CN107275646A - 一种核壳结构的质子交换膜燃料电池催化剂及其制备方法 - Google Patents

一种核壳结构的质子交换膜燃料电池催化剂及其制备方法 Download PDF

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CN107275646A
CN107275646A CN201710459015.8A CN201710459015A CN107275646A CN 107275646 A CN107275646 A CN 107275646A CN 201710459015 A CN201710459015 A CN 201710459015A CN 107275646 A CN107275646 A CN 107275646A
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徐峰
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Abstract

本发明属于燃料电池催化剂的制备领域，具体为一种核壳结构的质子交换膜燃料电池催化剂及其制备方法。其中贵金属的质量分数9~90%，黑磷烯的质量分数为10~91%。本发明的催化剂具有良好的抗SO2中毒的性能，能够提高燃料电池的稳定性及耐久性，具有非常重要的意义。

Description

一种核壳结构的质子交换膜燃料电池催化剂及其制备方法
技术领域
本发明属于燃料电池催化剂的制备领域，具体为一种二维层状材料黑磷烯包覆贵金属催化剂的核壳结构燃料电池催化剂。
背景技术
质子交换膜燃料电池以氢气为燃料、氧气（空气）为氧化剂，具有高功率、工作温度低、低污染甚至零污染等优点，被公认为理想的洁净能源。但氢气和氧气（空气）中存在二氧化硫等杂质气体，会毒化铂基催化剂，使得电池的性能大幅下降甚至失效。因而提高质子交换膜燃料电池催化剂抗二氧化硫中毒性能，是保障电池性能、提高电池稳定性的重要途径。
二氧化硫分子在铂表面的吸附能低于氢，会抢先占据铂表面并阻碍氢在铂表面的吸附。因而提高催化剂抗二氧化硫中毒性能，可以通过提高催化剂对二氧化硫的氧化能力，亦可通过降低二氧化硫在催化剂表面的吸附而实现。黑磷烯是一种二维材料，可沉积于催化剂表面形成保护层，阻碍二氧化硫在催化剂表面的吸附；同时由于其具有多元环状结构，可保障氢的顺利通过并吸附于催化剂表面而发生氧化反应。
发明内容
本发明目的旨在提供一种具有抗二氧化硫中毒性能的质子交换膜燃料电池催化剂及其制备方法。
实现上述目的的方案为：
一种核壳结构的质子交换膜燃料电池催化剂，所述催化剂为二维层状材料黑磷烯包覆的贵金属，催化剂的颗粒尺寸为1~100 nm。
贵金属的质量分数9~90%，黑磷烯的质量分数为10~91%，二者质量分数和为100%。
所述黑磷烯是以红磷为原料制备而成，其层数为1~20层。
贵金属为金、银、铂、钌、铑、钯、锇、铱中的一种或几种。
制备方法包括如下具体步骤：
1）将贵金属与红磷混合并在保护气氛下烘干；
2）将步骤1）所得贵金属与红磷的混合物研磨；
3）将步骤2）所得研磨后的混合物置于管式炉中，在保护气氛下升温至500~800°C并保温2~4小时，而后降温至300~400 °C并保温2~4小时，最后冷却得到所述的核壳结构的质子交换膜燃料电池催化剂。
步骤1）和步骤3）中所述的保护气氛是氮气、氩气、氦气中的一种或氮气、氩气、氦气任意体积比的混合气体。
本发明的有益效果在于：
本发明通过在金属催化剂表面形成黑磷烯保护层，阻碍二氧化硫在催化剂表面的吸附，同时由于黑磷烯保护层具有多元环状结构，可保障氢的顺利通过并吸附于催化剂表面而发生氧化反应，使得催化剂在确保其催化性能的同时具有良好的抗二氧化硫中毒性能，能够提高燃料电池的稳定性能及寿命。
附图说明
图1为实施例1制得的催化剂的二氧化硫电化学氧化性能曲线。
将实施例1所制备的P@Pt催化剂做二氧化硫电化学氧化实验并与Pt/C催化剂做对比，结果显示催化剂在1.2 V 均出现了二氧化硫的氧化峰。但P@Pt催化剂的峰值明显比Pt/C催化剂小，说明P@Pt催化剂中Pt表面所吸附的二氧化硫少于Pt/C催化剂，即P@Pt催化剂具有较好的抗二氧化硫中毒的性能。
具体实施方式
本发明用下列实施例来进一步说明本发明，但本发明的保护范围并不限于下列实施例。
实施例1
1）将铂催化剂与红磷混合并在氮气气氛下烘干，其中铂颗粒的尺寸为1nm；
2）将步骤1）所得铂催化剂与红磷的混合物研磨；
3）将步骤2）所得研磨后的混合物置于管式炉中，在氮气气氛下升温至800 °C并保温4小时，而后降温至400 °C并保温4小时，最后冷却得到具有抗二氧化硫中毒性能的燃料电池催化剂，其中黑磷烯的层数为1层，铂金属的质量分数90%，黑磷烯的质量分数为10%。
实施例2
1）将钯催化剂与红磷混合并在氦气气氛下烘干，其中铂颗粒的尺寸为100 nm；
2）将步骤1）所得钯催化剂与红磷的混合物研磨；
3）将步骤2）所得研磨后的混合物置于管式炉中，在氦气气氛下升温至500 °C并保温2小时，而后降温至300 °C并保温2小时，最后冷却得到具有抗二氧化硫中毒性能的燃料电池催化剂，其中黑磷烯的层数为20层，钯金属的质量分数9%，黑磷烯的质量分数为91%。
实施例3
1）将铂金催化剂与红磷混合并在氩气气氛下烘干，其中铂颗粒的尺寸为50 nm；
2）将步骤1）所得铂金属催化剂与红磷的混合物研磨；
3）将步骤2）所得研磨后的混合物置于管式炉中，在氩气气氛下升温至650 °C并保温3小时，而后降温至350 °C并保温3小时，最后冷却得到具有抗二氧化硫中毒性能的燃料电池催化剂，其中黑磷烯的层数为10层，铂金属的质量分数17%，黑磷烯的质量分数为83%。
实施例4
1）将钌催化剂与红磷混合并在体积比为1:1的氮气/氦气混合气氛下烘干，其中钌颗粒的尺寸为30 nm；
2）将步骤1）所得钌金属催化剂与红磷的混合物研磨；
3）将步骤2）所得研磨后的混合物置于管式炉中，在体积比为1:1的氮气/氦气混合气氛下升温至700 °C并保温3.5小时，而后降温至320 °C并保温3小时，最后冷却得到具有抗二氧化硫中毒性能的燃料电池催化剂，其中黑磷烯的层数为15层，钌金属的质量分数12%，黑磷烯的质量分数为88%。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (6)

1.一种核壳结构的质子交换膜燃料电池催化剂，其特征在于，所述催化剂为二维层状材料黑磷烯包覆的贵金属，催化剂的颗粒尺寸为1~100 nm。
2.根据权利要求1所述的催化剂，其特征在于，贵金属的质量分数9~90%，黑磷烯的质量分数为10~91%，二者质量分数和为100%。
3.根据权利要求1所述的催化剂，其特征在于，所述黑磷烯是以红磷为原料制备而成，其层数为1~20层。
4.根据权利要求1所述的催化剂，其特征在于，贵金属为金、银、铂、钌、铑、钯、锇、铱中的一种或几种。
5.一种制备如权利要求1-4任一所述的核壳结构的质子交换膜燃料电池催化剂的方法，其特征在于，包括如下具体步骤：
1）将贵金属与红磷混合并在保护气氛下烘干；
2）将步骤1）所得贵金属与红磷的混合物研磨；
3）将步骤2）所得研磨后的混合物置于管式炉中，在保护气氛下升温至500~800 °C并保温2~4小时，而后降温至300~400 °C并保温2~4小时，最后冷却得到所述的核壳结构的质子交换膜燃料电池催化剂。
6.根据权利要求5所述的核壳结构的质子交换膜燃料电池催化剂的制备方法，其特征在于，步骤1）和步骤3）中所述的保护气氛是氮气、氩气、氦气中的一种或氮气、氩气、氦气任意体积比的混合气体。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109449449A (zh) * 2018-10-26 2019-03-08 哈尔滨工业大学 一种抗so2毒化的燃料电池氧还原贵金属催化剂及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104505523A (zh) * 2015-01-13 2015-04-08 哈尔滨工业大学 一种铂基催化剂/石墨烯复合材料及其制备方法
CN104787736A (zh) * 2015-04-04 2015-07-22 成都育芽科技有限公司 一种大规模制备双层结构黑磷的方法
CN105435780A (zh) * 2015-12-29 2016-03-30 南京大学（苏州）高新技术研究院 一种担载纳米铂钌合金的掺氮石墨烯催化剂
CN106159282A (zh) * 2015-03-30 2016-11-23 宜兴市四通家电配件有限公司 质子交换膜燃料电池膜电极电催化剂及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104505523A (zh) * 2015-01-13 2015-04-08 哈尔滨工业大学 一种铂基催化剂/石墨烯复合材料及其制备方法
CN106159282A (zh) * 2015-03-30 2016-11-23 宜兴市四通家电配件有限公司 质子交换膜燃料电池膜电极电催化剂及其制备方法
CN104787736A (zh) * 2015-04-04 2015-07-22 成都育芽科技有限公司 一种大规模制备双层结构黑磷的方法
CN105435780A (zh) * 2015-12-29 2016-03-30 南京大学（苏州）高新技术研究院 一种担载纳米铂钌合金的掺氮石墨烯催化剂

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
新型: "都柏林三一学院采用黑磷取代石墨烯研究取得新进展", 《化工新型材料》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109449449A (zh) * 2018-10-26 2019-03-08 哈尔滨工业大学 一种抗so2毒化的燃料电池氧还原贵金属催化剂及其制备方法和应用

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