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Active site construction to boost electrochemical property for Li–S batteries: a review

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Abstract

Lithium–sulfur (Li–S) batteries, as a research hotspot, are expected to address the need for energy storage systems with high energy density. However, the slow reaction kinetics of polysulfides due to the loss of electrical contact of soluble polysulfides and further shuttle effect hinder the further progression of Li–S batteries. This paper reviews the recent efficient approach to remedy the above issues: active site construction in the electrode materials or separators. The active site construction includes the increasing surface area, inducing molecular and single-atom catalysts, inducing heteroatomic doping, vacancies, or functional group. The high specific surface area can provide more sites for loading sulfur and also the more active sites for adsorption. Many porous materials are designed to provide more transfer paths for ions. Molecular and single-atom catalysts use some catalysts such as Fe–N–C or single metal atoms in various matrixes, representing the high catalytic activity. Defects can improve the electronic conductivity to quicken lithium ions diffusion in electrode materials, but also render more active sites to enhance catalytic activity and adsorption of electrode materials, accelerating the conversion of long-chain polysulfides to the next short-chain polysulfides and final products Li2S2/Li2S. The common active site construction and characterization methods of diversiform materials, for example, carbon materials, metal oxides, metal sulfides, and some other metal-free materials, are reviewed in this paper.

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Figure 1
Figure 2

Copyright 2018, Elsevier.) b SEM images of b-(a, b) pristine (without melamine), b-(c) NBC-5, b-(d, e) NBC-10, b-(f, g) NBC-15, b-(h) NBC-20. NBC means N-doped bagasse carbon, and the number notes the ratio of bagasse to melamine 1:5, 1:10, 1:15, 1:20. (Adapted with permission from reference [78]. Copyright 2019, Elsevier.)

Figure 3

Copyright 2019, American Chemical Society.) b HR-TEM images of CVD and Co3O4-DHS. (Adapted with permission from reference [90], Copyright 2020, American Chemical Society.) c HR-TEM, FFT, and IFFT images of Co3O4 and Co3O4−x. (Adapted with permission from reference [103], Copyright 2020, Elsevier.)

Figure 4

Copyright 2015, Science.) b STEM image of SrTiO3 film with Sr vacancies and the intensity of Sr and Ti–O. (Adapted with permission from reference [104]. Copyright 2016, American Physical Society.)

Figure 5

Copyright 2020, Wiley.) c, d Fe K-edge XANES and Fourier transform (FT) EXAFS signals of FeN/GN samples with various Fe contents in comparison with FePc, Fe foil, and Fe2O3. (Adapted with permission from reference [64]. Copyright 2015, Science.) e EPR spectra of Co3O4 with different doping contents of Fe. (Adapted with permission from reference [109]. Copyright 2020, American Chemical Society.) f, g RS and KPMF images of graphite. (Adapted with permission from reference [112]. Copyright 2019, Wiley.)

Figure 6

Copyright 2020, American Chemical Society.) b DOS of NiSe2 (001) and Fe–NiSe2 (001). (Adapted with permission from reference [114]. Copyright 2021, Wiley.) c HR-TEM and crystal structures of Co-doped MoS2. (Adapted with permission from reference [115]. Copyright 2019, Wiley.)

Figure 7

Copyright 2020, Elsevier.) b EIS spectra of the cells with N-PCNW-modified and Celgard separator. (Adapted with permission from reference [118]. Copyright 2016, Elsevier.) c Diffusion of polysulfides test of NHCs-modified and pristine separator. (Adapted with permission from reference [120]. Copyright 2015, Elsevier.)

Figure 8

Copyright 2018, Elsevier.) b CV curves of Li2S6|Li2S6 symmetrical cells with CP-P-NTC, CP- TC, and CP. (Adapted with permission from reference [108]. Copyright 2020, Elsevier.) c Precipitation of Li2S based on N-CoSe2, CoSe2, and Super-P. (Adapted with permission from reference [75]. Copyright 2020, American Chemical Society.)

Figure 9

Copyright 2019, Wiley.) b CV curves and Tafel plots of ODFO@3DGC@S, FO@3DGC@S, and 3DGC@S. c Theoretical simulation of ODFO and OF. (Adapted with permission from reference [125]. Copyright 2020, American Chemical Society.)

Figure 10

Copyright 2020, American Chemical Society.)

Figure 11

Copyright 2020, American Chemical Society.)

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    Limin Mao & Jian Mao

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Mao, L., Mao, J. Active site construction to boost electrochemical property for Li–S batteries: a review. J Mater Sci 57, 7131–7154 (2022). https://doi.org/10.1007/s10853-022-07082-2

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