固体氧化物燃料电池LaxSr2-3x/2Fe1.5Ni0.1Mo0.4O6-δ阳极性能研究

doi:10.15541/jim20190225

摘要/Abstract

摘要：

本研究利用固相反应法合成了一系列镧取代La_xSr_2-3_x_/2Fe_1.5Ni_0.1Mo_0.4O_6-_δ (La_xSFNM, x=0, 0.1, 0.2, 0.3, 0.4)钙钛矿陶瓷材料, 并研究其作为固体氧化物燃料电池阳极的电化学性能。X射线衍射(XRD)测试表明合成的粉末具有立方钙钛矿结构。在高温下利用氢气还原La_xSFNM样品, 发现其晶粒表面析出纳米尺度的Fe-Ni合金颗粒, 并且偏析纳米颗粒的密度随着La ³⁺掺杂量的增加而显著降低。在对称电池阻抗测试中, 随着La ³⁺掺杂量的增加, 阳极极化阻抗逐渐降低, 掺入量为0.3时阻抗达到最小值。La_0.3SFNM对称电池在750 ℃下极化阻抗仅为0.16 W?cm ², 进一步增加掺杂量时, La_0.4SFNM对称电池极化阻抗增加至0.17 W?cm ²。La_0.3SFNM材料良好的电极反应催化活性源于适当分布的Fe-Ni合金纳米偏析颗粒与La_xSFNM陶瓷基体的共同作用。利用流延法制备一系列以La_xSFNM为阳极、SmBa_0.5Sr_0.5Co₂O₆为阴极、LSGM为电解质的单电池, 使用氢气作为燃料时, La ³⁺掺杂量x=0.3的单电池表现出最高的功率密度, 在750、650和550 ℃时峰值功率密度可达1.26、0.90和0.52 W·cm ^-2。上述结果表明, La_0.3Sr_1.55Fe_1.5Ni_0.1Mo_0.4O_6-_δ可以用作高性能SOFC阳极催化剂。

关键词: 固体氧化物燃料电池, 阳极材料, 高温原位脱溶

Abstract:

Lanthanum-substituted La_xSr_2-3_x_/2Fe_1.5Ni_0.1Mo_0.4O_6-_δ (La_xSFNM, x=0, 0.1, 0.2, 0.3, 0.4) oxides were synthesized by the solid-state reaction method, and investigated as potential anodes for Solid Oxide Fuel Cells(SOFC). X-ray diffraction patterns of as-synthesized powders confirm the formation of the cubic perovskite structure. Reduction in H₂ promotes the segregation of nano-scale metallic Fe-Ni alloy particles on the grain surfaces. Scanning electron microscopy observations indicate that increasing La ³⁺ dopants results in a decrease in the density of the exsolved nanoparticulates. Based upon impedance measurements on symmetrical fuel cells, the anode polarization resistance decreases with the La ³⁺ dopant increasing, and attains a minimal value of 0.16 W?cm ² for La_0.3SFNM at 750 ℃, followed by a slight increase to 0.17 W?cm ² for La_0.4SFNM. The highest catalytic activity of La_0.3SFNM toward electro- oxidation of hydrogen fuels could be ascribed to the synergy between the exsolved Fe-Ni alloy nanoparticulates and the supporting La_xSFNM oxides. Thin La_0.9Sr_0.1Ga_0.8Mg_0.2O₃(LSGM) electrolyte fuel cells with La_0.3SFNM anodes and SmBa_0.5Sr_0.5Co₂O₆ cathodes exhibit the highest power densities, e.g., 1.26, 0.90 and 0.52 W?cm ^-2 at 750, 650 and 550 ℃, respectively. These results demonstrate La_0.3SFNM oxide as a promising high performance SOFC anode.

Key words: Solid Oxide Fuel Cells, anode materials, in-situ exsolution

中图分类号:

TM911

夏天, 孟燮, 骆婷, 占忠亮. 固体氧化物燃料电池La_xSr_2-3_x_/2Fe_1.5Ni_0.1Mo_0.4O_6-_δ阳极性能研究[J]. 无机材料学报, 2020, 35(5): 617-622.

XIA Tian, MENG Xie, LUO Ting, ZHAN Zhongliang. La ³⁺-substituted Sr₂Fe_1.5Ni_0.1Mo_0.4O_6-_δ as Anodes for Solid Oxide Fuel Cells[J]. Journal of Inorganic Materials, 2020, 35(5): 617-622.

图/表 7

Fig. 1 Room temperature XRD patterns of LaxSFNM (x=0, 0.1, 0.2, 0.3, 0.4) (a) After calcination at 1200 ℃ for 12 h; (b) Reduced in wet H2 (3vol% H2O) at 750 ℃ for 12 h

Fig. 2 Surface morphologies of (a) SFNM ceramic pellets before reduction and (b-f) LaxSFNM ceramic pellets after reduction in humidified 10vol% H2/N2 (3vol% H2O) at 750 ℃ for 4 h (b) SFNM; (c) La0.1SFNM; (d) La0.2SFNM; (e) La0.3SFNM; (f) La0.4SFNM

Fig. 3 (a) SEM image of reduced La0.3SFNM ceramic surface and (b-g) elemental mapping of La (b, blue), Sr (c, magenta), Fe (d, red), Ni (e, yellow), Mo (f, brown) and O (g, green)

Fig. 4 (a) Nyquist and (b) Bode plots of impedance data for symmetrical anode fuel cells, i.e., Nano-LaxSFNM@LSGM | LSGM | Nano-LaxSFNM@LSGM, operating in humidified H2 (3vol% H2O, 100 mL·min-1) at 750 ℃, (c) distributions of relation time (DRT) plots of the data shown in (a) and (b)

Fig. 5 (a) Cross-sectional micrograph of measured fuel cell (Nano-La0.3SFNM@LSGM|LSGM|Nano-SBSCO@LSGM), and (b) high magnification view of the impregnated catalyst

Fig. 6 (a) Voltage and power density versus current density for the functioning fuel cell (Nano-La0.3SFNM@LSGM|LSGM| Nano-SBSCO@LSGM), measured in 97vol% H2-3vol% H2O at 100 sccm; (b) Peak power densities at different temperatures for single cells with varied LaxSFNM anodes

Fig. 7 Cell voltage as a function of operation time for the single fuel cell (Nano-La0.3SFNM@LSGM|LSGM|Nano-SBSCO@LSGM), operated under constant current density at 550 and 650 ℃

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