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Towards superior lithium–sulfur batteries with metal–organic frameworks and their derivatives

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Abstract

Lithium–sulfur batteries (LSBs) are one of the most promising energy storage devices in the future due to their high theoretical specific capacity (1675 mA·h·g–1) and energy density (2600 W·h·kg–1). However, the severe capacity decay caused by the shuttle effect of polysulfides needs to be addressed before the practical application. Metal–organic frameworks (MOFs) and their derivatives are known for their large specific surface area, high porosity, abundant functional groups, and good chemical stability. Thus, they have been widely investigated in LSBs. This review introduces the principles of the LSBs and origination of the shuttle effect first summarizes various methods of limiting polysulfide diffusion by MOFs and their derivatives both in cathodes and separators, and provides an in-depth discussion of the immobilization mechanisms, which helps to understand the advantages and disadvantages of each method. The mechanisms, such as structure and pore size tuning, chemical absorption, and catalytic conversion, are discussed. Finally, based on the method of MOFs and their derivatives to inhibit the diffusion of polysulfides, the application prospect of MOFs and their derivatives in LSBs technology are proposed.

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Fig. 1

Reproduced with permission from Ref. [32]. Licensed under CC BY-NC 3.0

Fig. 2

Reproduced with permission from Ref. [29]. Licensed under CC BY 4.0. b TEM image with hollow structure CoS/ImIP. Reproduced with permission from Ref. [41]. Copyright 2019 WILEY–VCH Verlag GmbH & Co. KGaA. c TEM image of V2O3@C, illustrated with a model of the layered lasagna structure. Reproduced with permission from Ref. [42]. Copyright 2020 Royal Society of Chemistry. d Aperture distribution curves of MPCN and MPCN-S composites. Reproduced with permission from Ref. [44]. Copyright 2016 Royal Society of Chemistry. e Pore size distribution of NC/CNT. Reproduced with permission from Ref. [45]. Copyright 2019 Elsevier. f Long-term cycling performance of cells with Celgard and PSS@HKUST-1/Celgard-7.5%, with a sulfur loading of 1.3 mg·cm–2. Reproduced with permission from Ref. [47]. Copyright 2018 American Chemical Society. g Simulated crystal structure of Cu2(CuTCPP). Reproduced with permission from Ref. [48]. Copyright 2019 Elsevier

Fig. 3

Reproduced with permission from Ref [51]. Copyright 2018 Royal Society of Chemistry

Fig. 4

Reproduced with permission from Ref. [8]. Copyright 2019 American Chemical Society. b Illustration of the sulfur-loading effect and the interaction with LiPS during the galvanostatic charge/discharge process. Reproduced with permission from Ref. [64]. Copyright 2022 WILEY–VCH Verlag GmbH & Co. KGaA. c Preparation schematic diagram of S/NiO-NiCo2O4@ppy. Reproduced with permission from Ref. [62]. Copyright 2019 Royal Society of Chemistry. d Schematic diagram of Mo2C-C NOs@S composite material preparation strategy. Reproduced with permission from Ref. [56]. Copyright 2020 Elsevier. e Cyclic performance of S/CoS2-NC, S/NC and S/super P electrodes at 0.2 C for 100 cycles. Reproduced with permission from Ref. [63] Copyright 2018 Elsevier. f X-ray diffraction patterns of ZIF-67@SPAN-CNT and Co2S-SPAN-CNT. Reproduced with permission from Ref. [66] Copyright 2020 American Chemical Society. g Absorption energies of Li2Sn and S8 species on the surface of NixCo3-xS4/N-doped carbides. Reproduced with permission from Ref. [58]. Copyright 2020 Elsevier

Fig. 5

Copyright 2018 Elsevier. d Cycle performance at 0.5 C of LSBs assembled with different partitions (NOF: Ni-MOF). Reproduced with permission from Ref. [69]. Copyright 2018 Elsevier

Fig. 6

Reproduced with permission from Ref. [71]. Copyright 2019 American Chemical Society. b Cycling performance of LSBs with different separators running 1000 cycles (2.0 mg·cm–2 sulfur load) at 2 C. Reproduced with permission from Ref. [72]. Copyright 2020 Elsevier. c Diagram of the preparation process of P-CoS2 nano-boxes. Reproduced with permission from Ref. [73]. Copyright 2021 American Chemical Society. d Cyclic performance of FeSA-CN/S electrode at 4.0 C. Reproduced with permission from Ref. [74]. Copyright 2020 Royal Society of Chemistry

Fig. 7

Reproduced with permission from Ref. [78]. Copyright 2018 Royal Society of Chemistry. b Pictures of Li2S6 solution and Li2S6 solution after adding Z-CoS2, commercial CoS2, and ZIF-67 powder. Reproduced with permission from Ref. [79]. Copyright 2019 Royal Society of Chemistry

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Grant No. 52272258), the Fundamental Research Funds for the Central Universities (Grant No. 2021JCCXJD01), Key R&D and transformation projects in Qinghai Province (Grant No. 2021-HZ-808) and Hebei Province (Grant No. 21314401D), and American Chemical Society Petroleum Research Fund (Grant No. PRF-59722-ND10).

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Author notes

  1. Ning Yuan and Yi-Rui Deng have contributed equally to this work.

Authors and Affiliations

  1. School of Chemical and Environmental Engineering, China University of Mining and Technology (Beijing), Beijing, 100083, China

    Ning Yuan, Yi-Rui Deng, Shan-Hu Wang, Na-Chuan Zou & Rui-Ping Liu

  2. School of Mechanical Engineering, Qinghai University, Xining, 810016, China

    Li Gao & Bing-Xin Liu

  3. School of Materials Science and Engineering, Tsinghua University, Beijing, 100083, China

    Jin-Lin Yang

  4. Department of Mechanical Engineering, University of Alaska Fairbanks, Fairbanks, AK, 99775-5905, USA

    Jun-Qing Zhang & Lei Zhang

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  10. Lei Zhang
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Yuan, N., Deng, YR., Wang, SH. et al. Towards superior lithium–sulfur batteries with metal–organic frameworks and their derivatives. Tungsten 4, 269–283 (2022). https://doi.org/10.1007/s42864-022-00186-x

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