酸处理石墨化碳载体对燃料电池催化剂性能的影响

doi:10.7503/cjcu20160426

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (12): 2236.doi: 10.7503/cjcu20160426

酸处理石墨化碳载体对燃料电池催化剂性能的影响

闫海旭^1,², 杨美妮^1,², 曾浩^1,², 浦鸿汀³, 林瑞^1,²()

1. 同济大学新能源汽车工程中心, 上海 201804
2. 同济大学汽车学院, 上海 201804
3. 同济大学材料科学与工程学院, 上海 201804

收稿日期:2016-06-13 出版日期:2016-12-10 发布日期:2016-11-22
作者简介:联系人简介: 林瑞, 女, 博士, 教授, 主要从事新能源技术方向新材料及燃料电池技术研究. E-mail:ruilin@tongji.edu.cn
基金资助:
国家自然科学基金(批准号: 21276199)、中央高校基本科研基金(批准号: 0500219216)和同济大学青年英才计划攀登高层项目及高等学校学科创新引智计划项目(批准号: B08019)资助

Effect of Acid-treatment of Graphitized Carbon Supports on Performance of Fuel Cell Catalysts^†

YAN Haixu^1,², YANG Meini^1,², ZENG Hao^1,², PU Hongting³, LIN Rui^1,^2,^*()

1. Clean Energy Automotive Engineering Center, Tongji University, Shanghai 201804, China
2. School of Automotive Studies, Tongji University, Shanghai 201804, China
3. School of Materials Science and Engineering, Tongji University, Shanghai 201804, China

Received:2016-06-13 Online:2016-12-10 Published:2016-11-22
Contact: LIN Rui E-mail:ruilin@tongji.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.21276199), the Fundamental Research Funds for the Central Universities, China(No.0500219216), the Young Talents “Climbing” Program of Tongji University and the Programme of Introducing Talents of Discipline to Universities, China(No.B08019)

摘要/Abstract

摘要：

通过1700 ℃高温处理XC-72CB得到石墨化碳黑(GCB), 并采用酸处理对GCB碳载体进行官能团修饰. 透射电子显微镜(TEM)、 X射线粉末衍射(XRD)和拉曼光谱的结果显示, 酸处理后GCB的石墨化程度增加; N₂吸附-脱附结果证明GCB比表面积减小, 微孔数量减少; 热重分析结果表明, GCB热稳定性增强; 红外光谱和拉曼光谱结果显示, GCB表面引入了含氧官能团, 并同时保持了GCB的有序化结构. 采用循环伏安(CV)法和线性扫描伏安(LSV)法测试了不同预处理后催化剂的电化学性能, 表明其电化学活性表面积(ECSA, 75.25 m²/g)和质量比活性(MA, 0.093 A/mg)均高于商业Pt/C(JM)催化剂. TEM结果表明, 使用经过浓硫酸和浓硝酸混合酸处理的GCB(简称OGCB)作为载体得到的Pt/OGCB平均粒径为2.28 nm, 略小于商业Pt/C(JM)催化剂(约2.5 nm); 经5000周电化学循环伏安测试后, Pt/OGCB的电化学活性表面积衰减17.3%, 质量比活性衰减29.5%, 而Pt/C(JM)的ECSA衰减达到25.1%, MA衰减达到42.5%.

关键词: 质子交换膜燃料电池, 石墨化碳黑, 酸处理, 耐久性

Abstract:

The graphitized carbon black(GCB) was obtained by a high temperature(1700 ℃) treatment of the XC-72 commercial carbon black(XC-72 CB). The functional groups of GCB were modified by acid treatment. Transmission electron microscopy(TEM), X-ray diffraction, Raman spectrum and infrared spectroscopy displayed the GCB with acid treatment had a higher degree of graphitization. Oxygen-containing functional groups were introduced into the GCB surface and the ordered structure of the GCB was maintained at the same time. Nitrogen adsorption and desorption experiment showed the GCB had smaller specific surface area and less micropore compared to XC-72 CB. Thermogravimetric analysis showed that GCB had the better heat stability. Cyclic voltammetry and linear sweep voltammetry test showed that the electrochemical specific activity area(ECSA)(75.25 m²/g) and the mass activity(MA)(0.093 A/mg) of conc. H₂SO₄ and conc. HNO₃ treated GCB(abbreviated as OGCB) were higher than those of the commercial one. TEM showed the Pt/OGCB had an average particle diameter of 2.28 nm, smaller than the commercial one. After durability test of 5000 cycles, the ECSA and MA of Pt/OGCB decreased by 17.3% and 29.5%, respectively, smaller than those of Pt/C(JM)(25.1% and 42.5%). Both activity and durability performance of Pt/OGCB catalyst were better than those of commercial Pt/C(JM) catalyst in oxygen reduction reaction. In addition, in single cell test, the durability of Pt/OGCB catalyst was also better than that of the commercial catalyst. The results show that OGCB has a promising application prospect in the field of proton exchange membrane fuel cell(PEMFC) catalyst support.

Key words: Proton exchange membrane fuel cell, Graphitized carbon black, Acid treatment, Durability

中图分类号:

O646

TrendMD:

闫海旭, 杨美妮, 曾浩, 浦鸿汀, 林瑞. 酸处理石墨化碳载体对燃料电池催化剂性能的影响. 高等学校化学学报, 2016, 37(12): 2236.

YAN Haixu, YANG Meini, ZENG Hao, PU Hongting, LIN Rui. Effect of Acid-treatment of Graphitized Carbon Supports on Performance of Fuel Cell Catalysts^†. Chem. J. Chinese Universities, 2016, 37(12): 2236.

图/表 17

Fig.1 TEM image(A) and SAED pattern(B) of GCB

Fig.2 XRD patterns of XC-72 CB(a) and GCB(b)

Fig.3 Raman spectra of XC-72 CB(a) and GCB(b)

Table 1 Raman spectroscopy data of XC-72 CB before and after 1700 ℃ treatment

Sample	Half-peak width/cm^-1				I_D/I_G	I_2D/I_G
Sample	D	G		2D
XC-72 CB	260.3	84.1	898.9		3.72	0.85
GCB	45.7	58.3	48.6		0.64	1.39

Fig.4 TG(A) and DSC(B) curves of XC-72 CB(a) and GCB(b)

Fig.5 IR spectra of GCB before and after pretreatmenta. GCB; b. HNO3-GCB; c. H2SO4-GCB; d. OGCB.

Fig.6 Raman spectra of GCB before and after pretreatmenta. GCB; b. HNO3-GCB; c. H2SO4-GCB; d. OGCB.

Fig.7 TEM images of different catalysts(A) Pt/GCB; (B) Pt/HNO3-GCB; (C) Pt/H2SO4-GCB; (D) Pt/OGCB.

Fig.8 Particle size distribution of different catalysts(A) Pt/GCB; (B) Pt/HNO3-GCB; (C) Pt/H2SO4-GCB; (D) Pt/OGCB.

Fig.9 Full scan XPS spectra of the four catalysts(A), C1s XPS spectra of Pt/OGCB catalyst(B) and Pt4f XPS spectra of Pt/GCB(C), Pt/HNO3-GCB(D), Pt/H2SO4-GCB(E) and Pt/OGCB(F) catalyst(A) a. Pt/GCB; b. Pt/HNO3-GCB; c. Pt/H2SO4-GCB; d. Pt/OGCB.

Fig.10 CV curves of catalysts Pt/GCB(a), Pt/HNO3-GCB(b), Pt/H2SO4-GCB(c) and Pt/OGCB(d)

Fig.11 LSV curves of catalysts Pt/GCB(a), Pt/HNO3-GCB(b), Pt/H2SO4-GCB(c) and Pt/OGCB(d)

Fig.12 TEM images of Pt/OGCB catalysts and Pt/C(JM) after 5000 cycles accelerated durability tests(A) Pt/OGCB(after 5000 cycles); (B) Pt/C(JM)(fresh); (C) Pt/C(JM)(after 5000 cycles).

Fig.13 Prticle size distribution of Pt/OGCB catalysts and Pt/C(JM) after 5000 cycles accelerated durability tests(A) Pt/OGCB(after 5000 cycles); (B) Pt/C(JM)(fresh); (C) Pt/C(JM)(after 5000 cycles).

Fig.14 CV curves of catalysts befor(a) and after(b) 5000 cycles accelerated durability tests(A) Pt/OGCB; (B) Pt/C(JM).

Fig.15 LSV curves of catalysts before(a) and after(b) 5000 cycles accelerated durability tests(A) Pt/OGCB; (B) Pt/C(JM).

Fig.16 Single-cell performance of MEAPt/C(JM)(A) and MEAPt/OGCB(B)

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酸处理石墨化碳载体对燃料电池催化剂性能的影响

Effect of Acid-treatment of Graphitized Carbon Supports on Performance of Fuel Cell Catalysts^†

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酸处理石墨化碳载体对燃料电池催化剂性能的影响

Effect of Acid-treatment of Graphitized Carbon Supports on Performance of Fuel Cell Catalysts†

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Effect of Acid-treatment of Graphitized Carbon Supports on Performance of Fuel Cell Catalysts^†