直接甲烷固体氧化物燃料电池Ni-BZCYYb阳极抗积炭性能研究

吕秀清; 孙海珍; 安静; 张保柱; 何婧; 陈绘丽

doi:10.19906/j.cnki.JFCT.2022094

直接甲烷固体氧化物燃料电池Ni-BZCYYb阳极抗积炭性能研究

doi: 10.19906/j.cnki.JFCT.2022094

吕秀清^1,,
孙海珍^2,,
安静^{1, 3,},
张保柱^1,,
何婧^1,,
陈绘丽^3, ,

1.
晋中学院化学化工系, 山西晋中 030619
2.
中国科学院山西煤炭化学研究所煤转化国家重点实验室公共技术服务中心, 山西太原 030001
3.
山西大学分子科学研究所能量转换与存储材料山西省重点实验室, 山西太原 030006

基金项目: 晋中学院博士科研启动经费和山西省高等学校教学改革创新项目（J2021638）资助

详细信息

通讯作者:
Tel: + 86-18636860248, E-mail: huilichen@sxu.edu.cn

中图分类号: TM911.44
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出版历程
- 收稿日期: 2022-11-16
- 修回日期: 2022-12-09
- 录用日期: 2022-12-20
- 网络出版日期: 2022-12-26
- 刊出日期: 2023-04-15

Improved coking resistance of direct methane solid oxide fuel cell with Ni-BZCYYb anode

LÜ Xiu-qing^1
,,
SUN Hai-zhen^2
,,
AN Jing^{1, 3
,},
ZHANG Bao-zhu^1
,,
HE Jing^1
,,
CHEN Hui-li^{3
, ,}

1.
Department of Chemistry and Chemical Engineering, Jinzhong University, Jinzhong 030619, China
2.
Analytical Instrumentation Center, State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
3.
Institute of Molecular Science, Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Shanxi University, Taiyuan 030006, China

Funds: The project was supported by the Ph. D. Research Funding of Jinzhong University and Teaching Reform and Innovation Program of Higher Education in Shanxi Province (J2021638).

摘要

摘要:
直接以甲烷（CH₄）为燃料的固体氧化物燃料电池（Solid Oxide Fuel Cell，SOFC）具有操作系统简单、发电效率高、环境友好等优点，但传统镍基阳极使用CH₄时极易产生积炭，导致电池性能下降甚至破裂。因此，如何有效抑制积炭的产生是目前镍基阳极面临的重要挑战。本文针对传统Ni - Y_0.08Zr_0.92O_2−δ（Ni-YSZ）阳极使用CH₄时存在严重的积炭行为，采用质子导体BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ（BZCYYb）代替氧离子导体YSZ，考查了Ni-BZCYYb对CH₄水蒸气重整反应的催化活性和抗积炭性能，同时与Ni-YSZ进行比较。以Ni-BZCYYb为阳极的SOFC，在700–600 ℃、湿CH₄（97% CH₄-3% H₂O）为燃料时取得了较好的电化学性能，同时，该电池在600 ℃、恒电流密度下稳定运行100 h电压没有明显降低。但以Ni-YSZ为阳极的SOFC在相同条件运行不到6 h电压降为零。通过对比表明，BZCYYb提高了阳极的抗积炭能力，Ni-BZCYYb可以应用于以CH₄为燃料的SOFC中，是优异的抗积炭阳极材料。
- SOFC /
- 甲烷重整 /
- Ni-BZCYYb阳极 /
- 抗积炭
Abstract:
Solid oxide fuel cell (SOFC) is a promising power-generation device. Direct operation of SOFC on methane has several important advantages, such as simple system, high efficiency and low emissions. The challenge of the state-of-the-art nickel cermet anode is prone to coke formation when operating on methane, which may cause rapidly deteriorate of the performance and durability on SOFC. In this work, the anode Ni-BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ (BZCYYb) was investigated for wet methane (97% CH₄-3% H₂O) conversion in the temperature range of 700 to 600 ℃. The Ni-BZCYYb anode showed a good electrochemical performance for the steam reforming of methane. Furthermore, under a constant current density, a good operational stability was achieved at 600 ℃ for 100 h operating. For comparison, a conventional Ni-YSZ anode was also prepared, the voltage of cell dropped to zero after feeding wet CH₄ for ~ 6 h. These results indicate that the Ni-BCZYYb is a good candidate as the anode in SOFC on methane fuel.
- SOFC /
- methane reforming /
- Ni-BZCYYb anode /
- coking resistance

HTML全文

FIG. 2211. FIG. 2211.

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图 1 BZCYYb、BSCF和BSCF-BZCYYb (质量比1∶1) 混合粉体的XRD谱图

Figure 1 XRD patterns of BZCYYb, BSCF, and calcined BSCF-BZCYYb (1∶1 mass ratio)

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图 2 CH₄-H₂O (1∶1)条件下Ni-BZCYYb和Ni-YSZ对CH₄水蒸气重整反应的催化活性(a)；800 ℃时的稳定性测试 (b)

Figure 2 Catalytic activity of Ni-BZCYYb and Ni-YSZ for steam reforming of CH₄ (a); Time dependence of CH₄ conversion rate under CH₄-H₂O (1∶1) gas mixture for Ni-BZCYYb and Ni-YSZ at 800 ℃ (b)

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图 3 Ni-BZCYYb和Ni-YSZ在湿CH₄气氛中处理后的TG曲线

Figure 3 Thermogravimetric analysis of Ni-BZCYYb and Ni-YSZ powders pre-treated in wet CH₄ at 650 and 700 ℃

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图 4 新鲜电池和分别在650与700 ℃、湿CH₄中处理后的(a) Ni-YSZ|YSZ和(b)Ni-BZCYYb|BZCYYb半电池的照片

Figure 4 Digital photos of the fresh and treated cells in wet CH₄ at 650 and 700 ℃ for 1 h (a) Ni-YSZ|YSZ and (b) Ni-BZCYYb|BZCYYb

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图 5 Ni-BZCYYb电池在700–600 ℃的 (a) I-V-P曲线和 (b) EIS曲线

Figure 5 (a) I-V-P curves and (b) EIS curves of Ni-BZCYYb cell in wet CH₄ from 700 to 600 ℃

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图 6 (a) Ni-BZCYYb和Ni-YSZ电池在600 ℃、0.3 A/cm²下的恒流放电曲线；(b) 恒流放电测试结束后两种电池形貌的照片

Figure 6 (a) Time-dependent voltage under a constant current density of 0.3 A/cm² at 600 ℃ of Ni-BZCYYb and Ni-YSZ; (b) The digital photographs of two cells after testing in wet CH₄

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图 7 Ni-YSZ电池 (a) 稳定性测试前和 (b) 稳定性测试后阳极表面的SEM照片和相应碳元素的EDS图

Figure 7 SEM images of anode surfaces and corresponding EDS mapping of carbon elemental for Ni-YSZ cell (a) the fresh H-reduced and (b) after operation with wet CH₄ under a 0.3 A/cm² current at 600 ℃

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图 8 Ni-BZCYYb电池 (a) 稳定性测试前和 (b) 稳定性测试后阳极表面的SEM照片和相应碳元素的EDS图

Figure 8 SEM images of anode surfaces and corresponding EDS mapping of carbon elemental for Ni-BZCYYb cell (a) the fresh H-reduced and (b) after operation with wet CH₄ under a 0.3 A/cm² current at 600 ℃

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表 1 分别在650和700 ℃下、湿CH₄中处理后的电池与新鲜电池之间的质量差

Table 1 Weight difference between the fresh cell and the treated cell in wet CH₄ at 650 and 700 ℃

Temperature t/℃	m₀ /g		m_t /g		100(m_t−m₀)/m₀ /%
Temperature t/℃	Ni-BZCYYb	Ni-YSZ	Ni-BZCYYb	Ni-YSZ	Ni-BZCYYb	Ni-YSZ
650	0.344	0.341	0.361	0.376	4.94	10.26
700	0.343	0.345	0.365	0.396	6.41	14.78
m₀: the weight of fresh cells; m_t: the weight of treated cells

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