Preparation and electrochemical stability of Co-doped La1.5Sr0.5Ni1−xCoxO4+δ cathode materials
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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。
Abstract:A series of Co-doped La1.5Sr0.5Ni1−xCoxO4+δ cathode materials ( x =0, 0.2, 0.4 and 0.6) were synthesized by sol-gel method and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), coefficient of thermal expansion (CTE) measurement and scanning electron microscope (SEM). The results suggest that all La1.5Sr0.5Ni1−xCoxO4+δ samples have a single pure phase with the perovskite-like structure and the doping with the Co element can increase the CTE value. Using La1.5Sr0.5Ni1−xCoxO4+δ as the cathode materials in the solid oxide fuel cell (SOFC), their electrical conductivity and electrochemical impedance spectroscopy were measured. The results indicate that the conductivity increases with the increase of Co doping amount and the La1.5Sr0.5Ni0.6Co0.4O4+δ sample with x = 0.4 displays the highest conductivity of 51.21 S/cm at 800 ℃; however, a higher content of Co (x > 0.4) leads to a decrease of the conductivity. In addition, La1.5Sr0.5N0.6Co0.4O4+δ exhibits the lowest polarization resistance of 4.180 Ω·cm2 in electrochemical impedance spectrum at 700 ℃, displaying its excellent electrochemical properties as the cathode materials.
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Key words:
- solid oxide fuel cell /
- perovskite-like structure /
- cathode material
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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/Å b/Å c/Å V/Å La1.5Sr0.5NiO4+δ 3.81254 3.81254 12.74016 185.184 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+δ 3.82768 3.82768 12.66534 185.590 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
Sample x Thermal expansion
coefficient (10−6 K−1)La1.5Sr0.5NiO4+δ 0 11.82 La1.5Sr0.5Ni0.8Co0.2O4+δ 0.2 14.95 La1.5Sr0.5Ni0.6Co0.4O4+δ 0.4 15.53 La1.5Sr0.5Ni0.4Co0.6O4+δ 0.6 17.66 Sm0.2Ce0.8O1.9 SDC 13.43 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
Sample Omoisture /eV Oadsorbed /eV Ovacancy /eV Olattice /eV (Oadsorbed + Ovacancy)/Olattice LSN 532.46 531.48 530.60 528.90 2.78 LSNC0.2 532.28 531.28 530.94 528.73 3.17 LSNC0.4 532.12 531.13 530.97 528.35 3.24 LSNC0.6 532.10 531.45 530.88 529.12 3.26 表 4 LSNC-x (x=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
Sample Ni3+ 2p1/2 /eV Ni2+ 2p1/2 /eV Ni3+ 2p3/2 /eV Ni2+ 2p3/2 /eV Ni3+ /% Ni2+ /% LSN 862.24 860.70 855.38 851.60 56.25 43.75 LSNC0.2 862.20 860.72 855.49 851.61 49.53 50.48 LSNC0.4 862.25 860.74 855.21 851.54 49.47 50.53 LSNC0.6 862.26 861.01 855.39 851.68 40.77 59.23 表 5 LSNC-x (x=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 ${\text{Co} }^{3 + }\text{}$ /% ${\text{Co} }^{2 + }\text{}$ /% LSNC0.2 795.47 796.82 780.47 782.01 94.40 5.610 LSNC0.4 795.22 796.89 780.38 782.03 85.06 14.94 LSNC0.6 795.52 796.71 780.41 782.13 67.23 32.77 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 ℃
Sample Polarization resistance value /
(Ω·cm2)La1.5Sr0.5NiO4 + δ 4.426 La1.5Sr0.5Ni0.8Co0.2O4 + δ 4.355 La1.5Sr0.5Ni0.6Co0.4O4 + δ 4.180 La1.5Sr0.5Ni0.4Co0.6O4 + δ 6.238 -
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