Fabrication of Ni0.5Cu0.5Ba0.05Ox coated SDC stereoscopic anode by hard template method for solid oxide fuel cells
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摘要: 为在固体氧化物燃料电池中有效利用干甲烷为燃料，需制作多孔立体阳极。采用硬模板法和浸渍法制备Ni0.5Cu0.5Ba0.05Ox包覆管状SDC阳极材料（Ni0.5Cu0.5Ba0.05Ox/SDC），为作对比，用溶胶凝胶法制备粉末状Ni0.5Cu0.5Ba0.05Ox，机械混合SDC粉末制备Ni0.5Cu0.5Ba0.05Ox-SDC。将这两种阳极材料分别制作电解质支撑的单电池Ni0.5Cu0.5Ba0.05Ox/SDC|YSZ|LSM-YSZ与Ni0.5Cu0.5Ba0.05Ox-SDC|YSZ|LSM-YSZ，并进行发电性能测试以及长期稳定性实验。结果表明，800℃下，干甲烷环境中，Ni0.5Cu0.5Ba0.05Ox-SDC为阳极的单电池最大功率密度为324.99 mW/cm2，运行10 h后，电压下降5.60%；而以Ni0.5Cu0.5Ba0.05Ox/SDC为阳极的单电池最大功率密度达到384.54 mW/cm2，运行100 h后，电压未严重衰减。实验后阳极的SEM照片表明，Ni0.5Cu0.5Ba0.05Ox-SDC阳极内孔隙狭小，易被积炭堵塞；而Ni0.5Cu0.5Ba0.05Ox/SDC阳极呈立体多孔结构，有利于燃料气体与反应后气体的扩散。催化剂颗粒均匀地包覆在SDC纤维管表面，有利于增加三相界面，提高电池的稳定性。Abstract: The fabrication of porous and stereoscopic anode is crucial for the effective use of dry methane as fuel in solid oxide fuel cells (SOFCs). In this work, tubular SDC coated with Ni0.5Cu0.5Ba0.05Ox (Ni0.5Cu0.5Ba0.05Ox/SDC) was prepared by hard template method combined with wet impregnation method. For comparison, Ni0.5Cu0.5Ba0.05Ox powder was also prepared by sol-gel method and then mixed with SDC to get anode Ni0.5Cu0.5Ba0.05Ox-SDC. Corresponding electrolyte-supported unit cells Ni0.5Cu0.5Ba0.05Ox/SDC|YSZ|LSM-YSZ and Ni0.5Cu0.5Ba0.05Ox-SDC|YSZ|LSM-YSZ were then fabricated for the power generation performance and long-term stability test. Fueled with dry methane at 800℃ on a fuel cell with Ni0.5Cu0.5Ba0.05Ox-SDC as anode, the maximum power density is only 324.99 mW/cm2 and the voltage drops 5.60% after 10 h operation; however, with Ni0.5Cu0.5Ba0.05Ox/SDC as the anode, the maximum power density reaches 384.54 mW/cm2 and no degradation in voltage is observed for 100 h. As reveled by SEM, the narrow pores in Ni0.5Cu0.5Ba0.05Ox-SDC anode are prone to block by carbon deposition; in contrast, Ni0.5Cu0.5Ba0.05Ox/SDC has a three-dimensional porous structure for the diffusion of fuel and reactant gas. The surface of SDC fiber tube is coated by the catalyst particles, which can improve the three phase boundary and enhance the cell stability.
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Key words:
- solid oxide fuel cell /
- anode /
- hard template /
- carbon deposition /
- long term stability
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图 2 不同方法制备的复合阳极材料的XRD谱图
Figure 2 XRD patterns of the as-prepared anode materials by different methods
(a): Ni0.5Cu0.5Ba0.05Ox; (b): SDC; (c): Ni0.5Cu0.5Ba0.05Ox coating tubular SDC
图 3 不同单电池实验后阳极的EDS分析
Figure 3 EDS analysis for different anodes of unit cell after tests
(a): Ni0.5Cu0.5Ba0.05Ox-SDC； (b): Ni0.5Cu0.5Ba0.05Ox/SDC
图 4 不同方法制备的阳极材料的SEM照片
Figure 4 SEM images of the anode materials prepared by different methods
(a): Ni0.5Cu0.5Ba0.05Ox; (b): Ni0.5Cu0.5Ba0.05Ox coating tubular SDC
图 5 以Ni0.5Cu0.5Ba0.05Ox-SDC为阳极的单电池的发电性能
Figure 5 Power generating performances of unit cell with Ni0.5Cu0.5Ba0.05Ox-SDC as anode
(a): in hydrogen; (b): in dry methane ■, □: 800 ℃; ●, ○: 750 ℃; ▲, △: 700 ℃; ◆, ◇: 650 ℃
图 6 以Ni0.5Cu0.5Ba0.05Ox包覆管状SDC为阳极的单电池的发电性能
Figure 6 Power generating performances of unit cell with Ni0.5Cu0.5Ba0.05Ox/SDC as anode
(a): in hydrogen; (b): in dry methane ■, □: 800 ℃; ●, ○: 750 ℃; ▲, △: 700 ℃; ◆, ◇: 650 ℃
图 8 单电池实验后的阳极表面和截面照片
Figure 8 Surface (a), (c) and cross section (b), (d) SEM images of different anodes after performance tests
(a), (b): Ni0.5Cu0.5Ba0.05Ox-SDC； (c), (d): Ni0.5Cu0.5Ba0.05Ox/SDC
图 9 不同阳极的单电池运行后的积炭现象照片
Figure 9 Carbon deposition on the unit cells with different anodes after running
(a): Ni0.5Cu0.5Ba0.05Ox-SDC, 10 h； (b): Ni0.5Cu0.5Ba0.05Ox/SDC, 100 h
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