Co掺杂La1.5Sr0.5NiO4 + δ阴极材料的制备及电化学稳定性能研究

李宁; 李松波; 安胜利; 杜旭; 薛良美; 倪洋

doi:10.1016/S1872-5813(22)60057-4

Co掺杂La_1.5Sr_0.5NiO_{4 + δ}阴极材料的制备及电化学稳定性能研究

doi: 10.1016/S1872-5813(22)60057-4

1.
内蒙古科技大学化学与化工学院, 内蒙古包头 014010
2.
内蒙古科技大学材料与冶金学院, 内蒙古包头 014010

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

作者简介:
李松波(1972–)，教授，通讯联系人，Email: lisongbo@imust.edu.cn

中图分类号: TM911.4
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- 被引次数: 0
出版历程
- 收稿日期: 2022-06-13
- 录用日期: 2022-07-25
- 修回日期: 2022-07-19
- 网络出版日期: 2022-08-15

Preparation and electrochemical stability performance of Co doped La_1.5Sr_0.5NiO_{4 + δ} cathode materials

1.
School of Chemistry and Chemical Engineering, Inner Mongolia University of Science & Technology, Inner Mongolia Baotou 014010, China
2.
School of Metallurgical and Material Engineering, Inner Mongolia University of Science & Technology, Inner Mongolia Baotou 014010, China

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

摘要: 利用溶胶凝胶法合成了Co掺杂La_1.5Sr_0.5NiO_{4 + δ}的阴极材料La_1.5Sr_0.5Ni_1−xCo_xO_{4 + 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SEM探究了材料的相结构、元素组成、热力学性能和表面形貌。实验结果表明，全部试样均成功合成出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增加。为了探究材料应用于SOFC阴极的可行性，进行了电导率及电化学阻抗谱的测定。电导率随着Co元素掺杂量的提高而升高，800 ℃时La_1.5Sr_0.5Ni_0.6Co_0.4O_{4 + δ}电导率最高，为51.21 S/cm，当Co的掺杂量大于0.4时，电导率明显下降。该材料在电化学阻抗谱测试中也呈现出了最低的极化电阻，在700 ℃时其值为4.180 Ω·cm²，表现出较好的优于其他部分材料的电化学性能。
- 固体氧化物燃料电池 /
- 类钙钛矿 /
- 阴极材料
Abstract: The cathode material La_1.5Sr_0.5Ni_1−xCo_xO_{4 + δ} (x=0, 0.2, 0.4, 0.6) of Co doping La_1.5Sr_0.5NiO_{4 + δ} (x = 0, 0.2, 0.4, 0.6) is synthesized using a sol gel method. Through the measurement of X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric, the thermal expansion coefficient, the scanning electron microscope tests the phase structure, elements, thermodynamic properties, and surface morphology of the material. The result shows, all samples successfully synthesized a single pure phase with perovskite-like structure, the doping of Co elements has increased the thermal expansion coefficient of the material. In order to explore the material to be used in the feasibility of the SOFC cathode, the measurement of electrical conductivity and electrochemical impedance spectroscopy was carried out. Conductivity increases with the increase of Co element doping, at 800 ℃, La_1.5Sr_0.5Ni_0.6Co_0.4O_{4 + δ} conductivity is the highest, with 51.21 S/cm, when the value of Co is greater than 0.4, the conductivity is significantly reduced. The material also exhibits the lowest polarization resistance in electrochemical impedance spectrum test, at 700 ℃ value of 4.180 Ω·cm², exhibits better electrochemical properties.
- solid oxide fuel cell /
- perovskite-like structure /
- cathode material

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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)

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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 (a) Thermal expansion curves of LSNC-x (x=0, 0.2, 0.4, 0.6) samples at 30−800 ℃; (b) thermal expansion curves of SDC at 50−800 ℃

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图 3 LSNC-x在400−800 ℃的电导率曲线

Figure 3 Curves of electrical conductivity for LSNC-x (x=0, 0.2, 0.4, 0.6) samples at 400−800 ℃

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图 4 LSNC-x（x=0、0.2、0.4、0.6）的XPS谱图

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

(a): O 1s；(b): Ni 2p；(c): Co 2p

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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 with LSNC-x (x =0.2, 0.4, 0.6) as cathodes

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图 6 LSNC-x (x=0.2、0.4、0.6)阴极材料的TG曲线

Figure 6 TG curves of LSNC-x (x=0.2, 0.4, 0.6) cathode materials

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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 spectroscopy of LSNC-x (x=0, 0.2, 0.4, 0.6) at 700 ℃; (b) Electrochemical impedance spectra of LSNC-0.4 at different temperatures

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表 1 LSNC-x晶体结构的晶胞参数

Table 1 Cell parameters of LSNC-x crystal structure

Crystal cell parameter	La_1.5Sr_0.5NiO_{4 + δ}	La_1.5Sr_0.5Co_0.2Ni_0.8O_{4 + δ}	La_1.5Sr_0.5Co_0.4Ni_0.6O_{4 + δ}	La_1.5Sr_0.5Co_0.6Ni_0.4O_{4 + δ}
a/ai	3.81254	3.81936	3.82437	3.82768
b/ai	3.81254	3.81936	3.82437	3.82768
c/ai	12.74016	12.70324	12.68348	12.66534
V/ai³	185.184	185.30	185.506	185.590

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表 2 四组样品和SDC的热膨胀系数值

Table 2 Thermal expansion coefficient values of four groups of samples and SDC

x	Sample	Coefficient of thermal expansion
0	La_1.5Sr_0.5NiO_{4 + δ}	11.82 × 10⁻⁶ K⁻¹
0.2	La_1.5Sr_0.5Ni_0.8Co_0.2O_{4 + δ}	14.95 × 10⁻⁶ K⁻¹
0.4	La_1.5Sr_0.5Ni_0.6Co_0.4O_{4 + δ}	15.53 × 10⁻⁶ K⁻¹
0.6	La_1.5Sr_0.5Ni_0.4Co_0.6O_{4 + δ}	17.66 × 10⁻⁶ K⁻¹
SDC	Sm_0.2Ce_0.8O_1.9	13.43 × 10⁻⁶ K⁻¹

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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 peak of LSNC-x XPS graph (x=0, 0.2, 0.4, 0.6)

Sample	O_moisture /eV	O_adsorbed /eV	O_vacancy /eV	O_lattice /eV	(O_adsorbed + O_vacancy)/O_lattice
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

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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 peak of LSNC-x XPS graph (x=0, 0.2, 0.4, 0.6)

Sample	Ni³⁺ 2p_1/2	Ni³⁺ 2p_1/2	Ni³⁺ 2p_1/2	Ni³⁺ 2p_1/2	Ni³⁺ 2p_1/2	Ni³⁺ 2p_1/2
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

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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 peak of LSNC-x XPS graph (x=0, 0.2, 0.4, 0.6)

Sample	$ {\text{Co}}^{3 + }\;{2p_{{1/2}}} $	$ {\text{Co}}^{2 + }\;{2p_{{1/2}}} $	$ {\text{Co}}^{3 + }\;{2p_{{3/2}}} $	$ {\text{Co}}^{2 + }\;{2p_{{3/2}}} $	$ {\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

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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 LSNC-x (x=0, 0.2, 0.4, 0.6) at 700 ℃

x	Sample	Polarization resistance value /（Ω·cm²）
0	La_1.5Sr_0.5NiO_{4 + δ}	4.426
0.2	La_1.5Sr_0.5Ni_0.8Co_0.2O_{4 + δ}	4.355
0.4	La_1.5Sr_0.5Ni_0.6Co_0.4O_{4 + δ}	4.180
0.6	La_1.5Sr_0.5Ni_0.4Co_0.6O_{4 + δ}	6.238

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表 7 与已有阴极材料极化电阻对比表

Table 7 Comparison of polarization resistance with existing cathode materials

Cathode material	Polarization resistance value /（Ω·cm²）
La_1.5Sr_0.5Ni_0.6Co_0.4O_{4 + δ}	4.18
La1.8Sr0.2NiO_{4 + δ}	5.31
La1.4Sr0.6NiO_{4 + δ}	7.62

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