CN104159666B - 中孔石墨颗粒用于电化学应用的用途 - Google Patents

中孔石墨颗粒用于电化学应用的用途 Download PDF

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CN104159666B
CN104159666B CN201380008563.9A CN201380008563A CN104159666B CN 104159666 B CN104159666 B CN 104159666B CN 201380008563 A CN201380008563 A CN 201380008563A CN 104159666 B CN104159666 B CN 104159666B
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mesopore
graphite
particle
graphite granule
loaded
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CN104159666A (zh
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F·舒瑟
D·C·嘉勒诺努内兹
H-J·邦嘉德
S·梅萨韦拉
K·J·J·梅洛菲尔
J·梅尔
C·鲍尔迪棕内
J-F·德里雷特
S·马利亚潘
T·泰斯弗
V·佩内克
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Studiengesellschaft Kohle gGmbH
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Abstract

本发明涉及载有烧结稳定的金属纳米颗粒的中孔石墨颗粒用于燃料电池和其它电化学应用的用途，例如作为燃料电池和电池的电极的层组分。

Description

中孔石墨颗粒用于电化学应用的用途
本发明涉及载有烧结稳定的金属纳米颗粒的中孔石墨颗粒用于燃料电池和其它电化学应用的用途，例如作为电池、PEM燃料电池的电极中的电化学主动和被动层的组分或电化学元件和电化学能量转换器的组分。
在本发明上下文中的中孔石墨颗粒及其生产描述于2012年2月8日的申请号2012/154508的欧洲专利申请，本申请要求该申请的优先权。
如此文中所描述，载有烧结稳定的金属纳米颗粒的中孔石墨颗粒可通过这样的方法获得，其中
-优选在溶液中，将具有中孔基础框架的颗粒用可石墨化的/可碳化的有机化合物浸渍，
-使如此获得的颗粒经受高温石墨化步骤以便在多孔基础框架中形成石墨框架，
-使如此获得的石墨化颗粒经受除去基础框架和由此获得称为n-HGS(中空石墨球)颗粒的中孔石墨框架的过程，
-将如此获得的中孔石墨颗粒(n-HGS颗粒)用催化活性金属例如Ti，V，Cr，Mn，Fe，Co，Ni，Cu，Zn，Al，Mo，Se，Sn，Pt，Ru，Pd，W，Ir，Os，Rh，Nb，Ta，Pb，Bi，Au，Ag，Sc，Y及其混合物的盐的溶液浸渍，
-使如此获得的石墨中孔颗粒经受氢化步骤以便获得在中孔颗粒上和/或在中孔颗粒的孔中的催化活性金属颗粒。
在该过程中，金属盐还原为金属，其能够在化学上于氢存在下发生或在升高的温度热发生。
该制备过程后进行又一步骤，其中将如此获得的具有金属载量的石墨中孔颗粒在优选600℃至1000℃的温度范围煅烧，以便尤其是稳定化颗粒和催化活性金属。
在颗粒加载金属并未进行的情况下，在中间步骤中作为中空石墨球获得的n-HGS颗粒也类似地适于电化学应用，其中球形壳的多孔性、机械和电化学稳定性和电导率能够得以利用。
能用于本发明过程中的具有多孔基础框架的颗粒可以具有固体核心和多孔壳或者整个颗粒中的多孔结构，从而基础框架的除去和有机化合物的石墨化导致形成具有中空核心和多孔壳的颗粒或者具有整体多孔结构的颗粒。
本文所用颗粒一般具有尺寸2至50nm的石墨化步骤中在其中形成石墨网络的中孔。在此所用颗粒的核心和多孔壳可能由多种不同物质构成。例如，核心可以是聚合物有机或无机材料，其被无机材料比如二氧化硅、二氧化锆、二氧化钛或水化前体的多孔层围绕。
可以使用的可石墨化的/可碳化的有机化合物并不具体限于特殊类别的物质，只要通常在超过600℃的升高的温度于无氧气氛中进行的石墨化过程在颗粒的多孔基础框架内导致石墨网络结构；并且可以是可聚合的烃单体比如乙烯基化合物比如乙烯基苯或至少两种有机、树脂形成性化合物比如间苯二酚/甲醛的组合，中间相沥青(Mesophase-Pitch)或者在碳化过程中提供高碳收率的其它聚合物的单体。
特别有利与本发明意图的中空石墨球(HGS)能够有利地通过具有固体核心和中孔壳的二氧化硅颗粒的"纳米浇铸"制备。这些二氧化硅颗粒能够制备如下：在至少一种孔形成剂比如烃-硅化合物存在下，将至少一种可水解的硅化合物反映，以形成具有SiO2前体框架的颗粒，干燥和煅烧如此获得的颗粒，以获得所希望的具有中孔壳的二氧化硅颗粒。此处可水解的硅化合物优选是硅氧烷化合物比如四烷氧基甲硅烷，其能够水解为SiO2前体框架，该框架任选地具有能够在煅烧期间转化为Si-O-Si键的羟基基团。
该水解能够在加入烃-硅化合物以获得SiO2前体基础框架之前开始，然后将其在烃-硅化合物存在下反应，获得SiO2前体基础框架。该烃-硅化合物在随后的煅烧步骤期间用于产生纳米孔，并且硅化合物一般具有结合至硅的至少一个长链C10-C30-烷基。具有固体SiO2核心和围绕核心的中孔壳的所述颗粒一般具有100nm至600nm的直径，和20nm至80nm的壳厚度。相应地，固体SiO2核心能够具有60nm至450nm的直径。优选，固体核心的直径是200nm至400nm和围绕核心的壳厚度是20nm至50nm。
将如此获得的中孔二氧化硅颗粒用作为石墨化催化剂的金属盐溶液处理，其中颗粒的中孔壳的总孔隙体积优选被作为石墨化催化剂的金属盐浸渍，其中所述金属盐一般匹配后续步骤中用于填充中孔的单体。对于一些应用，金属盐必须是完全惰性化的或随后彻底洗涤除去，尤其是在Fe盐作为"降解催化剂"以随后的电化学应用中降解聚合物的情况下。
通过此过程能够获得的具有中空核心和中孔壳的中空石墨球一般具有60nm至440nm或多至560nm的直径，而壳的层厚度一般是20nm至50nm。HGS颗粒一般具有通过BJH方法测定的双峰孔尺度分布，其主要孔尺度分布为2至6nm，优选3至4nm，而第二孔尺度分布为6至20nm，尤其是8至12nm。
如此获得的HGS颗粒显示600℃至700℃的增加的热稳定性特性，其中40％的石墨区域甚至在多至800℃时热稳定。BET表面积大于1000m2每克，尤其是大于1400m2每克，和残余金属含量小于0.5％重量；残余含量优选降至该金属或其盐不再显示任意催化效果的程度(ppm范围或"完全包衣")。
然后，这些n-HGS颗粒能够用催化活性金属的金属盐溶液处理，所述催化活性金属是比如Ti，V，Cr，Mn，Fe，Co，Ni，Cu，Zn，Al，Mo，Se，Sn，Pt，Ru，Pd，Au，Ag，W，Ir，Os，Rh，Nb，Ta，Pb，Bi，Y，Sc，Au，Ag，Sc，Y及其混合物或如上所述的组合，优选通过浸渍步骤，其中如上文所提及，优选金属盐的含醇溶液的体积完全吸收入HGS颗粒的孔中，以便形成前体M-HGS颗粒。在后续步骤中，在干燥之后或在蒸发溶剂之后，在200℃至400℃升高的温度在多至10小时期间内使如此获得的前体M-HGS颗粒经受用氢的氢化步骤，以便获得金属-HGS颗粒(M-HGS)和除去金属盐的挥发性反应产物例如氢卤酸。
金属纳米颗粒以高浓度均匀分布在M-HGS颗粒的孔体系内的表面上，和具有2至6nm尺寸的孔的经定义的中孔度和石墨壳的大表面积不仅允许在孔体系中形成金属纳米颗粒，而且还导致高载量的具有均匀尺度分布和高抗聚结稳定性的金属纳米颗粒。金属载量优选是10％重量至40％重量，有时也是5％重量多至50％重量，基于HGS颗粒的总重量。
有利地，随后进行处理，其中在600°至1000℃的温度煅烧金属-HGS颗粒多至多个小时的时间段以提高金属纳米颗粒的稳定性。
最终如此获得的载有金属纳米颗粒的中孔石墨颗粒(此后也称为M-HGS颗粒)具有，特别是在中孔壳结构的孔中的大活性表面积，对于氧的还原的低初始电势("氧还原初始电势")和可与现有技术已知的金属加载Vulkan颗粒(商业电催化剂)比拟的极限电流密度。
这些特性使得可按照上述EP 12154508制备的材料特别适于用于电化学应用。特别地，在燃料电池的情况下，氢和小有机燃料分子例如NH3、N2H4在阳极的氧化以及氧在阴极的还原使得有效电催化成为必需的，以便获得实际应用所需要的电流密度和电压。对于燃料电池中这种用途，M-HGS材料的下述特性是尤其有利的：
-大的比表面积导致增加的反应物吸收能力并且导致催化剂颗粒沉积的许多锚定位置等)。
-壳层中的小孔通过它们的"捕获/固定"增加催化剂颗粒的稳定性。
-材料具有良好的电导率，用于将废热运离的良好热导率和优异的抗腐蚀性。
-由于多孔性成为可能的是，有效的水和氧运输和其它流体物质比如水、水蒸气、氨、甲醇以及质子(H+)的运输和(对于其它应用)氢氧根离子(OH-)进入和通过颗粒的运输。
-表面结构允许在电极的催化剂层中电解质对颗粒表面的良好可润湿性，其又允许颗粒壳层中的催化活性位点的良好可接触性。
-材料的机械稳定性允许良好的可加工性，尤其是在压制包含阳极、膜和阴极的膜-电极组件的情况下。
由于窄的颗粒尺度分布，与标准物质比如基于可商购的Vulcan XC72的电催化剂的情况相比，可能实现更均质的层结构，其中HGS层结构是有规律的并且使得更佳的层结构定义成为可能。这导致改善的可加工性，原因是在更廉价条件下更快产生均质层。由于多孔壳结构，孔中的催化活性位点是更加可接触的，其例如在阴极侧导致质子(H+)和氧(O2)向催化剂颗粒的改善的供给或导致更佳的催化剂利用，从而在减少量的活性金属于实现相同效能的情况下更薄的层也是可能的。这使得节约成本成为可能，原因是降低的贵金属消耗。
此外，具有中空核心和多孔壳的颗粒的结构使得可能改善催化剂层中的质量转移，催化剂层通常包括3个相：空体积(P1：气体和水运输)，基于HGS的催化剂颗粒(P2：电流和热运输以及催化活性)和膜聚合物(P3：质子运输)。气体和液体能够不仅扩散通过"球之间的间隙"而且还额外地通过球内部，从而总体更佳地扩散并且运至反应中心或从反应中心运出。
从球至球的电子运输能够通过球壳完成，而气体运输能够通过多孔壳和从球至相邻球的中空空间内部地完成。在该情况中，离子或电荷传输能够发生在围绕球的聚合物网络中，从而在"球密堆积"的情况中，不同于"固体"标准材料的情况，使得可能用聚合物网络完全充溢或填充球间间隙，其导致离子电导率的增加和催化剂层的稳定性。最终，由此导致离子至催化剂颗粒的改善的供给(引起更佳的催化剂利用率)和从而催化剂层效能的增加。
同时，在使用未用催化剂金属包衣的HGS颗粒(n-HGS)的情况下，使得进入和通过催化无活性的中间层的气体扩散的改善更为容易，所述中间层通常存在于燃料电池中的气体扩散电极(GDE)中、也称为微孔层(MPL)，其中具有PTFE的标准MPL结构能够在此用作粘合剂。n-HGS颗粒壳的多孔性或渗透性也允许球的中空空间内部用"液体Teflon"(THV或类似物，可溶的PTFE类聚合物)包衣，其导致通过颗粒的水运输的改善。如果适当选择具有疏水特性的包衣或粘合剂，则可能在MPL层中仅使用一种添加剂，其在球内部以及在球周围的外部能够充当使表面疏水化的试剂。
发明人已发现根据本发明的M-HGS颗粒的用途导致甚至更厚的催化剂层(dKS>50μm)的高性能，这是用现有技术已知的材料无法实现的。相应地，在与现有技术可比拟的性能下，可能降低催化剂层的厚度和因而减少催化剂的量。
由于M-HGS颗粒的尺寸和甚至相对厚的催化剂层的性能，在适当选择聚合物网络的情况下可能的是，省略气体扩散层(GDL)上的MPL层并将聚合物网络中的催化剂层直接施加于GDL上，以产生由仅两个子层而不是通常的三个子层组成的GDE。此处，GDL层的朝向催化剂层的、接近表面的孔能够由催化剂层本身部分填充，和能够实现催化剂层至GDL层的紧密粘着。
除了根据本发明的HGS颗粒在低温或中等温度的聚合物电解质膜燃料电池(LT-和IT-PEMFC)和具有磷酸(HT-PEMFC)的高温变型的用途，所述HGS颗粒同样能够在直接甲醇燃料电池(DMFC)中用作阳极或用作阴极，其与现有技术已知的材料相比导致氧、水以及甲醇和二氧化碳(阳极侧产品)的改善的运输和同时提供改善的腐蚀抗性。
根据本发明的材料能够类似地在电解中用于阴极(H2侧)或在电化学甲醇转化器中用于阴极(H2侧)或用于阳极(甲醇侧)和阴极(H2侧)。
原则上，根据本发明的n-HGS颗粒也适于用作锂离子电池和锂-硫电池的组分，特别是电极的组分。更小的颗粒直径和高电导率一方面使得可能将它们用作电导率添加剂，除此以外颗粒还能够用作阳极或阴极上的包衣的组分。特别是在锂离子电池的情况下，硅基阳极用于研究阶段；由于硅的4000mAh/g的高理论容量，它们正成为密切研究的对象。然而，由于在晶格掺入锂原子的情况下的硅体积扩展，产生机械应力且它们破坏Si微晶。在使用M-HGS颗粒或Si-HGS颗粒的情况下，采用结合于中空核心中的硅微晶，锂电池阳极成为可能，其具有与现有技术已知的阳极中的Si复合物相比增加的循环稳定性。
另外，根据本发明提供n-HGS颗粒和M-HGS颗粒用于金属-空气电池或金属-空气燃料电池的在一次电池和二次电池中的用途。在此，HGS颗粒能够用来增加催化活性或空气电极中的质量转移。
从全部上文能够发现的是，HGS颗粒能够根据本发明用于电化学或电化学能量转换器领域的许多应用。尤其是，通过HGS材料的在高比表面积，中空性和多孔性(球内、球壳)，良好的电导率，良好的热导率，优异的腐蚀抗性和良好的可润湿性方面的特征使得所述可用性成为可能。另外，于可调节的平均球直径的假单分散性和窄的颗粒尺度分布也是有利的。此外，由于颗粒构造成中空球而导致的增加的机械强度是有利的，在涂层和挤压操作期间尤其如此，原因是颗粒在机械负荷下不破裂。

Claims (15)

1.在相互联接的3D孔结构中载有烧结稳定的金属纳米颗粒的中孔石墨颗粒用作电化学应用中的催化剂的用途，其中所述颗粒具有中空球结构，所述中空球结构具有层厚20nm至50nm的中孔石墨壳和直径60nm多至560nm的中空核心，并且中孔石墨壳的催化活性金属的载量按载有金属的颗粒的总重量计是5-50％重量，所述催化活性金属选自Ti，V，Cr，Mn，Fe，Co，Ni，Cu，Zn，Al，Mo，Se，Sn，Pt，Ru，Pd，W，Ir，Os，Rh，Nb，Ta，Pb，Bi，Au，Ag，Sc，Y及其组合，
其中所述载有烧结稳定的金属纳米颗粒的中孔石墨颗粒可以通过下述方法获得，其中
-将具有中孔基础框架的颗粒用可石墨化的/可碳化的有机化合物浸渍，
-使如此获得的颗粒经受高温石墨化步骤以便在多孔基础框架中形成石墨框架，
-使如此获得的石墨化颗粒经受除去基础框架以获得中孔石墨框架的过程，
-将如此获得的中孔石墨颗粒用催化活性金属盐的溶液浸渍，
-使如此获得的中孔石墨颗粒经受氢化步骤以便获得在中孔石墨颗粒上和/或在中孔石墨颗粒的孔中的催化活性金属颗粒，和
-将如此获得的具有金属载量的中孔石墨颗粒在600℃至1000℃的温度范围煅烧。
2.根据权利要求1的中孔石墨颗粒的用途，其中中空核心的直径是60nm至440nm。
3.根据权利要求1的中孔石墨颗粒的用途，其中所述中孔石墨壳的催化活性金属的载量按载有金属的颗粒的总重量计是10至40％重量。
4.根据权利要求1的中孔石墨颗粒的用途，其中中孔石墨壳的催化活性金属选自Ti，V，Cr，Mn，Fe，Co，Ni，Cu，Zn，Al，Mo，Se，Sn，Pt，Ru，Pd，W，Ir，Os，Rh，Nb，Ta，Pb，Bi，Au，Ag，Sc，Y的基于贵金属的合金。
5.根据权利要求1的中孔石墨颗粒的用途，其中将如此获得的中孔石墨颗粒用Ti，V，Cr，Mn，Fe，Co，Ni，Cu，Zn，Al，Mo，Se，Sn，Pt，Ru，Pd，W，Ir，Os，Rh，Nb，Ta，Pb，Bi，Au，Ag，Sc，Y及其混合物的催化活性金属盐的溶液浸渍。
6.根据权利要求1的中孔石墨颗粒的用途，其中所述颗粒具有中孔石墨壳，所述中孔石墨壳载有催化活性金属，所述催化活性金属选自Fe，Co，Ni，Cu，Ru，Pd，Au，Ag，Sn，Mo，Mn，Y，Sc中的至少一种以及Pt。
7.根据权利要求1至6中任一项的载有烧结稳定的金属纳米颗粒的中孔石墨颗粒的用途，用作电化学池中的电极组分。
8.根据权利要求1至6中任一项的载有烧结稳定的金属纳米颗粒的中孔石墨颗粒的用途，用作电化学池中的氧化催化剂。
9.根据权利要求8的载有烧结稳定的金属纳米颗粒的中孔石墨颗粒的用途，其中所述电化学池是燃料电池。
10.根据权利要求1至6中任一项的载有烧结稳定的金属纳米颗粒的中孔石墨颗粒的用途，用作电化学池中的还原催化剂。
11.根据权利要求10的载有烧结稳定的金属纳米颗粒的中孔石墨颗粒的用途，其中所述电化学池是燃料电池。
12.未载有烧结稳定的金属纳米颗粒的中孔石墨颗粒在电化学应用中的用途，其中所述颗粒具有中空球结构，所述中空球结构具有层厚20nm至50nm的中孔石墨壳和直径60nm多至560nm的中空核心，任选与根据权利要求1至6中任一项的中孔石墨颗粒组合，
其中所述未载有烧结稳定的金属纳米颗粒的中孔石墨颗粒可以通过下述方法获得，其中
-将具有中孔基础框架的颗粒用可石墨化的/可碳化的有机化合物浸渍，
-使如此获得的颗粒经受高温石墨化步骤以便在多孔基础框架中形成石墨框架，
-使如此获得的石墨化颗粒经受除去基础框架以获得中孔石墨框架的过程。
13.根据权利要求12的未载有烧结稳定的金属纳米颗粒的中孔石墨颗粒在电化学应用中的用途，其中所述中空核心的直径是60nm至440nm。
14.根据权利要求1至6中任一项的用途，其中所述电化学应用包括用作燃料电池、电化学池、电化学转化器的膜-电极组件的层结构中的层组分，和用作电池的电极层的组分。
15.根据权利要求14的用途，其中所述电化学池是电解池。
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