Sulfonyl chloride-intensified metal chloride intercalation towards graphite for efficient sodium storage
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摘要: 金属氯化物-石墨插层化合物具有导电性优异，石墨层间距大等特点，可用作钠离子电池负极材料。然而，在传统金属氯化物插层石墨过程中，不可避免的用到氯气，既增加了实验操作的风险，也对实验设备提出更高要求。基于上述原因，本文创新性地使用SO2Cl2作为氯源来促进BiCl3插层石墨。该方法不仅有效提高了BiCl3插层效率，也避免了直接使用氯气带来的安全性风险。采用该方法所合成的三氯化铋-石墨插层化合物（BiCl3-GICs）的层间距为1.26 nm，BiCl3插层含量高达42%。以其为负极材料，组装的钠离子电池具有高的比容量（213 mAh g−1 at 1 A g−1）和优异的倍率性能（170 mAh g−1 at 5 A g−1）。此外，原位拉曼光谱表明，首圈放电后石墨与插层的BiCl3相互作用减弱，该过程有效促进了钠离子在石墨层内的存储。采用该方法可成功制备多种类型金属氯化物-石墨插层化合物，为开发高性能储能材料提供了可行思路。
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关键词:
- 磺酰氯 /
- 金属氯化物-石墨插层化合物 /
- 插层强化过程 /
- 负极材料 /
- 钠离子电池
Abstract: Metal chloride-intercalated graphite with excellent conductivity and large interlayer spacing is highly desired for applications in sodium ion batteries. However, halogen vapor is usually indispensable in initiating the intercalation process, which makes equipment design and experiments challenging. In this work, SO2Cl2 was innovatively used as chlorine generator to intensify the intercalation process of BiCl3 into graphite (BiCl3-GICs), which avoided potential risks such as Cl2 leakage in traditional methods. Additionally, the operational efficiency in experiment is effectively improved. After reacting SO2Cl2, BiCl3, and graphite at 200 °C for 20 h, the as-synthesized BiCl3-GICs delivered a large interlayer spacing (1.26 nm) and a high amount of BiCl3 intercalation (42%), which endows SIBs with high specific capacity of 213 mAh g−1 at 1 A g−1 and fantastic rate performance (170 mAh g−1 at 5 A g−1). Moreover, the in-situ Raman spectra revealed that electronic interaction between graphite and intercalated BiCl3 is weakened during the first discharge, which is favorable for the sodium storage. This work broadly enables the intercalation intensification process of other metal chloride-intercalated graphite, offering possibilities for developing advanced energy storage devices. -
Figure 2. (a) XRD patterns and (b) TGA curves of the BiCl3-GICs samples fabricated at various temperatures (reaction time: 10 h). (c) XRD patterns and (d) TGA curves of the BiCl3-GICs samples prepared at various reaction time (reaction temperature: 200 °C). (e) Raman spectra, and (f) FT-IR spectra of graphite and the BiCl3-GICs
Figure 3. (a) The full XPS survey spectrum of BiCl3-GICs. (b) High-resolution XPS profiles of (b) C 1s, (c) Bi 4f, and (d) Cl 2p in BiCl3-GICs, respectively
Figure 4. SEM images of (a-b) graphite and (c-d) BiCl3-GICs. (e-f) TEM images of BiCl3-GICs. (g) The matching mapping images of the elements C, Cl and Bi
Figure 5. (a) Raman spectra and (b) XRD patterns of WCl6-GICs, MoCl5-GICs, and graphite. The elemental mapping images of (c) the C, W and Cl elements in the WCl6-GICs and (d) the C, Mo and Cl elements in the MoCl5-GICs. Cycling test for (e) WCl6-GICs and (f) MoCl5-GICs at 1 A g−1
Figure 6. (a) Cycling performance of BiCl3-GICs and graphite at 1 A g−1. (b) CV curves and (c) GCD curves of graphite and BiCl3-GICs for the first cycle. (d) The CV curves and (e) GCD curves of BiCl3-GICs for the first three cycles. (f) EIS curves of BiCl3-GICs and graphite
Figure 7. (a-b) Rate performance of BiCl3-GICs. (c) Comparison of rate performance between this work and the reported SIB anodes. (d) CV curves of BiCl3-GICs at various scan rates. (e) The calculated logarithm connection between scan rate and current based on the CV curves. (f) b-values of different redox peaks
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