一锅法合成多金属硫化物/碳复合材料及其储锂性能

ZHANG Wei-cai; YANG Chao-wei; HU Shu-yu; FANG Ya-wei; LIN Xiao-min; XIE Zhuo-hao; ZHENG Ming-tao; LIU Ying-liang; LIANG Ye-ru

doi:10.1016/S1872-5805(23)60781-4

一锅法合成多金属硫化物/碳复合材料及其储锂性能

doi: 10.1016/S1872-5805(23)60781-4

张伟财^{1, 2,},
杨朝炜²,
胡书宇²,
方亚伟²,
林晓敏²,
谢卓豪²,
郑明涛^{1, 2},
刘应亮^{1, 2, ,},
梁业如^{1, 2, ,}

1.
岭南现代农业科学与技术广东省实验室茂名分中心，广东茂名 525000
2.
华南农业大学材料与能源学院生物基材料与能源教育部重点实验室，广东广州 510642

基金项目: 茂名实验室自主科研项目（2022ZD002）；国家自然科学基金项目（51972121，52373074）

详细信息

通讯作者:
刘应亮，教授. E-mail：tliuyl@scau.edu.cn

梁业如，教授. E-mail：liangyr@scau.edu.cn

中图分类号: TQ127.1⁺1
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- 被引次数: 0
出版历程
- 收稿日期: 2023-04-19
- 录用日期: 2023-08-29
- 修回日期: 2023-08-28
- 网络出版日期: 2023-10-16
- 刊出日期: 2023-11-23

A one-pot method to prepare a multi-metal sulfide/carbon composite with a high lithium-ion storage capability

1.
Maoming Branch, Guangdong Laboratory of Lingnan Modern Agriculture, Maoming 525000, China
2.
Key Laboratory for Biobased Materials and Energy of Ministry of Education, College of Materials and Energy, South China Agricultural University, Guangzhou 510642, China

Funds: This work was financially supported by Independent Research Project of Maoming Laboratory (2022ZD002) and National Natural Science Foundation of China (51972121 and 52373074)

More Information

Author Bio:
张伟财，博士. E-mail：anbianyuke@163.com

Corresponding author: LIU Ying-liang, Professor. E-mail: tliuyl@scau.edu.cn; LIANG Ye-ru, Professor. E-mail: liangyr@scau.edu.cn

摘要

摘要: 多金属硫化物/碳（MMS/C）复合材料因其良好的结构稳定性、充足的活性位点和有益的协同效应，在能源、催化、传感、环境科学等领域具有良好的应用潜力。然而，MMS/C复合材料繁琐、低效和对环境有害的制备方法制约了其发展。本文报道了一种简易、通用的制备策略合成了系列MMS/C复合材料。该策略的关键是采用了碳源−非碳前驱体一体化的离子交换树脂−金属离子杂化组装体作为构筑单元，可实现均匀的多相有机/无机界面，在高温条件下原位生成封装于碳骨架中的金属硫化物。通过改变金属离子的种类，实现了14 种 MMS/C 复合材料的合成。基于其组分和结构优势，所制MMS/C复合材料表现出高效、快速和持久的锂离子存储性能。其中，ZnS-Co₉S₈/C复合材料在0.1 A·g⁻¹电流密度下循环600次后仍具有651 mAh·g⁻¹的可逆储锂容量；当电流密度提高20倍时，容量保持率超过54%，展现出优异的倍率性能。本文提出的均一、多相有机/无机界面合成策略有望扩展用于制备其他金属化合物（如金属磷化物、金属硒化物等）/碳复合材料，为多金属化合物/碳复合材料的合成提供有效的途径。
- 多金属硫化物/碳复合材料 /
- 简便合成 /
- 一锅法 /
- 锂离子电池 /
- 负极材料
Abstract: Because of their high electrochemical activity, good structural stability, and abundant active sites, multi-metal sulfide/carbon (MMS/C) composites are of tremendous interest in diverse fields, including catalysis, energy, sensing, and environmental science. However, their cumbersome, inefficient, and environmentally unfriendly synthesis is hindering their practical application. We report a straightforward and universal method for their production which is based on homogeneous multi-phase interface engineering. The method has enabled the production of 14 different MMS/C composites, as examples, with well-organized composite structures, different components, and dense heterointerfaces. Because of their composition and structure, a typical composite has efficient, fast, and persistent lithium-ion storage. A ZnS-Co₉S₈/C composite anode showed a remarkable rate performance and an excellent capacity of 651 mAh·g⁻¹ at 0.1 A·g⁻¹ after 600 cycles. This work is expected to pave the way for the easy fabrication of MMS/C composites.
- Multi-metal sulfide/carbon composites /
- Facile synthesis /
- One-pot route /
- Lithium-ion battery /
- Anode

HTML全文

FIG. 2780. FIG. 2780.

FIG. 2780.. FIG. 2780.

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Figure 1. Synthetic scheme for preparing MMS/C composites by taking BMS/C composites as example. (a) Traditional post-synthesis strategy and (b) simplified post-synthesis strategy. (c) One-pot synthetic route by using a homogeneous multi-phase interfacial engineering

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Figure 2. (a) Digital photos of IER-S before and after coordination. (b) Schematic illustration of Zn²⁺ and Co²⁺ combined with IER-S. (c) EDS images, (d) FTIR spectra of IER-S before and after coordination. (e) S 2p and (f) O 1s spectra of IER-S-Zn/Co. The inset in (f) shows a schematic diagram of the structure of 2 benzenesulfonates coupling to a divalent metal ion

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Figure 3. (a) Mass content and relative amount of substance of Zn, Co, and S elements in IER-S-Zn/Co. (b) XRD patterns of distinct samples obtained by heating IER-S-Zn/Co under different temperatures. (c) TGA curve obtained by heat treatment IER-S-Zn/Co under N₂ flow. (d) Schematic of the evolution for IER-S-Zn/Co during the heating process. (e) SEM image, (f) EDS mapping images, (g) HRTEM image, (h) TGA curve, (i) XRD pattern and (j) S 2p spectrum of ZnS-Co₉S₈/C

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Figure 4. (a) Digital photos of different IER-S-M₁/M₂ hybrid assemblies. (b) Synthesis schematic of BMS/C composites. (c) XRD patterns and (d–g) SEM images of BMS/C composites

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Figure 5. (a) Schematic illustration for fabrication of TMS/C composites. (b) Digital photos of different IER-S-M₁/M₂/M₃ hybrid assemblies. (c-e) EDS mapping images, (f-h) SEM images, and (i) XRD patterns of TMS/C composites

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Figure 6. Cycling performances of ZnS-Co₉S₈/C, Co₉S₈/C, and ZnS/C anodes at (a) 0.1 A·g⁻¹ and (b) 1 A·g⁻¹, (c) Rate performances of the ZnS-Co₉S₈/C, Co₉S₈/C and ZnS/C anodes, (d) Nyquist plots, (e) resistance, and (f) D_Li of ZnS-Co₉S₈/C, Co₉S₈/C and ZnS/C anodes in LIB

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Figure 7. Schematic illustration of fast electron and ion transportation of ZnS-Co₉S₈/C anode

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