CN102639744A - 用于电化学应用的高导电性表面以及制备所述高导电性表面的方法 - Google Patents

用于电化学应用的高导电性表面以及制备所述高导电性表面的方法 Download PDF

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CN102639744A
CN102639744A CN2010800435179A CN201080043517A CN102639744A CN 102639744 A CN102639744 A CN 102639744A CN 2010800435179 A CN2010800435179 A CN 2010800435179A CN 201080043517 A CN201080043517 A CN 201080043517A CN 102639744 A CN102639744 A CN 102639744A
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王丛桦
张琳
小杰拉尔德·A·宫塔兹
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Abstract

公开了使用新型结构化金属-陶瓷复合粉末的方法以通过在金属基体表面上热喷涂结构化粉末来改善耐腐蚀金属基体的表面电导率。结构化粉末具有金属芯并由诸如金属氮化物材料的导电陶瓷材料完全或部分包围。在惰性气氛中进行热喷涂方法之前，所述金属芯可具有在其上形成的陶瓷材料，或者热喷涂可在活性气氛中进行使得陶瓷涂层在所述热喷涂方法过程中和/或在沉积之后而在所述芯上形成。通过所述热喷涂方法，所述金属芯将导电陶瓷材料结合在所述基体表面上。

Description

用于电化学应用的高导电性表面以及制备所述高导电性表面的方法
本申请要求2009年9月28日提交的第61/246,523号美国临时申请的优先权。该临时申请的整体内容通过引用并入本文。
背景
领域
本发明涉及增强电化学应用的表面电导率。更具体地，本发明涉及使用热喷涂方法在诸如金属基体的耐腐蚀表面上沉积少量导电陶瓷材料以保持低表面接触电阻。
背景讨论
金属部件广泛用于多种电化学装置，包括但不限于氯碱工艺中的电极以及燃料电池中的隔板。金属部件还用于电池、电解器和电化学气体分离装置。在这些应用的大部分中，金属部件需要具有金属表面的高电导率(或低电阻)以降低电化学装置的内部电损耗用于高运行效率。这些应用的主要挑战在于金属部件必须为耐腐蚀的同时保持其高的电导率。
第6,379,476号美国专利公开了具有大量碳化物和/或硼化物的导电金属内含物的特种不锈钢。这些导电内含物通过热处理过程而在合金主体内部生长，并且从钝化膜下的不锈钢中突出穿过钝化膜的外表面，从而降低不锈钢的接触电阻。
美国专利申请US2005/0089742公开了使导电金属内含物突出穿过金属表面的表面层和钝化膜的方法。
第7,144,628号美国专利公开了使用热喷涂方法以将耐腐蚀金属涂层沉积在金属基体表面的方法。
典型的热喷涂方法已用于表面工程的多种行业。用于所述方法的粉末包括纯金属、纯陶瓷、其中各个单独的颗粒为金属或陶瓷的混合金属和陶瓷粉末以及其中各个单独的颗粒具有金属和陶瓷组分二者的合金粉末。合金粉末通常具有在各个颗粒主体中均匀分布的金属和陶瓷。金属充当粘结剂以将陶瓷粉末保持在一起，并在将其热喷涂在基体上之后使陶瓷粉末与基体结合。
活性热喷涂方法包括在活性气体气氛中喷涂金属粉末。如Lugscheider在Advanced Engineering Materials 2000(高级工程材料2000)，2，No.5，P281-284中所讨论的，在喷涂方法中，金属粉末能与氮气或甲烷反应以形成氮化物和碳化物颗粒。这些颗粒包封在金属涂层中以改善涂层耐磨性。
欧洲专利申请EP 1808920A1(2006)公开了使用过渡金属碳化物或氮化物和/或基于所述氮化物或碳化物的固体溶液作为燃料电池的催化剂的方法。其能降低燃料电池成本，并改善催化剂杂质耐量。
概述
本发明的目的是公开改善耐腐蚀金属部件的表面电导率的方法。其中，本发明的可能应用为电化学装置，包括燃料电池、电池、电解器以及气体分离装置。
公开的方法的优点在于其能以低成本制造用于具有高电导率和耐腐蚀性的电化学电力装置的金属部件。
附图简述
图1A为具有金属芯和完全覆盖所述金属芯的导电陶瓷外层的粉末结构的示意图。
图1B为具有金属芯和部分覆盖所述金属芯的导电陶瓷外层的粉末结构的示意图。
图1C为具有金属芯和导电陶瓷外层以及在所述金属芯中捕获的导电陶瓷颗粒的粉末结构的示意图。
图2为在一些实施方案中使用的热喷涂系统的示意图。
图3为具有由氮化物或氧化物-氮化物合金表面层覆盖的Ti或Cr金属/合金层片的金属基体的示意图。
图4为采用一个实施方案的金属部件作为隔板的燃料电池的示意图。
详细描述
在下列详细描述中，阐述了诸如材料类型和尺寸的多个具体细节从而提供对下面所讨论的优选实施方案的深入理解。与优选实施方案有关的所讨论的细节不应理解为限制本发明。此外，为了易于理解，将某些方法步骤描述为单独的步骤，然而，不应将这些步骤解释为必须不同，也不应将这些步骤解释为在其性能方面是顺序相关的。
本文公开了使用新型结构化金属-陶瓷复合粉末的方法以改善耐腐蚀金属基体的表面电导率。图1A示出第一个实施方案的粉末的示意图。粉末具有金属芯11A和完全覆盖金属芯11A表面的导电陶瓷表面层12A。制备粉末的常规方法为在高温下，在诸如氮气或甲烷的受控气氛中烧结金属粉末。金属与大气气体反应以在金属芯表面上形成导电陶瓷层。金属芯能为耐腐蚀金属，例如镍、钴、铝、铬、钛、铌、钨、钽或它们的合金。导电陶瓷层能为前述中任一种的碳化物、氮化物、硼化物、氧化物，和/或这些材料的合金，例如氮氧化钛TiOxNy。
图1B示出具有不同结构的粉末的示意图。其具有金属芯11B和部分覆盖金属芯11B的导电陶瓷表面层12B。金属芯能为耐腐蚀金属，例如镍、钴、铝、铬、钛、铌、钨、钽或它们的合金。导电陶瓷层能为前述中任一种的碳化物、氮化物、硼化物、氧化物，和/或这些材料中任一种的合金。
图1C示出具有另一种不同结构的粉末的示意图。其具有金属芯11C、完全或部分覆盖金属芯11C表面的导电陶瓷表面层12C以及一些少量的在金属芯11C中捕获的导电芯片13C。在形成导电陶瓷表面层12C的过程中，将导电芯片13C自然捕获进入金属芯。(例如，可以使用等离子反应烧结方法，其实际上为在受控气氛中等离子喷涂进入真空区(不是基体)。在等离子烧结方法中，金属芯达到高达2500℃并熔化，并与大气气体反应以在表面上形成导电陶瓷层。在该过程中，导电陶瓷层可能破裂，并可将在金属液滴表面上形成的导电陶瓷捕获在金属芯中)。金属芯能为耐腐蚀金属，例如镍、钴、铝、铬、钛、铌、钨、钽或它们的合金。导电陶瓷层和芯片能为前述中任一种的碳化物、氮化物、硼化物、氧化物，和/或这些材料中任一种的合金。
制备新型结构化粉末的常规方法为通过在活性气氛中金属粉末的高温(700℃-1300℃)反应，例如对于氮化物涂层为氮气大气，对于碳化物涂层为烃大气。金属粉末与大气中的气体反应以在表面上形成导电陶瓷层。
在表面具有导电陶瓷的新型结构化粉末(图1A-C)能在喷涂前通过热化学反应而形成，或在热喷涂方法过程中通过金属液滴与热喷涂火焰或等离子体羽流的大气气体反应而原位形成。在后一种情况下，在一个步骤中进行导电陶瓷层和粉末沉积的形成。陶瓷层形成反应能在金属液滴处于飞行状态时发生，或在金属液滴沉积在表面上之后发生，或在两种情况下发生(即，当金属液滴处于飞行状态时，在与大气的化学反应过程中形成一些陶瓷涂层，并且在金属液滴已沉积在表面上之后形成其它陶瓷材料)。
使用图1A-C所述的新型结构化粉末的优选方法为通过热喷涂方法将粉末沉积在金属基体上以改善基体材料的表面电导率。能以连续层形式或以覆盖一部分基体表面的孤岛形式形成喷涂层片。
金属基体能为耐腐蚀金属，例如钛、铌、锆、钽以及它们的合金，或具有耐腐蚀表面处理的低成本碳钢、不锈钢、铜、铝以及它们的合金。
在图2中示意性地示出可用于本发明的热喷涂系统。在受控气氛条件下进行该方法以保持惰性气氛(例如，氩气或氢气)或活性气氛(例如，氮气或甲烷)21。应使用惰性或活性气体操作粉末供给器22。喷嘴23用于喷射粉末以形成熔化的金属液滴24，并将其喷出至金属基体25。喷嘴23能为等离子喷嘴或能为本领域已知的其它种类的喷嘴。
在本发明的一个实施方案中，通过热喷涂方法沉积一些钛或铬金属或合金颗粒，并结合在金属基体表面上。在含氮气的大气中进行热喷涂方法。通过热喷嘴将钛或铬金属颗粒喷出并且在火焰中熔化。钛或铬熔化液滴与大气中的氮气反应，在液滴表面上产生氮化物或氧化物-氮化物层。然后，将液滴溅射在基体表面上，并以层片形式结合在基体上。层片的表面还能与含氮气的大气反应，生成覆盖层片表面的氮化物，其具有在层片中或在层片-基体接触面上捕获的一些氧化物-氮化物芯片的氮化物。在图3中示出该实施方案的示意图。图3例示由钛或铬层片32部分覆盖的金属基体31以及在层片32上的薄氮化物或氧化物-氮化物覆盖物33。将氮化物或氧化物-氮化物芯片34封装在一些或所有层片32中。层片32的厚度为约0.1μm至100μm，并且优选为约1μm至5μm。氮化物或氧化物-氮化物层33的厚度为约1nm至5μm，优选为约5nm至1μm。
由于氮化钛和氮化铬(或氧化物-氮化物)为耐腐蚀且导电的，因此在电化学系统中钛或铬层片的氮化物或氧化物-氮化物覆盖物将充当金属基体与其它部件的电接触点。层片能以孤岛形式覆盖金属基体表面或被连接在一起。为了最小化材料用量，不必覆盖金属基体的整个表面。
表1示出多孔复写纸(SGL 24BA)与在表面上喷涂钛-氧化钛-氮化物层片的304不锈钢箔的接触电阻。通过在含氮气的受控气氛中等离子喷涂钛粉末而形成钛-氧化钛-氮化物层片。如表1所示，在150psi的压缩压力下喷涂的304SS的初始接触电阻为14mΩ.cm2。在pH3H2SO4+0.1ppm HF溶液中，在0.8VNHE阴极极化下，在腐蚀24小时之后，接触电阻保持几乎相同低的值。另一方面，裸露的304SS在腐蚀环境中具有显著的表面氧化，其导致在腐蚀之后显著高的接触电阻增加(100mΩ.cm2至200mΩ.cm2)。
表1.304SS箔与多孔复写纸的接触电阻的比较
在另一实施方案中，通过热喷涂方法在粉末表面上沉积具有氮化物层的一些钛或铬金属(或合金或前述)颗粒，并结合在金属基体表面上。在热喷涂沉积方法之前，通过高温气体渗氮方法处理粉末表面上的氮化物。在惰性(氩气或氢气)大气中或在含氮气的大气中进行热喷涂方法以防止热喷涂方法过程中氮化物的大规模氧化。通过热喷嘴将颗粒的钛或铬芯喷出并在火焰中熔化。颗粒溅射在基体的表面上，并以具有暴露在表面上的氮化物的层片形式结合在基体上。为了进一步改善表面电导率，能将其它化学品或电化学蚀刻方法用于去除氮化物表面上的金属，并在层片表面上进一步暴露氮化物。
在另一实施方案中，将在粉末颗粒表面上具有碳化钨层的钨金属粉末颗粒沉积在耐腐蚀金属基体表面上。颗粒溅射在金属基体上并结合在其表面上。为了进一步增加层片的表面积并改善化学稳定性，金属基体表面上的层片能经历化学或电化学蚀刻过程以溶解不太稳定的相，并增加表面粗糙度用于高表面积。表面上的碳化钨用作用于溴-氢或溴-锌液流电池的电极催化剂，或用作用于氢产生的水电解器，并且金属基体用作电池堆的隔板。
如上述讨论的，本文公开类型的金属部件可用于多种机电装置。例如，使用本文公开的技术形成的金属部件可用作在燃料电池中使用的燃料电池堆的隔板。示例性的燃料电池400在图4中例示。燃料电池400包括放置在容器49中的燃料电池堆40。燃料电池堆40包括三个膜电极组件/气体扩散层(MEA/GDL)，其各自包括在PEM11的对侧上具有阳极42和阴极43的质子交换膜41以形成MEA和在对侧上邻近MEA的的气体扩散层44。将可使用本文公开的技术形成的隔板45布置在邻近的MEA/GDL之间，并且端板46在由三个MEA/GDL形成的燃料堆40的相对端上存在。在图4中例示的隔板45称为双极性隔板，因为它们具有在一侧上的阳极42和在另一侧上的阴极43。具有通过本文公开的技术形成的单极隔板的燃料电池堆也在本发明的范围内，其中阳极和阴极在邻近的MEA中交换。这些类型的燃料电池堆中的任一个可与其它部件(岐管等，在图4中未示出)结合以形成本领域熟知的燃料电池装置。本文公开类型的金属部件可用于形成2010年5月10日提交的标题为“使用金属隔板的高功率燃料堆”的第12/777,126号共同待审的美国专利申请中公开类型的隔板，其整体内容通过引用并入本文。
本文公开类型的金属部件的另一用途为用于电解器。例如，本文公开类型的金属部件可用作第4,643,818号美国专利和第7,763,152号美国专利中公开类型的电解器中的电极。本文公开类型的金属部件的其它用途为作为上述讨论的电池堆中的隔板以及氢气-空气燃料电池的电极催化剂；用于诸如在第5,290,410号美国专利中所公开的那些氯-碱电解电池；以及用于电化学气体分离装置。应当理解，在上述专利中例示的装置为说明可与本发明的金属部件一起使用的多种装置，并且这些专利的细节不应理解为以任何方式限制这类用途。在本段中上述列举的所有专利的内容均通过引用并入本文。
提供前述实施例仅出于解释的目的，并且根本不应理解为限制。当对各个实施方案进行参考时，本文使用的词语为描述和说明的词语，而不是限制的词语。此外，尽管示出对特殊方法、材料和实施方案的参考，但不存在对本文公开的细节的限制。相反，实施方案延伸至诸如在附加的权利要求范围内的所有功能等效的结构、方法和用途。
此外，摘要的目的在于一般地能使专利局和公众，且特别是不熟悉专利或法律术语或用语的本领域科学家、工程师和从业者通过粗略检验而快速确定本申请技术公开内容的性质。摘要不旨在以任何方式限制本发明的范围。

Claims (17)

1.用于制备具有高导电性表面的金属部件的方法，其包括：
在受控气氛中使用热喷涂方法将结构化粉末沉积在金属基体上；
其中所述粉末包含多个颗粒，各一颗粒具有由导电陶瓷涂层至少部分包围的金属芯，并且其中所述颗粒与所述金属基体的表面结合。
2.如权利要求1所述的方法，其中所述导电陶瓷涂层完全包围所述颗粒的金属芯。
3.如权利要求1所述的方法，其中所述导电陶瓷涂层部分包围所述颗粒的金属芯。
4.如权利要求1所述的方法，其中所述金属芯具有在其中捕获的陶瓷颗粒。
5.如权利要求1所述的方法，其中所述金属芯由选自钨、镍、钴、铝、铬、钛、铌、钽以及前述中任一种的合金的耐腐蚀材料形成。
6.如权利要求1所述的方法，其中所述导电陶瓷涂层由选自前述中任一种的碳化物、氮化物、硼化物、氧化物以及这些材料中任一种的合金的材料形成。
7.如权利要求1所述的方法，其中所述受控气氛为活性气氛，并且其中所述导电陶瓷涂层通过所述金属芯与所述活性气氛的反应而在所述热喷涂方法过程中在所述金属芯上形成。
8.如权利要求7所述的方法，其中所述活性气氛包含氮气，并且其中所述金属芯包括钛、铬、钨、铌、钽或它们的合金。
9.如权利要求1所述的方法，其中所述受控气氛为惰性气氛，并且其中在所述热喷涂方法之前在所述金属芯上形成所述导电陶瓷涂层。
10.如权利要求9所述的方法，其中使用在所述沉积步骤之前进行的等离子烧结方法而在所述金属芯上形成所述导电陶瓷涂层。
11.如权利要求1所述的方法，其中所述颗粒完全覆盖所述金属基体的表面。
12.如权利要求1所述的方法，其中所述颗粒形成多个覆盖一部分所述金属基体表面的岛。
13.如权利要求1所述的方法，其还包括：
在所述沉积步骤之后蚀刻所述表面以去除暴露的金属使得表面上另外的陶瓷材料暴露。
14.如权利要求1所述的方法，其中与所述金属基体表面结合的粉末颗粒的金属芯的最大厚度为约0.1微米至100微米。
15.如权利要求14所述的方法，其中覆盖与所述金属基体表面结合的粉末颗粒的金属芯的陶瓷涂层的厚度为约1纳米至5微米。
16.由权利要求1所述的方法形成的金属部件。
17.燃料电池堆，其包括：
第一燃料电池，所述第一燃料电池包括
膜电极组件，其包括质子交换膜、在所述质子交换膜一侧上的第一电极和在所述质子交换膜对侧上的第二电极；
在所述膜电极组件第一侧上的第一气体扩散层；
在所述膜电极组件第二侧上的第二气体扩散层；
第二燃料电池；以及
在所述第一燃料电池和所述第二燃料电池之间的隔板，所述隔板为由权利要求1所述的方法形成的金属部件。
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