介孔碳载体缓解碱性聚电解质燃料电池阳极水淹

doi:10.1016/S1872-2067(23)64564-4

催化学报 ›› 2024, Vol. 57: 51-58.DOI: 10.1016/S1872-2067(23)64564-4

介孔碳载体缓解碱性聚电解质燃料电池阳极水淹

江文涌^a, 葛创新^c, 王功伟^a, 陆君涛^a, 肖丽^a^,^b^,^*(), 庄林^a^,^c^,^*()

^a武汉大学化学与分子科学学院, 化学电源材料与技术湖北省重点实验室, 湖北武汉 430072
^b武汉大学索维奇分子科学中心, 湖北武汉 430072
^c武汉大学高等研究院, 湖北武汉 430072

收稿日期:2023-09-20 接受日期:2023-11-12 出版日期:2024-02-18 发布日期:2024-02-10
通讯作者: * 电子信箱: chem.lily@whu.edu.cn (肖丽),lzhuang@whu.edu.cn (庄林).
基金资助:
国家自然科学基金(21991154);国家自然科学基金(21991150);国家自然科学基金(22122204);国家自然科学基金(21872108);武汉大学创新团队(2042022kf1174);武汉大学创新团队(2042022kf0029)

Alleviating anode flooding by mesoporous carbon supports for alkaline polymer electrolyte fuel cells

Wenyong Jiang^a, Chuangxin Ge^c, Gongwei Wang^a, Juntao Lu^a, Li Xiao^a^,^b^,^*(), Lin Zhuang^a^,^c^,^*()

^aCollege of Chemistry and Molecular Sciences, Hubei Key Laboratory of Electrochemical Power Sources, Wuhan University, Wuhan 430072, Hubei, China
^bSauvage Center for Molecular Sciences, Wuhan University, Wuhan 430072, Hubei, China
^cThe Institute for Advanced Studies, Wuhan University, Wuhan 430072, Hubei, China

Received:2023-09-20 Accepted:2023-11-12 Online:2024-02-18 Published:2024-02-10
Contact: * E-mail: chem.lily@whu.edu.cn (L. Xiao),lzhuang@whu.edu.cn (L. Zhuang).
Supported by:
National Natural Science Foundation of China(21991154);National Natural Science Foundation of China(21991150);National Natural Science Foundation of China(22122204);National Natural Science Foundation of China(21872108);Fundamental Research Funds for the Central Universities(2042022kf1174);Fundamental Research Funds for the Central Universities(2042022kf0029)

摘要/Abstract

摘要：

碱性聚电解质燃料电池(APEFCs)相较于目前研究最多的质子交换膜燃料电池(PEMFCs), 其优势体现在阴/阳两极均可使用价格低廉的非贵金属催化剂, 有望降低燃料电池的使用成本. APEFCs的研究在过去20年飞速发展, 主要集中在高效碱性聚电解质(APE)隔膜和阴/阳极催化剂等关键材料的研发. 目前, APEFCs的性能已接近于PEMFCs, 针对其研究也逐渐从关键材料的研发扩展到电池的稳定性和水管理等更深层次问题. 相较于PEMFCs, APEFCs的水管理问题更为复杂. 每当阳极产生4个水分子, 阴极会消耗2个水分子, 容易导致阴极缺水和阳极水淹, 进而影响电池的性能和稳定性. 对APEFCs水管理的优化将是实现电池性能和稳定性突破的重要方向.

本文主要研究碳载体对APEFCs水管理的影响, 合成了一系列介孔碳负载的Ru催化剂(Ru/MCP-x, x为MCP的孔径, x = 30, 50, 100 nm), 并以Ru/XC72催化剂为对照. 扫描电镜和N₂吸附-脱附结果表明, 介孔碳载体具有三维贯通的孔结构, 而XC72为实心碳颗粒. 溶液电化学测试结果表明, 不同催化剂在0.1 mol/L的KOH溶液中的氢氧化反应(HOR)活性相当. 以Ru/MCP-x和Ru/XC72为阳极催化剂进行电池装配(记为Ru/MCP-x电池和Ru/XC72电池), 结果表明, 当使用高进气流量(1000 mL/min)时, Ru/MCP-x电池和Ru/XC72电池性能接近; 当使用更接近实际工况的低进气流量(200 mL/min)时, 所有电池性能均有所下降, 且降幅存在明显差距. 其中, Ru/MCP-50电池和Ru/MCP-100电池的降幅分别为36%和35%, 而Ru/MCP-30电池和Ru/XC72电池的降幅分别为43%和72%. 通过在低进气流量下改变进气湿度, 结果发现, Ru/MCP-30电池和Ru/XC72电池性能大幅下降的原因是阳极发生水淹. 弛豫时间分布(DRT)方法可以将不同弛豫时间的极化过程在时域中分离开来, 从而可以分辨各极化过程对电池性能的影响. 利用电化学交流阻抗(EIS)技术结合DRT方法进一步分析各电池在不同电流密度下的阻抗行为, DRT结果表明, 在低进气流量下Ru/XC72电池的传质极化电阻显著高于Ru/MCP-x电池, 说明阳极水淹导致了Ru/XC72电池的气体传质受阻, 因而电池性能大幅下降. 当MCP孔径增加至50和100 nm时, 传质极化电阻在不同电流密度下始终处于较低水平, 电池未发生明显水淹. 这说明孔径的增加有效地缓解了低进气流量下阳极的水淹问题, 从而保持较高的电池性能.

综上, 本文利用EIS-DRT方法比较了不同阳极碳载体对APEFCs性能和气体传质极化电阻的影响, 表明介孔碳载体有利于缓解APEFCs中的阳极水淹问题, 具有作为阳极载体的潜力.

关键词: 钌, 介孔碳, 碱性聚电解质燃料电池, 水淹, 弛豫时间分布

Abstract:

Water management is one of the critical issues affecting the performance and stability of alkaline polymer electrolyte fuel cells (APEFCs). This study focuses on the effect of carbon supports on the water management of APEFCs. A series of carbon-supported Ru catalysts (Ru/MCP-x) were prepared using mesoporous carbon powder (MCP-x) with three-dimensional through-nanopore structures as supports and compared with Ru/XC72. The results show that although the catalysts’ hydrogen oxidation reaction (HOR) catalytic activities are similar in KOH solutions, the APEFCs performance can be severely different. APEFCs assembled with Ru/MCP-x and Ru/XC72 (noted as Ru/MCP-x cell and Ru/XC72 cell) have little performance difference at high inlet H₂ flow (1000 mL/min), but have a noticeable difference at low inlet H₂ flow (200 mL/min). By combining the electrochemical AC impedance and distribution of relaxation time (DRT) method, we quantitatively identify that severe gas transfer resistance occurred in the anode catalyst layer of the Ru/XC72 cell under low inlet H₂ flow, which is more in line with the actual APEFCs operating conditions, led to considerable degradation of the Ru/XC72 cell performance. The high gas transfer resistance is later ascribed to the anode flooding by combining the voltammetry curves and DRT plots. In contrast, for Ru/MCP-x cells, increasing the carbon supports' mesopore diameter dramatically reduced the gas transfer resistance and mitigated the anode flooding. This study shows a quantitative comparison of the impacts of different carbon supports on APEFCs performance and gas transfer resistance, indicating that mesoporous carbon materials have the potential to be supports for APEFCs anode catalysts to alleviate the anode flooding.

Key words: Ru, Mesoporous carbon, Alkaline polymer electrolyte fuel cell, Flooding, Distribution of relaxation time

江文涌, 葛创新, 王功伟, 陆君涛, 肖丽, 庄林. 介孔碳载体缓解碱性聚电解质燃料电池阳极水淹[J]. 催化学报, 2024, 57: 51-58.

Wenyong Jiang, Chuangxin Ge, Gongwei Wang, Juntao Lu, Li Xiao, Lin Zhuang. Alleviating anode flooding by mesoporous carbon supports for alkaline polymer electrolyte fuel cells[J]. Chinese Journal of Catalysis, 2024, 57: 51-58.

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图/表 5

Fig. 1. SEM images of MCP-30 (a), MCP-50 (b), MCP-100 (c) and XC72 (d). XRD patterns (e) and electron conductivity-pressure diagram (f) of MCP-30, MCP-50, MCP-100 and XC72.

Fig. 2. SEM images of Ru/MCP-30 (a), Ru/MCP-50 (b), Ru/MCP-100 (c) and Ru/XC72 (d). TEM images of Ru/MCP-30 (e), Ru/MCP-50 (f), Ru/MCP-100 (g), and Ru/XC72 (h). Inset plots of Figs. 2(e)-(h) are the particle size distribution of Ru nanoparticles.

Fig. 3. XRD patterns (a), thermogravimetric curves (b), LSV curves (c) and mass activity image (d) of Ru/XC72, Ru/MCP-30, Ru/MCP-50 and Ru/MCP-100.

Fig. 4. Cell performance with Ru/XC72, Ru/MCP-30,Ru/MCP-50 and Ru/MCP-100 as anode catalysts at inlet gas flow of 1000 (a) and 200 (b) mL/min. (c) The difference of peak power density of cells assembled with Ru/XC72, Ru/MCP-30, Ru/MCP-50 and Ru/MCP-100 as anode catalysts at inlet gas flow of 1000 and 200 mL/min. (d) Nyquist plot of cells assembled with Ru/XC72, Ru/MCP-30, Ru/MCP-50 and Ru/MCP-100 at 1 A/cm2.

Fig. 5. DRT curves of APEFC assembled with Ru/XC72 and Ru/MCP-50 as anode catalysts under the conditions of 0.25 A/cm2 (a), 0.5 A/cm2 (b), 0.75 A/cm2 (c) and 1 A/cm2 (d) at 200 mL/min intake gas flow.

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介孔碳载体缓解碱性聚电解质燃料电池阳极水淹

Alleviating anode flooding by mesoporous carbon supports for alkaline polymer electrolyte fuel cells

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