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Regulating Li+ migration and Li2S deposition by metal-organic framework-derived Co4S3-embedded carbon nanoarrays for durable lithium-sulfur batteries

金属-有机框架衍生的Co4S3/C纳米阵列调控锂硫电池中锂离子迁移和硫化锂沉积

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Abstract

The shuttle effect of lithium polysulfides and the uncontrollable deposition of lithium sulfides (Li2S) severely hinder the realization of high-performance lithium-sulfur (Li-S) batteries. Herein, we fabricated a carbon cloth (CC)-based self-supported interlayer (denoted as Co4S3/C@CC), which is covered with Co4S3-embedded porous carbon nanoarrays through a facile two-step method with cobalt-based metal-organic framework (Co-MOF) nanosheets as the template. The interconnected carbon network and the polar Co4S3 nanoparticles in the Co4S3/C@CC interlayer not only effectively suppress the polysulfide shuttle, but also significantly facilitate the lithium ion (Li+) conduction with a considerable Li+ transference number of 0.86. Besides, the rich interfaces between the polar Co4S3 nanoparticles and the conductive carbon substrate serve as reaction sites to accelerate the polysulfide conversion and guide the flower-like growth of Li2S, which ultimately mitigates the interlayer surface passivation and improves the sulfur utilization. Therefore, the Li-S batteries with the Co4S3/C@CC interlayer deliver an excellent rate capacity (368.7 mA h g−1 at 10 C), a stable cycling performance (a low fading rate of 0.045% per cycle over 1400 cycles at 2.0 C), and a high initial areal capacity (4.83 mA h cm−2 at 0.2 C under a sulfur loading of 4.6 mg cm−2). This work provides a perspective on the self-supported catalytic interlayer for the selective Li+ conduction and Li2S regulation toward high-performance Li-S batteries.

摘要

多硫化锂的飞梭效应与不可控硫化锂(Li2S)的沉积现象严重阻碍了高性能锂硫电池的实现. 在本研究中, 我们制备了一种负载有Co4S3/C多孔纳米阵列的自支撑碳布(CC)基夹层(Co4S3/C@CC), 其中Co4S3/C多孔纳米阵列是以钴基金属-有机框架(Co-MOF)纳米片为模板制备而成的. Co4S3/C@CC夹层中相互连接的碳网络和极性Co4S3纳米粒子不仅能有效地抑制多硫化物飞梭, 而且能显著地促进锂离子(Li+)的传导,其Li+迁移数高达0.86. 此外, 极性Co4S3纳米粒子与导电碳基底之间丰富的界面能够作为反应中心以加速多硫化物的转化与引导Li2S的花状生长, 最终减轻Li2S对夹层表面的钝化以及提高硫的利用率. 因此, 载有Co4S3/C@CC夹层的锂硫电池可以提供出色的倍率容量(在10 C时比容量为368.7 mA h g−1)、稳定的循环性能(在2.0 C下1400周循环过程中衰减率为0.045%)以及高初始面容量(在0.2 C且硫含量为4.6 mg cm−2时面容量达到4.83 mA h cm−2). 这项工作展现了自支撑催化夹层对高性能锂硫电池中选择性Li+传导和Li2S沉积的调控能力.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (51871188 and 51931006).

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Authors and Affiliations

  1. College of Materials, Xiamen University, Xiamen, 36005, China

    Jianbin Liu  (刘剑斌), Yifan Song  (宋一凡), Cunjian Lin  (林存键), Qingshui Xie  (谢清水), Dong-Liang Peng  (彭栋梁) & Rong-Jun Xie  (解荣军)

  2. Fujian Provincial Key Laboratory of Materials Genome, Xiamen University, Xiamen, 361005, China

    Jianbin Liu  (刘剑斌), Yifan Song  (宋一凡), Cunjian Lin  (林存键), Qingshui Xie  (谢清水), Dong-Liang Peng  (彭栋梁) & Rong-Jun Xie  (解荣军)

  3. State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen, 61005, China

    Jianbin Liu  (刘剑斌), Yifan Song  (宋一凡), Cunjian Lin  (林存键), Qingshui Xie  (谢清水), Dong-Liang Peng  (彭栋梁) & Rong-Jun Xie  (解荣军)

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  1. Jianbin Liu  (刘剑斌)
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Contributions

Author contributions Xie RJ, Peng DL, and Liu J conceived and designed the project, wrote and revised the paper; Liu J was primarily responsible for the experiments; Song Y and Lin C helped perform the experiments; Xie Q provided the useful suggestions. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Dong-Liang Peng  (彭栋梁) or Rong-Jun Xie  (解荣军).

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Conflict of interest The authors declare that they have no conflict of interest.

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Supplementary information Supporting data are available in the online version of the paper

Jianbin Liu is currently a PhD student at the College of Materials, Xiamen University. He received his BS degree at the School of Materials Science and Engineering, Fuzhou University in 2016. His research interests focus on the luminescent MOF materials and MOF-derived nanostructured energy materials.

Dong-Liang Peng received his PhD degree in condensed matter physics, Lanzhou University in 1997. He received another PhD degree at the Department of Materials Science and Engineering, Nagoya Institute of Technology (Japan) in 2002. Now, he is a professor at the College of Materials, Xiamen University. His research focuses on the nanostructured materials, and their applications in electromagnetics and energy storage and conversion.

Rong-Jun Xie received his PhD degree from Shanghai Institute of Ceramics, Chinese Academy of Sciences in 1998. He worked for the National Institute for Materials Science in Japan as a senior researcher (2003–2007), principal researcher (2007–2014), and chief researcher (2014–2018). Since then, he has been a full professor at the College of Materials, Xiamen University. His research focuses on the designing and developing of luminescent materials for solid state lighting and displays.

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40843_2021_1815_MOESM1_ESM.docx

Regulating Li+ migration and Li2S deposition by metal-organic framework-derived Co4S3-embedded carbon nanoarrays for durable lithium-sulfur batteries

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Liu, J., Song, Y., Lin, C. et al. Regulating Li+ migration and Li2S deposition by metal-organic framework-derived Co4S3-embedded carbon nanoarrays for durable lithium-sulfur batteries. Sci. China Mater. 65, 947–957 (2022). https://doi.org/10.1007/s40843-021-1815-2

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