CN102933735A - 在一个或多个面上的基底涂层 - Google Patents
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Abstract
在一个或多个面上的基底涂层,包括通过以下方法可生产的催化活性材料,该方法包括在真空下在一个真空室内沉积材料,其中进行了下列步骤:(a)将至少一个基底装入该真空室,(b)关闭并且抽空该真空室,(c)通过引入一种气态还原剂到该真空室内清洁该基底,(d)去除该气态还原剂,(e)通过真空电弧蒸发施加一个中间层,其中将一个包括相同或相似材料的基底引入到该真空室内,(f)将该真空室设定到一个150°C至400°C的温度,(g)通过真空电弧蒸发施加一个涂层,其中将选自下组的至少一种金属引入到该真空室,该组是钌、铱、钛及其混合物,并且在整个涂覆期间供应氧气,(h)在最后一个步骤中将该真空室再次充满,并且将所涂覆的基底从该真空室取出,其中在真空下在不同的压力下(如果是合适的)进行上述的一些步骤以及从一个步骤到对应的下一步骤的过渡,这些压力是由一种保护气体设定的,其特征在于在一个或多个面上的基底涂层免除了至少99%的原先包含在该基底本身中的组分,其中所施加到该中间层上的涂层免除了至少99%的非氧化金属。
Description
本发明涉及一种用于在基底的一个或多个面上涂覆催化活性材料的方法,该方法包括在真空下在一个真空室内沉积材料,其中进行了下列步骤:
(a)将至少一个基底装入该真空室,
(b)关闭并且抽空该真空室,
(c)通过引入一种气态还原剂到该真空室内清洗该基底,
(d)去除该气态还原剂,
(e)通过真空电弧蒸发施加一个中间层,其中将一个包括相同或相似材料的基底引入到该真空室内,
(f)将该真空室设定到一个150°C至400°C的温度,
(g)通过真空电弧蒸发施加一个涂层,其中将选自下组的至少一种金属引入到该真空室内,该组是钌、铱、钛及其混合物,并且在整个涂覆期间供应氧气,
(h)在最后一个步骤中将该真空室再次充满,并且将所涂覆的基底从该真空室取出,
其中在真空下施加不同的压力(如果是合适的)进行上述的这些步骤以及从一个步骤到下一个步骤的过渡,这些压力是由一种保护气体设定的。
在氯碱电解中使用的电极要用一个催化活性层涂覆。这些涂层通过成熟的喷雾、浸没或机械施加过程来实现。
为了改进该电极质量,DE 3118320A1提出通过喷雾、气相沉积或等离子体气相沉积在真空下将一种由至少两种不同组分组成的多组分合金施加到一个由导电材料制成的载体上,其方式为使得该涂层是非晶相的并且具有跨越该整个可及表面的活性中心。这个涂层可以由过渡金属(如镍、钒、钛、铬、钴、铌、钼和钨组成,所述过渡金属包含少量贵金属(如钌、铂或钯)。该表面的非晶相的且活性的结构是通过浸取或蒸发同样在涂覆期间施用的元素(如锂、硼、碳、氮、氧、铝、硅、锌)以及后续的退火来获得的。
由钨、碳化钨或其混合物组成的基底涂层在DE 3232809A1中披露。此外,其中包含镍、钴、铬、钼、硼和碳这些元素中的至少一种。从该基底对该多孔的活性层进行密封通过用耐酸的含氟树脂的浸渍而实现。
从DE 1671422A1获知一种已知的阳极涂层。其中描述了钛阳极,这些钛阳极涂覆有铂族金属的氧化物和包含可被钝化的金属的混合物,例如30摩尔百分比的氧化钌和70摩尔百分比的氧化钛的混合物。
在DE 2734084A1中描述了金属钌的阴极涂层,带有通过电流沉积或通过CVD过程产生的封闭该载体的一个金属层。
在另一个过程中,在该载体上通过电解涂覆或通过含盐沉淀物的热分解产生一个含钌层。在DE 2811472A1中,该载体表面用钌化合物涂覆,然后蒸发溶剂并且使该化合物在非氧化气氛中分解。
DE 3322169C2要求保护一种载体的阴极涂层,其中该涂层是含铂金属的层,并且该层由一些包含氧化钌和氧化镍的部分层组成,并且在该层的各个部分层中这些氧化物的质量比是变化的。
DE 3344416C2同样披露了一种用于生产电极的方法,该电极包括一个由氧化钌和氧化镍的混合物制成的涂层。在这个方法中,以包含用于溶解钌盐和镍的物质的溶液处理载体,其结果是溶解了在该载体中包含的一部分镍,并且通过蒸发该溶剂将钌盐和镍盐沉积在该载体上。在含氧气氛中对该载体进行加热产生了一个由氧化钌和氧化镍制成的涂层。
WO95/05499披露了一种从由金属制成的基底和具有至少一个由电催化活性材料制成的外层的涂层来生产电极的方法,该材料包含氧化钌和非贵金属的混合物,其中这个混合物通过物理气相沉积过程(PVD过程)来施用。同样提供了该基底表面的预处理,提出喷砂或酸处理作为方法。本领域的普通技术人员了解该表面的这种酸洗(Anbeizung)导致初始包含在该基底中的一些组分的迁移(通过扩散)到一个所施加的涂层中。这导致在该涂层中催化剂的均匀分布,其结果是获得了涂层组分和基底组分的混合物。
DE 10 2006 057386A1披露了一种物理气相沉积过程(PVD过程),其中在第一步骤中将一个基底装入到一个真空室。在抽空该真空室之后,通过将气态还原剂引入到该真空室内清洁该基底。此外,通过将一种气态组分沉积到该基底表面上增大了该基底表面的尺寸。通过一种已知的过程如等离子涂覆过程、物理气体沉积、溅射过程或类似的过程来实现该涂层并且该涂层可以由一种或多种金属或它们的氧化物组成。取决于该过程如何运行,在整个或部分涂覆期间可以引入氧化性气体到该真空室内,使得主要产生了包含金属和它们的氧化物的涂层。
基于所引用的现有技术水平,对于改进的电极涂层的鉴别具有进一步的要求,从而具有进一步减小的电池电压以确保更加经济的工作方式。本发明的目的在于提供具有优化特性的替代的基底涂层。
出人意料地,发现一方面大体上无基底组分并且另一方面也大体上无非氧化金属的涂层对于电解槽电压具有积极的效果。本领域的普通技术人员没有预期到这一结果,因为(如开篇所示)在现有技术中有意地引发基底组分的迁移或直接施用同样包含基底组分的不同组合物的混合物。此外,在现有技术中任何地方都没有强调纯金属氧化物层对于该电池电压具有特别积极的效果。
本发明涉及一种用于在基底的一个或多个面上涂覆催化活性材料的方法,包括在真空下在一个真空室内材料的沉积,其中进行了下列步骤:
(a)将至少一个基底装入真空室,
(b)关闭并且抽空该真空室,
(c)通过引入一种气态还原剂到该真空室内清洗该基底,
(d)去除该气态还原剂,
(e)通过真空电弧蒸发施加一个中间层,其中将一个包括相同或相似材料的基底引入到该真空室内,
(f)将该真空室设定到一个150°C至400°C的温度,
(g)通过真空电弧蒸发施加一个涂层,其中将选自下组的至少一种金属引入到该真空室,该组是钌、铱、钛及其混合物,并且在整个涂覆期间供应氧气,
(h)在最后一个步骤中将该真空室再次充满,并且将所涂覆的基底从该真空室取出,
其中在真空下施压不同的压力(如果是合适的)进行上述的这些步骤以及从一个步骤到对应的下一步骤的过渡,这些压力是由一种保护气体设定的,在一个或多个面上的基底涂层是免除了(freigehalten)至少99%的初始包含在该基底内的组分,其中所施加到该中间层上的涂层是免除了至少99%的非氧化金属。
在这个方法中,在过程步骤(e)中产生的中间层优选地是由选自钌、铱、钛和其混合物的组的金属制成的。另一个有利的工作方式是过程步骤(g)的氧气供应以脉冲方式进行。
在本发明的一个优选实施方案中,该基底涂层完全免除了初始包含在该基底中的组分,所施加到该中间层上的涂层完全免除了非氧化金属。这意味着,当进行该过程时,这些单独的过程步骤使初始包含在该基底中的组分停止迁移到所施加的层。此外,供应的氧气的量使得所施加的层是纯金属氧化物层。以此方式,在该外涂层中避免了金属/金属氧化物和基底组分的混合物。
术语“完全免除”理解为意味着这落入现有技术水平已知的规定的测量方法的技术检测限范围内。本主权利要求的特征部分的技术特征的确定是通过XPS光谱法(物理电子学公司(Physical Electronics)的XPS系统(PHI 5800ESCA系统))证明的。
在用以生产该基底涂层的过程中,以上步骤以及从一个步骤到对应的下一步骤的过渡,可以通过在真空下施加不同的压力(如果是合适的)进行。因而,该基底从未脱离该真空并且成功地防止了中间氧化层的形成或者新杂质的沉积。此外,前述的在真空下的沉积过程用以产生在任何时候都可以重现的均匀的基底表面。
出人意料地,发现在涂覆过程期间在氧气存在下将温度调整到150°C至400°C之间的值对于单质钌与氧的反应具有积极效果并且对于涂层的形成具有积极效果,这些涂层大体上是不含非氧化金属的并且旨在根据本发明施加到该中间层上。
该真空电弧沉积过程用于施加该涂层。出人意料地,结果是这个过程特别地适合于纯金属二氧化物层的生产。在这个过程中,局部的沉积在阴极弧的弧化端发生,该阴极弧在由弧自身产生的蒸气中燃烧。从现有技术水平已知的是,这个过程的特征在于大约100nm/min的高沉积速率。例如在US 5317235中描述了这个方法。它披露了一种弧金属沉积装置,该装置防止由金属离子沉积成金属小球。
该基底优选自下组,该组包括不锈钢和镍族的元素连同由镍族元素涂覆的不锈钢。
所施加到该中间层的涂层有利地是由二氧化钌制成的。任选地,这个涂层是由二氧化钌:二氧化铱:二氧化钛的金属氧化物的混合物组成的。
根据本发明的中间层优选地以其表面的不平坦性为特征。其结果是,这将引发该基底的表面增大,这通过气态组分的沉积来实现。在这个过程中,要施用的材料理想地与是该基底材料相同的。此类不平坦性还可以存在于施加到该中间层上的涂层上。
已知的真空沉积的过程提供的巨大优点是,该表面是不被遮盖的并且因而已有的、所希望的粗糙度不被再度整平(egalisiert)、而是产生了岛状的、斑点状的突起,这些突起构成了实际的表面增大并且随后的更平的层良好地结合在其上。
有利的是,该基底涂层由一个中间层和一个施加到其上的涂层组成,具有一个1至50μm、优选1至30μm、特别优选1至10μm并且最优选1.5至2.5μm的层厚度。
该方法可以进行改进,其方式为使得该涂覆步骤(g)或该去除步骤(h)之后接着是在350°C至650°C之间的一个温度下对所涂覆的基底的热处理。在这个热处理中发生晶间的过程(在此不会更详细地描述),该热处理将改进该涂层的长期的结合强度。
对实施本发明的方法还可以进行补充,其方式为在大气条件下并且在第一步骤(a)之前,进行一个或多个过程步骤用于增大该表面的尺寸、使该表面结构成形和/或清洁该表面。在理想情况下,为此目的使用例如机械过程如喷砂过程和/或化学过程如刻蚀过程。取决于之前所施用的处理,对该基底表面随后进行第一次清洗以及/或者干燥。
以下通过图1详细地展示了本发明。它示出:
图1:实施本发明的阴极涂层的XPS谱
在一个实验中,将一个如WO 98/15675A1中所描述的2.7m2的镍阴极作为基底装入一个真空室内。在该真空室内,该基底曝露于氩和氢的混合物并且因而是预清洁过的。在第一步骤中,对该真空室进行抽空(10-5bar)。随后,在250°C至350°C下通过引入氢气对该氧化层进行还原。然后,增大了该表面的尺寸。单质镍用作为一种对应于该基底材料的材料源。通过真空电弧沉积用约10-5bar真空和250°C至350°C的真空室温度,将这种镍沉积在该基底上作为中间层直到该表面增加到约50倍的尺寸为止。
随后,为该中间层提供一个通过真空电弧沉积由二氧化钌制成的涂层,其中在涂覆期间以脉冲方式将氧气引入该真空室内。在这样做时,在300°C温度下进行工作。以此方式,如WO 08/067899A1中披露,将所产生的二氧化钌(如预期的)原位沉积到该中间层上。
这产生了一个基底涂层,如图1中通过XPS谱所示,该涂层是不含基底组分的。这意味着,该温和的施用方法防止该基底组分迁移进入该基底涂层。此外,施加到该中间层上的涂层完全由二氧化钌组成并且不被非氧化的基底污染。
这个特殊的基底涂层包括一个金属中间层和一个如下的涂层,该涂层不含基底组分和非氧化金属两者并且必须选自WO 08/067899涵盖的多个可能的的涂层,出人意料地发现该基底涂层对于该电池电压具有特别积极的效果。本领域的普通技术人员没有预期到这点,因为如开篇所示,在现有技术中有意引发基底组分的迁移或者直接施用同样包含基底组分的不同的组合物的混合物。
作为比较实验,使用的阴极原则上是通过以上方法已生产出的。然而,氧气的引入在用钌的涂覆中省略。为此目的,将钌沉积在该基底上两分钟以上,并且然后才通过引入氧气进行再氧化。然而其结果是,不能实现完全纯的二氧化钌层。而是该涂层由二氧化钌和单质钌的混合物组成。
此外,使用了可商购的阴极,根据在DE 3322169C2和DE 334416C2中披露的现有技术水平这些阴极是可获得的。
为了进行该实验,一个电解器配置有15个2.7m2尺寸的元件。在这个实验中,使用相同类型的(C-截面的)15个阳极、15个N2030型膜和11个带有商品涂层的阴极(如根据DE 3322169C2或根据DE 334416C2或根据WO08/067899),以及设置有不含基底组分并且不含非氧化金属的实施本发明的涂层的四个阴极。
在该阳极侧上,该设备用205g/l NaCl溶液运行并且在该阴极侧上用32重量百分比的苛性钠溶液运行。该电解器在6kA/m2电流密度并且在88°C温度下运行75DOL。对于电池电压,在50DOL之后实现稳定的工作。
出人意料地,与带有所选的商品涂层的11个元件相比,在设置有实施本发明的基底涂层的四个元件的情况下,可以实现减小30mV的槽电压(标准化为90°C,32重量百分比NaOH和6kA/m2),因而产生更加经济的电解器的运行方式。
Claims (8)
1.一种用于在基底的一个或多个面上涂覆催化活性材料的方法,该方法包括在真空下在一个真空室内沉积材料,其中进行了下列步骤:
(a)将至少一个基底装入该真空室,
(b)关闭并且抽空该真空室,
(c)通过引入一种气态还原剂到该真空室内来清洁该基底,
(d)去除该气态还原剂,
(e)通过真空电弧蒸发施加一个中间层,其中将一个包括相同或相似材料的基底引入到该真空室内,
(f)将该真空室设定到一个150°C至400°C的温度,
(g)通过真空电弧蒸发施加一个涂层,其中将选自下组的至少一种金属引入到该真空室,该组是钌、铱、钛及其混合物,并且在整个涂覆期间供应氧气,
(h)在最后一个步骤中将该真空室再次充满,并且将所涂覆的基底从该真空室取出,
其中如果是合适的,在不同的压力下进行上述的一些步骤以及从一个步骤到对应的下一个步骤的过渡,这些压力是由一种保护气体设定的,
其特征在于
在一个或多个面上的基底涂层免除了至少99%的原先包含在该基底本身内的组分,其中所施加到该中间层上的涂层免除了至少99%的非氧化金属。
2.根据权利要求1所述的基底涂层,其特征在于该基底涂层完全免除了初始包含在该基底中的组分并且所施加到该中间层上的涂层完全免除了非氧化金属。
3.根据权利要求1或2中的一项所述的基底涂层,其特征在于该基底选自下组,该组包括不锈钢和镍族的元素连同由镍族的元素涂覆的不锈钢。
4.根据以上权利要求之一所述的基底涂层,其特征在于所施加到该中间层上的涂层由二氧化钌组成。
5.根据权利要求1至3中的一项所述的基底涂层,其特征在于所施加到该中间层上的涂层是由二氧化钌:二氧化铱:二氧化钛的金属氧化物的混合物组成的。
6.根据以上权利要求之一所述的基底涂层,其特征在于该中间层在其表面上具有不平坦性。
7.根据以上权利要求之一所述的基底涂层,其特征在于施加到该中间层上的涂层在其表面上具有不平坦性。
8.根据以上权利要求之一所述的基底涂层,其特征在于该基底涂层由一个中间层和一个施加到其上的涂层组成,并且具有一个1至50μm、优选1至30μm、特别优选1至10μm并且最优选1.5至2.5μm的层厚度。
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CA2801793A1 (en) | 2011-12-15 |
US10030300B2 (en) | 2018-07-24 |
CN102933735B (zh) | 2016-08-17 |
EP2580366B1 (de) | 2020-05-06 |
CA2801793C (en) | 2018-05-29 |
KR20130133157A (ko) | 2013-12-06 |
WO2011154094A1 (de) | 2011-12-15 |
US20130206584A1 (en) | 2013-08-15 |
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