CN107849680A - 一种用于处理金属部件表面以达到较低的接触电阻的方法 - Google Patents
一种用于处理金属部件表面以达到较低的接触电阻的方法 Download PDFInfo
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- CN107849680A CN107849680A CN201680021911.XA CN201680021911A CN107849680A CN 107849680 A CN107849680 A CN 107849680A CN 201680021911 A CN201680021911 A CN 201680021911A CN 107849680 A CN107849680 A CN 107849680A
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- titanium
- metal parts
- niobium
- concentration
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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Abstract
本发明提供一种用于处理金属部件表面以达到较低的接触电阻的方法。该方法包括改变表面化学组成,以及在金属部件表面产生包括小峰或者凹坑的微纹理表面结构。小峰和凹坑具有直径在10纳米和10微米之间。小峰和凹坑是圆形或不规则的横截面形状,小峰和凹坑高度或深度在10纳米和10微米之间,分布密度在40万/cm2到50亿/cm2之间。
Description
本申请要求2015年4月15日提交的美国临时专利申请序列号No.62/147,755的优先权,其全部公开内容通过引用结合到本文中。
技术领域
本发明申请涉及降低用于电化学装置的金属部件的表面接触电阻的方法,所述电化学装置包括,但不限于,燃料电池,电解槽,电池和电容器。更具体地,本发明申请涉及通过表面形态和化学组成的改进,来改善金属部件的电表面接触电阻。
背景技术
在许多电化学装置中,一些金属部件需要与相邻部件有低的表面接触电阻。金属部件可以是电极,集电器,气体或液体扩散层,或者其他多功能部件,例如燃料电池和电解槽中的双极板。金属部件在其工作环境中还必须具有耐腐蚀性,以确保长期稳定运行。大多数耐腐蚀金属和合金依赖于表面氧化物层进行腐蚀保护,但是大部分表面氧化物层不导电。
一个示例性应用是电解器中的金属组分。电解器是使用电力进行化学反应的电化学装置。典型的反应包括将水分解成氢气和氧气,或将氯化钠转化为氯气和氢氧化钠。一种实用的电解器包括多个电池,以保证有充分生产能力的。这些电池使用双极板和其它必需部件串联连接,组成一个电池堆。其它必需部件包括气体扩散层,端板,电池框架,垫片等等。这些部件在操作期间暴露于高电化学势。通常由商业纯钛制成的金属组件将被不断氧化,导致较厚的表面氧化物层和较高的接触电阻。高表面接触电阻将导致电解器的内部能量损失较大。目前的解决方案是在钛部件用电镀方法的镀一层金属铂,以确保低表面接触电阻。但是金属铂的高材料成本限制其更广泛的商业应用。
另一示例性应用是锂电池的集电极。集电器的功能是从电极活性材料收集电子,以保持电池的运行。它要求在高电压工作条件下具有低的表面接触电阻。基于LiPF6电解液的商用3.6V锂离子电池采用高纯度铝箔作为集电极。它在中小功率电池中工作正常。然而,大功率锂电池的电流密度和工作电压都比传统应用要高得多。内部欧姆损耗高(在高电流下),铝在高电压下不稳定。因此,大功率锂电池需要更好的表面导电和耐腐蚀的集电极材料。
另一个实例是质子交换膜(PEM)燃料电池堆中的双极板。双极隔板的功能是1)将一个电池的氢气与相邻电池的空气分离;2)从电极收集电子;3)促进电池中的物质(气体和水)传输,以及4)保持燃料电池堆的适当的工作温度。PEM燃料电池内的操作环境有很强的腐蚀性(在酸性溶液和高电位下)。电流密度非常高(2-4A/cm2)。由金属箔制成的双极板,如不锈钢箔,具有重量轻,传热性能好于传统石墨板等优点。然而,由于耐腐蚀金属板的表面氧化物层的高电阻率,怎样保持金属双极板和气体扩散层(与双极板直接接触的部件)低接触电阻是一个挑战。
接触电阻和耐腐蚀性具体要求取决于具体应用。例如,PEM电解器中的金属成分必须具有适合在高电化学电位(超过2.0VNHE)的微酸性溶液中超过10年的稳定运行的耐腐蚀性,与多孔钛气体扩散层的接触电阻低于2m cm2。在PEM燃料电池中,金属双极板必须具有足够的耐腐蚀性,以便在酸性溶液中在超过0.8VNHE的电势下在80-90℃下稳定运行6,000小时以上,并且与碳毡气体扩散层的表面接触电阻必须低于10mΩ·cm2。用于锂电池的集电极必须在高电位(高达5VLi/Li+)的有机盐电解质溶液(通常含有氟)中是稳定的。集电极与电极的表面接触电阻应低于100mΩcm2。电容器集电极的要求也与其化学系统(基于水性或有机电解质)有关,超级电容器的工作电流密度比传统电容器的电流密度高得多。因此,需要更低电阻的集电极。
在电化学装置中,固体金属部件在大多数情况下在一定的压缩压力下与其它固体部件接触。众所周知,固体-固体电接触建立在固体表面的高点的直接接触上。降低接触电阻的常用方法是使用可在压力下变形的软金属材料,例如金,银,锡和铜,以增加固体组分之间的接触面积。这种类型的表面改性的例子在美国专利No.6,685,988,其在金属表面上沉积锡以降低接触电阻。然而,这些软质材料价格很高或者缺乏适合相应电化学应用所需的耐腐蚀性。
有很多方法已经公开用于这些应用。美国专利号6,379,476公开了一种特殊的不锈钢合金用于PEM燃料电池,其表面有导电夹杂物。该特殊合金的表面氧化层可以保护不锈钢在PEM燃料电池中的腐蚀,导电夹杂物可以保持低的表面接触电阻。美国专利申请公开号2005/0089742公开了一种金属合金表面蚀刻掉的方法,类似于美国专利No.6,379,476,用以暴露导电夹杂物作为电接触点。
美国专利6,723,462公开了一种特殊的铬镍奥氏体合金,其可以形成比常规不锈钢,例如市售的316L,更具导电性的表面氧化物。它可以用作PEM燃料电池的双极板。
美国专利号5,098,485公开了一种将电绝缘的或导电不良的金属表面氧化物层转换成用于电容器的更导电的表面的方法。
WO 2007/013508公开了含有贵金属元素的Ti合金。该合金中的贵金属将与钛形成具有低表面电阻的贵金属和氧化钛复合表面层。它可以用作燃料电池中的电极或双极板。
除了开发具有低电阻表面氧化物层的特殊合金之外,另一种广泛使用的方法是用具有耐腐蚀性和表面导电的材料(通常为贵金属)涂覆金属部件。美国专利申请公开号2003/0124427教导了通过溅射工艺在钛板上沉积薄金层的方法。镀金钛板用作有机溶剂基的Li/CFx电池中的集电器。镀铂钛板已广泛用于电解槽。镀金不锈钢板也用于PEM燃料电池应用。通常,如果涂层材料具有合理的成本,并且涂覆工艺可靠和成本低,在低成本耐腐蚀的基板材料上涂覆导电涂层是常用的方法。
Neil Aukland报道了一组含有1-3at.%的铌或钽的低表面接触电阻钛合金(J.Mater.Res。,Vol.19,No.6,pp.1723-1729,2004年6月)。该合金可以形成半导电铌掺杂的氧化钛(或钽掺杂的氧化钛)表面层,该掺杂的氧化钛比纯钛表面形成的纯氧化钛有更低的表面接触电阻。该方法通过避免使用贵金属,具有金属成本低的优点。然而,其表面接触电阻对于PEM燃料电池应用仍然太高。
因此,期待具有适合电化学应用,有高耐腐蚀性和低表面接触电阻的金属部件。它既可以是特殊合金也可以是在金属基材上的表面涂层。同时,对于低成本的特殊合金和金属基材上的表面涂层的处理方法用于生产可靠耐用的,用于电化学装置的金属部件也有需求。
发明内容
公开的实施例提供了改变金属部件表面以实现较低的接触电阻的方法。该方法包括改变金属组分的表面以形成小的峰和凹坑,这些小的峰和凹坑能够成为与其它固体部件接触的高压接触点。小的峰和凹坑的直径在10纳米和10微米之间,高度在10纳米和10微米之间,分布密度在40万/cm2到50亿/cm2之间。该方法还包括改变Ti合金或Ti合金涂层的表面氧化物层组成,以获得更多的导电表面氧化物层。
附图说明
图1是用于表面接触电阻测量的设置。
图2A是铌掺杂的氧化钛的导电与铌的浓度的关系。
图2B是Ti-Nb合金的相图。
图3是包括圆型峰顶的金属板表面结构的示意性横截面图。
图4是包括尖锐峰顶的金属板表面结构的示意性横截面图。
图5是包括谷和凹坑的金属板表面结构的示意性横截面图。
图6是根据一个实施例的,52°视角的钛箔表面的SEM照片。表面包括许多具有尖锐顶部的小峰。
图7是根据一个实施例的,52°视角的316L不锈钢箔表面钛涂层的SEM照片。表面包括许多小圆形钛峰。
图8是根据一个实施方案的5,000×放大倍率的氢氟酸蚀刻的钛涂覆的316L不锈钢箔的SEM照片。
图9是根据一个实施方案的50,000×放大倍率的氢氟酸蚀刻的钛涂覆的316L不锈钢箔的SEM照片。
图10是根据一个实施方案的溅射的钛涂覆的316L不锈钢箔的SEM照片。
图11是根据一个实施方式的溅射Ti2Nb-SS的SEM图。
图12是根据一个实施方案的X10,000放大倍率下的蚀刻Ti2Nb-SS的SEM照片。
图13是根据一个实施方案的X50,000放大倍数下的蚀刻Ti2Nb-SS的SEM照片。
图14是根据一个实施方案的阴极弧等离子沉积的Ti-2Nb在不锈钢表面上的SEM图。
图15是根据一个实施方案的蚀刻阴弧等离子沉积的Ti-2Nb在不锈钢表面上的SEM照片。
具体实施方式
在下面的详细描述中,阐述了多种具体细节,例如材料和尺寸的类型,以提供对下面讨论的优选实施例的透彻理解。这些结合优选实施例讨论的细节不应被理解为对要求保护的发明的限制。此外,为了易于理解,某些方法步骤被描述为单独的步骤;然而,这些步骤不应被解释为在其性能中必然是不同的或者依赖于顺序的。
本文公开的实施例的目的是提供金属表面结构和处理工艺,以提供其低表面接触电阻并保持高耐腐蚀性。本发明用金属表面形态修饰来达到目的。更具体地,金属表面形态修饰是将表面转化为包括大量突出,峰,尖峰,谷,凹坑的微纹理结构。微纹理结构产生大量的高压接触点和更多的实际接触区域,其可以降低固体部件的表面接触电阻。
本文公开的实施方案的另一个目的是提供在金属部件上调整钛合金和钛合金涂层的表面氧化物化学组成以获得导电氧化物表面层的方法。更具体地,通过钛合金与氧的反应,在钛合金表面上生长表面氧化物。该表面氧化物的组成被调整到比合金内含更高的铌或钽浓度,以实现氧化物表面层的更高导电性。
在本说明书中,除非另有说明,符号“%”是指合金或氧化物中所有金属元素的原子%(金属基浓度)。高价元素是指其阳离子的价位大于+4的元素。高价元素的实例是铌,钽,钒,钼和钨。低价元素是指其阳离子的价值为小于或等于+4的元素。低价元素的实例是铝,锆,铪,钇,铁,镍和铬。
在本说明书中,掺杂的氧化钛是氧化钛与其它金属氧化物的混合物。钛是混合物中主要的金属元素。次要金属元素称为掺杂剂。例如,5%铌掺杂的氧化钛具有Nb0.05Ti0.95Ox的成分。其中氧含量x在2和1之间,它与掺杂剂浓度和掺杂的氧化钛的处理条件有关。
在本说明书中,掺杂的氧化钛也可以描述为氧化物层中所有金属元素(包括钛)的加权平均价位。尽管钛在掺杂氧化物中也可能以+2和+3价位存在,在计算中钛的价位为计算为+4,。成分为A+6 mB+5 nC+4 oD+3 pE+2 qOx的氧化物的平均价位计算方式为:
加权平均价位=6m+5n+4o+3p+2q,其中m,n,o,p和q是各金属元素的原子浓度,m+n+o+p+q=1。例如Nb0.08Al0.02Ti0.9Ox的加权平均价位等于0.08x5+0.02x3+0.9x4=+4.06。在同样的计算中,纯二氧化钛(TiO2)的加权平均价值为+4,Nb0.05Ti0.95Ox为+4.05。
在本说明书中,掺杂的五氧化二铌是五氧化二铌与其它金属氧化物的混合物。铌是混合物中主要的金属元素。次要金属元素称为掺杂剂。例如,10%钛掺杂的五氧化二铌具有Ti0.2Nb1.8Ox的配方。氧含量x在5和4之间。
在本说明书中,表面层组合物通过俄歇电子能谱(AES)或X射线光电子能谱(XPS)测定。这些方法能检测固体表面5-9nm深度的化学成分。其他方法可以检测具有不同深度范围的表面组成,但在本说明书中未使用。
在本说明书中,一些实施方案包括具有突出,尖峰,峰,谷和凹坑的金属表面形态。术语“峰”用于描述从基材表面突出的所有表面特征,例如尖峰,突出物和峰。术语“凹坑”用于描述低于基底表面的所有表面特征,例如谷和凹坑。这些峰和凹坑的尺寸被表征为高度和宽度。高度是峰顶到峰底的垂直距离。深度是凹坑顶部和底部之间的垂直距离。圆形峰和凹坑的宽度(或深度)是半高处的直径。不规则形状的峰和凹坑可以表征为最接近的圆形,或多个圆形连接在一起。窄片形状的峰和宽的宽度以半高(或深度)的宽度为特征。所有尺寸均为统计平均值。
本说明书所公开的方法的优点在于,它们可以以低成本生产高导电性和耐腐蚀性金属部件。以保证电化学装置的的长期运行。
图1是在公开的实施例中用于测量表面接触电阻(CR)的装置。附图标记1是测量的金属部件的样品,通常是平的金属板。附图标记2和3是与压在样品1上,与它接触的部件。附图标记4和5是把样品1和接触部件2和3压在一起的电极。附图标记6是在压力机,它提供加在组件1-5上的压力。接触部件2和3的典型材料是多孔碳毡片,例如TGP-H-060东丽碳纸。铂镀层钛网也用作接触元件2和3用于某些应用。电极4和5是镀金不锈钢。附图标记7是向组件1-5提供直流电流(I)的直流电源。附图标记8是测量电极4和样品1(V1)之间的电压降的电压计。附图标记9是测量两个电极4和5(V)之间的电压降的另一个电压表。附图标记10是测量通过组件1-5的电流的电流表。样品1和接触元件2和3之间的典型接触面积的尺寸为1平方英寸,直流电流为6.45A,这使得通过接触元件(2和3)和样品1接触表面的电流密度(i)为1A/cm2。
在测量时,首先测量电极4和5以及样品1和电极4之间的电压降(V和V1)。然后测量只有接触元件2和3(无样品1)下电极4和5之间的电压降(Vbase)作为基线电压降。接触元件2与样品1的表面接触电阻(CR)计算为:
CR=(V1-Vbase/2)/i
样品的穿透电阻(TPR)计算公式为:
TPR=(V-Vbase)/i
因为金属部件的体电阻非常小,所以穿透电阻TPR实际上是样品1与接触元件2的表面接触电阻(CR1-2)和样品1与接触元件3的表面接触电阻(CR1-3)。
TPR=CR1-2+CR1-3
表面接触电阻测量通常在15psi至300psi之间的压缩压力下进行,这个压力对应于不同应用的压力范围。例如,锂电池和电容器的压缩压力为~15psi,PEM燃料电池的压缩压力为100-200psi;在高压电解器中压缩压力要更高。这个压力把所有的电池组件压缩在一起以达到最佳性能。
虽然氧化钛是电绝缘体,但是它可以通过掺杂高价元素(M+5,M+6或M+7,M是金属元素)将其改变为半导体。高价元素包括铌,钽,钒,钼和钨。掺杂二氧化钛的导电性由掺杂剂浓度决定。图2A表示掺铌氧化钛的电导率与铌浓度的关系。它显示铌浓度在5-7%之间的铌掺杂的氧化钛达到最高体电导率(σb)。另一方面,晶界电导率(σgb)与制造工艺有关。A.Trenczek-Zajac和M.Rekas在Materials Science-Poland,Vol.24,No.1,2006中报道,掺铌氧化钛可以在更高的铌的浓度下,达到最高的电导率。
此外,如果掺杂剂浓度太高,则掺杂的氧化钛不能保持二氧化钛晶体结构,例如金红石,锐钛矿或板钛矿结构。掺杂的氧化钛将失去其半导电性质,而变成绝缘体。据报道,如果铌浓度高于15%,会生成不导电的TiNb2O7相。因此,期待获得氧化钛中掺杂剂的优化浓度。在掺铌氧化钛的情况下,铌的优化浓度为4-15%。
图2B是由T.B.Masslski,J.L.Murray,L.H.Bennett和H.Baker编辑的,由美国金属学会1986年出版“二元合金相图”中的钛-铌合金的相图。该图显示钛铌合金在400-882℃的温度下具有单一的α相,铌的浓度为0~2%。在铌浓度高于37%时,合金在400℃时将具有单一的β相。在铌浓度为2%至37%之间,合金将为低铌浓度的α相和高铌浓度β相的混合物。尽管在400℃以下没有报道钛-铌相图的数据,但预期相位结构将类似于400℃,只是α和β相的铌浓度范围可能略微不同于在400℃。例如,α相中的最大铌浓度可以在1-3%的范围内,并且在室温下β相中的最小铌浓度可以在35-40%的范围内。
众所周知,合金在室温下的实际相结构也与相变反应动力学的条件有关。在一些情况下,也可以在室温下以两相结构浓度范围获得合金的单相结构。
掺杂的氧化钛可以制备为氧化物陶瓷材料。它也能够以薄的表面氧化物层的形式在钛合金表面上生长。
金属表面氧化物层的组成与金属基材的表面组成高度相关。通常,具有较高铌浓度的钛合金表面将形成具有较高铌掺杂浓度的氧化钛表面层。例如,低铌含量α相合金表面将形成低浓度铌掺杂氧化钛表面层。高铌含量的β相合金将形成高浓度铌掺杂的氧化钛表面层。
在两相Ti-Nb合金的情况下,表面氧化物的组成不均匀。低铌含量的α相上的表面氧化层将具有低浓度的铌掺杂的氧化钛,并且高铌含量的β-金属相上的表面氧化物层将具有与氧化钛混合的高浓度的铌。例如,具有2%铌的α相上的表面氧化物通常具有接近2%的铌掺杂的氧化钛的组成,并在具有40%铌的β相上的表面氧化物通常具有接近40%浓度氧化铌的氧化钛混合物。
如上所述,低铌含量α相上的表面氧化物层是半导电的,但是在高铌含量(高达40%)的情况下,因为铌掺杂剂浓度会改变氧化物的晶体结构并导致非导电相,β相上的表面氧化物可能是非导电的。因此,必须控制合金中的铌浓度以避免表面氧化物层中的高电阻相。
其他Ti合金,如Ti-Ta,Ti-V,Ti-Mo和Ti-W在保持Ti合金的α相中的高掺杂剂元素浓度方面具有相似的限制。必须仔细控制其配方以避免表面氧化物层中的高电阻相。
钛合金和掺杂的钛氧化物的这些固有性质是在Neil Aukland的工作中制約其达到更低的表面接触电阻的原因。它们只能在钛合金中获得3%的铌或钽的浓度,以避免表面氧化物层中的高电阻相。但它不能在掺杂的氧化钛表面层中提供足够高浓度的掺杂剂,以达到更低的表面接触电阻以满足PEM燃料电池应用的目标。
另一种类型的稳定半导体氧化物是低元素掺杂的五氧化二铌。例如,掺杂五氧化铌的+4价态的钛会使一些Nb+5离子转变为Nb+4状态,这使得五氧化二铌更具导电性。与掺杂的氧化钛半导体类似,掺杂的氧化铌必须保持五氧化物晶体结构的金属离子与氧的比例为2:5。最常见的掺杂剂是氧化钛。还可以使用其它低价金属元素,例如锆,钇,铪和氧化钪。
所公开的实施方案的目的是克服这些限制,通过修饰表面氧化物层的化学组成以实现低表面接触电阻的方法。
图3是金属表面峰的的示意性横截面图。峰的顶部为圆形。附图标记11是作为基板的金属部件的主体。附图标记12是金属部件表面上的峰。峰12可以具有与金属体11相同的材料或不同的材料。
图4是金属表面峰的示意性横截面图。峰的顶部为尖锐的形状。附图标记21是金属部件的主体。附图标记22是金属部件表面上的峰。峰22可以具有与金属体21相同的材料或不同的材料。
在本文公开的一个实施方案中,金属部件的表面结构被调整为具有小的峰。小峰形成与其他固体部件之间的大量高压接触点和实际接触面积。在一些实施方案中,小峰在高接触压力下发生弹性或者塑性变形,形成与其他接触部件的高的表面接触面积和低的电接触电阻。在这些实施方案中,小峰的表现类似于先前技术中的软接触材料。但其柔软度是通过小尺寸实现的,而不是像金和锡一样的材料固有特性。在一些实施例中,峰可以在接触点上以高压来穿过接触部件的高电阻表面层,达到低电阻接触。
峰的直径可以在10纳米至10微米之间的圆形或不规则形状。他们可以垂直于表面,或者不垂直于表面。它还可以是厚度在5纳米至5微米之间的薄片形状。峰的高度在10纳米至10微米之间。峰的分布密度(每平方厘米内峰的总量)在50万/cm2至50亿/cm2之间。峰顶可以具有如图3所示的圆形形状,或如图4所示的尖锐形状。在一些实施例中,峰的直径或宽度范围为5nm-10nm,5nm-100nm,50nm-500nm,10nm-20μm,5nm-0.5μm,20nm-1μm,100nm-0.9μm,20nm-5μm,100nm-2μm,0.5μm-5μm,或1μm-10μm。在一些实施方案中,峰的高度可以10nm-100nm,50nm-500nm,10nm-10μm,50nm-0.5μm,20nm-1μm,100nm-0.9μm,20nm-5μm,100nm-10μm,0.5μm至5μm,或1μm-10μm的范围内。在一些实施方案中,峰的分布密度在50万-1亿/cm2,100万-2亿/cm2,500万-2亿/cm2,500万-5亿/cm2,1千万-10亿/cm2,2千万-20亿/cm2,5千万-50亿/cm2,1亿-50亿/cm2的范围内。
在一个实施例中,金属基板11的表面涂覆有另一种材料(图3中未示出),以获得更好的耐腐蚀性和电导率。峰12可以是与涂层材料相同或不同的材料。该涂层材料的厚度在5nm至5μm之间。在一些实施方案中,涂层的厚度为5-20nm,10-50nm,20-200nm,50-500nm,0.1-0.5μm,0.2-1μm,0.5-2μm,1μm-5μm和2-5μm。
在一个实施例中,金属基底11表面被改变为具有微观纹理表面结构,然后用另一种材料(图3中未示出)涂覆微织构金属基底,以获得更好的耐腐蚀性和电导率。该涂层材料的厚度在5nm至5μm之间。在一些实施方案中,涂层的厚度为5-20nm,10-50nm,20-200nm,50-500nm,0.1-0.5μm,0.2-1μm,0.5-2μm,1-5μm和2-5μm。
在一个实施例中,金属部件的表面被改变为在表面上具有小凹坑。这些凹坑具有尖锐的边缘,其作为高压点,以降低与其它部件接触时接触电阻。凹坑可以具有直径在5纳米至20微米之间的圆形或不规则形状。凹坑还可以具有宽度在10纳米至10微米之间的窄间隙形状。凹坑的深度为50纳米至10微米。凹坑的分布密度在50万/cm2至50亿/cm2之间。在一些实施例中,凹坑的直径或宽度范围为5nm-10nm,5nm-100nm,50nm-500nm,10nm-20μm,5nm-0.5μm,20nm-1μm,100nm-0.9μm,20nm-5μm,100nm-2μm,0.5μm-5μm,1μm-10μm或5μm-20μm。在一些实施例中,凹坑深度在50nm–500nm,50nm–10m,70nm–0.5m,70nm–1m,100nm–0.9m,100nm–5m,100nm–10m,0.5m–5m,or 1m–10m。在一些实施方案中,凹坑的分布密度在50万-1亿/cm2,100万-2亿/cm2,500万-5亿/cm2,,1千万-10亿/cm2,2千万-20亿/cm2,5千万-50亿/cm2,1亿-50亿/cm2的范围内。
图5是在金属部件31的表面上具有凹坑32的金属表面的示意性横截面图。
在一个实施例中,如图3-5所示,金属部件表面具有峰和凹坑。峰和凹坑的尺寸和分布与上述第一实施例中描述的相同。
在一个实施方案中,制备低合金元素浓度的单相钛合金基底或钛合金涂层。然后,用化学蚀刻法清除合金表面原有的表面氧化物层。利用钛和合金元素的蚀刻速率不同,通过适当地控制蚀刻条件使蚀刻表面的合金元素浓度高于其在合金基体内的浓度。钛和合金元素之间的蚀刻速率差由蚀刻剂浓度,蚀刻时间,蚀刻温度决定。在低蚀刻浓度和短蚀刻时间下,钛蚀刻和合金元素蚀刻的差异可能太小,不能富集表面氧化物层中的合金元素。为了获得高合金元素浓度的表面层,应在足够的蚀刻剂浓度和蚀刻时间的条件下进行蚀刻。在室温下,由于在室温下相变的动力学限制,具有高合金元素浓度的蚀刻表面仍然是原始的单相结构。因此,在具有较高合金元素(掺杂剂)浓度的蚀刻钛合金表面上自然形成薄的氧化物表面层。蚀刻的钛合金表面上的氧化物表面层具有比原始钛合金表面上形成氧化物更高的掺杂剂浓度。较高的掺杂剂浓度可以增加导电表面氧化物层并降低合金与其它组分的表面接触电阻。
在一个实施方案中,制备低合金元素浓度的单相钛合金或合金涂层。然后,将合金表面加热至高温。合金元素可以扩散并富集在表面氧化物层上,导致高掺杂剂浓度的表面氧化物层。热处理温度为100-800℃,持续10秒至1小时。在一些实施方案中,氧化温度为100-300℃,250-400℃,400-600℃,550-700℃,500-800℃。在一些实施方案中,热处理时间为10秒至1分钟,30秒至5分钟,1分钟至20分钟,10分钟至1小时。在一个实施例中,合金元素是铌或钽。
合金元素是高价金属元素,包括Nb,Ta,V,Mo,W。在二元Ti合金中高价元素的浓度在0.01和3%之间,以维持α单相结构。在一些实施方案中,钛中高价元素的浓度在0.01-0.1%,0.01-0.5%,0.1-1%,0.2-1%,0.5-1%,0.2-2.5%,0.5-3%,1-2%和1-3%。在一些实施方案中,含有多种合金元素的钛合金中必须包括高价元素,合金的组成必须选择以保持单相结构,并且总合金元素的浓度应小于30%。在一些实施方案中,总合金元素浓度为0.1-1%,0.5-2%,0.5-5%,1-8%,1-10%,2-15%,5-20%,1-30%,5-30%和10-30%。
二元合金的表面氧化物层中的高价元素的浓度为3-25%。在一些实施方案中,表面氧化物层中的高价元素浓度为3-5%,3-8%,4-10%,5-10%,5-15%,5-15%,7-20%,7-25%,10-25%和15-25%。在含有多于一种合金元素的蚀刻表面氧化物层的一些实施方案中,高价(M+5,M+6,M+7)元素的浓度必须足够高以补偿低价(M+3,M+2,M+1)元素,并保持表面氧化物中金属元素的加权平均价位在+4.02至+4.25的范围内。在一些实施例中,加权平均价位在+4.02至+4.05,+4.02至+4.10,+4.03至+4.20,+4.05至+4.10,+4.05至+4.15,+4.05至+4.20,+4.07至+4.15,+4.10至+4.20,+4.15至+4.20和+4.15至+4.25。
钛合金表面上的表面氧化物层的组成可以通过初始钛合金的组成,蚀刻方法,蚀刻剂组成和蚀刻条件(温度,浓度,蚀刻时间等)来调整。
蚀刻方法包括湿化学蚀刻,电化学蚀刻,等离子体增强的离子蚀刻,蒸气蚀刻或其它干蚀刻工艺。在等离子体蚀刻工艺中,蚀刻剂是在等离子体下由氟或含氯化合物产生的氟或氯自由基。自由基浓度在大的离子体功率下会更高。由于钛与氧气的活性高,因此蚀刻后的钛合金表面将一旦与氧气或水接触就会自然生长出新的氧化物表面层。
钛合金上的半导体掺杂的氧化钛表面层可以通过用受控表面氧化过程(例如热氧化,等离子体氧化,湿化学氧化和阳极氧化)来增加厚度以提高其电化学稳定性。较厚的氧化物层会增加合金的表面接触电阻,但会使其在电化学装置的工作环境中更稳定。热氧化温度在100-800℃之间。在一些实施方案中,热氧化温度在100-200℃,100-400℃,200-450℃,200-500℃,300-500℃,400-600℃和500-800℃的范围内。
在另一个实施方案中,低成本金属用作电化学装置中金属部件的基底材料。在低成本的金属基底表面上涂覆钛合金以提高耐腐蚀性并降低基底金属的表面接触电阻。钛合金含有高价合金元素,并且在其被涂覆在基材表面上之后具有单相结构。相可以是α相,β相或非晶相。对于在室温下不是单相的钛合金涂层材料,涂层工艺必须在涂覆过程中迅速将涂层合金从高温淬火以将高温单相冷凝至低温。合适的涂层工艺包括热喷涂和阴极弧等离子沉积。钛合金涂层表面将形成具有低表面接触电阻并增强低成本金属基底材料的耐腐蚀性的半导电表面氧化物层。合金元素是高价金属元素,包括在含Nb,Ta,V,Mo,W的二元Ti合金中,高价元素的浓度控制在0.01至20%之间,以维持单相涂层。在含多种合金元素的钛合金的情况下,必须包含高价元素,并且合金元素的总浓度为0.01~40%。在一些实施方案中,总合金元素浓度在0.01-0.2%,0.1-1%,0.5-2%,0.5-5%,1-8%,1-10%,1-30%,1-40%,2-15%,5-20%,5-30%,5-40%,15-30%,10-30%,10-40%。
在一些实施方案中,可以通过化学蚀刻的方法,调整表面氧化物层使其具有最佳成分和形貌,以达到最低的表面接触电阻。蚀刻的钛合金涂层表面形成掺杂的氧化钛表面层。对于具有高合金元素的二元钛合金的涂层,表面氧化物层中的掺杂剂浓度为3-15%。在一些实施方案中,表面氧化物层中的高价元素浓度为3-5%,3-8%,4-10%,5-10%和5-15%。对于多元素合金的涂层,表面氧化物层中高价(M+5,M+6,M+7)元素的浓度必须足够高以补偿低价(M+3,M+2,M+1)元素,并保持表面氧化物中金属元素的加权平均价位在+4.02至+4.25的范围内。在一些实施例中,加权平均价位在+4.02至+4.05,+4.02至+4.10,+4.03至+4.20,+4.05至+4.10,+4.05至+4.15,+4.05至+4.20,+4.07至+4.15,+4.10至+4.20,+4.15至+4.20和+4.15至+4.25。
半导体掺杂的氧化钛表面层在钛合金涂层上的电化学稳定性可以通过用受控的表面氧化过程(例如热氧化,等离子体氧化,湿化学氧化)增加表面氧化物厚度来增强和阳极氧化。较厚的氧化物层会增加合金的初始表面接触电阻,但会使其在电化学装置的工作环境中更稳定。热氧化温度在100-800℃之间。在一些实施例中,热氧化温度在100-200℃,100-400℃,200-450℃,200-500℃,300-500℃,400-600℃和500-800℃的范围内。
低成本基底材料可以是铁,铬,镍,钴,锰,铝和含有这些元素的合金中的一种。基材的实例是商业纯钛,316L不锈钢和6061铝合金。
Ti合金涂层厚度在0.01微米至100微米之间,优选在0.05微米至5微米之间。在一些实施例中,钛合金涂层的厚度为0.01m–0.05m,0.01m–0.1m,0.05m–0.2m,0.05m–0.5m,0.1m–0.5m,0.1m-1m,0.5m-3m,0.5m-5m,0.5m-10m,1m-10m,0.5m-50m,1m-50m,5m-50m,5m-100m and 10m-100m。
用于钛合金涂层的沉积方法包括物理气相沉积(PVD)和热喷涂工艺。
可以通过初始钛合金的组成,蚀刻方法,蚀刻剂组成和蚀刻条件(温度,浓度,蚀刻时间等)和热氧化来调整蚀刻的钛合金涂层表面层的组成。蚀刻方法包括湿化学蚀刻,电化学蚀刻,等离子体增强反应离子蚀刻,蒸气蚀刻或其它干蚀刻工艺。
涂层板的表面接触电阻可通过将表面形态改变为以小峰和凹坑构成的微结构化表面的方式进一步降低。峰和凹坑的尺寸和分布与上述相同。
微结构化表面上的峰和凹坑可以通过从金属基底表面去除一些材料或者在金属基底表面添加材料的方法实现。例如可以通过化学蚀刻Ti合金涂覆的金属基材或者在基板表面上沉积Ti合金涂层来获得微纹理表面结构。其他处理过程还包括冷轧,喷砂,喷水,激光雕刻和沉积其他材料以在表面上形成峰。沉积方法可以是PVD,热喷涂,电镀和其他添加剂制造工艺。
典型的金属板通过多步轧制和应力释放热处理来生产。结果,多晶结构的晶粒相当大,例如直径为10-100μm。这种材料的蚀刻只能获得不能充分降低金属板表面接触电阻的大尺寸(>10微米)的峰值和凹坑。在一个实施方案中,金属组分或其表面层的晶粒尺寸减小至<10微米,甚至<1微米。然后,可以使用化学蚀刻方法从表面除去一些晶粒,以获得具有低接触电阻的上述所需的微观结构表面结构。
可以通过金属基材表面的快速熔融和固化来获得晶粒尺寸减小以获得表面层的无定形或纳米结构化结构。再结晶层的厚度为0.5~20μm。然后使用热处理步骤获得指定的晶粒尺寸。通常,较高的热处理温度和更长的处理时间将导致较大的晶粒尺寸。对于典型的不锈钢和钛合金,热处理温度在800-1200℃之间,热处理时间为0.5-5小时。
表面层的晶粒尺寸也可以通过在低于800℃的温度下沉积涂层材料来获得。低沉积温度将确保涂层的小晶粒尺寸。在一个实施例中,使用物理气相沉积工艺将涂层材料沉积在金属衬底表面上。涂层的典型晶粒尺寸小于1微米。
在一个实施方案中,通过快速固化方法如熔态旋分法制备金属基材,以获得无定形或纳米结晶结构。然后使用热处理步骤获得金属基材的指定晶粒尺寸。通常,较高的热处理温度和更长的处理时间将导致较大的晶粒尺寸。对于典型的不锈钢和钛合金,热处理温度在800-1200℃之间,热处理时间为0.5-5小时。
通过用受控的表面氧化过程(例如热氧化,等离子体氧化,湿化学氧化和阳极氧化)增加表面氧化物厚度,可以增强钛合金涂层上的半导体掺杂的氧化钛表面层的电化学稳定性。较厚的氧化物层增加了合金的初始表面接触电阻,但是它使得氧化物层在电化学器件的操作环境中更加稳定。热氧化温度在100-800℃之间。在一些实施方案中,其在100-200℃,100-400℃,200-450℃,200-500℃,300-500℃,400-600℃和500-800℃的范围内。
在一个实施例中,铌合金用作低成本金属基底(例如不锈钢或铝)上的涂层材料。铌合金含有低价合金元素,如钛,锆,铪,钇,钪,铝。这些合金元素在铌合金中的浓度在1%和25%之间。在低成本金属基板上涂覆铌合金之后,在表面上形成掺杂的五氧化二铌表面层。掺杂的五氧化二铌表面层可以在室温下通过空气中的天然氧化形成,或通过阳极氧化增强氧化,用氧化剂如硝酸或过氧化氢进行湿化学氧化,热氧化或等离子体氧化。半导体掺杂的五氧化二铌表面层可以保持电化学应用中金属组分的低电气表面接触电阻。在一些实施方案中,铌合金涂层材料中的掺杂剂元素浓度为1-5%,1-10%,1-15%,2-15%,2-20%,3-30%,5-20%,5-25%和10-25%。热氧化温度在100-600℃之间。在一些实施方案中,其在100-200℃,100-400℃,200-450℃,200-500℃,300-500℃,400-600℃和500-800℃的范围内。
铌合金涂层的厚度在0.01-10微米之间。在一些实施例中,铌合金涂层的厚度为0.01m–0.05m,0.01m–0.1m,0.05m–0.2m,0.05m–0.5m,0.1m–0.5m,0.1m-1m,0.5m-3m,0.5m-5m,0.5m-10m and 1m-10m。
实施例1
选择商业纯钛箔进行表面改性以降低表面接触电阻。将3cm×5cm的钛箔在室温下浸泡在50ml 1.5wt%氢氟酸溶液中约2小时。首先,氢氟酸蚀刻掉钛的天然氧化物表面层。然后,不断蚀刻钛箔的金属部分。在蚀刻过程中,氢氟酸被消耗;其浓度不断降低,并且在贫化氢氟酸溶液中的钛的蚀刻速率降低。
该蚀刻工艺将平坦钛表面的形态转化为小峰。图6是在52°视角下蚀刻的钛表面的SEM照片。它包括大量具有尖锐顶部的小峰。一些峰处于宽度在50-100nm之间的薄片形状。一些峰的直径为50-100nm。峰的高度在50nm和1微米之间。峰的分布密度估计接近10亿/cm2。
为了稳定表面氧化物层,将蚀刻的钛箔在空气中在450℃下热氧化1小时。然后用两块碳毡(TGP-H-060东丽碳纸)测量钛箔的穿透电阻(TPR)。表1总结了450℃热氧化后的蚀刻的钛箔和原始钛箔的穿透电阻。该表显示,在150psi下,蚀刻钛的TPR为18.1m.cm2。相比之下,原始钛箔在150psi下的TPR为1.04cm2,比通过蚀刻改变表面形态的钛箔高约58倍。
表1. 450℃热氧化后原始钛和蚀刻钛的电穿透板电阻
蚀刻的钛表面是超亲水性的。由于去除高应力表面层,箔比原来的冷轧箔更软和更柔韧。超亲水表面性质对于燃料电池和电解堆的水管理具有额外的优点。箔的高柔性可能有利于在电解堆中更容易地变形,以便于密封和集成。
实施例2
使用316L不锈钢箔作为基材。商业纯钛通过阴极弧等离子镀的方法沉积在表面上(CA-Ti-SS)。阴极弧等离子镀是一种工业涂层工艺,可以将钛靶表面熔化并将熔融的钛液滴与钛蒸气一起喷射到基底。钛蒸汽和液滴沉积在不锈钢基材表面上。蒸汽用钛涂覆不锈钢表面,液滴在涂层表面形成小的圆形钛峰。图7是具有大量圆形钛峰的316L不锈钢箔的52°视角的SEM照片。不锈钢上Ti涂层的厚度为0.5-2微米。峰的直径为0.5至10微米。峰的高度在0.5和15微米之间。峰值的分布密度估计为1百万-10千万/平方厘米。
相比之下,316L不锈钢箔也可以用直流磁控溅射法涂覆钛(SP-Ti-SS)。溅射工艺能够在衬底表面上沉积相对平坦的涂层。图10是具有溅射钛表面的316L不锈钢箔的SEM照片。成品表面保持冷轧不锈钢箔的原始形态,无大量峰和凹坑。
用氢氟酸蚀刻进行钛涂覆的不锈钢箔表面的进一步改性。将钛涂不锈钢箔在2wt.%的氢氟酸溶液中浸泡30秒(蚀刻CA-Ti-SS或蚀刻的SP-Ti-SS)。图8和9分别是放大倍率为5000X(蚀刻CA-Ti-SS)和50,000X(蚀刻SP-Ti-SS)的蚀刻钛涂层不锈钢箔表面的SEM照片。蚀刻工艺在钛涂层的在圆峰和峰底部的平坦表面上产生许多凹坑。坑具有锐利的边缘。凹坑的直径在0.5和10微米之间。坑的分布密度估计为约10千万-10亿/平方厘米。
钛涂布的不锈钢箔的表面性质的表征方法是夹在两片碳毡(TGP-H-060东丽碳纸)中,在35-300psi的压缩压力范围内测量表面接触电阻(CR)。表2总结了测量结果。该表显示,具有小圆峰的CA-Ti-SS比相对平坦的SP-Ti-SS具有更低的CR。具有额外凹坑的蚀刻CA-Ti-SS和蚀刻SP-Ti-SS具有比作为涂覆箔更低的穿透电阻。
表2.钛涂层不锈钢箔的电穿通板电阻
蚀刻的钛涂层的SS表面是超亲水性的,这对于燃料电池堆中的水管理具有额外的优点。本例中的低表面电阻表面改性钛涂层不锈钢可用作PEM燃料电池的双极板材料。
实施例3
制备钽浓度为2%的钛-钽二元合金(Ti-2Ta)。用#320砂纸研磨合金表面(研磨Ti-2Ta)。将另一块#320砂纸研磨的Ti-2Ta合金在2重量%氢氟酸溶液中化学蚀刻2分钟(蚀刻Ti-2Ta)。预计研磨Ti-2Ta的表面层组成与合金体内相同(2%Ta),但由于Ti的蚀刻速率更快,蚀刻Ti-2Ta在表层具有高的Ta浓度。新鲜的Ti-2Ta合金将自然地在表面生长一层薄的Ta掺杂氧化钛。蚀刻Ti-2Ta合金表面氧化层中的钽掺杂浓度高于研磨Ti-2Ta合金。研磨和蚀刻Ti-2Ta合金的表面接触电阻用碳毡(TGP-H-060东丽碳纸)在35-300psi压缩压力范围内测量,并总结在表3中。该表显示,由于表面氧化层中较高的Ta浓度,因此刻蚀Ti-2Ta具有比研磨的Ti-2Ta更低的接触电阻。
表3.新鲜Ti-2Ta与碳毡的接触电阻
氧化物表面层越厚,研磨和蚀刻的Ti-2Ta之间的接触电阻的差异变得越大。把研磨和蚀刻的Ti-2Ta合金在空气中在300℃下热氧化1小时后,它们的接触电阻用碳毡测量,并总结在表4中。该表显示,热氧化的研磨Ti-2Ta与碳毡的接触电阻在150psi压缩压力下为150.56m .cm2。在同样压缩压力下,热氧化的蚀刻Ti-2Ta的碳毡的接触电阻为27.09m cm2,远低于研磨的Ti-2Ta。
表4.热氧化Ti-2Ta与碳毡的接触电阻
实施例4
制备铌浓度为2%(Ti-2Nb)的钛-铌二元合金直流磁控溅射靶,用于在不锈钢(SS)箔表面(Ti2Nb-SS)上沉积5微米厚的Ti-2Nb涂层。溅射Ti-2Nb在SS表面的扫描电子显微镜(SEM)图如图11所示。它包括在溅射沉积过程中生长的小颗粒和大颗粒团簇。涂层表面分析通过能量色散X射线光谱(EDS)和AES进行。发现涂层的主体与目标材料(Ti-2Nb)具有相同的组成,但是沉积的Ti-2Nb层的表面层具有低得多的铌浓度。还发现其组成偏析与溅射处理条件有关。在不同的溅射工艺条件下,沉积的Ti-2Nb层的表面层中铌浓度更接近靶料。
使用2wt.%氢氟酸溶液蚀刻50秒的湿法化学蚀刻方法去除贫铌的钛合金涂层表面层(蚀刻Ti2Nb-SS)。AES分析表明,表面氧化物层的铌浓度(金属基质,不包括氧,氮和其他吸收的杂质)增加到5.7%,估计的表面氧化物厚度小于10nm。表层中铌浓度的增加是钛比铌的蚀刻速度更快的结果。图12和13是蚀刻Ti2Nb-SS的SEM图。蚀刻Ti2Nb-SS的表面形貌包括许多峰和凹坑。峰的直径为0.05至1微米,具有不规则形状。凹坑的宽度为0.1至5微米。这些峰和凹坑增加了金属板和电化学装置中的其他组分之间的高压接触点的量,这将导致较低的接触电阻。
为了进一步稳定表面氧化物层,将有蚀刻Ti-2Nb涂层的SS箔在空气中在300℃下热氧化1小时,以生长更厚的掺铌氧化钛层(氧化Ti 2Nb-SS)。在氧化表面进行AES分析,发现表面氧化物层的铌浓度(金属基底,不包括氧,氮和其他吸收的杂质)增加到8.2%,表面氧化物层的厚度约为98nm。显而易见的是,热氧化过程可以进一步富集表面氧化层中的铌,产生无水的厚的氧化物表面层,它比在室温下蚀刻时形成的水合氧化物表面层更稳定。高温处理也可以导致更好的结晶掺杂的氧化钛层,其具有较高的导电性。
使用碳毡(TGP-H-060东丽碳纸)在35-300psi的压缩压力范围内测量经蚀刻的Ti2Nb-SS和氧化的Ti2Nb-SS的贯通电阻,并总结在表5中。发现氧化的Ti2Nb-SS具有比蚀刻的Ti2Nb-SS更高的接触电阻。
蚀刻和氧化的Ti2Nb-SS的稳定性是通过电化学腐蚀试验来评估。将涂覆的不锈钢样品在80℃下浸入pH3H2SO4+0.1ppm HF溶液中。在样品上施加0.8VNHE的电化学电位并保持100小时。然后,测量腐蚀样品的穿透电阻,并总结在表5中。发现虽然蚀刻Ti2Nb-SS的穿透电阻小于氧化Ti2Nb-SS的穿透电阻,但是在腐蚀后蚀刻Ti2Nb-SS的电阻有所增加。然而,氧化Ti2Nb-SS在腐蚀后没有电阻增加,这表明氧化的Ti2Nb-SS具有优异的耐腐蚀性。
表5.在80℃下pH3 H2SO4+0.1ppm HF溶液中0.8VNHE100小时腐蚀试验前后蚀刻和氧化的Ti2Nb-SS穿透电阻比较
实施例5
制备铌浓度为2%(Ti-2Nb)的钛-铌二元合金阴极电弧沉积靶。用于在不锈钢(SS)箔表面(CA Ti2Nb-SS)上沉积2微米厚的Ti-2Nb涂层。溅射的Ti-2Nb在SS表面上的扫描电子显微镜(SEM)图显示在图14中。它包括从衬底表面突出的小峰。峰的直径在0.05μm和10μm之间。峰的高度在0.5和15微米之间。峰值的分布密度估计为1百万-10千万/平方厘米。涂层表面分析通过EDS和XPS进行。发现涂层的体积和表面层具有与靶材(Ti-2Nb)相同的组成(Ti中含约2%Nb)。
通过在2wt.%氢氟酸溶液中蚀刻30秒的CA Ti2Nb-SS(蚀刻CA Ti2Nb-SS)。图15是蚀刻后的CA Ti2Nb-SS的SEM照片。这表明蚀刻步骤在表面上产生了许多凹坑。这些坑具有锋利的边缘,孔的直径在1至10微米之间。此外,蚀刻表面没有显示涂层材料的晶界,这表明由阴极弧沉积的涂层是非晶结构的。通过AES分析蚀刻的CA Ti2Nb-SS的表面氧化物层组成。发现通过蚀刻将表面氧化物层中的铌浓度(金属基)富集至6.3%。
表面上的峰和凹坑将有效地增加金属板与其它部件的高压接触点的数量,从而降低接触电阻。蚀刻前后的CA Ti2Nb-SS的穿透电阻是使用碳毡(TGP-H-060东丽碳纸)在35-300psi的压缩压力范围内测量,并总结在表6中。CA Ti2Nb-SS和蚀刻的CA Ti2Nb-SS都具有较低的TPR。蚀刻的样品由于掺杂的氧化钛表面中较高的铌浓度和由具有尖锐边缘的凹坑产生的额外的高压接触点,因此具有较低的电阻。
表6.通过沉积和蚀刻的CA Ti2Nb-SS的平板电阻
实施例6
钛板表面用沙子喷砂以在表面上产生小的峰和凹坑。砂的平均粒度在22和0.1微米之间(#400和更细)。成品表面具有0.01-1微米的尺寸(宽度)的峰值,尺寸(宽度和深度)的凹坑为1-20微米。
喷砂钛板表面通过PVD工艺涂覆有Ti-2Nb合金薄层。Ti-2Nb涂层的厚度为0.005-5μm。半导电铌掺杂的氧化钛表面层在涂覆的钛板上天然地形成。可以应用蚀刻步骤来改变表面氧化物层的组成,以进一步改进掺杂氧化钛层的表面电导,其中掺杂元素如铌的浓度较高。
涂覆的钛合金可用于燃料电池,电解槽和电容器以降低它们的内部电阻。根据应用要求,可以通过氧化过程来增加铌掺杂的氧化钛表面层的厚度。氧化过程可以是等离子体氧化,阳极氧化(电氧化),具有氧化剂的溶液中的化学氧化和在含氧气氛中在高温下的热氧化。
优选的氧化方法是空气中的热氧化。温度在100-600℃之间。气氛也可以处于不同的压力(从高压到真空)和其它含氧化合物,如蒸汽和二氧化碳,以获得更好的表面氧化物层质量。
实施例7
制备铌浓度为2%的钛-铌二元合金DC磁控溅射靶(Ti-2Nb),用于在不锈钢(SS)箔表面上沉积5微米厚的Ti-2Nb涂层。然后将Ti-2Nb涂覆的SS放置在Plasma Etch,Inc生产的PE-200RIE反应等离子蚀刻系统中。蚀刻条件为100W,持续30分钟,O2的流速为15毫升/分钟,CF4的流速为85毫升/分钟。真空度约为0.2托。用碳毡(TGP-H-060东丽碳纸)测量经等离子蚀刻的Ti-2Nb涂覆的SS的穿透电阻。测量发现,在150psi的压缩压力下,反应等离子体蚀刻的Ti-2Nb涂覆的不锈钢的穿透电阻降低到7.58m/cm2。AES表面分析发现,表面氧化物层中的铌浓度为18%。
实施例8
制备铌浓度为2%(Ti-2Nb)的钛-铌二元合金DC磁控溅射靶。用于在不锈钢(SS)箔表面上沉积5微米厚的Ti-2Nb涂层。将Ti-2Nb涂覆的SS放入含有XeF2颗粒的铝真空室中。保持在200ml/min的氩气流量下真空度为0.45托,将Ti-2Nb涂覆的SS保持在真空中蚀刻60分钟。用碳毡(TGP-H-060东丽碳纸)测量经蚀刻的Ti-2Nb涂布的SS的贯通板电阻。已经发现,在150psi的压缩压力下,蚀刻的Ti-2Nb涂覆的不锈钢的贯通板电阻降至17.40m/cm2。
实施例9
制备铌浓度为2%(Ti-2Nb)的钛-铌二元合金DC磁控溅射靶。用于在不锈钢(SS)箔表面上沉积5微米厚的Ti-2Nb涂层。将Ti-2Nb涂覆的SS放入PE-200RIE反应等离子体蚀刻系统中,在不同条件下进行蚀刻。表7总结了氧气流量为15cc/min,CF4气体流量为85cc/min,真空度为0.2托时的蚀刻条件下,蚀刻后表面氧化物层的最终Nb浓度。该结果显示表面氧化物层中的Nb浓度急剧增加。最终浓度与等离子体蚀刻功率和蚀刻时间有关。在高蚀刻功率和长蚀刻时间下,会产生更多的氟自由基,因此在蚀刻板的表面氧化物层中Nb浓度的富集更显着。该实验表明,可以通过蚀刻条件来调整表面组成。在另一个实验中也发现,低功率和短时间的等离子体蚀刻不会富集表面氧化物层中的铌。
表7. Ti2Nb-SS等离子体蚀刻条件和表面层中的Nb浓度
实施例10
用为真空熔化和冷轧的方法制备含有3%Nb的Ti-Nb合金板。然后,将该合金板抛光以获得光滑的表面。从抛光的片材上切下两片样品。一片在400℃下空气中氧化1小时,另一片在600℃下空气中氧化1小时。对这些样品进行XPS分析。发现两种样品的表面氧化层中的Nb浓度在热氧化后增加。400℃氧化样品表面的Nb浓度为5.3%,600℃氧化样品的Nb浓度为8.5%。该实验表明,通过热处理条件可以控制表面氧化物层中的掺杂剂(Nb)浓度。较高的处理温度将导致氧化物层中高的Nb浓度。
实施例11
制备铌浓度为7%(Ti-7Nb)的钛-铌二元合金阴极电弧沉积靶。用于在不锈钢(SS)箔表面(CA Ti-7Nb-SS)上沉积2μm厚的Ti-7Nb涂层。通过适当的工艺控制,Ti-7Nb涂层处于单一非晶相,表面有许多圆形峰。该涂层可以降低金属箔的表面接触电阻。除了通过阴极电弧沉积沉积的小峰之外,还可以通过使用2wt.%氢氟酸溶液的表面蚀刻工艺在表面上产生小凹坑进一步降低其电阻。在蚀刻后,表面氧化物层中的铌浓度也增加。
实施例12
制备铌浓度为1%(Ti-1Nb)的钛-铌二元合金DC磁控溅射靶。用于在不锈钢(SS)箔表面上沉积0.5μm厚的Ti-1Nb涂层。在将涂覆的不锈钢暴露于空气之前,在Ti-1Nb溅射之后,将涂覆的不锈钢移至另一个真空室。真空控制在0.01毫巴,氯气和氩气混合物流量为200毫升/分钟,持续2分钟。气态真空蚀刻可以富集Ti-1Nb涂层表面上的铌浓度,以增加涂层不锈钢的表面电导率。
实施例13
通过电子束蒸发在不锈钢表面涂覆一层薄的金属钛。涂覆后的样品表面有宽度为0.01-1微米的峰和宽度和深度为1-20微米的谷。
在钛涂层的不锈钢表面上涂覆Ti-2Ta合金涂层以获得半导体钽掺杂的氧化钛表面氧化物层。Ti-2Ta层的厚度在0.005至0.1微米之间。
可以通过表面蚀刻(增加掺杂的氧化物表面层中的钽浓度)和热氧化(以稳定掺杂的氧化物表面层)来优化钽掺杂的氧化钛层的性质。
实施例14
使用铝箔作为Li离子电池和电容器中的集电极的基板材料。铝箔首先用具有特殊表面纹理的辊冷轧进行冷轧。辊冷轧上的纹理可以将铝表面压印成包括许多小峰和凹坑的形态。峰的尺寸(宽度)为0.1-1微米,凹坑的尺寸(宽度和深度)为1-20微米
将Ti-2Ta合金涂层施加在铝表面上以获得半导体钽掺杂的氧化钛表面氧化物层。Ti-2Ta层的厚度在0.005至0.1微米之间。
通过表面蚀刻(增加掺杂的氧化物表面层中的钽浓度)和热氧化(以稳定掺杂的氧化物表面层),可以优化钽掺杂的氧化钛层的性质。
实施例15
制备钛浓度为2%(Nb-2Ti)的铌-钛二元合金DC磁控溅射靶。用于在不锈钢(SS)箔表面上沉积2微米厚的Ti-2Nb涂层。然后将涂覆的不锈钢表面在室温下用30%氢氧化钠+10%过氧化氢混合物溶液进行改性。该溶液将缓慢地蚀刻铌合金涂层以改变表面氧化物层组成并在表面上产生小坑以实现低表面接触电阻。
实施例16
选择适当孔径的多孔Ti盘作为水电解槽的气体扩散层。Ti盘的直径为8英寸。将Ti盘在500ml 1.5wt.%氢氟酸溶液中浸泡60分钟用于表面蚀刻。该蚀刻工艺在表面上产生小的钛峰。这些峰降低了气体扩散层与电极催化剂和电致动器电池的双极板的接触电阻。
实施例17
使用铌浓度为1%的钛-铌合金粉末(Ti-1Nb)制成多孔Ti-1Nb板作为PEM电解槽的气体扩散层。在高温烧结步骤建立固体多孔结构后,将板在2wt.%氢氟酸溶液中蚀刻30秒。蚀刻步骤将多孔Ti-1Nb板表面的铌浓度增加到7-9%。然后,具有高铌浓度的氧化物表面层在板表面上生长,由于与电极催化剂和双极板的低表面接触电阻。
实施例18
使用316L不锈钢板作为基材。基板表面通过高强度激光扫描迅速熔化并重结晶。这种熔融/再结晶过程将使不锈钢的晶粒尺寸从典型的5-10微米降低到小于5微米。然后,将该板浸入不锈钢蚀刻溶液中15秒钟。蚀刻剂溶液含有15%氯化铁,3%氯化铜,25%盐酸的蒸馏水。蚀刻板具有微纹理表面结构。其表面上的突出点与表面再结晶后的细晶粒尺寸相同(<5μm)。最后,通过溅射法在微纹理不锈钢板涂覆10nm厚的Ti涂层。这个Ti涂覆微纹理不锈钢将具有低表面接触电阻。
实施例19
使用钛板作为基材。平板表面上沉积有一层Ti颗粒,颗粒的直径在0.5-5微米之间。钛基材的表面颗粒密度在5千万-5亿颗粒/cm2之间。然后,表面被高强度层快速扫描,立即熔化颗粒。扫描时间非常短,基板表面不是或没有显着熔化。然后将熔融的Ti颗粒冷却并以圆形峰形式结合在Ti板表面上,分布密度为5千万-5亿颗粒/cm2。这些峰作为高压接触点与其它组件接触,以降低表面接触电阻。
实施例20
在本实施例中,使用不锈钢作为基材。使用热喷涂工艺来沉积小的不锈钢粉末以形成在基材表面上具有小的不锈钢峰的微纹理不锈钢。不锈钢粉末的粒径为0.5-5微米。在喷涂过程中,它们被控制在相对低的速度和较冷的熔融不锈钢颗粒的状态,以避免它们在基材表面上沉积为平坦的碎屑。最终的峰的直径为1-10μm,高度为0.2-5μm。然后,通过DC磁控溅射法将微纹理不锈钢涂覆50nm厚的Ti-2Nb合金。Ti-2Nb合金的表面氧化层将保护不锈钢的腐蚀并保持低的表面接触电阻。
实施例21
在本实施例中,使用钛板作为基材。使用热喷涂工艺将Ti-2Nb合金粉末沉积并粘合在基材表面上。然后,将涂覆的Ti板在3%HF溶液中化学蚀刻120秒以除去在热喷涂工艺中形成的厚表面氧化物层,并且增加蚀刻板的表面氧化物层中的Nb浓度。然后将蚀刻的板在空气中在300℃下热处理30分钟。通过热氧化形成致密的表面无水氧化物,这种氧化物比在室温下形成的表面氧化物层更耐腐蚀。成品Ti板在表面氧化物层中具有较高的(3-15%)铌浓度(金属基),它能满足电解器应用的低表面电阻和高耐腐蚀性的要求。
如上所述,应当理解本文公开的实施例不限于上述具体特征。例如,本文列出的生长条件仅仅是示例,并且应当理解生长可以在将基材放置在器件内或之后发生。所使用的确切方法(即,热氧化,阳极氧化,等离子体氧化)将取决于应用的类型或处理成本。
提供上述实施例仅仅是为了说明的目的,而不一任何方式构成对本发明的限制。虽然参考各种实施例做出说明,但是这里使用的术语仅为是描述和说明,而不是作出限制。此外,尽管参照特定装置,材料和实施例进行说明,但本发明并不限制于所公开的细节。相反,本发明的实施方案可以扩展到所有功能等同的结构,方法和用途,例如在所附权利要求书的范围内。
Claims (34)
1.一种具有低的表面接触电阻的金属部件,所述部件包括:
金属基材;和
表面包括大量的小峰和/或者凹坑的微纹理表面结构,
其中所述小峰和凹坑具有圆形或不规则形状,其分布密度在40万/cm2至50亿/cm2。
2.根据权利要求1所述的金属部件,其中所述微纹理表面包括具有直径在10纳米和10微米之间的圆形或不规则形状的峰和凹坑,和在10纳米和10微米之间的高度或者深度。
3.根据权利要求1所述的金属部件,其中所述金属部件涂覆有其它材料以改善所述部件的耐腐蚀性和表面电导率。
4.根据权利要求1所述的金属部件,其中所述微纹理表面通过在所述金属基底表面上添加材料形成峰而获得。
5.根据权利要求4所述的金属部件,其中所述添加材料可通过物理气相沉积,热喷涂,3-D印刷或电镀等方法实现。
6.根据权利要求1所述的金属部件,其中通过部分去除所述金属基板表面上的材料形成峰和凹坑,以获得所述微纹理化表面。
7.根据权利要求6所述的金属部件,其中,可以通过化学蚀刻,喷砂,冷轧,水喷射,激光雕刻等方法从金属部件表面去除材料。
8.根据权利要求7所述的金属部件,通过对金属部件进行喷砂从部件表面去除部分材料,以在金属部件的表面形成凹坑。
9.根据权利要求8所述的金属部件,其中所述喷砂部件涂覆有钛-铌合金。
10.一种用于处理金属部件表面以实现较低的接触电阻的方法,包括:
改变金属部件的表面以形成适合作为与其它固体部件形成大量的高压接触点的微纹理结构。
11.根据权利要求10所述的方法,其中所述组件包括不锈钢基底,并且所述改变步骤包括:
在金属部件的表面上沉积钛或钛合金以涂覆不锈钢表面并形成具有圆形或不规则形状的小峰,其直径在10纳米和10微米之间,高度在10纳米和10微米之间,分布密度在40万/cm2至50亿/cm2之间。
12.根据权利要求11所述的方法,其中所述钛或钛合金通过阴极弧等离子镀工艺沉积。
13.根据权利要求11所述的方法,其中所述沉积的钛或钛合金涂层的厚度为约0.5-2μm。
14.根据权利要求10所述的方法,其中所述部件包括钛基底,并且所述修改步骤包括:
在基底表面上沉积钛或钛合金颗粒作为形成微纹理表面结构的材料,通过在基底表面上熔化和粘合这些颗粒以形成小峰,小峰是直径在1-10微米之间的圆形或不规则形状,高度介于0.2和5微米之间,分布密度在50万/cm2至10亿/cm2之间。
15.根据权利要求10所述的方法,其中所述部件包括不锈钢基底,并且所述修改步骤包括:
快速熔化和凝固不锈钢基材的表面;
在高温下对基材进行热处理以使表面层重结晶;
在酸性溶液中化学蚀刻基材,得到微纹理表面;和
通过物理气相沉积用Ti合金薄层涂覆蚀刻后的不锈钢。
16.根据权利要求15所述的方法,其中所述蚀刻溶液是HNO3和HF溶液的混合物。
17.根据权利要求15所述的方法,其中热处理条件为800-1200℃。
18.根据权利要求15所述的方法,其中所述钛合金包含铌或钽。
19.一种具有低的表面接触电阻的金属部件,所述部件包括:
具有含有铌或钽的钛合金表面的金属基材,
其中表面氧化物层中的铌或钽的浓度高于钛合金内的铌或钽的浓度。
20.根据权利要求19所述的金属部件,其中所述钛合金中的铌或钽的浓度为约0.01%至3%。
21.根据权利要求19所述的金属部件,其中所述表面氧化物层中的铌或钽的浓度在约4%和10%之间。
22.根据权利要求19所述的金属部件,还包括含有铌或钽的钛合金基底。
23.根据权利要求19所述的金属部件,还包括在所述基材的表面上覆盖有钛合金涂层的金属基板,所述钛合金涂层含有铌或钽。
24.根据权利要求23所述的金属部件,其中所述钛合金涂层由热喷涂或物理气相沉积中的一种方法提供。
25.根据权利要求19所述的金属部件,其中所述表面氧化物层中的高浓度的铌或钽通过以下方式获得:
化学蚀刻钛合金的表面以除去原始表面氧化层;和
在蚀刻的钛合金上自然形成薄的氧化物表面层。
26.根据权利要求25所述的金属部件,其中所述化学蚀刻工艺包括将钛合金表面浸入含有氢氟酸的溶液中。
27.根据权利要求25所述的金属部件,其中所述化学蚀刻工艺在具有含氟或含氯化学物质或自由基的气相的低压环境中进行。
28.根据权利要求19所述的金属部件,其中所述表面氧化物层中的高浓度的铌或钽通过所述钛合金表面的热氧化获得。
29.根据权利要求28所述的金属部件,其中所述热氧化温度在100-800℃之间。
30.根据权利要求19所述的金属部件,其中所述部件包括:
纯钛板作为基材;和
通过热喷涂方法在纯钛基材表面上沉积钛合金涂层;
把沉积钛合金涂层的基材进行化学蚀刻,以去除其原始的表面氧化物层并增加表面氧化物层中合金元素的浓度。
31.根据权利要求30所述的金属部件,其中所述钛合金包含铌或钽,其浓度在0.01-3%之间。
32.根据权利要求30所述的金属部件,其中所述表面氧化物层中的所述铌或钽的浓度在3-15%之间。
33.根据权利要求30所述的金属部件,其中所述蚀刻的钛合金表面上的表面氧化物层通过在预定温度下的热氧化进一步修饰,以获得致密的,无水的和铌或钽的富含表面氧化物层。
34.根据权利要求33所述的金属部件,其中所述热氧化温度在100-800℃之间。
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Cited By (5)
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---|---|---|---|---|
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Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016168649A2 (en) | 2015-04-15 | 2016-10-20 | Treadstone Technologies, Inc. | Method of metallic component surface moodification for electrochemical applications |
US20180195185A1 (en) * | 2017-01-06 | 2018-07-12 | Leon Kazarian | Proton exchange membrane electrolyzer |
JP7064723B2 (ja) * | 2017-03-31 | 2022-05-11 | 株式会社Flosfia | 成膜方法 |
US20210167411A1 (en) * | 2017-06-21 | 2021-06-03 | Sumitomo Electric Industries, Ltd. | Redox flow battery |
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WO2019086939A1 (fr) * | 2017-11-06 | 2019-05-09 | Aperam | Plaque bipolaire pour l'assemblage des éléments d'une unité de pile à combustible et son procédé de fabrication, unité de pile à combustible la comportant et pile à combustible comportant cette unité |
KR20200128408A (ko) * | 2018-02-28 | 2020-11-12 | 매뉴팩터링 시스템즈 리미티드 | 촉매작용 장치 및 방법 |
IT201800020476A1 (it) * | 2018-12-20 | 2020-06-20 | Bb S P A | Metodo per il trattamento superficiale di un manufatto in metallo |
US11885026B2 (en) | 2020-02-26 | 2024-01-30 | Treadstone Technologies, Inc. | Component having improved surface contact resistance and reaction activity and methods of making the same |
DE102021202214A1 (de) * | 2020-03-10 | 2021-09-16 | Reinz-Dichtungs-Gmbh | Separatorplatte mit periodischen Oberflächenstrukturen im Nanometer- bis Mikrometerbereich |
CN114068274A (zh) * | 2020-08-03 | 2022-02-18 | 中微半导体设备(上海)股份有限公司 | 半导体零部件、等离子体处理装置及耐腐蚀涂层形成方法 |
DE202021104874U1 (de) | 2021-09-09 | 2022-12-12 | Reinz-Dichtungs-Gmbh | Platte für ein elektrochemisches, medienführendes System, Kontaktelement und Übertragungseinrichtung |
CN115058727B (zh) * | 2022-06-06 | 2024-03-29 | 北京科技大学 | 一种用于质子交换膜电解池钛基双极板的表面改性方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6372376B1 (en) * | 1999-12-07 | 2002-04-16 | General Motors Corporation | Corrosion resistant PEM fuel cell |
CN1130746C (zh) * | 1996-05-31 | 2003-12-10 | 美国3M公司 | 具有纳米结构发射体的场发射器件中的电极及其制备方法 |
TW200719508A (en) * | 2005-07-26 | 2007-05-16 | Pionetics Corp | Electrochemical ion exchange with textured membranes and cartridge |
CN101366129A (zh) * | 2005-04-21 | 2009-02-11 | 宋健民 | 类钻碳热电能转换装置及其使用和制造方法 |
CN101416294A (zh) * | 2006-03-30 | 2009-04-22 | 株式会社美高仁工业 | 微细金属凸点的形成方法 |
CN101490301A (zh) * | 2006-07-14 | 2009-07-22 | 丹佛斯公司 | 利用混合的钽和钛的氧化物的表面层处理钛物体的方法 |
CN103031523A (zh) * | 2011-09-30 | 2013-04-10 | 先健科技(深圳)有限公司 | 一种医疗器械的金属部件上的含铜复合涂层的制备方法及医疗器械 |
Family Cites Families (97)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3623920A (en) | 1969-03-17 | 1971-11-30 | Japan Atomic Energy Res Inst | Method for producing a stainless steel resistive to high temperature and neutron irradiation |
CH533691A (de) | 1971-01-07 | 1973-02-28 | Metaux Precieux Sa | Procédé pour déposer une couche d'un alliage d'or violet sur un objet |
US3755105A (en) | 1971-06-28 | 1973-08-28 | G Messner | Vacuum electrical contacts for use in electrolytic cells |
JPS582453B2 (ja) | 1975-02-28 | 1983-01-17 | 日本電気株式会社 | ダイキボハンドウタイシユウセキカイロソウチ |
US4031268A (en) | 1976-01-05 | 1977-06-21 | Sirius Corporation | Process for spraying metallic patterns on a substrate |
JPS5569278A (en) | 1978-11-17 | 1980-05-24 | Kureha Chem Ind Co Ltd | Frame of carbon fiber-high molecular composite material electrolytic cell |
DE3215314C2 (de) * | 1982-04-23 | 1984-12-06 | M.A.N. Maschinenfabrik Augsburg-Nürnberg AG, 8000 München | Verfahren zur Herstellung von Oxidschichten auf einer Titanbasislegierungsoberfläche |
US4532191A (en) | 1982-09-22 | 1985-07-30 | Exxon Research And Engineering Co. | MCrAlY cladding layers and method for making same |
US4643818A (en) | 1984-08-07 | 1987-02-17 | Asahi Kasei Kogyo Kabushiki Kaisha | Multi-cell electrolyzer |
CN1010760B (zh) | 1984-11-13 | 1990-12-12 | 三菱电机株式会社 | 装饰板的制造方法 |
US5314601A (en) | 1989-06-30 | 1994-05-24 | Eltech Systems Corporation | Electrodes of improved service life |
US5213848A (en) * | 1990-02-06 | 1993-05-25 | Air Products And Chemicals, Inc. | Method of producing titanium nitride coatings by electric arc thermal spray |
US5098485A (en) | 1990-09-19 | 1992-03-24 | Evans Findings Company | Method of making electrically insulating metallic oxides electrically conductive |
JP2719049B2 (ja) | 1991-01-28 | 1998-02-25 | 日本碍子株式会社 | ランタンクロマイト膜の製造方法及び固体電解質型燃料電池用インターコネクターの製造方法 |
SE505714C2 (sv) | 1991-09-19 | 1997-09-29 | Permascand Ab | Elektrod med kanalbildande trådar, sätt att tillverka elektroden, elektrolyscell försedd med elektroden samt sätt vid elektrolys |
JPH07331460A (ja) | 1994-06-02 | 1995-12-19 | Nippon Telegr & Teleph Corp <Ntt> | ドライエッチング方法 |
US5624769A (en) | 1995-12-22 | 1997-04-29 | General Motors Corporation | Corrosion resistant PEM fuel cell |
US5682067A (en) | 1996-06-21 | 1997-10-28 | Sierra Applied Sciences, Inc. | Circuit for reversing polarity on electrodes |
ATE326561T1 (de) | 1997-01-31 | 2006-06-15 | Elisha Holding Llc | Ein elektrolytisch verfahren zur herstellung einer ein mineral enthaltende beschichtung |
US6599643B2 (en) | 1997-01-31 | 2003-07-29 | Elisha Holding Llc | Energy enhanced process for treating a conductive surface and products formed thereby |
US6153080A (en) | 1997-01-31 | 2000-11-28 | Elisha Technologies Co Llc | Electrolytic process for forming a mineral |
US6592738B2 (en) | 1997-01-31 | 2003-07-15 | Elisha Holding Llc | Electrolytic process for treating a conductive surface and products formed thereby |
US6322687B1 (en) | 1997-01-31 | 2001-11-27 | Elisha Technologies Co Llc | Electrolytic process for forming a mineral |
EP0935265A3 (en) | 1998-02-09 | 2002-06-12 | Wilson Greatbatch Ltd. | Thermal spray coated substrate for use in an electrical energy storage device and method |
US6207522B1 (en) | 1998-11-23 | 2001-03-27 | Microcoating Technologies | Formation of thin film capacitors |
WO2000044059A1 (fr) | 1999-01-21 | 2000-07-27 | Asahi Glass Company, Limited | Pile a combustible a electrolyte polymere solide |
CN1117882C (zh) | 1999-04-19 | 2003-08-13 | 住友金属工业株式会社 | 固体高分子型燃料电池用不锈钢材 |
US6649031B1 (en) | 1999-10-08 | 2003-11-18 | Hybrid Power Generation Systems, Llc | Corrosion resistant coated fuel cell bipolar plate with filled-in fine scale porosities and method of making the same |
CA2327031C (en) | 1999-11-29 | 2007-07-03 | Vladimir Gorokhovsky | Composite vapour deposited coatings and process therefor |
DE19957981A1 (de) | 1999-12-02 | 2001-06-07 | Abb Research Ltd | Hochtemperatursupraleiteranordnung und Verfahren zu deren Herstellung |
DE19962136A1 (de) | 1999-12-22 | 2001-06-28 | Merck Patent Gmbh | Verfahren zur Rauhätzung von Siliziumsolarzellen |
US7300559B2 (en) * | 2000-04-10 | 2007-11-27 | G & H Technologies Llc | Filtered cathodic arc deposition method and apparatus |
JP4035968B2 (ja) | 2000-06-30 | 2008-01-23 | セイコーエプソン株式会社 | 導電膜パターンの形成方法 |
WO2002038828A1 (fr) | 2000-11-10 | 2002-05-16 | Honda Giken Kogyo Kabushiki Kaisha | Procédé de traitement de surface de produit d'acier inoxydable pour pile à combustible |
US7968251B2 (en) | 2000-11-24 | 2011-06-28 | GM Global Technology Operations LLC | Electrical contact element and bipolar plate |
JP2004528677A (ja) | 2000-11-29 | 2004-09-16 | サーモセラミックス インコーポレイテッド | 抵抗加熱器及びその使用法 |
US6472014B1 (en) * | 2001-04-17 | 2002-10-29 | Novellus Systems, Inc. | Uniform surface texturing for PVD/CVD hardware |
US6915964B2 (en) | 2001-04-24 | 2005-07-12 | Innovative Technology, Inc. | System and process for solid-state deposition and consolidation of high velocity powder particles using thermal plastic deformation |
US7314685B2 (en) | 2001-07-30 | 2008-01-01 | Greatbatch Ltd. | Oxidized titanium as a cathodic current collector |
US6685988B2 (en) | 2001-10-09 | 2004-02-03 | Delphi Technologies, Inc. | Kinetic sprayed electrical contacts on conductive substrates |
US7005214B2 (en) | 2001-11-02 | 2006-02-28 | Wilson Greatbatch Technologies, Inc. | Noble metals coated on titanium current collectors for use in nonaqueous Li/CFx cells |
CA2413558C (en) | 2001-12-05 | 2007-06-05 | Honda Giken Kogyo Kabushiki Kaisha | Fuel cell metallic separator and method for manufacturing same |
CA2469410C (en) | 2001-12-07 | 2009-09-22 | Honda Giken Kogyo Kabushiki Kaisha | Metal separator for fuel cell and its production method |
WO2003050904A1 (fr) | 2001-12-12 | 2003-06-19 | Honda Giken Kogyo Kabushiki Kaisha | Separateur de metaux destine a une pile a combustible et procede de production correspondant |
CA2468510C (en) | 2001-12-18 | 2011-11-29 | Honda Giken Kogyo Kabushiki Kaisha | Method of producing fuel cell-use separator and device for producing it |
US7235912B2 (en) * | 2002-03-08 | 2007-06-26 | Chien-Min Sung | Diamond-like carbon thermoelectric conversion devices and methods for the use and manufacture thereof |
JP2003268567A (ja) | 2002-03-19 | 2003-09-25 | Hitachi Cable Ltd | 導電材被覆耐食性金属材料 |
EP1369504A1 (en) | 2002-06-05 | 2003-12-10 | Hille & Müller | Metal strip for the manufacture of components for electrical connectors |
AU2002348943A1 (en) | 2002-09-11 | 2004-04-30 | Moltech Invent S.A. | Non-carbon anodes for aluminium electrowinning and other oxidation resistant components with iron oxide-containing coatings |
US7338699B2 (en) | 2002-10-31 | 2008-03-04 | Tosoh Corporation | Island projection-modified part, method for producing the same, and apparatus comprising the same |
US7144648B2 (en) | 2002-11-22 | 2006-12-05 | The Research Foundation Of State University Of New York | Bipolar plate |
US20040265550A1 (en) | 2002-12-06 | 2004-12-30 | Glatkowski Paul J. | Optically transparent nanostructured electrical conductors |
US6924002B2 (en) | 2003-02-24 | 2005-08-02 | General Electric Company | Coating and coating process incorporating raised surface features for an air-cooled surface |
US7070833B2 (en) | 2003-03-05 | 2006-07-04 | Restek Corporation | Method for chemical vapor deposition of silicon on to substrates for use in corrosive and vacuum environments |
JP4327489B2 (ja) | 2003-03-28 | 2009-09-09 | 本田技研工業株式会社 | 燃料電池用金属製セパレータおよびその製造方法 |
JP3988936B2 (ja) | 2003-05-13 | 2007-10-10 | 信越化学工業株式会社 | シラン表面処理球状シリカチタニア系微粒子、その製造方法、および、それを用いた静電荷像現像用トナー外添剤 |
US7670707B2 (en) | 2003-07-30 | 2010-03-02 | Altergy Systems, Inc. | Electrical contacts for fuel cells |
US20050158621A1 (en) | 2003-09-30 | 2005-07-21 | Benoit Stephen A. | Battery with flat housing |
US7344798B2 (en) | 2003-11-07 | 2008-03-18 | General Motors Corporation | Low contact resistance bonding method for bipolar plates in a pem fuel cell |
US7846591B2 (en) | 2004-02-17 | 2010-12-07 | Gm Global Technology Operations, Inc. | Water management layer on flowfield in PEM fuel cell |
KR100794294B1 (ko) | 2004-03-04 | 2008-01-14 | 고경현 | 내마모성 금속-세라믹 복합체 코팅 형성 방법 |
US7052741B2 (en) | 2004-05-18 | 2006-05-30 | The United States Of America As Represented By The Secretary Of The Navy | Method of fabricating a fibrous structure for use in electrochemical applications |
US7309540B2 (en) | 2004-05-21 | 2007-12-18 | Sarnoff Corporation | Electrical power source designs and components |
US20060003174A1 (en) | 2004-06-30 | 2006-01-05 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Titanium material and method for manufacturing the same |
US7955754B2 (en) | 2004-07-20 | 2011-06-07 | GM Global Technology Operations LLC | Enhanced stability bipolar plate |
US20060222777A1 (en) | 2005-04-05 | 2006-10-05 | General Electric Company | Method for applying a plasma sprayed coating using liquid injection |
KR100802328B1 (ko) | 2005-04-07 | 2008-02-13 | 주식회사 솔믹스 | 내마모성 금속기지 복합체 코팅층 형성방법 및 이를이용하여 제조된 코팅층 |
US7758921B2 (en) | 2005-05-26 | 2010-07-20 | Uchicago Argonne, Llc | Method of fabricating electrode catalyst layers with directionally oriented carbon support for proton exchange membrane fuel cell |
CA2571099C (en) | 2005-12-21 | 2015-05-05 | Sulzer Metco (Us) Inc. | Hybrid plasma-cold spray method and apparatus |
EP1808920A1 (en) | 2006-01-12 | 2007-07-18 | Stichting PowerPlus | Nanosized catalysts for the anode of a PEM fuel cell |
KR101344990B1 (ko) | 2006-04-20 | 2013-12-24 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 도전성 내플라즈마 부재 |
JP2009542006A (ja) | 2006-06-19 | 2009-11-26 | キャボット コーポレイション | 光起電力導電性機能物及びその形成方法 |
US20080145633A1 (en) | 2006-06-19 | 2008-06-19 | Cabot Corporation | Photovoltaic conductive features and processes for forming same |
JP4198726B2 (ja) | 2006-09-06 | 2008-12-17 | クロリンエンジニアズ株式会社 | イオン交換膜電解槽 |
US20080085439A1 (en) | 2006-09-28 | 2008-04-10 | Hilliard Donald B | Solid oxide electrolytic device |
CN101918619A (zh) | 2008-01-08 | 2010-12-15 | 特来德斯通技术公司 | 用于电化学应用的高导电性表面 |
US7618893B2 (en) | 2008-03-04 | 2009-11-17 | Applied Materials, Inc. | Methods of forming a layer for barrier applications in an interconnect structure |
FR2928492B1 (fr) | 2008-03-06 | 2011-10-21 | Ceram Hyd | Materiau pour un dispositif electrochimique. |
AU2009302811A1 (en) | 2008-10-08 | 2010-04-15 | Massachusetts Institute Of Technology | Catalytic materials, photoanodes, and photoelectrochemical cells for water electrolysis and other electrochemical techniques |
US8852777B2 (en) | 2008-12-05 | 2014-10-07 | Deeya Energy, Inc. | Methods for the preparation and purification of electrolytes for redox flow batteries |
WO2010129957A2 (en) | 2009-05-08 | 2010-11-11 | Treadstone Technologies, Inc. | High power fuel stacks using metal separator plates |
WO2011011064A2 (en) | 2009-07-24 | 2011-01-27 | Stc.Unm | Efficient hydrogen production by photocatalytic water splitting using surface plasmons in hybrid nanoparticles |
US9209464B2 (en) | 2009-09-24 | 2015-12-08 | Corning Incorporated | Current collectors having textured coating |
JP2013506050A (ja) | 2009-09-28 | 2013-02-21 | トレッドストーン テクノロジーズ インク. | 電気化学分野の製品のための高い電気伝導性を有する表面の形成方法 |
DE102010043085A1 (de) * | 2010-10-28 | 2012-05-03 | Bayer Materialscience Aktiengesellschaft | Elektrode für die elektrolytische Chlorherstellung |
WO2013126883A1 (en) * | 2012-02-23 | 2013-08-29 | Treadstone Technologies, Inc. | Corrosion resistant and electrically conductive surface of metal |
JP5574066B2 (ja) | 2012-07-31 | 2014-08-20 | 新日鐵住金株式会社 | 対カーボン接触導電性と耐久性を高めた燃料電池セパレータ用チタンまたはチタン合金材、及びこれを用いた燃料電池セパレータ、並びにそれらの製造方法 |
CA2891182C (en) | 2013-02-01 | 2018-07-31 | Nippon Steel & Sumitomo Metal Corporation | Titanium or titanium alloy for fuel cell separator having high contact conductivity with carbon and high durability, fuel cell separator including the same, and fuel cell |
US9567681B2 (en) * | 2013-02-12 | 2017-02-14 | Treadstone Technologies, Inc. | Corrosion resistant and electrically conductive surface of metallic components for electrolyzers |
JP2016517611A (ja) * | 2013-02-26 | 2016-06-16 | トレードストーン テクノロジーズ インク | 電池用の耐腐食性金属コンポーネント |
AU2014292972B2 (en) * | 2013-07-26 | 2018-05-10 | Smith & Nephew, Inc. | Biofilm resistant medical implant |
US10033052B2 (en) | 2014-01-22 | 2018-07-24 | Nippon Steel & Sumitomo Metal Corporation | Titanium material or titanium alloy material having surface electrical conductivity, and fuel cell separator and fuel cell using the same |
RU2636651C1 (ru) | 2014-01-22 | 2017-11-27 | Ниппон Стил Энд Сумитомо Метал Корпорейшн | Материал на основе титана или материал на основе титанового сплава, обладающий поверхностной электрической проводимостью, а также способы его изготовления, и сепаратор топливного элемента, топливный элемент с его использованием |
CN106456291B (zh) * | 2014-03-28 | 2019-08-06 | 植体B有限公司 | 可更新的牙科植体 |
JP5880798B1 (ja) | 2014-06-16 | 2016-03-09 | 新日鐵住金株式会社 | 固体高分子形燃料電池のセパレータ用チタン材、これを用いたセパレータ、およびこれを備えた固体高分子形燃料電池 |
WO2016168649A2 (en) * | 2015-04-15 | 2016-10-20 | Treadstone Technologies, Inc. | Method of metallic component surface moodification for electrochemical applications |
US20160344127A1 (en) * | 2015-05-20 | 2016-11-24 | Delphi Technologies, Inc. | Electroconductive material with an undulating surface, an electrical terminal formed of said material, and a method of producing said material |
-
2016
- 2016-04-15 WO PCT/US2016/027827 patent/WO2016168649A2/en unknown
- 2016-04-15 CN CN201680021911.XA patent/CN107849680B/zh active Active
- 2016-04-15 US US15/130,330 patent/US10435782B2/en active Active
- 2016-04-15 CN CN202011291999.1A patent/CN112575282B/zh active Active
- 2016-04-15 EP EP16780869.0A patent/EP3283665A4/en active Pending
-
2019
- 2019-10-07 US US16/594,349 patent/US10934615B2/en active Active
-
2021
- 2021-03-01 US US17/188,571 patent/US11718906B2/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1130746C (zh) * | 1996-05-31 | 2003-12-10 | 美国3M公司 | 具有纳米结构发射体的场发射器件中的电极及其制备方法 |
US6372376B1 (en) * | 1999-12-07 | 2002-04-16 | General Motors Corporation | Corrosion resistant PEM fuel cell |
CN101366129A (zh) * | 2005-04-21 | 2009-02-11 | 宋健民 | 类钻碳热电能转换装置及其使用和制造方法 |
TW200719508A (en) * | 2005-07-26 | 2007-05-16 | Pionetics Corp | Electrochemical ion exchange with textured membranes and cartridge |
CN101416294A (zh) * | 2006-03-30 | 2009-04-22 | 株式会社美高仁工业 | 微细金属凸点的形成方法 |
CN101490301A (zh) * | 2006-07-14 | 2009-07-22 | 丹佛斯公司 | 利用混合的钽和钛的氧化物的表面层处理钛物体的方法 |
CN103031523A (zh) * | 2011-09-30 | 2013-04-10 | 先健科技(深圳)有限公司 | 一种医疗器械的金属部件上的含铜复合涂层的制备方法及医疗器械 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110958800A (zh) * | 2018-09-27 | 2020-04-03 | 苹果公司 | 用于钛部件的纹理化表面 |
CN113348273A (zh) * | 2019-01-21 | 2021-09-03 | 杰富意钢铁株式会社 | 燃料电池的隔离件用的奥氏体系不锈钢板及其制造方法 |
CN114080457A (zh) * | 2019-07-09 | 2022-02-22 | 杰富意钢铁株式会社 | 用于硫化物系固体电池的集流体的铁素体系不锈钢板及其制造方法 |
CN113422084A (zh) * | 2021-04-30 | 2021-09-21 | 上海交通大学 | 一种钛合金表面微纳颗粒复合导电增强结构及其制备方法 |
CN113422084B (zh) * | 2021-04-30 | 2023-02-03 | 上海交通大学 | 一种钛合金表面微纳颗粒复合导电增强结构及其制备方法 |
CN114653943A (zh) * | 2022-04-20 | 2022-06-24 | 宁波福至新材料有限公司 | 一种pem水解制氢钛金属双极板及其制备方法 |
CN114653943B (zh) * | 2022-04-20 | 2024-02-27 | 宁波福至新材料有限公司 | 一种pem水解制氢钛金属双极板及其制备方法 |
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WO2016168649A2 (en) | 2016-10-20 |
CN112575282A (zh) | 2021-03-30 |
US20210254208A1 (en) | 2021-08-19 |
CN112575282B (zh) | 2023-12-19 |
WO2016168649A3 (en) | 2016-11-24 |
US10435782B2 (en) | 2019-10-08 |
US11718906B2 (en) | 2023-08-08 |
EP3283665A2 (en) | 2018-02-21 |
US20200102642A1 (en) | 2020-04-02 |
CN107849680B (zh) | 2020-11-13 |
US20160305011A1 (en) | 2016-10-20 |
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US10934615B2 (en) | 2021-03-02 |
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