PEM燃料电池Pt/C电催化剂制备和性能研究
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摘要
质子交换膜燃料电池（PEMFC）具有高能量密度、运行温度低和稳定性能
较好等优点，在航天领域、潜艇、电动车、飞船等领域有广泛的应用前景。目前，
虽然 PEMFC 的各项技术已经趋于成熟，正处于大规模商业化应用的前夜。为使
PEMFC 能够早日实现商品化生产，各国科研工作者正在致力于相关材料的研究，
力图降低 PEMFC 成本，提高相关材料的性能。其中包括高性能 Pt/C 电催化剂的
研究。
本实验研究了 Pt/C 电催化剂制备的浸渍还原法，其中主要包括载体碳黑的
热处理技术。通过优化碳黑热处理的工艺条件，如温度和环境，使碳黑载体的性
能得到明显改善。采用 TEM、XRD、XPS、CV、MEA 等测试手段对所制备的
Pt/C 电催化剂性能进行了全面的分析。Pt/C 电催化剂的 TEM 照片显示，采用氮
气氛中 600℃热处理的碳黑载体制备的 Pt/C 催化剂中 Pt 颗粒的平均粒径为
3.3nm，降低了约 1nm；分散度也有了一定的提高。碳载体的 XRD 和 XPS 测试
说明，热处理使碳载体表面组成发生了变化，使其更有利于生成颗粒细小且均匀
的 Pt/C 电催化剂。
本实验还研究了胶体法制备 Pt/C 电催化剂的相关工艺。研究工作包括胶体
的稳定性和不同的还原剂和浓度对 Pt/C 电催化剂性能的影响。采用经优化的胶
体法制备工艺，所制备的 Pt/C 电催化剂中 Pt 颗粒的平均粒径为 3.05nm，已经接
近 Johnson Mattey 公司的 Pt/C 电催化剂水平。
为了提高催化活性和防止催化剂在使用过程中的团聚，本实验还初步探讨了
在Pt/C电催化剂中引入金属助剂Re。实验采用分步浸渍还原法，在制备过程中首
先用Fe/H2SO4把KReO4还原成Re的氧化物ReO3， 然后用H2在高温下把ReO3还原
成Re，最后在Re/C上沉积Pt得到PtRe/C电催化剂。采用循环伏安法表征了PtRe/C
电催化剂的性能，证明了其较好的电催化活性。
The proton exchange membrane fuel cell (PEMFC) is a highly attractive power
source for mobile and stationary applications due to its high power density at lower
temperatures and its compact design. At present, a large amount of work has been
devoted to reduce the material costs of PEMFCs to achieve their widespread
application, including the method of preparing a Pt catalyst with a large specific
surface area to minimize the amount (and cost) of Pt required for a given level of
activity.
This paper presents a detailed study of the impregnation-reduction method for
the preparation of Pt/C catalysts，including the heat-treatment technology for the
treatment of the carbon black support. The carbon black supports heat-treated in N2
stream at 600℃ exhibit a positive role of promoting Pt dispersion to a higher degree.
The particle size and the dispersion degree of Pt supported on carbon are observed by
TEM. The surface structure and composition of supports and Pt/C electrocatalysts are
analyzed by XRD and XPS. The results show that the performance of Pt/C
electrocatalysts is improved a lot. The supported Pt/C electrocatalysts about 3.3nm
platinum crystallites have been prepared by this method.
This paper has also studied the colloid method for preparing Pt/C electrocatalysts,
concluding the colloid stability, both the different reducers and the solution
concentrations which affect the performance of Pt/C electrocatalysts. The prepared
Pt/C electrocatalysts has an average platinum crystallite of 3.05nm which is similar to
that of Johnson Mattey catalyst.
This paper has studied the preparation method of PtRe/C catalysts. PtRe/C
catalyst has been successfully prepared by the impregnation-reduction method. The
process includes two steps. First, the reagent Fe/H2SO4 is used to reduce KReO4 to
ReO3, and then H2 is used to reduce ReO3 to metal Re. The so obtained Re/C is
impregnated in H2PtCl6 solution and reduced to PtRe/C by HCHO solution. CV method is
used to evaluate the electrochemical performance of the prepared PtRe/C.
较好等优点，在航天领域、潜艇、电动车、飞船等领域有广泛的应用前景。目前，
虽然 PEMFC 的各项技术已经趋于成熟，正处于大规模商业化应用的前夜。为使
PEMFC 能够早日实现商品化生产，各国科研工作者正在致力于相关材料的研究，
力图降低 PEMFC 成本，提高相关材料的性能。其中包括高性能 Pt/C 电催化剂的
研究。
本实验研究了 Pt/C 电催化剂制备的浸渍还原法，其中主要包括载体碳黑的
热处理技术。通过优化碳黑热处理的工艺条件，如温度和环境，使碳黑载体的性
能得到明显改善。采用 TEM、XRD、XPS、CV、MEA 等测试手段对所制备的
Pt/C 电催化剂性能进行了全面的分析。Pt/C 电催化剂的 TEM 照片显示，采用氮
气氛中 600℃热处理的碳黑载体制备的 Pt/C 催化剂中 Pt 颗粒的平均粒径为
3.3nm，降低了约 1nm；分散度也有了一定的提高。碳载体的 XRD 和 XPS 测试
说明，热处理使碳载体表面组成发生了变化，使其更有利于生成颗粒细小且均匀
的 Pt/C 电催化剂。
本实验还研究了胶体法制备 Pt/C 电催化剂的相关工艺。研究工作包括胶体
的稳定性和不同的还原剂和浓度对 Pt/C 电催化剂性能的影响。采用经优化的胶
体法制备工艺，所制备的 Pt/C 电催化剂中 Pt 颗粒的平均粒径为 3.05nm，已经接
近 Johnson Mattey 公司的 Pt/C 电催化剂水平。
为了提高催化活性和防止催化剂在使用过程中的团聚，本实验还初步探讨了
在Pt/C电催化剂中引入金属助剂Re。实验采用分步浸渍还原法，在制备过程中首
先用Fe/H2SO4把KReO4还原成Re的氧化物ReO3， 然后用H2在高温下把ReO3还原
成Re，最后在Re/C上沉积Pt得到PtRe/C电催化剂。采用循环伏安法表征了PtRe/C
电催化剂的性能，证明了其较好的电催化活性。
The proton exchange membrane fuel cell (PEMFC) is a highly attractive power
source for mobile and stationary applications due to its high power density at lower
temperatures and its compact design. At present, a large amount of work has been
devoted to reduce the material costs of PEMFCs to achieve their widespread
application, including the method of preparing a Pt catalyst with a large specific
surface area to minimize the amount (and cost) of Pt required for a given level of
activity.
This paper presents a detailed study of the impregnation-reduction method for
the preparation of Pt/C catalysts，including the heat-treatment technology for the
treatment of the carbon black support. The carbon black supports heat-treated in N2
stream at 600℃ exhibit a positive role of promoting Pt dispersion to a higher degree.
The particle size and the dispersion degree of Pt supported on carbon are observed by
TEM. The surface structure and composition of supports and Pt/C electrocatalysts are
analyzed by XRD and XPS. The results show that the performance of Pt/C
electrocatalysts is improved a lot. The supported Pt/C electrocatalysts about 3.3nm
platinum crystallites have been prepared by this method.
This paper has also studied the colloid method for preparing Pt/C electrocatalysts,
concluding the colloid stability, both the different reducers and the solution
concentrations which affect the performance of Pt/C electrocatalysts. The prepared
Pt/C electrocatalysts has an average platinum crystallite of 3.05nm which is similar to
that of Johnson Mattey catalyst.
This paper has studied the preparation method of PtRe/C catalysts. PtRe/C
catalyst has been successfully prepared by the impregnation-reduction method. The
process includes two steps. First, the reagent Fe/H2SO4 is used to reduce KReO4 to
ReO3, and then H2 is used to reduce ReO3 to metal Re. The so obtained Re/C is
impregnated in H2PtCl6 solution and reduced to PtRe/C by HCHO solution. CV method is
used to evaluate the electrochemical performance of the prepared PtRe/C.
引文
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[1] 陈延禧，聚合物电解质燃料电池的研究进展，电源技术.1996，20（1）：21-27
[2] 衣宝廉，燃料电池－原理·技术·应用，北京：化学工业出版社，2003
[3] 李晓婷，质子交换膜燃料电池电催化剂的研究：硕士学位论文，天津：天津
大学，2000
[4] 朱科，质子交换膜燃料电池电催化剂和膜电极的研究，硕士学位论文，天津：
天津大学，2002
[5] Appleby A J., Goulkes F R., Fuel Cell Hand book, Van Nostrand Reinhold, New
Yonk, 1989: 12-284
[6] Paola Costamagna, Supramaniam Srinivasan, Quantum jumps in the PEMFC
science and technology from the 1960s to the year 2000 Part I. Fundamental
scientific aspects, Journal of Power Sources 2001, 102: 242-252
[7] Feng Zheng, Phase stability and processing of Sr and Mg doped lanthanum
gallate, a dissertation submitted for the degree of Ph.D, University of
Washington: Materials
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