Preparation and electrochemical properties of novel silicon-carbon composite anode materials with a core-shell structure
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摘要: 通过对氧化硅预处理得到多组分硅pSi（Si、SiO、SiO2），再利用化学气相沉积法（CVD）设计了具有核壳结构的pSi与碳纳米纤维（CNF）的复合材料（pSi-CNF）。多组分硅中Si、SiO提供电化学可逆容量，SiO2可以抑制硅的体积膨胀；碳纳米纤维包覆形成的壳层结构可以有效提高复合材料的导电性，同时进一步抑制硅的体积膨胀保持核壳结构的完整。通过SEM、TEM、EDS、XRD、Raman和XPS对复合物的微观结构进行分析。结果表明：pSi-CNF的粒径为5~20 µm，碳纳米纤维的直径为5~40 nm, pSi-CNF复合材料中含有Si、SiO和SiO2多种组分硅，有明显特征峰；碳纳米纤维均匀包覆于硅表面，形成核壳结构。电化学性能测试表明，在0.2 A·g−1的电流密度下，经100次循环后其可逆容量为1 411 mAh·g−1，容量保持率为74%，具有良好的循环稳定性和较高的可逆容量；在1 A·g−1的电流密度下，经300次循环后其可逆容量为735 mAh·g−1，容量保持率为86%，且具有良好的倍率性能。Abstract: Multi-component porous Si-SiOx (pSi) consisting of Si, SiO and SiO2 was formed by the pretreatment of SiO at 950 °C for 3 h in an inert atmosphere (He) using a disproportionation reaction. Hybrids of pSi and carbon nanofibers (pSi-CNFs) with a core-shell structure were prepared by catalytic chemical vapor deposition (CVD) using Fe-Ni species as the catalyst and a mixture of CO/H2/C2H4 (volumetric ratio 3∶1∶1) as the reactant for 0.5, 1 and 2 h, and were characterized by SEM, TEM, EDS, XRD, Raman spectroscopy and XPS. Results indicate that the pSi-CNF particle sizes are 5−20 μ m with the diameters of the CNFs being 5−40 nm. The CNFs are uniformly coated on the surface of the pSi to form a core-shell structure. Electrochemical performance testing shows that the reversible capacity of the pSi-CNF (0.5 h) remains at 1 411 mAh.g−1 and the capacity retention is 74% after 100 cycles at a current density of 0.2 A.g−1. The reversible capacity remains at 735 mAh.g−1 at a current density of 1 A g−1 after 300 cycles with a capacity retention of 86%. In the pSi, Si and SiO provide the electrochemical reversible capacity. The core-shell structure with the CNF coating effectively improves the conductivity of the composites, and also inhibits the volume expansion of silicon to maintain the integrity of the core shell structure.
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Key words:
- Silicon carbon composite /
- Anode material /
- Chemical vapor deposition /
- Carbon nanofiber
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Figure 1. SEM images of (a) pSi and (b) pSi-CNF, TEM images of (c) pSi-CNF, STEM of (d) pSi-CNF and (e, f) mapping images of different elements.
Figure 2. (a) XRD patterns of SiO, pSi, and pSi-CNF , (b) Raman spectrum of pSi-CNF materials, (c) full XPS spectrum of pSi, (d) XPS spectrum and peak-fitted spectra of Si 2p and (e) TGA curves of three pSi-CNF composites.
Figure 3. CV curves of (a) pSi and (b) pSi-CNF electrodes at a scan rate of 0.1 mV·s−1.
Figure 4. (a, c) Charge and discharge curves of pSi-CNF electrodes at 0.2 A·g−1 and different current densities, (b) cycle performance curves of SiO-CNF, pSi and pSi-CNF at 0.2 A·g−1 and (d) rate performance curves of SiO-CNF, pSi and pSi-CNF.
Figure 5. (a) Cycle performance curves, (b)rate performance curves of pSi-CNF anode materials with different carbon amounts and (c) long-cycle performance curves of pSi-CNF and pSi.
Figure 7. SEM images of pSi and pSi-CNF anodes (a, b) before cycle and (c, d) at the 100th cycle.
Table 1. Comparison of electrochemical performance between pSi-CNF materials and other silicon-carbon composite anode materials.
Categories of Si Synthesis method Cycling stability Specific capacity (mAh g−1) Cycle number Current/rate Ref. Micrometer-sized Si Si@SiO2 cluster formation and etching 1160 1000 0.5 C [27] Simple Si/C composite Pyrolysis of polymers with Si 1200 30 0.1 C [28] Yolk-shell Si/C SiO2 and carbon coating 1500 1000 1 C [29] Si/graphene Freeze-drying 840 300 1.4 A g−1 [30] Si/CNT Growth of CNT on substrate and sputtering of Si 2500 100 0.2 C [31] pSi-CNF (this work) Disproportionation and CVD 1411 100 0.2 A g−1 
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