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摘要: 硅负极是锂离子电池理想的候选材料。然而，其显著的体积膨胀会导致严重的材料断裂，失去电接触，从而限制了其实际应用。本研究提出了一种新的自上而下的多孔硅制备策略，并引入聚丙烯腈（PAN）作为掺氮碳涂层，旨在保持硅负极的内部空间，缓解硅负极在锂化和脱锂过程中向外膨胀的问题。随后，我们探讨了温度对PAN热转变行为和复合电极电化学行为的影响。在400 °C下处理后，PAN涂层保留了11.35 wt%的高氮掺杂含量，这明确证实了C―N和C―O键的存在，从而改善了离子电子传输特性。这种处理方法不仅保留了更完整的碳层结构，还引入了碳缺陷，即使在大电流下也能稳定循环。当以4 A g−1的电流循环时，优化后的负极在循环200次后仍能显示出857.6 mAh g−1的比容量，显示出其在高容量储能应用方面的巨大潜力。Abstract: Silicon anodes as a promising candidate for lithium-ion batteries. However, their significant volume expansion leads to severe material fracture and electrical disconnection, which limits their practical application. This study proposed a new top-down strategy for microsized porous silicon and introducing polyacrylonitrile (PAN) as nitrogen-doped carbon coating, which designed to maintain the internal space and alleviate the outward expansion of the silicon anode during the lithiation and delithiation process. Subsequently, we explored the effect of temperature on the thermal transition behavior of PAN and the electrochemical behavior of the composite electrode. After the treatment at 400 °C, the PAN coating retained a high nitrogen doping content of 11.35 wt%, which explicitly confirmed the existence of C-N and C-O bonds that improved the ionic-electronic transport properties. This treatment not only retained a more intact carbon layer structure, but also introduced carbon defects, exhibiting remarkably stable cycling even at high rates. When cycled at 4 A g−1, the optimized anode exhibited a specific capacity of 857.6 mAh g−1 even after 200 cycles, demonstrating great potential for high-capacity energy storage applications.
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Key words:
- Porous silicon /
- Lithium-ion batteries /
- Polyacrylonitrile /
- Electrochemical behavior
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Figure 1. (a) Schematic of the porous silicon preparation process. SEM images of (b) M-Si, (c) P-Si, and (d) P-Si@C-PAN
Figure 2. (a) SEM of porous silicon, (b) Nitrogen adsorption and desorption isotherms of porous silicon, (c) XRD of P-Si, and P-Si@C-PAN-400, (d) Raman spectra of M-Si, P-Si, and P-Si@C-PAN-400, and (e) STEM and elemental mapping images of P-Si@C-PAN
Figure 3. (a) Thermogravimetric analysis of P-Si@C-PAN-400 and P-Si@C-PAN-800, (b) XPS survey of P-Si@C-PAN-400 and P-Si@C-PAN-800. High resolution of C 1s XPS spectra of (c) P-Si@C-PAN-400 and (d) P-Si@C-PAN-800. (e) Electrochemical cycling performance of P-Si, P-Si@C-PAN-400, and P-Si@C-PAN-800. (f) EIS of P-Si, P-Si@C-PAN-400, and P-Si@C-PAN-800
Figure 4. (a) TGA and DTG of PAN (b) TGA (c) Raman Spectroscopy (d) Fourier Transform Infrared Spectroscopy (FTIR) of P-Si@C-PAN-300, P-Si@C-PAN-400, P-Si@C-PAN-500
Figure 5. GITT curves of (a) P-Si@C-PAN-300, (b) P-Si@C-PAN-400, and (c) P-Si@C-PAN-500. (d) comparison for Li+ diffusion coefficients of different samples treated at different temperatures. CV curves measured at different scan rates for (e) P-Si@C-PAN-300, (f) P-Si@C-PAN-400, and (g) P-Si@C-PAN-500. (h) Linear relationship between log i (peak current) and log v (scan rate) for the three samples
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