A high-rate and ultrastable anode enabled by surface oxidation and intercalation modification of hard carbon for lithium ion capacitors
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摘要: 由于锂离子电容器正负极材料的储能机理不同，正极材料对其功率密度和倍率性能有很大限制。硬碳是一种很有前景的锂离子电容器负极材料，对碳材料进行改性是提高锂离子电容器电化学性能的重要手段之一。本研究采用氧化插层法制备的硬碳插层复合材料(ZnCl2-OHC)，0.05 A·g−1电流密度下半电池可逆容量为257.4 mAh·g−1。ZnCl2-OHC作负极、活性炭作正极的全电池容量保持可达43.3%，比未经处理硬碳作负极的全电池提高了两倍以上，1 A·g−1电流密度下充放电5000次后容量保持率约为98.4%。因此，通过硬碳的表面氧化和插层改性可以作为未来提升锂离子电容器负极性能的一种途径。Abstract: Due to the difference of energy storage mechanism between anode and cathode materials, the power density or rate performance of lithium ion capacitor is greatly limited by anode materials. Hard carbon is a promising anode material for lithium ion capacitors. The modification of carbon materials is one of the important means of improving the electrochemical performance of lithium ion capacitor. Hard carbon intercalation composite (ZnCl2-OHC) was prepared by oxidation intercalation. The reversible capacity of half cell prepared with ZnCl2-OHC is 257.4 mAh·g−1 at current density of 0.05 A·g−1, and the capacity retention rate of full cell prepared with ZnCl2-OHC as anode and activated carbon as cathode can still reach 43.3%, which raises more than two times as compared with untreated hard carbon. At the same time, after 5000 charge-discharge cycles at the current density of 1 A·g−1, the capacity retention rate is about 98.4%. Therefore, surface oxidation and intercalation modification of hard carbon can be seen as a promising way of the improvement of anode for lithium ion capacitors in the future.
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Key words:
- lithium ion capacitors /
- anode materials /
- hard carbon /
- intercalation
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Figure 1. SEM image of (a)(b) untreated HC, (c)(d) OHC without ultrasound treatment, (e)(f) OHC with ultrasound treatment
Figure 2. SEM image of (a) untreated hard carbon, (b) intercalated hard carbon, (c) 400 °C intercalated hard carbon, (d) 500 °C intercalated hard carbon and their (e) XRD pattern
Figure 3. SEM images of different hard carbon materials, (a) HC, (b) OHC, (c) ZnCl2-HC, (d) ZnCl2-OHC and (e) XRD pattern of hard carbon treated by different means
Figure 6. (a) XPS survey spectrum of HC and ZnCl2-OHC and XPS (b) C1s (c) Zn2p (d) Cl2p spectra of ZnCl2-OHC
Figure 8. Half-cell cycling performance (a-b) and charge/discharge curve (c-d) of the different electrodes
Figure 9. CV curves of (a)HC、(b)OHC、(c)ZnCl2-HC and (d)ZnCl2-OHC at different sweep speeds
Table 1. Pore structure parameters of hard carbon materials before and after treatment
Component Specific surface area /m2·g−1 SBET SLANGUIR HC 2.28 6.29 OHC 11.58 30.53 ZnCl2-HC 8.31 22.39 ZnCl2-OHC 47.91 120.66 
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Table 2. Analysis of elements on the surface of ZnCl2-OHC
Name Start BE Peak BE End BE Height CPS Atomic % C1s 297.98 283.47 279.18 32914.62 83.75 Cl2p 210.03 197.4 190.13 1095.69 2.14 O1s 544.98 531.39 525.18 3586.45 12.73 Zn2p 1052.03 1021.11 1015.13 4324.72 1.38
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