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Sc3+掺杂对碳热还原法制备Li3V2(PO4)3/C正极材料储锂性能的影响

冯雪刚 李娜丽 刘甜甜

冯雪刚, 李娜丽, 刘甜甜. Sc3+掺杂对碳热还原法制备Li3V2(PO4)3/C正极材料储锂性能的影响[J]. 钢铁钒钛, 2022, 43(6): 31-37. doi: 10.7513/j.issn.1004-7638.2022.06.005
引用本文: 冯雪刚, 李娜丽, 刘甜甜. Sc3+掺杂对碳热还原法制备Li3V2(PO4)3/C正极材料储锂性能的影响[J]. 钢铁钒钛, 2022, 43(6): 31-37. doi: 10.7513/j.issn.1004-7638.2022.06.005
Feng Xuegang, Li Nali, Liu Tiantian. Effect of Sc3+ doping on lithium storage performance of Li3V2(PO4)3/C cathode material synthesized by carbothermal reduction method[J]. IRON STEEL VANADIUM TITANIUM, 2022, 43(6): 31-37. doi: 10.7513/j.issn.1004-7638.2022.06.005
Citation: Feng Xuegang, Li Nali, Liu Tiantian. Effect of Sc3+ doping on lithium storage performance of Li3V2(PO4)3/C cathode material synthesized by carbothermal reduction method[J]. IRON STEEL VANADIUM TITANIUM, 2022, 43(6): 31-37. doi: 10.7513/j.issn.1004-7638.2022.06.005

Sc3+掺杂对碳热还原法制备Li3V2(PO4)3/C正极材料储锂性能的影响

doi: 10.7513/j.issn.1004-7638.2022.06.005
基金项目: 四川省科技厅应用基础研究项目(2018JY0284);钒钛资源综合利用四川省重点实验室项目(2019FTSZ14);攀枝花学院校级科研项目(2020YB021);国家级大学生创新创业训练计划项目(202111360005)。
详细信息
    作者简介:

    李娜丽,1985年出生,女,福建泉州人,博士,讲师,通讯作者,主要研究方向为新能源材料,E-mail:nalili0630@163.com

    通讯作者:

    李娜丽,1985年出生,女,福建泉州人,博士,讲师,通讯作者,主要研究方向为新能源材料,E-mail:nalili0630@163.com

  • 中图分类号: TF841.3,TM912

Effect of Sc3+ doping on lithium storage performance of Li3V2(PO4)3/C cathode material synthesized by carbothermal reduction method

  • 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%。
  • 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(abcβ: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 /nmb /nmc /nmβV /nm3
    Li3V2(PO4)3/C0.860 10.859 51.20390.550.889 6
    Li3V1.90Sc0.05(PO4)3/C0.860 80.860 21.20390.520.891 0
    Li3V1.85Sc0.15(PO4)3/C0.86130.860 71.20590.510.893 1
    Li3V1.80Sc0.20(PO4)3/C0.862 10.861 71.20690.480.895 6
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  • 收稿日期:  2022-09-23
  • 刊出日期:  2023-01-13

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