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Co掺杂La1.5Sr0.5Ni1−xCoxO4+δ阴极材料的制备及其电化学稳定性能

李宁 李松波 安胜利 杜旭 薛良美 倪洋

李宁, 李松波, 安胜利, 杜旭, 薛良美, 倪洋. Co掺杂La1.5Sr0.5Ni1−xCoxO4+δ阴极材料的制备及其电化学稳定性能[J]. 燃料化学学报(中英文), 2023, 51(4): 511-518. doi: 10.1016/S1872-5813(22)60057-4
引用本文: 李宁, 李松波, 安胜利, 杜旭, 薛良美, 倪洋. Co掺杂La1.5Sr0.5Ni1−xCoxO4+δ阴极材料的制备及其电化学稳定性能[J]. 燃料化学学报(中英文), 2023, 51(4): 511-518. doi: 10.1016/S1872-5813(22)60057-4
LI Ning, LI Song-bo, AN Sheng-li, DU Xu, XUE Liang-mei, NI Yang. Preparation and electrochemical stability of Co-doped La1.5Sr0.5Ni1−xCoxO4+δ cathode materials[J]. Journal of Fuel Chemistry and Technology, 2023, 51(4): 511-518. doi: 10.1016/S1872-5813(22)60057-4
Citation: LI Ning, LI Song-bo, AN Sheng-li, DU Xu, XUE Liang-mei, NI Yang. Preparation and electrochemical stability of Co-doped La1.5Sr0.5Ni1−xCoxO4+δ cathode materials[J]. Journal of Fuel Chemistry and Technology, 2023, 51(4): 511-518. doi: 10.1016/S1872-5813(22)60057-4

Co掺杂La1.5Sr0.5Ni1−xCoxO4+δ阴极材料的制备及其电化学稳定性能

doi: 10.1016/S1872-5813(22)60057-4
基金项目: 国家自然科学基金(51974167)和内蒙古自治区高等学校科学研究项目(NJZZ22449)资助
详细信息
    通讯作者:

    E-mail: lisongbo@imust.edu.cn

  • 中图分类号: TM911.4

Preparation and electrochemical stability of Co-doped La1.5Sr0.5Ni1−xCoxO4+δ cathode materials

Funds: The project was supported by National Natural Science Foundation of China (51974167) and Scientific Research Program of Inner Mongolia higher education institutions (NJZZ22449)
  • 摘要:

    利用溶胶凝胶法合成了La1.5Sr0.5NiO4+δ掺杂Co的阴极材料La1.5Sr0.5Ni1−xCoxO4+δ (x=0、0.2、0.4、0.6)。通过X射线衍射、X射线光电子能谱、热重、热膨胀系数的测定和扫描电镜等技术探究了材料的相结构、元素组成、热力学性能和表面形貌。结果表明,所合成的样品为具有类钙钛矿型结构的单一纯相,掺杂Co元素使材料的热膨胀系数有所提高。将该材料应用于固体氧化物燃料电池(SOFC)阴极,进行了电导率及电化学阻抗谱的测定。结果发现,La1.5Sr0.5Ni1−xCoxO4+δ的电导率随着Co元素掺杂量的提高而升高,当 x = 0.4 时La1.5Sr0.5Ni0.6Co0.4O4+δ的电导率最高,达51.21 S/cm(800 ℃);当 x 值大于0.4时,其电导率明显下降。此外,La1.5Sr0.5Ni0.6Co0.4O4+δ在电化学阻抗谱测试中也呈现出了最低的极化电阻(4.180 Ω·cm2,700 ℃),表现出较好的电化学性能。

  • FIG. 2210.  FIG. 2210.

    FIG. 2210.  FIG. 2210.

    图  1  (a) LSNC-x (x=0、0.2、0.4、0.6) 的XRD谱图;(b) LSNC-x (x=0、0.2、0.4、0.6) 的XRD主峰放大谱图

    Figure  1  (a) XRD patterns of LSNC-x (x=0, 0.2, 0.4, 0.6);(b) Magnified XRD spectra of LSNC-x (x=0, 0.2, 0.4, 0.6)

    图  2  (a) LSNC-x (x=0、0.2、0.4、0.6) 在30−800 ℃的热膨胀曲线;(b) SDC在50−800 ℃的热膨胀曲线

    Figure  2  Thermal expansion curves of (a) LSNC-x (x = 0, 0.2, 0.4, 0.6) at 30–800 ℃ and (b) SDC at 50–800 ℃

    图  3  LSNC-x在400−800 ℃的电导率曲线

    Figure  3  Electrical conductivity of carious LSNC-x samples ( x = 0, 0.2, 0.4 and 0.6) at 400–800 ℃

    图  4  LSNC-x (x=0、0.2、0.4、0.6) 的XPS谱图

    Figure  4  XPS spectra of various LSNC-x samples ( x = 0, 0.2, 0.4 and 0.6)

    (a): O 1s;(b): Ni 2p;(c): Co 2p

    图  5  LSNC-x (x=0.2、0.4、0.6)为阴极的对称电池的SEM照片

    Figure  5  SEM images of symmetrical cells prepared with the LSNC-x materials (x =0.2, 0.4 and 0.6) as the cathode

    图  6  LSNC-x (x=0.2、0.4、0.6)阴极材料的TG曲线

    Figure  6  TGA curves of various LSNC-x samples (x = 0.2, 0.4 and 0.6)

    图  7  (a) LSNC-x (x=0、0.2、0.4、0.6)在700 ℃时的交流阻抗谱; (b) LSNC-0.4在不同温度下的电化学阻抗谱

    Figure  7  (a) Electrochemical impedance spectra of various LSNC-x samples at 700 ℃ and (b) Electrochemical impedance spectra of LSNC-0.4 at different temperatures

    表  1  LSNC-x晶体结构的晶胞参数

    Table  1  Cell parameters of crystal structure of various LSNC-x materials

    Sample a b c V
    La1.5Sr0.5NiO4+δ3.812543.8125412.74016185.184
    La1.5Sr0.5Co0.2Ni0.8O4+δ 3.81936 3.81936 12.70324 185.30
    La1.5Sr0.5Co0.4Ni0.6O4+δ 3.82437 3.82437 12.68348 185.506
    La1.5Sr0.5Co0.6Ni0.4O4+δ3.827683.8276812.66534185.590
    下载: 导出CSV

    表  2  四组样品和SDC的热膨胀系数值

    Table  2  CTE values of SDC and four La1.5Sr0.5Ni1−xCoxO4+δ samples

    SamplexThermal expansion
    coefficient (10−6 K−1)
    La1.5Sr0.5NiO4+δ011.82
    La1.5Sr0.5Ni0.8Co0.2O4+δ0.214.95
    La1.5Sr0.5Ni0.6Co0.4O4+δ0.415.53
    La1.5Sr0.5Ni0.4Co0.6O4+δ0.617.66
    Sm0.2Ce0.8O1.9SDC13.43
    下载: 导出CSV

    表  3  LSNC-x x=0、0.2、0.4、0.6)的XPS谱图O 1s峰拟合

    Table  3  Fitting results of O 1s XPS spectra of various LSNC-x samples

    SampleOmoisture /eVOadsorbed /eVOvacancy /eVOlattice /eV(Oadsorbed + Ovacancy)/Olattice
    LSN532.46531.48530.60528.902.78
    LSNC0.2532.28531.28530.94528.733.17
    LSNC0.4532.12531.13530.97528.353.24
    LSNC0.6532.10531.45530.88529.123.26
    下载: 导出CSV

    表  4  LSNC-xx=0、0.2、0.4、0.6)的XPS谱图Ni 2p峰拟合

    Table  4  Fitting results of Ni 2p XPS spectra of various LSNC-x samples

    SampleNi3+ 2p1/2 /eVNi2+ 2p1/2 /eVNi3+ 2p3/2 /eVNi2+ 2p3/2 /eVNi3+ /%Ni2+ /%
    LSN862.24860.70855.38851.6056.2543.75
    LSNC0.2862.20860.72855.49851.6149.5350.48
    LSNC0.4862.25860.74855.21851.5449.4750.53
    LSNC0.6862.26861.01855.39851.6840.7759.23
    下载: 导出CSV

    表  5  LSNC-xx=0、0.2、0.4、0.6)的XPS谱图Co 2p峰拟合

    Table  5  Fitting results of Co 2p XPS spectra of various LSNC-x samples

    Sample$ {\text{Co}}^{3 + }\;{2p_{{1/2}}} $ /eV$ {\text{Co}}^{2 + }\;{2p_{{1/2}}} $ /eV$ {\text{Co}}^{3 + }\;{2p_{{3/2}}} $$ {\text{Co}}^{2 + }\;{2p_{{3/2}}} $ /eV${\text{Co} }^{3 + }\text{}$ /%${\text{Co} }^{2 + }\text{}$ /%
    LSNC0.2795.47796.82780.47782.0194.405.610
    LSNC0.4795.22796.89780.38782.0385.0614.94
    LSNC0.6795.52796.71780.41782.1367.2332.77
    下载: 导出CSV

    表  6  LSNC-x (x=0、0.2、0.4、0.6)在700 的极化电阻值

    Table  6  Polarization resistance values of various LSNC-x samples at 700 ℃

    SamplePolarization resistance value /
    (Ω·cm2
    La1.5Sr0.5NiO4 + δ4.426
    La1.5Sr0.5Ni0.8Co0.2O4 + δ4.355
    La1.5Sr0.5Ni0.6Co0.4O4 + δ4.180
    La1.5Sr0.5Ni0.4Co0.6O4 + δ6.238
    下载: 导出CSV
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  • 收稿日期:  2022-06-13
  • 修回日期:  2022-07-19
  • 录用日期:  2022-07-25
  • 网络出版日期:  2022-08-15
  • 刊出日期:  2023-04-15

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