质子交换膜燃料电池催化层化学稳定性研究

doi:10.13208/j.electrochem.171101

电化学（中英文） ›› 2018, Vol. 24 ›› Issue (3): 227-234. doi: 10.13208/j.electrochem.171101

质子交换膜燃料电池催化层化学稳定性研究

高燕燕^1,2，侯明^1*，姜永燚^1,2，梁栋³，艾军¹，郑利民¹

1.中科院大连化学物理研究所，辽宁大连 116023; 2.中国科学院大学，北京 100039； 3.大连擎研科技有限公司，辽宁大连 116023

收稿日期:2017-11-01 修回日期:2017-11-21 出版日期:2018-06-28 发布日期:2017-12-26
通讯作者: 侯明 E-mail:houming@dicp.ac.cn
基金资助:
国家科技支撑计划项目（No. 2015BAG06B00）和国家重点研发计划（No.2016YFB0101302）资助

Chemical Stability Investigations of Catalyst Layer in PEMFC

GAO Yan-yan^1,2, HOU Ming^1*, JIANG Yong-yi^1,2, LIANG Dong³, AI Jun¹, ZHENG Li-min¹

1.Dalian Institute of Chemical Physics，Chinese Academy of Sciences, Dalian 116023, Liaoning, China; 2. University of Chinese Academy of Sciences, Beijing 100039, China; 3. Dalian Innoreagen Co., Ltd, Dalian 116023, Liaoning, China

Received:2017-11-01 Revised:2017-11-21 Published:2018-06-28 Online:2017-12-26
Contact: HOU Ming E-mail:houming@dicp.ac.cn

摘要/Abstract

摘要： 本文采用 Fenton 试剂离线加速衰减测试考察质子交换膜燃料电池（PEMFC）催化层的化学稳定性. 在经100 h Fenton 试剂处理后，氟离子流失测试和傅里叶红外光谱表征（ATR-FTIR）证明催化层中全氟磺酸离聚物（Nafion）发生了化学降解；通过透射电镜（TEM）观察到催化层中发生了明显的 Pt 颗粒团聚和炭载体腐蚀，与TEM表征相一致，循环伏安测试（CV）表明电化学活性面积（ECSA）降低了58%，并伴随着双电层区域的明显减少；FTIR测试进一步表征了炭载体的表面状态，并没有观察到明显的含氧官能团的产生，减少的炭载体可能以CO₂的形式释放出去. 全电池测试表明，自由基攻击对催化层组成和结构造成了明显损坏，显著增加了催化层中的质子传导阻力和局部气体传输阻力，导致全电池性能大幅降低.

关键词: 质子交换膜燃料电池, 催化层, 化学稳定性

Abstract:

This work was intended to study the effect of free radicals on the chemical stability of catalyst layer via ex situ accelerated stress test (AST). Fenton reagent was used as the free radical provider in this research. Apart from the decomposition of Nafion in catalyst layer, the agglomerated Pt nanoparticles and the corroded carbon support were also observed after being treated in Fenton reagent for 100 h. Firstly, the existence of fluoride (F) ions evidenced the chemical decomposation of Nafion after being attacked by trace radical species, which was supported by the intensity decrease in the C-F stretching and vibration peak (1250 cm^-1) observed in attenuated total reflection Fourier transform infrared (ATR-FTIR) spectrum. The transmission electron microscopic (TEM) studies showed that the severe Pt nanoparticles agglomeration and carbon support corrosion happened. To gain more insight, the cyclic voltammetry (CV), ATR-FTIR and single cell performance measurements were conducted. A large loss (58%) of the electrochemical active surface area (ECSA) was observed. Another meaningful finding was the reduced double layer region, which demonstrated the reduction of carbon support. Notably, further ATR-FTIR analysis revealed the disappearance in the spectra at 1719 cm^-1 ~ 1578 cm^-1 which were assigned to the hydroquinone-quinine (HQ-Q) redox couple on the oxidized carbon surface. On the bases of these results, it could be concluded that carbon support might be decayed by releasing CO₂ instead of forming oxides on its surface. Finally, the single cell performance data indicated an obvious performance loss in high current density range, due to the proton and local gas transport limitations in the decayed electrodes.

Key words: proton exchange membrane fuel cell, catalyst layer, chemical stability

中图分类号:

高燕燕，侯明，姜永燚，梁栋，艾军，郑利民. 质子交换膜燃料电池催化层化学稳定性研究[J]. 电化学（中英文）, 2018, 24(3): 227-234.

GAO Yan-yan, HOU Ming, JIANG Yong-yi, LIANG Dong, AI Jun, ZHENG Li-min. Chemical Stability Investigations of Catalyst Layer in PEMFC[J]. Journal of Electrochemistry, 2018, 24(3): 227-234.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.171101

https://electrochem.xmu.edu.cn/CN/Y2018/V24/I3/227

参考文献

[1] Wang H J, Li H, Yuan X Z(editors). PEM fuel cell failure mode analysis[M]. CRC Press, Boca Raton, the USA, 2011: 352.
[2] Kongkanand A, Zhang J X, Liu Z Y, et al. Degradation of PEMFC observed on NSTF electrodes[J]. Journal of The Electrochemical Society, 2014, 161(6): F744-F753.
[3] Gribov E N, Maltseva N V, Golovin V A, et al. A simple method for estimating the electrochemical stability of the carbon materials[J]. Interntional Journal of Hydrogen Energy, 2016, 41(40): 18207-18213.
[4] Zhao D, Yi B L. The effect of platinum in a Nafion membrane on the durability of the membrane under fuel cell conditions[J]. Journal of Power Sources, 2010, 195(15): 4606-4612.
[5] Zhang S S, Yuan X Z, Hin J N C, et al. A review of platinum-based catalyst layer degradation in proton exchange membrane fuel cells[J]. Journal of Power Sources, 2009, 194(2): 588-600.
[6] Zhang S S, Yuan X Z, Wang H J, et al. A review of accelerated stress tests of MEA durabilityin PEM fuel cells[J]. Interntional Journal of Hydrogen Energy, 2009, 34(1): 388-404.
[7] Ono L K, Yuan B, Heinrich H, et al. Formation and thermal stability of platinum oxides on size-selected platinum nanoparticles: Support effects[J]. Journal of Chemical Physics, 2010, 114(50): 22119-22133.
[8] Inoue M, Nakazawa A, Umeda M, et al. Effect of H₂O₂ on Pt electrode dissolution in H₂SO₄ solution based on electrochemical quartz crystal microbalance study[J]. Interntional Journal of Hydrogen Energy, 2012, 37(2): 1226-1235.
[9] Itaya H, Shironita S, Nakazawa A, et al. Effects of metal ions on Pt electrode dissolution in H₂SO₄ solution enhanced by the presence of H₂O₂[J]. Journal of Renewable and Sustainable Energy, 2014, 6: 043112.
[10] Kongkanand A, Ziegelbauer J M. Surface platinum electrooxidation in the presence of oxygen[J]. Journal of Physical Chemistry, 2012, 116(5): 3684-3693.
[11] Gribov E N, Maltseva N V, Golovin V A, et al. A simple method for estimating the electrochemical stability of the carbon materials[J]. Interntional Journal of Hydrogen Energy, 2016, 41(40): 18207-18213.
[12] Wang Y J, Fang B Z, Li H, et al. Progress in modified carbon support materials for Pt and Pt-alloy cathode catalysts in polymer electrolyte membrane fuel cells[J]. Progress in Materials Science, 2016, 82: 445-498.
[13] Arenz M, Zana A. Fuel cell catalyst degradation: Identical location electron microscopy and related methods[J]. Nano Energy, 2016, 29: 299-313.
[14] Eslamibidgoli M J, Eikerling M H. Atomistic mechanism of Pt extraction at oxidized surfaces: Insights from DFT[J]. Electrocatalysis, 2016, 7(4): 345-354.

[1]	陈浩杰, 唐美华, 陈胜利. 质子交换膜燃料电池阴极催化层疏水性优化[J]. 电化学（中英文）, 2023, 29(9): 2207061-.
[2]	黄龙, 徐海超, 荆碧, 李秋霞, 易伟, 孙世刚. 质子交换膜燃料电池铂基催化剂研究进展[J]. 电化学（中英文）, 2022, 28(1): 2108061-.
[3]	王睿卿, 隋升. PEMFC阴极催化层结构分析[J]. 电化学（中英文）, 2021, 27(6): 595-604.
[4]	魏荣强, 李世安, 刘艺辉, 杨治, 沈秋婉, 杨国刚. 流道与肋宽比对气体扩散层性能影响的数值研究[J]. 电化学（中英文）, 2021, 27(5): 579-585.
[5]	张焰峰, 肖菲, 陈广宇, 邵敏华. 基于非贵金属氧还原催化剂的质子交换膜燃料电池性能[J]. 电化学（中英文）, 2020, 26(4): 563-572.
[6]	潘晓娜, 刘丽来, 王治璞, 王丹, 李云, 杨培霞, 张锦秋, 安茂忠. 离子液体凝胶聚合物电解质的三元组分相互作用研究[J]. 电化学（中英文）, 2020, 26(3): 406-412.
[7]	杨智, 沈亚云, 周娥, 魏成玲, 秦好丽, 田娟. 前驱体中N含量对FeN/C催化剂氧还原活性的影响研究[J]. 电化学（中英文）, 2020, 26(1): 130-135.
[8]	饶妍，李赏，周芬，田甜，钟青，宛朝辉，谭金婷，潘牧. 低铂膜电极结构优化途径[J]. 电化学（中英文）, 2018, 24(6): 677-686.
[9]	刘勇，丁涵，司德春，彭杰，张剑波. 静电纺丝制备质子交换膜燃料电池催化剂层综述[J]. 电化学（中英文）, 2018, 24(6): 639-654.
[10]	郭建伟，王建龙. 电化学阻抗谱在质子交换膜燃料电池动态的先导应用[J]. 电化学（中英文）, 2018, 24(6): 687-696.
[11]	何大平，木士春. 质子交换膜燃料电池铂电催化剂稳定策略[J]. 电化学（中英文）, 2018, 24(6): 655-663.
[12]	池滨, 叶跃坤, 江世杰, 廖世军. 低温质子交换膜燃料电池自增湿膜电极研究进展[J]. 电化学（中英文）, 2018, 24(6): 628-638.
[13]	肖燕，常英杰，张伟，贾秋红. 启动工况下质子交换膜燃料电池动态性能仿真分析[J]. 电化学（中英文）, 2018, 24(2): 166-173.
[14]	汤永安, 代琳, 邹受忠. 铂合金纳米立方块催化剂的氧还原反应活性比较[J]. 电化学（中英文）, 2017, 23(2): 199-206.
[15]	蒋尚峰，衣宝廉. 有序化膜电极研究进展[J]. 电化学（中英文）, 2016, 22(3): 213-218.

质子交换膜燃料电池催化层化学稳定性研究

Chemical Stability Investigations of Catalyst Layer in PEMFC

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics