阳极支撑型锥管串接式直接碳固体氧化物燃料电池组的制备及性能

doi:10.15541/jim20230597

无机材料学报 ›› 2024, Vol. 39 ›› Issue (7): 819-827.DOI: 10.15541/jim20230597 CSTR: 32189.14.10.15541/jim20230597

所属专题：【能源环境】燃料电池(202409)

阳极支撑型锥管串接式直接碳固体氧化物燃料电池组的制备及性能

叶梓滨(), 邹高昌, 吴琪雯, 颜晓敏, 周明扬, 刘江()

华南理工大学环境与能源学院, 广州 510006

收稿日期:2023-12-27 修回日期:2024-02-18 出版日期:2024-07-20 网络出版日期:2024-03-08
通讯作者: 刘江, 教授. E-mail: Jiangliu@scut.edu.cn
作者简介:叶梓滨(1998-), 男, 硕士研究生. E-mail: 1193676345@qq.com
基金资助:
国家自然科学基金(91745203);国家自然科学基金(U1601207)

Preparation and Performances of Tubular Cone-shaped Anode-supported Segmented-in-series Direct Carbon Solid Oxide Fuel Cell

YE Zibin(), ZOU Gaochang, WU Qiwen, YAN Xiaomin, ZHOU Mingyang, LIU Jiang()

School of Environment and Energy, South China University of Technology, Guangzhou 510006, China

Received:2023-12-27 Revised:2024-02-18 Published:2024-07-20 Online:2024-03-08
Contact: LIU Jiang, professor. E-mail: Jiangliu@scut.edu.cn
About author:YE Zibin (1998-), male, Master candidate. E-mail: 1193676345@qq.com
Supported by:
National Natural Science Foundation of China(91745203);National Natural Science Foundation of China(U1601207)

摘要/Abstract

摘要：

针对阳极支撑型直接碳固体氧化物燃料电池(DC-SOFC)的浓差极化阻抗大的问题, 本研究采用改进后的凝胶注模法制备了阳极支撑型锥管状固体氧化物燃料电池(SOFC)。通过适当增加溶剂的含量, 改善了浆料的流动性, 提高了成品的质量; 通过增大造孔剂的含量, 提高了阳极的孔隙率, 减小了气体的扩散阻力。改进后的SOFC以氢气为燃料, 在800 ℃运行时, 开路电压为1.05 V, 电化学阻抗谱的极化阻抗更小, 电池的最大功率密度为0.67 W•cm^-2(阴极有效面积为2.2 cm²), 明显优于改进前的SOFC。改进后的SOFC直接采用担载质量分数5% K的活性炭为燃料, 在800 ℃运行时, 开路电压为1.030 V, 接近理论电压, 最大功率密度达0.74 W•cm^-2, 以400 mA进行恒流放电, 碳燃料的有效利用率为31%, 高于改进前电池的碳燃料的有效利用率17%。将改进后的4个锥管状单电池串联成电池组, 直接采用担载质量分数5% K催化剂的活性炭为燃料, 在800 ℃运行时, 最大功率达8.0 W, 高于改进前的4节DC-SOFC电池组(4.1 W), 该电池组碳燃料的有效利用率为15%, 峰值功率密度可达0.91 W•cm^-2, 超过了文献报道的最高值。

关键词: 直接碳固体氧化物燃料电池, 凝胶注模法, Boudouard反应, 锥管串接式, 钾催化剂

Abstract:

To solve the problem of large concentration polarization impedance of anode-supported direct carbon solid oxide fuel cell (DC-SOFC), tubular cone-shaped anode-supported segmented-in-series solid oxide fuel cell (SOFC) was prepared by an improved gel-casting method. By appropriately increasing content of the solvent, fluidity of the slurry and quality of the obtained product were improved. By increasing content of the pore-forming agent, the porosity of the anode was increased, reducing the diffusion resistance of gas. As-improved SOFC was fueled by hydrogen and operated at 800 ℃ with an open-circuit voltage of 1.05 V. The polarization impedance of the electrochemical impedance spectrum decreased while the maximum power density was 0.67 W•cm^-2 and the active area of the cathode was 2.2 cm². These SOFC electrochemical performances were significantly higher than that before improvement. Activated carbon loaded on the anode with 5% (in mass) K as catalyst was directedly used as the fuel of SOFCs. Using this anode-supported direct carbon, the DC-SOFC was prepared, showing an open circuit voltage of 1.030 V and a peak power density of 0.74 W•cm^-2 at 800 ℃. This DC-SOFC was discharged at a constant current of 400 mA, and its effective utilization rate of carbon fuel was 31% which was higher than that before improvement (17%). Four improved tubular cone-shaped single cells were connected in series to form a four-cell stack, showing a peak power of 8.0 W and a corresponding power density of 0.91 W•cm^-2 at 800 ℃, which was higher than that before improvement (4.1 W), exceeding the maximum of previous reported DC-SOFC, and displayed an effective utilization rate of 15% for carbon fuel.

Key words: direct carbon solid oxide fuel cell, gel-casting, Boudouard reaction, tubular cone-shaped segmented-in-series, potassium catalyst

中图分类号:

TQ174

叶梓滨, 邹高昌, 吴琪雯, 颜晓敏, 周明扬, 刘江. 阳极支撑型锥管串接式直接碳固体氧化物燃料电池组的制备及性能[J]. 无机材料学报, 2024, 39(7): 819-827.

YE Zibin, ZOU Gaochang, WU Qiwen, YAN Xiaomin, ZHOU Mingyang, LIU Jiang. Preparation and Performances of Tubular Cone-shaped Anode-supported Segmented-in-series Direct Carbon Solid Oxide Fuel Cell[J]. Journal of Inorganic Materials, 2024, 39(7): 819-827.

图/表 8

表S1 原料和化学试剂

Table S1 Raw materials and chemical reagents

化学试剂	生产公司	纯度
NiO	加拿大Inco公司	98%
YSZ	宜兴市熠辉耐磨材料有限公司	99.9%
丙烯酰胺	上海阿拉丁生化科技有限公司	分析纯
N, N'-亚甲基双丙烯酰胺	上海阿拉丁生化科技有限公司	分析纯
柠檬酸铵	上海麦克林生化科技有限公司	分析纯
聚乙二醇	上海阿拉丁生化科技有限公司	99.0%
邻苯二甲酸二辛酯	上海麦克林生化科技有限公司	99.0%
三乙醇胺	上海麦克林生化科技有限公司	99.0%
聚乙烯醇缩丁醛	上海阿拉丁生化科技有限公司	99.0%
Al₂O₃	淄博信富盟化工有限公司	99.0%
GDC	中国科学院宁波材料技术与工程研究所	99.50%
银导电胶DAD-87	上海合成树脂研究所	99.99%
粒状活性炭	上海阿拉丁试剂有限公司	触媒载体用
碳酸钾	上海麦克林生化科技有限公司	99%

图1 固体氧化物燃料电池的制备过程

Fig. 1 Preparation of solid oxide fuel cells (a) Illustration of process for preparing anode supports; (b) Photo of a series of tubular cone-shaped SOFCs at different preparation stages (2-6) in contrast to green anode support (1); (c) The segmented-in-series four-cell stack; The tubular cone-shaped SOFCs marked with 2-6 are pre-sintered anode support, anode support with a co-sintered functional layer, anode support coated with electrolyte layer, completed tubular cone-shaped cell with one end closed, and completed tubular cone-shaped cell with both ends open, respectively

图2 四节电池组测试示意图

Fig. 2 Illustration of testing system of the segmented-in-series four-cell stack

表1 凝胶注模成型浆料成分对比

Table 1 Comparison of the composition of gel-casting slurries

Component	Ref.[34]	Ref.[37]	This work
NiO-YSZ	49.7%	57.5%	44.2%
AM	7.9%	11.5%	7.1%
MBAM	0.8%	0.6%	0.9%
Deionized water	20.7%	17.2%	26%
Graphite	10%	11.5%	13.2%
AC	1.7%	-	1.3%
Polyacrylic acid	-	1.7%	-
TEA	1.0%	-	-
PEG-600	8.2%	-	7.3%

图3 工艺改进前后以氢气为燃料的SOFC单电池的电化学性能及其微观结构

Fig. 3 Electrochemical performance and microstructure of hydrogen-fueled SOFC single cell before and after process improvement (a, b) Output performances; (c) Electrochemical impedance spectra; (d) Comparison of the corresponding fitted resistances; (e, f) Microstructures of the SOFC observated by SEM. Colorful figures are available on website

图4 以担载质量分数5% K的活性炭为燃料的DC-SOFC单电池的电化学性能

Fig. 4 Electrochemical performance of a single DC-SOFC using 5% (in mass) K activated carbon (a) Output performances; (b) Open circuit voltages; (c) Electrochemical impedance spectra; (d) Comparison of the corresponding fitted resistances; (e) Discharge characteristics. Colorful figures are available on website

图5 测试后的DC-SOFC阳极微观结构

Fig. 5 Microstructure of the DC-SOFC anode after testing (a-d) Surface SEM image (a) and EDS mappings of K (b), C (c) and Ag (d); (e-g) Cross-sectional SEM image (e) and EDS mappings of K (f) and C (g)

图6 采用担载质量分数5% K活性炭作为燃料的锥管串接式电池组的(a)输出性能及(b)放电特性

Fig. 6 (a) Output performance and (b) discharge characteristic of the tubular cone-shaped segmented-in-series stack fueled by 5% (in mass) K-loaded activated carbon

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阳极支撑型锥管串接式直接碳固体氧化物燃料电池组的制备及性能

Preparation and Performances of Tubular Cone-shaped Anode-supported Segmented-in-series Direct Carbon Solid Oxide Fuel Cell

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