Structural Regulation of Metal Organic Framework-derived Hollow Carbon Nanocages and Their Lithium-Sulfur Battery Performance

doi:10.6023/A22030117

Abstract

Lithium-sulfur battery has attracted extensive research interest because of its high theoretical specific capacity, low cost and environmental friendliness. However, its practical application is still limited by the low utilization of sulfur, serious shuttle and polarization effects. To solve these problems, confining sulfur in a highly conductive host, with the assistance of chemical adsorption of intermediate lithium polysulfides (LiPS) by polar sites and catalytic promotion of LiPS conversion by catalytic sites, can effectively boost the charge transfer and suppress the shuttle and polarization effects, hence leading to the high utilization of sulfur and the improved performances of lithium-sulfur batteries. Hollow carbon nanocages have become an ideal host for sulfur encapsulation because of the large inner cavity, high conductivity, and tunable surface and electronic structures. In this study, three kinds of hollow carbon nanocages with similar size but different composition and structure of shells were prepared by etching the ZIF8, ZIF67 and ZIF8@ZIF67@ZIF8 precursors with tannic acid solution, followed by the carbonization. Used as the cathodes for lithium-sulfur batteries after sulfur filling, the sample derived from ZIF8@ZIF67@ZIF8 shows the best electrochemical performance. Specifically, the specific capacity reaches 1010 mAh•g^-1 at 0.1 C (1 C=1675 mA•g^-1), and remains 664 mAh•g^-1 at 1 C; after 300 cycles tests at 0.5 C, the capacity is retained at 492 mAh•g^-1, significantly better than the control samples derived from ZIF8 and ZIF67. The excellent performance of the former is closely related to its unique structure and composition: (ⅰ) the Co species presented in the precursor can improve the conductivity of derived carbon nanocages; (ⅱ) the evaporation of Zn species brings about large specific surface area and rich micro/mesopores, which is conducive to the sulfur filling and the catalytic conversion of S species by the active Co species. Therefore, the shuttle and polarization effects are efficiently suppressed and the utilization of sulfur is improved accordingly, leading to the better performances of lithium-sulfur batteries. This study opens a new avenue to regulate the performance of lithium-sulfur batteries by constructing novel carbon nanocages hosts based on the metal organic framework (MOF) precursors.

Key words: lithium-sulfur battery, cathode material, metal organic framework (MOF)-derived carbon nanocages, electrocatalysis, confinement effect

Cite this article

Jiawei He, Liu Jiao, Xueyi Cheng, Guanghai Chen, Qiang Wu, Xizhang Wang, Lijun Yang, Zheng Hu. Structural Regulation of Metal Organic Framework-derived Hollow Carbon Nanocages and Their Lithium-Sulfur Battery Performance[J]. Acta Chimica Sinica, 2022, 80(7): 896-902.

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Fig. & Tab. 4

Figure 1. Morphology evolution during the synthesis of carbon nanocages by MOF pyrolysis. (a) Schematic diagram of the preparation process; (b1, c1, d1) SEM images of ZIF8, ZIF67 and ZIF8@ZIF67@ZIF8; (b2, c2, d2) SEM images after etching; (b3, c3, d3) TEM images after carbonization

Figure 2. DF-STEM image of S@ZIF8@ZIF67@ZIF8/NC and corresponding element distribution mappings. (a) DF-STEM image; (b~f) element mappings for (b) C, (c) N, (d) Zn, (e) Co, (f) S

Figure 3. Electrochemical performances of three cathode materials. (a) Cycling stabilities at 0.5 C; (b) rate capabilities; (c) EIS spectra. Inset is the corresponding equivalent circuit

Figure 4. Electrocatalytic functions of ZIF8@ZIF67@ZIF8/NC and ZIF8/NC, and the electrochemical performances of the corresponding cathodes. (a) CV curves and (b) EIS curves of ZIF8@ZIF67@ZIF8/NC and ZIF8/NC in Li2S6-based electrolyte; (c) CV curves and (d) charge-discharge profiles for S@ZIF8@ZIF67@ZIF8/NC and S@ZIF8/NC

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