CN102482770A - 通过真空沉积技术以连续工艺活化电极表面 - Google Patents

通过真空沉积技术以连续工艺活化电极表面 Download PDF

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CN102482770A
CN102482770A CN2010800390178A CN201080039017A CN102482770A CN 102482770 A CN102482770 A CN 102482770A CN 2010800390178 A CN2010800390178 A CN 2010800390178A CN 201080039017 A CN201080039017 A CN 201080039017A CN 102482770 A CN102482770 A CN 102482770A
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CN102482770B (zh
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A·L·安托齐
A·F·古洛
L·亚科佩蒂
G·N·马特利
E·拉姆尼
C·厄戈赫
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Abstract

本发明涉及通过物理气相沉积技术通过在金属基材上连续沉积贵金属层来制造用于电解应用的金属电极的方法。

Description

通过真空沉积技术以连续工艺活化电极表面
技术领域
本发明涉及制造用于电解应用的催化电极的方法。
背景技术
现有技术已知在电解应用中使用涂覆催化剂的电极：例如由装备有基于贵金属或其氧化物的涂层的金属基体(例如钛、锆或其它阀金属、镍、不锈钢、铜或其合金)组成的电极，在水或碱金属氯化物电解过程中作为析氢阴极，在各种类型的电冶金过程中作为析氧阳极，或再次在碱金属氯化物电解中用于碱金属氯化物。通过合适的热处理将要沉积的金属的前体溶液分解，通过由合适的电解浴的电沉积(galvanic electrodeposition)，通过火焰或等离子喷涂过程或通过化学或物理气相沉积，可以热制备这种类型的电极。
气相沉积技术可具有允许更精确控制涂层沉积参数的优点。它们通常特征在于：在一定的真空度下操作，其可为较高或较低，这取决于不同类型的应用(阴极弧沉积、脉冲激光沉积、等离子溅射任选离子辅助等)；这意味着现有技术已知的方法的主要特征在于分批过程，这需要将基材装载到合适的沉积室中，这必须经历长过程的减压，持续几个小时以能够接着处理单个工件。通过给气相沉积装置配置两个分隔的室，即调节室，其中维持适中的真空水平(例如10-3-1Pa)，和沉积室，其可与调节室联通布置，由此接收已经在一定真空度下要处理的工件。因此使沉积室经受例如为产生高效率等离子所需要的高真空条件(例如10-6-10-3Pa)，而不需要从大气条件开始。在后一种情况中，真空沉积仍受分批型方法的固有限制所影响。
发明内容
在所附的权利要求中阐述本发明的各个方面。
在一个实施方案中，本发明涉及制造适用于电解应用的电极的方法，其包括通过化学或物理气相沉积技术以连续型工艺将贵金属例如铂、钌或铱或其氧化物沉积到金属基材上。可在化学或物理气相沉积装置中进行连续沉积，所述装置提供有调节室，其可在适中减压水平下例如在10-3-1Pa的压力下操作；沉积室，其理想地具有尽可能小的体积，其在第一操作状态中可与调节室水力联系并且在第二操作状态中可与调节室隔离，并且经受高的减压水平，例如10-6-10-3Pa；任选的回收室(withdrawal chamber)，其在第一操作状态中可与沉积室水力联系并且在第二操作状态可与沉积室隔离，其可在与调节室相当的减压水平下操作。
在一个实施方案中，在如此前描述的装置的调节室中以预制工件的形式装载金属基材，例如布置成片，所述片切割成在连续供给设备的一系列架子或盘子中使用的最终尺寸；随后在适中的真空度下对整个装置进行减压。可用处于相互水力联系的调节室、沉积室和任选的回收室进行该第一减压步骤。在随后的步骤中，将沉积室隔离并且使其经受高真空度；该方面对于等离子辅助的沉积过程特别重要，因为其显著地提高了它们的效率。在动态真空(dynamic vacuum)中常规地进行等离子相中的沉积过程：减压的指示水平(例如10-6-10-3Pa)是通过不同技术(例如通过供给气体流(任选氩)穿过电磁场)产生高密度等离子所需的水平。合适称呼的沉积通过如下方式而发生：等离子与金属靶材相互作用，随后提取的金属离子输送到要处理的基材上，任选地添加电磁场、离子束等的辅助。在希望沉积从氧化物形式的靶材所蒸发的元素的情况中，还可以供给包含合适反应物例如氧的流。作为替代，可从由金属氧化物组成的靶材的蒸发开始来进行金属氧化物的沉积，由此简化工艺，尽管这通常对工艺速率有负面影响。金属或氧化物的蒸发和气态反应物的任选注射造成在沉积步骤期间实际真空度低于等离子产生的原始真空度(通常比调节室的真空度略高)。一旦已经将装载有要连续处理的工件的装置以对于不同的室所指示的各种真空度进行减压，则预制工件经受顺序供给到沉积室、化学或物理气相沉积和随后卸载到任选的回收室的循环。在所处理的工件的卸载之后，供给随后的基材并且恢复沉积室中的真空度，再次在显著减少的时间内与装置的其余部分隔离。对于合适形状的基材，直接卸载到大气中是可预见的；例如可从具有受控液封的槽卸载光滑和薄的基材，而不显著影响沉积室中的真空度。
在一个实施方案中，通过IBAD(离子束辅助沉积)技术，使用此前描述的方法来沉积金属或氧化物形式的钌层，该方法在10-610-3Pa压力下提供等离子的产生，在由离子束辅助的等离子作用下，从布置在沉积室中的金属钌靶材提取钌离子，并且随后用含有能量为1000-2000eV钌的束轰击要处理的基材。在一个实施方案中，IBAD沉积是双重类型，在此之前为通过用原位产生的较低能量水平(200-500eV)的氩离子轰击的基材清洁步骤。还可以以金属形式沉积钌，并且通过在氧化气氛中例如用在400-600℃下的空气的后续热处理随后将其转化成氧化物。
在另一实施方案中，在卷到卷(roll-to-roll)或卷到片(roll-to-sheet)的装置中进行沉积，通常在第一真空度下减压(例如10-3-1Pa)并且提供有通过合适的密封可减压到高真空(10-3-10-6Pa)的有限体积的沉积部分。适合这种类型配置的沉积技术是称为MPS(磁控等离子溅射)的技术，其通过磁场和射频电场的结合使用来提供高密度等离子的产生。另一种适合该范围的沉积技术通过磁场和调制的直流电流(DC等离子溅射)的结合使用来提供高密度等离子的产生。
在另一实施方案中，在网状物或板网的卷材上进行沉积；通过提供解卷绕(unrolling)、拉伸、机械膨胀以及经过通道穿过化学侵蚀溶液的任选蚀刻和随后再卷曲成卷材的连续过程，可从实心片的卷材开始获得适合该范围的板网的卷材。蚀刻对于赋予可控的粗糙度可为有用的，适合于沉积方法。作为替代，在将膨胀网状物卷绕回卷材后，可进行蚀刻过程。
在另一实施方案中，将膨胀网状物的卷材供给到化学或物理气相沉积装置中，任选为MPS装置，该装置适用于卷到卷的处理并且装备有用于装载和解卷绕该卷材的部分、通过第一密封槽任选与装载部分分离的沉积部分和通过第二密封槽任选与沉积部分分离的解卷绕部分。
在另一实施方案中，将板网的卷材供给到化学或物理气相沉积装置中，任选为MPS装置，该装置适合用于卷到片的处理并且装备有用于装载和解卷绕该卷材的部分、通过第一密封槽任选与装载部分分离的沉积部分和通过第二密封槽任选与沉积部分分离的回收部分。
为了获得所需尺寸的平坦电极，可将回收部分与连续切割装置合并。在一个实施方案中，在10-3-1Pa的压力水平下操作沉积装置，并且在从高真空水平例如10-3-10-6Pa开始获得的动态真空下操作沉积部分。
在以下实施例中给出一些由本发明人获得的最显著的结果，这并不意在作为本发明范围的限制。
实施例1
在18体积％的HCl中蚀刻一系列的1000×500×0.89mm尺寸的20片1级钛片，并且用丙酮脱脂。将片放置在用于连续制造的IBAD装置的调节室的各个盘子上，随后减压到130Pa。随后将片连续供给到沉积室，在沉积室中其在具有3.5.10-5Pa的压力下产生的等离子的动态真空下在两个步骤中经受离子轰击。在第一步骤中，片在低能量(200-500eV)下经受氩离子轰击，目的是从它们表面清除可能的残留物；在第二步骤中，用从1000-2000eV的能量下的等离子相提取的铂离子实施轰击，目的是沉积致密涂层。在完成0.3mg/cm2的Pt沉积时，将片转移到随后的减压室(保持在130Pa)。在对所有片的处理结束时，在回收片前用环境空气对减压室加压。
从一些这样获得的电极切割1cm2的样品以在标准条件下进行析氯电位测量，在3kA/m2的电流密度下，在浓度为290g/l，通过添加HCl调节到pH 2的NaCl溶液中，在50℃的温度下，获得1.13V/NHE值。
实施例2
用金刚砂将一系列的1000×500×0.3mm尺寸的10片镍片喷砂直至获得略微低于70μm的Rz粗糙度值，在20体积％的HCl中蚀刻并且用丙酮脱脂。利用相同的装置并且用在1000-2000eV的能量下从等离子相提取的钌离子在第二步骤中进行轰击，通过描述于实施例1中的IBAD方法用0.1mg/cm2钌膜涂覆所述片。在沉积后，提取片并且使其在400℃下在空气中经受热后处理1小时，从而将涂覆的钌氧化成RuO2。从一些这样获得的电极切割1cm2的样品以在标准条件下进行析氢电位测量，在10kA/m2的电流密度下，在32重量％的NaOH中，在90℃的温度下，获得-968mV/NHE值。
实施例3
将20米的500mm宽和0.36mm厚的镍膨胀网状物的卷材进行热脱脂，并且在20体积％的HCl中蚀刻直至获得约20μm的Rz粗糙度值。在用于连续的卷到卷的沉积的磁控等离子溅射(MPS)装置的供给部分中装载卷材，使其经受10-3Pa的压力。在0.2cm/s的线速率下操作该装置。在通过沉积部分期间，通过在纯Ar(使用在基材和室壁之间在200W的标称功率下在5.10-5Pa下产生的等离子，并且偏压为零)中溅射来进一步清洁片，随后通过反应溅射(200W、维持约5.10-1Pa的动态真空的20％Ar/O2混合物和约450℃的沉积温度)所获得的RuO2层将其涂覆。在沉积后，在回收部分中将涂覆有对应于3μm厚度的0.3mg/cm2RuO2的板网卷曲回卷材，在回收部分中一旦用环境空气对装置重新加压则将其提取。随后将这样活化的板网的卷材供给到连续切割机器中，其中获得100cm长的电极。从一些这样获得的电极，切割1cm2的样品以在标准条件下进行析氢电位测量，在10kA/m2的电流密度下，在32重量％的NaOH中，在90℃的温度下，获得-976mV/NHE值。
上述描述应该不旨在作为本发明的限制，其可根据不同的实施方案来实施而不偏离本发明的范围，其程度是完全由所附的权利要求所确定的。
本申请的说明书和权利要求书中，术语“包含(comprise)”及其变体例如“包括”和“含有”并不旨在排除其它元素或添加物的存在。
本说明书中包括的文件、法案、材料、装置、题目等的讨论，仅出于提供关于本发明背景的目的。并不建议或代表任何或全部这些事情形成现有技术基础的一部分或在本申请的每个权利要求的优先权日前与本发明相关领域中的公知常识。

Claims (11)

1.制造用于电解过程的电极的方法，其包括通过化学或物理气相沉积技术在金属基材上连续沉积贵金属或其氧化物的致密层。
2.根据权利要求1的方法，其包括以下步骤：
-将预制工件形式的所述金属基材装载到物理气相沉积装置的调节室中；
-在第一压力水平下将所述调节室减压；
-对所述的预制工件顺序自动执行装载入沉积室中、在低于所述第一压力水平的第二压力水平下物理气相沉积所述贵金属的致密层、顺序卸载到提取室中的循环。
3.根据权利要求2的方法，其中所述第一压力水平为10-3-1Pa，并且所述第二压力水平为10-6-10-3Pa。
4.根据权利要求2或3的方法，其包括在氧化气氛中热处理的随后步骤。
5.根据权利要求2或3的方法，其中所述的物理气相沉积步骤包括同时用气态反应物氧化所述贵金属。
6.根据权利要求3-5中任一项的方法，其中所述物理气相沉积装置为IBAD装置，并且通过用从具有1000-2000eV能量的等离子相提取的离子轰击来进行所述贵金属的致密层的所述物理气相沉积，在此之前为通过在200-500eV下的氩离子轰击的基材清洁步骤。
7.根据权利要求1的方法，其中所述物理气相沉积装置为卷到卷或卷到片型的MPS或DC等离子溅射装置，并且贵金属的所述致密层的所述物理气相沉积在10-3-1Pa的压力水平下进行。
8.根据权利要求7的方法，其包括随后在氧化剂气氛中热处理的步骤。
9.根据权利要求7的方法，其中所述物理气相沉积包括同时用气态反应物氧化所述贵金属。
10.根据在前权利要求中任一项的方法，其中所述金属基材由镍、钢或钛制成。
11.根据在前权利要求中任一项的方法，其中所述贵金属或其氧化物选自铂、钌、铱和其氧化物。
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