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三维多级钴酸镍结构的形貌调控及其电化学性能

李群 张阔 李艳华 王书桓 倪国龙

李群, 张阔, 李艳华, 等. 三维多级钴酸镍结构的形貌调控及其电化学性能[J]. 复合材料学报, 2024, 41(1): 281-292. doi: 10.13801/j.cnki.fhclxb.20230511.005
引用本文: 李群, 张阔, 李艳华, 等. 三维多级钴酸镍结构的形貌调控及其电化学性能[J]. 复合材料学报, 2024, 41(1): 281-292. doi: 10.13801/j.cnki.fhclxb.20230511.005
LI Qun, ZHANG Kuo, LI Yanhua, et al. Morphology control and electrochemical properties of three-dimensional hierarchical NiCo2O4 structure[J]. Acta Materiae Compositae Sinica, 2024, 41(1): 281-292. doi: 10.13801/j.cnki.fhclxb.20230511.005
Citation: LI Qun, ZHANG Kuo, LI Yanhua, et al. Morphology control and electrochemical properties of three-dimensional hierarchical NiCo2O4 structure[J]. Acta Materiae Compositae Sinica, 2024, 41(1): 281-292. doi: 10.13801/j.cnki.fhclxb.20230511.005

三维多级钴酸镍结构的形貌调控及其电化学性能

doi: 10.13801/j.cnki.fhclxb.20230511.005
基金项目: 国家自然科学基金(52104329);河北省自然科学基金(E2021209141);河北省高等学校科学技术研究项目(BJK2022003)
详细信息
    通讯作者:

    倪国龙,博士,讲师,研究方向为新材料制备及应用 E-mail: ngl@ncst.edu.cn

  • 中图分类号: TB34;TB33

Morphology control and electrochemical properties of three-dimensional hierarchical NiCo2O4 structure

Funds: National Natural Science Foundation of China (52104329); Natural Science Foundation of Hebei Province (E2021209141); Funded by Science and Technology Project of Hebei Education Department (BJK2022003)
  • 摘要: 形貌结构的调控对材料的电化学性能具有重要影响。本文采用溶剂热法结合煅烧在不同溶剂比及温度下合成不同形貌结构的钴酸镍,利用XRD及SEM和TEM等对样品的物相组成及形貌结构进行了表征,并对其电化学性能进行了分析。结果表明:当水与乙醇体积比为1∶1时,样品为中空的海胆状NiCo2O4,随着水比例的增加,形貌逐渐转变为规则的中心放射状的针状形貌,且有第二相物质的存在。在水与乙醇体积比为1∶1时,随着温度的增加,形貌主要由毛绒球向花状、海胆状、中心放射状的针状过渡,而样品均为纯NiCo2O4。90℃合成的样品具有较好的电化学性能,在1 A·g−1电流密度下,比电容高达1287.5 F·g−1,当扫速从20~100 mV·s−1变化时,电容保持率达到59.4%,循环1500圈,比电容保持率高达80.1%,此外,在整个电化学反应过程中扩散控制过程起主导作用。

     

  • 图  1  不同溶剂比例合成NiCo2O4的XRD图谱

    Figure  1.  XRD patterns of the obtained NiCo2O4 with different solvent ratios

    图  2  不同溶剂比例合成NiCo2O4的SEM图像

    Figure  2.  SEM images of the obtained NiCo2O4 with different solvent ratios

    图  3  不同溶剂比例合成NiCo2O4的XPS图谱

    Figure  3.  XPS spectra of the obtained NiCo2O4 with different solvent ratios

    Vo—Vacancy defect oxygen; Sat1, Sat2—Satellite peak 1 and satellite peak 2

    图  4  不同温度下合成NiCo2O4的XRD图谱

    Figure  4.  XRD patterns of the obtained NiCo2O4 at different synthesis temperature

    图  5  不同温度下合成NiCo2O4样品的SEM图像:((a), (b)) 90℃;((c), (d)) 110℃;((e), (f)) 130℃;((g), (h)) 150℃;(i) 90℃样品的元素面扫图

    Figure  5.  SEM images of the obtained NiCo2O4 samples at different synthesis temperature: ((a), (b)) 90℃; ((c), (d)) 110℃; ((e), (f)) 130℃; ((g), (h)) 150℃; (i) Elemental mapping images of sample obtained at 90℃

    图  6  不同温度下合成NiCo2O4的TEM图像

    Figure  6.  TEM images of the obtained NiCo2O4 at different synthesis temperature

    图  7  不同温度下合成NiCo2O4的机制示意图

    Figure  7.  Mechanism schematic diagram of the obtained NiCo2O4 at different synthesis temperature

    图  8  不同温度合成的NiCo2O4的CV曲线((a)~(d));(e) 100 mV·s−1扫速下的CV曲线对比图;(f) 扫速与比电容关系图

    Figure  8.  ((a)-(d)) CV curves of the obtained NiCo2O4 at different synthesis temperature; (e) CV curves at 100 mV·s−1; (f) Relationship between scan rate and specific capacity

    图  9  (a) 不同温度合成的NiCo2O4的N2吸脱附曲线(插图为孔径分布图);(b) 90℃的NiCo2O4的结构优势示意图

    Figure  9.  (a) Nitrogen adsorption-desorption isotherm of the obtained NiCo2O4 at different synthesis temperature (Inset of pore size distribution ); (b) Schematic illustration of the structural advantages of NiCo2O4 at 90℃

    dV/dD—Pore volume

    图  10  ((a)~(d)) 不同温度合成的NiCo2O4的GCD曲线;(e) 1 A·g−1电流密度下GCD曲线对比图;(f) 与图10(e)对应的电容值,插图为90℃的NiCo2O4电流密度与比电容关系图

    Figure  10.  ((a)-(d)) GCD curves of the obtained NiCo2O4 at different synthesis temperature; (e) GCD curves at 1 A·g−1; (f) Corresponding specific capacity of Fig. 10(e) (Inset of the relationship between current density and specific capacity of NiCo2O4 at 90℃)

    图  11  不同温度合成的NiCo2O4的EIS曲线

    Figure  11.  EIS curves of the obtained NiCo2O4 at different synthesis temperature

    Rs—Equivalent series resistance; Rct—Charge-transfer resistance; Cd—Double electric layer capacitance; w—Warburg’s resistance

    图  12  90℃的NiCo2O4循环稳定性测试

    Figure  12.  Cycle curves of the obtained NiCo2O4 at 90℃

    图  13  90℃的NiCo2O4电极的阴极峰电流与扫速的对数关系图(a)和不同扫速下电容和扩散控制的相对贡献(b)

    Figure  13.  Relationship between logarithm cathode peak current and logarithm scan rates (a) and relative contributions of capacitive and diffusion-controlled processes at different scanning rates (b) of NiCo2O4 at 90℃

    b—Constants obtained from the slope of the fitting linear curve of lg(scan rate) against lg(peak current)

    表  1  不同溶剂比例合成NiCo2O4的表面原子比

    Table  1.   Surface atomic ratios of the obtained NiCo2O4 with different solvent ratios

    SampleNi2p3/2/at%Co2p3/2/at%Ni2+/Ni3+
    (Atomic ratio)
    Co3+/Co2+
    (Atomic ratio)
    Ni/Co
    (Atomic ratio)
    Ni2+Ni3+ Co3+Co2+
    5 mL water77.122.972.227.83.372.600.37
    20 mL water69.830.280.119.92.314.020.60
    35 mL water65.334.775.124.91.883.010.71
    下载: 导出CSV
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  • 收稿日期:  2023-03-29
  • 修回日期:  2023-05-03
  • 录用日期:  2023-05-06
  • 网络出版日期:  2023-05-12
  • 刊出日期:  2024-01-01

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