CN101137772B - 圆柱形电极 - Google Patents
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Abstract
本发明涉及一种用于气体析出的圆柱形电极，包含非活化的导电芯，使提供催化活化的、容易分开的和更换的组件例如波状片或波状网固定到所述导电芯上。
Description
发明背景
本发明涉及用于电化学方法的圆柱形电极，特别是由具有表面催化活化作用的中心金属导体组成的圆柱形电极。
技术状况
圆柱形电极的应用已知用于电化学的几种情形；圆柱形电极，多数情形中同轴地置于中空圆柱形反电极的内部，通常应用于电渗析(US20030010639)、水电解(DE 19636171)、臭氧生产(JP 2001198574)和其他应用。然而，采用圆柱型、大部分共轴的电极形状的最重要的方法是从含水溶液中回收金属(例如参见US 6451183或DE 19749445)，和从各种污染物处理废水(工业废水、生活废水和其它废水)，使其可饮用或纯化(例如US 5635040)。圆柱形，特别是在小尺寸的电化学电池上，提供了重要的优点，特别是在流体分布方面。取决于所考虑的方法，圆柱形电极可以同时是阳极或阴极；多数情形中，这种电极适用于气体析出反应，例如氢阴极析出或者氧、臭氧或氯阳极析出。析出气体的反应，特别是阳极的反应，必须被催化由此以足够的效率进行；由此，现有技术的圆柱形电极由用经常基于金属氧化物的催化剂涂覆的金属圆柱形导电载体(通常为钛或其它阀金属(valve metal)，在阳极情形中)组成，取决于将析出的气体和所需电位的类型，是众所周知的。将催化剂涂层施加到圆柱形载体的方法，是将圆柱形载体用前体涂刷，且随后通过高温热处理的方式(350-700℃)将该前体转化。用前体溶液涂刷金属电极优选地通过静电喷雾方法来进行；此时在施加的均匀性方面来看，圆柱形相对于平面形来说是更少有利的。另外，该催化涂层具有有限的操作寿命(典型地为1-5年，取决于应用)。一旦最初的涂层失效，必须通过机械方法将其彻底清除并储存；该涂层清除操作对于圆柱形是特别费力的，特别是对于小尺寸的那些。任意情形中，保存电极的催化活性所需的长时间导致对设备操作不期望的限制，替换地强加了生产的临时暂停，整个设备的超尺寸使计划的环状电极再活化或者需要保存相当大量的替换电极，这点从投资成本观点来看是非常费力的方案。
由此，本发明的目的是提供一种用于电化学方法的圆柱形电极，其克服了现有技术的局限。另一方面，本发明的目的是提供一种圆柱形电极，其使得催化涂层的施加或者保存的容易性增加。另一方面，本发明的目的是在工艺管理效率方面提供一种用于圆柱形电极的催化再活化的改进方法。通过下列说明将阐明这些和其它目的，该说明为本发明的例证且并非限定其范围。
发明
第一方面，本发明涉及一种用于气体析出的电极，所述电极包括作为集电器的导电芯，可分离的组件例如网或实心的、穿孔的或多孔的片从外部固定到所述导电芯上，其由导电材料制成。非常优选的实施方式中，该可分离的组件上具有催化涂层且构成该电极的活性元件。本发明的电极形状特别适合用于电冶金或水处理工艺中氧、臭氧或氯析出的阳极的构造。此时，导电圆柱形芯有益地由阀金属制成，最典型的情形中为钛。该圆柱形芯可以为任意尺寸，最典型的直径为1-25cm，取决于应用。该可分离的组件优选为金属网或金属片，其可以有益地由导电芯的相同材料制成，优选地厚度为0.3-0.8mm，但是其它厚度同样是可能的。
第二方面，本发明涉及一种用于使具有失效的催化涂层的圆柱形阳极再活化的方法，所述方法包括将具有催化涂层的可分离的元件从外部施加到电极上。
本发明将更好地包括参照仅为示例性目的的下列附图。
附图说明
图1A-C显示本发明电极的第一种实施方式，图1A中显示了作为分开的组件的圆柱形导电芯和金属片或金属网，图1B和1C中显示了分别为俯视图和侧视图中装配的相同组件。
图2A-B显示了本发明电极的第二种实施方式，图2A中显示了沿着导电芯的母线焊接的金属片或金属网，且图2B中为在导电芯周围卷起(roll)且用焊点固定的相同金属片或金属网。
附图的详细说明
图1A-C中显示了本发明电极的第一种实施方式；特别地，图1A中显示了圆柱形导体(100)的俯视图，其可以由金属棒或金属中空圆柱体组成，所述金属例如为钛或者在阴极情形中为不锈钢。该圆柱形导体(100)，其装配好后作为本发明电极的导电圆柱形芯，也可以是现有技术的圆柱形电极，例如具有失效的催化涂层的电极。
(200)显示了在自身上卷起、封闭且焊接以形成波纹状圆柱体的波状金属片的俯视图，所述波状金属片至少在外表面上具有表面催化涂层。图中，波状片的波纹并非以实际比例表示的，而是大大放大的，以更好地理解该图。较小优选的实施方式中，该片(200)可以替换为相同形状的波状网。卷起为圆柱体的片(200)的直径稍微小于导电芯(100)的直径，但是这样的波纹形状是为了赋予其一定挠性，使得可以将其自身强制地插入到芯上。对于厚度降低(典型地0.5mm，总之为0.3-1mm)的波状片来说挠性更高。图2B显示了装配之后俯视图中的两块：在插入到波状片(200)上之后，可以进一步利用焊点(未显示)将这两块固定。图1C显示了侧视图的相同组件。特别是从图1B中可以看出，相对于直接在圆柱形导体上可获得的催化活化作用，波状片的使用具有的明显优点是，相当大地增加了活性表面。另外，一旦催化涂层失效，可以容易地清除该片(200)并用另一预先活化的片直接在现场替换，从而具有最小的停车时间且仅需要保持在现场储存的活化片，而非一组成套电极。通过这种方式，也降低了再活化时材料的处理成本。
图2A-B中显示了本发明的第二种实施方式；特别地，图2A显示了圆柱形导体(101)，此时其也可以由金属棒或金属中空圆柱体组成，所述金属在阳极情形中例如为钛或其它阀金属，或者在阴极情形中为镍或不锈钢。这种情形中，该圆柱形导体(101)也可以是现有技术的圆柱形电极，例如具有失效的催化涂层的电极。
(201)显示了具有催化涂层的、沿着圆柱形导体(101)的母线标记-焊接(flag-welded)的网；该图显示了作为连续焊接(300)的两块的接点，例如可通过激光获得，但是也可以是不同类型的焊接如点焊。该网(201)也可以替换为多孔的或穿孔的片或者在较小优选的实施方式中替换为实心片。图2B显示了在随后步骤中将网(201)向后折叠以包裹圆柱形芯，并且在重叠相对边之后利用焊点(301)在其自身上焊接。较小优选的实施方式中，该网(201)可以不存在重叠的边缘，而是两个边缘都焊接到导电芯(101)上；点焊(301)也可以替换为另一类型的固定，例如连续焊接。也在该情形中，适当的网(201)的形状可以使所获得电极的活性表面相对于圆柱形导体的直接活化大大增加；另外从外部固定到圆柱形芯(101)上的金属网(201)一旦催化活化作用失效时可以容易地替换，且替换为新的。
实施例
US 6451183中公开的、用于在铜电沉积管状电池中使用的电池的钛圆柱形阳极，由15cm厚钛中空圆柱体组成，采用在钛和氧化钽-基中间层之上的钛和氧化钽-基涂层(16g/m2全部)活化，如本领域中公知的那样。使该阳极在5％硫酸溶液中在25℃的温度和500A/m2的电流密度下进行标准氧析出试验。在8小时的试验期间，检测到3.30V的稳定电压(依据现有技术的电极)。
利用无催化活化的相同钛棒制备依据本发明的电极，将用依据现有技术的相同组成的先前样品活化的0.5mm厚钛网固定到电极上，采用图2中所示的构型；由此首先通过连续焊接将活化网沿着圆柱体的母线固定，随后在其自身周围卷起且利用三个焊点固定。
在相同的工艺条件下，使该电极进行先前样品的相同氧析出试验。在8小时的试验期间，检测到2.90V的稳定电压(本发明的电极)。
由此显示了本发明的电极(除了解决了主要与以非常实际的方式再活化失效的圆柱形电极相关的现有技术的不便之外)是如何能够在对应于更高预期寿命的更高能效(更低电压)下操作的，这可能归因于更大的暴露表面。
对本领域技术人员来说显而易见的是，可以相对于上述实施例采用其它变化或改进来实施本发明。
前述说明并非在于限定本发明，本发明可以依据不同实施方式来应用，而不背离其范围，且其范围由所附权利要求来明确限定。
在本发明的说明书和权利要求书中，术语“包括(comprise)”及其变化形式如“(comprising)”和“comprises”并非在于排除其它元件或添加剂的存在。
Claims (13)
1.用于气体析出的电极，所述电极包括导电圆柱形芯和从外部固定到所述导电圆柱形芯上并与其电连接的金属片或金属网，其中所述金属片或金属网为在其自身上卷起且沿着两个相对边缘焊接的波状片，由此形成最初直径小于所述导电圆柱形芯的直径且强制地插入到所述导电圆柱形芯上的圆柱体。
2.权利要求1的电极，其中利用焊点使卷起为圆柱体且插入到所述导电圆柱形芯上的所述波状片固定到所述导电圆柱形芯上。
3.权利要求1或2的电极，其中所述波状片的厚度为0.3-1mm。
4.权利要求1的电极，其中所述导电圆柱形芯是由钛或其它阀金属制成的。
5.权利要求1的电极，其中所述导电圆柱形芯的直径为1-25cm。
6.权利要求1的电极，其中对于氯、臭氧或氧析出，采用催化涂层使所述金属片或金属网活化。
7.权利要求1的电极，其中对于高-过电压氧析出，采用催化涂层使所述金属片或金属网活化。
8.金属电沉积方法，所述方法包括在前述权利要求中任一项的电极上氧的阳极析出。
9.水处理方法，所述方法包括在权利要求1-7中任一项的电极上氧、臭氧或氯的阳极析出。
10.用于使具有失效的催化涂层的圆柱形电极再活化的方法，所述方法包括将在其自身上卷起且沿着两个相对边缘焊接以形成圆柱体的波状片插入到所述电极上，所述波状片上具有催化涂层。
11.权利要求10的方法，其中所述在其自身上卷起的波状片形成直径小于圆柱形电极的直径的圆柱体。
12.权利要求10或11的方法，所述方法进一步包括利用焊点将所述波状片固定到圆柱形电极上。
13.用于使具有失效的催化涂层的圆柱形电极再活化的方法，所述方法包括沿着所述圆柱形电极的母线焊接具有催化涂层的金属片或金属网的一边，且将所述金属片或金属网在该圆柱形电极周围卷起，任选地利用焊点使所述金属片或金属网的相对边缘固定到所述焊接的边缘和/或所述圆柱形电极上。
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| ITMI2005A000373 | 2005-03-09 | ||
| IT000373A ITMI20050373A1 (it) | 2005-03-09 | 2005-03-09 | Elettrodo cilindrico |
| PCT/EP2006/002191 WO2006094814A2 (en) | 2005-03-09 | 2006-03-09 | Cylindrical electrode |
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| CN101137772A CN101137772A (zh) | 2008-03-05 |
| CN101137772B true CN101137772B (zh) | 2011-05-25 |
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| EP (1) | EP1859079B1 (zh) |
| JP (1) | JP5449765B2 (zh) |
| KR (1) | KR101298955B1 (zh) |
| CN (1) | CN101137772B (zh) |
| AT (1) | ATE403765T1 (zh) |
| AU (2) | AU2006222191B2 (zh) |
| BR (1) | BRPI0608888A2 (zh) |
| CA (1) | CA2599842C (zh) |
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| RU (1) | RU2395628C2 (zh) |
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| JP6193005B2 (ja) | 2013-06-14 | 2017-09-06 | Ｋｙｂ株式会社 | 保持装置及びそれを備えた高速めっき装置 |
| JP6189656B2 (ja) | 2013-06-14 | 2017-08-30 | Ｋｙｂ株式会社 | 給電部材及びそれを備えた高速めっき装置 |
| US10100439B2 (en) * | 2015-05-08 | 2018-10-16 | Sunpower Corporation | High throughput chemical vapor deposition electrode |
| CN104931411A (zh) * | 2015-06-09 | 2015-09-23 | 天津大学 | 供水管道耐腐蚀研究用具有多种涂层的可更换工作电极 |
| CN105274557A (zh) * | 2015-11-12 | 2016-01-27 | 厦门理工学院 | 一种电极及其制备方法 |
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| US10184189B2 (en) * | 2016-07-18 | 2019-01-22 | ECSI Fibrotools, Inc. | Apparatus and method of contact electroplating of isolated structures |
| KR102313539B1 (ko) * | 2018-11-21 | 2021-10-15 | 이연주 | 살균 전극 및 그 제작 방법 및 이를 이용한 축사 살균 장치 |
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Also Published As
| Publication number | Publication date |
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| JP2008532739A (ja) | 2008-08-21 |
| CA2599842A1 (en) | 2006-09-14 |
| BRPI0608888A2 (pt) | 2010-02-02 |
| CN101137772A (zh) | 2008-03-05 |
| PL1859079T3 (pl) | 2009-01-30 |
| ITMI20050373A1 (it) | 2006-09-10 |
| KR20070108894A (ko) | 2007-11-13 |
| CA2599842C (en) | 2013-09-03 |
| RU2007137120A (ru) | 2009-04-20 |
| NO20075043L (no) | 2007-10-05 |
| JP5449765B2 (ja) | 2014-03-19 |
| KR101298955B1 (ko) | 2013-08-23 |
| AU2006222191B2 (en) | 2010-06-10 |
| WO2006094814A2 (en) | 2006-09-14 |
| ATE403765T1 (de) | 2008-08-15 |
| EP1859079A2 (en) | 2007-11-28 |
| ZA200707403B (en) | 2008-12-31 |
| US20080053823A1 (en) | 2008-03-06 |
| DE602006002118D1 (de) | 2008-09-18 |
| WO2006094814A3 (en) | 2007-03-08 |
| RU2395628C2 (ru) | 2010-07-27 |
| AU2006222191A1 (en) | 2006-09-14 |
| EP1859079B1 (en) | 2008-08-06 |
| US7674359B2 (en) | 2010-03-09 |
| AU2010202011A1 (en) | 2010-06-10 |
| AU2010202011B2 (en) | 2011-09-08 |
| MX2007011015A (es) | 2007-11-12 |
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