Effect of glucose content on the lithium storage performance of Li3V2(PO4)3/C cathode materials prepared by sol-gel combustion method
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摘要: 通过改变葡萄糖添加量，采用改进的溶胶凝胶燃烧法成功制备出不同碳含量的亚微多孔Li3V2(PO4)3（LVP）/C复合材料。系统研究了葡萄糖添加量对LVP的结构、形貌及电化学性能的影响。添加葡萄糖虽然没有改变LVP的晶型结构和晶格参数，但是添加了葡萄糖的样品中出现了有利于电子传输和Li+扩散的纳米针状颗粒，且随着葡萄糖添加量的增加，纳米针状颗粒的体积分数增加，从而提高了LVP/C正极材料的倍率性能。葡萄糖碳化生成的无定形碳均匀包覆在LVP颗粒的表面，提高了复合材料的电导率，电导率随着葡萄糖添加量的增加而增加，但是葡萄糖添加量过多会导致碳包覆层过厚，不利于Li+的传输。得益于适当的葡萄糖添加量以及纳米针状颗粒和多孔结构，LVP/C-G15%样品具有优异的储锂性能，其在10 C的高倍率下循环200次后仍可提供75.1 mAh/g的放电比容量，容量保持率高达89.0%。
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关键词:
- Li3V2(PO4)3/C正极材料 /
- 储锂性能 /
- 葡萄糖添加量 /
- 溶胶凝胶燃烧法 /
- 碳含量
Abstract: In this paper, submicrometer porous Li3V2(PO4)3 (LVP)/C composites with different carbon contents were successfully prepared by a modified sol-gel combustion method by changing the amount of glucose added. The effects of glucose addition on the structure, morphology and electrochemical properties of LVP were systematically studied. Although the addition of glucose did not change the crystal structure and lattice parameters of LVP, nanoneedle-like particles appeared in the samples with glucose, which were beneficial to electron transport and Li+ diffusion. With the increase of glucose content, the volume fraction of nanoneedle-like particles increased, thus improving the rate performance of LVP/C cathode materials. The amorphous carbon generated by carbonization of glucose is evenly coated on the surface of LVP particles, which improves the conductivity of the composites. The conductivity increases with the increase of glucose content. However, excessive glucose addition will lead to too thick carbon coating, which is not conducive to the transmission of Li+. Benefiting from the appropriate amount of glucose addition, nanoneedle-like particles and porous structure, LVP/C-G15% sample has excellent lithium storage performance. It can still provide a discharge specific capacity of 75.1 mAh/g after 200 cycles at a high rate of 10 C, and the capacity retention rate is as high as 89.0%. -
图 1 LVP/C-Gx (x = 0, 5%, 10%, 15%和20%)复合材料的XRD图谱
Figure 1. XRD diffraction patterns of LVP/C-Gx (x = 0, 5%, 10%, 15% and 20%) composites
图 2 不同葡萄糖添加量样品的SEM形貌
Figure 2. SEM images of samples with different glucose additions
(a) LVP/C-G0；(b) LVP/C-G10%；(c) LVP/C-G15%；(d) LVP/C-G20%
图 4 LVP/C-Gx (x = 0, 10%, 15%和20%)样品的（a）恒电流充放电曲线；（b）倍率性能曲线；（c）LVP/C-G15%样品在10 C倍率下的循环性能曲线
Figure 4. (a) Galvanostatic charge-discharge curves, (b) Rate performance curves of LVP/C-Gx (x = 0, 10%, 15% and 20%) samples, (c) Long-term cycling performance curves of LVP/C-G15% sample at 10 C
图 5 LVP/C-Gx (x = 0, 10%, 15%和20%)复合材料的（a）EIS图谱和（b）低频区中Z'与ω−1/2的线性拟合曲线
Figure 5. (a) EIS spectra and (b) linear fitting curves of Z' vs. ω−1/2 at low frequencies of LVP/C-Gx (x = 0, 10%, 15% and 20%) composites
表 1 不同葡萄糖添加量的LVP/C样品的XRD-Rietveld精修晶体学参数
Table 1. Refined crystallographic parameters from XRD-Rietveld for LVP/C materials with different glucose additions
样品 a /nm b /nm c /nm Β/ (°) V /nm3 Rwp /% LVP/C-G0 0.8611 0.8605 1.205 90.56 0.8930 6.94 LVP/C-G5% 0.8610 0.8601 1.205 90.54 0.8925 7.06 LVP/C-G10% 0.8611 0.8602 1.205 90.55 0.8926 6.89 LVP/C-G15% 0.8610 0.8604 1.205 90.53 0.8928 6.68 LVP/C-G20% 0.8610 0.8603 1.205 90.54 0.8926 6.53 
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表 2 通过等效电路对EIS数据进行拟合得到的LVP/C-Gx (x = 0, 10%, 15%和20%)电极的动力学参数
Table 2. The kinetic parameters of LVP/C-Gx (x = 0, 10%, 15% and 20%) electrodes obtained by fitting the EIS data through the equivalent circuit
样品 Rs /Ω Rct /Ω σ /(Ω·s−1/2) LVP/C-G0 1.684 498.1 129.1 LVP/C-G10% 1.634 371.1 79.11 LVP/C-G15% 1.254 318.7 21.91 LVP/C-G20% 1.331 271.0 46.05
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