Effect of Sc3+ doping on lithium storage performance of Li3V2(PO4)3/C cathode material synthesized by carbothermal reduction method
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摘要: 通过碳热还原法成功制备出Sc3+掺杂Li3V2(PO4)3/C正极材料。系统研究了Sc3+掺杂量对Li3V2(PO4)3的结构、形貌及电化学性能的影响。Sc3+掺杂虽然没有改变Li3V2(PO4)3的晶格类型，但是使得Li3V2(PO4)3的晶格膨胀，晶胞体积增大，有利于电子传输和Li+扩散。此外，Sc3+掺杂使得不规则的多边形块状Li3V2(PO4)3颗粒球化并减小其尺寸。更为重要的是，合适的Sc3+掺杂量能显著增强Li3V2(PO4)3正极材料的电子电导率和Li+扩散系数。得益于适当的Sc3+掺杂量以及碳包覆和多孔结构，Li3V1.85Sc0.15(PO4)3/C样品具有优异的储锂性能，其在10 C的高倍率下可提供84.8 mAh/g的首次放电比容量，并且循环100圈后容量保持率高达93.5%。
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关键词:
- Li3V2(PO4)3 /
- Sc3+掺杂 /
- 碳热还原法 /
- 储锂性能 /
- 放电比容量
Abstract: In this paper, Sc3+ doped Li3V2(PO4)3/C cathode material was successfully prepared by carbothermal reduction method. The effects of Sc3+ doping amount on the structure, morphology and lithium storage properties of Li3V2(PO4)3 were systematically investigated. Although Sc3+ doping does not change the lattice type of Li3V2(PO4)3, it makes the lattice of Li3V2(PO4)3 expand and the unit cell volume increase, which is beneficial to electron transport and Li+ diffusion. In addition, Sc3+ doping makes irregular polygonal Li3V2(PO4)3 particles spheroidized and reduces the particle size. More importantly, the appropriate doping amount of Sc3+ can significantly enhance the electronic conductivity and Li+ diffusion coefficient of Li3V2(PO4)3 cathode material. Benefiting from the appropriate Sc3+ doping amount, carbon coating and porous structure, Li3V1.85Sc0.15(PO4)3/C samples possess superior lithium storage properties. The initial discharge specific capacity is 84.8 mAh/g at 10 C rate, and the capacity retention rate is as high as 93.5 % after 100 cycles. -
图 1 Li3V2-xScx(PO4)3/C（x = 0、0.05、0.15和0.20）样品的XRD图谱
Figure 1. XRD patterns of Li3V2-xScx(PO4)3/C (x = 0, 0.05, 0.15 and 0.20) composites
图 2 Li3V1.85Sc0.15(PO4)3/C样品的HRTEM形貌
Figure 2. HRTEM image of Li3V1.85Sc0.15(PO4)3/C sample
图 3 样品的SEM形貌
Figure 3. SEM images of samples
(a) Li3V2(PO4)3/C；(b) Li3V1.95Sc0.05(PO4)3/C；(c) Li3V1.85Sc0.15(PO4)3/C；(d) Li3V1.80Sc0.20(PO4)3/C
图 4 Li3V1.85Sc0.15(PO4)3/C复合正极材料的氮气吸脱附等温线，插入图为对应的孔径分布
Figure 4. N2 adsorption/desorption isotherm, the pore-size distribution curve corresponding BJH (inset) of Li3V1.85Sc0.15(PO4)3/C composite
图 5 样品的倍率性能和循环性能
(a) Li3V2-xScx(PO4)3/C(x = 0、0.05、0.15和0.20) 样品的倍率性能；(b) Li3V2-xScx(PO4)3/C(x = 0、0.05、0.15和0.20) 样品的恒流充放电曲线；(c) Li3V1.85Sc0.15(PO4)3/C样品在10 C倍率下的循环性能曲线
Figure 5. Rate capability and cycle performance of samples
图 6 Li3V2-xScx(PO4)3/C（x = 0、0.05、0.15和0.20）复合材料的（a）交流阻抗谱和（b）低频区中Z´与ω−1/2之间的线性拟合曲线
Figure 6. (a) EIS spectra and (b) the relationship between Z´ and ω−1/2 at low frequencies of Li3V2-xScx(PO4)3/C (x = 0, 0.05, 0.15 and 0.20) composites
表 1 单斜Li3V2−xScx(PO4)3/C样品精修后的晶格参数和对应的晶胞体积（a，b，c和β：单斜晶系的晶胞参数；V：晶胞体积）
Table 1. Refined lattice parameters of monoclinic Li3V2−xScx(PO4)3/C materials and the corresponding unit-cell volumes (a, b, c and β : unit-cell parameters of the monoclinic system; V : volume of unit-cell)
样品 a /nm b /nm c /nm β /° V /nm3 Li3V2(PO4)3/C 0.860 1 0.859 5 1.203 90.55 0.889 6 Li3V1.90Sc0.05(PO4)3/C 0.860 8 0.860 2 1.203 90.52 0.891 0 Li3V1.85Sc0.15(PO4)3/C 0.8613 0.860 7 1.205 90.51 0.893 1 Li3V1.80Sc0.20(PO4)3/C 0.862 1 0.861 7 1.206 90.48 0.895 6 
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