体材料阳极表现出超高且持久的体积锂/钠存储性能。具体而言,在锂离子电池中,它在0.1 A/g的电流密度下循环100次后,体积容量高达2692 mAh/cm³,在1.0 A/g的电流密度下具有超过1500次的超长循环稳定性,每次循环的容量衰减仅为0.019%。此外,透射电子显微镜(TEM)和扫描电子显微镜(SEM)表明,独特的双重包裹结构有效地减轻了电极循环过程中锡纳米颗粒的剧烈体积变化。此外,以HD N-C@Sn/G为阳极、LiCoO为阴极的全电池表现出优异的循环稳定性。这项工作为设计具有超长循环寿命的高体积容量合金基阳极提供了一条新途径和深刻见解。