CN100359046C - 一种电解用涂层阳极的制造方法 - Google Patents

一种电解用涂层阳极的制造方法 Download PDF

Info

Publication number
CN100359046C
CN100359046C CNB2005100235830A CN200510023583A CN100359046C CN 100359046 C CN100359046 C CN 100359046C CN B2005100235830 A CNB2005100235830 A CN B2005100235830A CN 200510023583 A CN200510023583 A CN 200510023583A CN 100359046 C CN100359046 C CN 100359046C
Authority
CN
China
Prior art keywords
titanium
electrolysis
coating
anode
tio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB2005100235830A
Other languages
English (en)
Other versions
CN1680625A (zh
Inventor
姚书典
沈嘉年
孙娟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Research Institute Of Metallurgical Equipment China Metallurgical Const
Shanghai University
University of Shanghai for Science and Technology
Original Assignee
Beijing Research Institute Of Metallurgical Equipment China Metallurgical Const
University of Shanghai for Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Research Institute Of Metallurgical Equipment China Metallurgical Const, University of Shanghai for Science and Technology filed Critical Beijing Research Institute Of Metallurgical Equipment China Metallurgical Const
Priority to CNB2005100235830A priority Critical patent/CN100359046C/zh
Publication of CN1680625A publication Critical patent/CN1680625A/zh
Application granted granted Critical
Publication of CN100359046C publication Critical patent/CN100359046C/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

本发明涉及一种电解用涂层阳极的制造方法，属电化学电极制造技术领域。该方法是以金属钛为基体，以原位生成的钛氧化物为中间层物质并在外层再涂敷铂涂层、或铂、钌的氧化物涂层构成涂层阳极；涂层可以通过电化学氧化法或热分解法来获得。本发明方法所制得的电解用涂层阳极具有良好的导电性。它可用于电化学电解工业中，如氯碱工业、水电解、污水处理、有机物合成及电沉积工业中。

Description

一种电解用涂层阳极的制造方法
技术领域
本发明涉及一种电解用涂层阳极的制造方法，属电化学电极制造技术领域。
背景技术
Ti金属或其合金，在电化学工业中作为阳极等方面的应用日趋增加，特别是以Ti金属为基体的并涂覆金属氧化物的阳极更为备受关注和重视，已被广泛地应用于氯碱工业、水电解、污水处理、有机物合成及电沉积工业中。
Ti基贵金属氧化物具有优良电催化活性，得到广泛的应用与研究。特别是自1965年荷兰人成功开发Ti基RuO2涂层阳极以来，阳极研究的大量工作便围绕着金属氧化物而展开。
阳极作为电化学工业中关键部件，一般应具备如下要求：具有良好的导电性；耐腐蚀性强；机械强度和机械加工性能好；寿命长、费用低；对阳极反应具有良好的电催化性能。
美国专利USPatent 5,593,556介绍了Ti基溅射Ta、Zr、Nb薄膜或其混合物薄膜进行表面改性的工艺以提高析氧阳极的耐用性。日本专利特公昭60-22704介绍Ti基和催化活性涂层之前设置涂敷Ti及/或Sn的氧化物和Ta及/或Nb的氧化物所组成的混合氧化物，日本专利特公昭60-22705是在专利文献(特公昭60-22704)基础上发展而来，在中间层设置的氧化物或混合氧化物中加入Pt，以进一步提高中间层的导电性。
研究表明，Ti基氧化物阳极的失效主要体现在活性氧化物的损失和Ti基的钝化。Ti基贵金属的钝化即涂层与Ti基间非导电层TiO2的形成，所以高耐用性涂层阳极关键在于必须解决好Ti基的钝化问题。
由于上述专利技术未能很好处理金属氧化物中间层，未能控制该氧化物的形貌，并且它不是原位制备氧化物，这也影响了Ti金属与中间层氧化物间存在的结合力问题。
发明内容
本发明的目的在于提供一种钛基涂层阳极的制造方法。本发明的又一目的是解决钛基金属的钝化问题，即钛基金属表面能原位生成氧化钛，并控制其形貌、厚度和导电性。
本发明的目的是通过以下技术手段来实现的：
一种电解用涂层阳极的制造方法，其特征在于该方法是以金属钛为基体，以原位生成的钛氧化物为中间层物质并在外层再涂敷铂构成涂层阳极；其制造方法的过程和步骤如下：先将纯钛板进行抛光，随后用超声波清洗，然后用氧化铝机械抛光，用0.5M的H2SO4于25℃下进行钛阳极氧化，氧化时的电流密度为：i＝5-50mA/cm2，使其原位生成二氧化钛，然后在含有Pt(NH3)2(NO2)2的H2SO4溶液中，采用电化学沉积法，在恒电位电源条件下沉积金属铂涂层，最终制成Ti/TiO2/Pt涂层电极。
一种电解用涂层阳极的制造方法，其特征在于该方法是以金属钛为基体，以原位生成的钛氧化物为中间层物质并在外层再涂敷氧化铱构成涂层阳极；其制造方法的过程和步骤如下：先将钛板用超声波清洗，再经喷砂处理，然后在10％草酸溶液中90～100℃下刻蚀2小时，在钛基表面用硫酸进行阳极氧化2分钟，使其原位生成TiO2，预先制备好Ti/TiO2；然后用含H2IrCl6·xH2O的异丙醇和正丁醇的混合溶液于80℃下烘烤12小时，异丙醇和正丁醇的配比为1∶1，然后将该混合液涂刷在钛基板上每次涂刷后在烘箱中100℃下烘烤5分钟，然后在在箱式热处理炉中300℃下烧结10分钟，然后空冷，如此重复涂刷10次，最后在650℃温度下烧结1小时，最终制成Ti/TiO2/IrO2的涂层阳极。
按本发明方法制备的涂层阳极，在电解工艺中表现出具有良好的导电性，本发明的特点是在原位制备氧化钛中间层，且在工艺中能控制该氧化物的厚度、形貌和导电性，防止了钛基的钝化问题。
具体实施方式
实施一：采用金属钛为基体，以原位生成的氧化钛为中间层，并在外层涂覆铂构成涂层阳极。采用99.99％的纯钛板，首先将其抛光，然后在用超声波清洗，然后用氧化铝机械抛光，在0.5MH2SO4于25℃下阳极氧化，氧化时的电流密度为：i＝5-50mAcm2，使其原位生成二氧化钛，然后在含有Pt(NH3)2(NO2)2的H2SO4溶液中，采用电化学法在恒电位电源条件下沉积金属铂，制成Ti/TiO2/Pt电极。
该电极由于电镀锡的阳极中效果很好。
实施二：采用金属钛为基体，以原位生成的氧化钛为中间层，并在外层涂覆氧化铱构成涂覆阳极。先将钛板用超声波清洗，钛板可用ASTM2级钛板，用46#白刚玉进行喷砂处理，喷砂后表面粗糙度为Ra3.0-3.5μm；然后在10％草酸溶液中100℃温度下刻蚀2小时，然后在硫酸中进行钛阳极氧化2分钟，使其原位生成二氧化钛，预先制备好Ti/TiO2；然后用H2IrCl6·xH2O的异丙醇和正丁醇的混合溶液于80℃温度下烘烤12小时，异丙醇和正丁醇的配比为1∶1；然后将该混合液涂刷在钛基板上；混合液中，Ir金属离子的浓度为：0.3mol·dm-3用软毛刷进行涂刷，每次涂刷后在烘箱中100℃下烘烤5分钟，然后在在箱式热处理炉中300℃下烧结10分钟，然后空冷，再涂刷下一层，如此反复涂敷10次，使涂层中沉积量达到W1＝5g/m2，最后在箱式热处理炉中烧结1小时.烧结温度为650℃。最终制成Ti/TiO2/IrO2的涂层阳极。
本实施例中的涂层阳极可用于含氯酚的降解处理，可提高氯酚的裂解产率。
本发明不受以上这些实施例的限制。本发明方法中，中间层物质的被覆量，以金属换算值计，为0.1×10-2～10×10-2mol/m2的范围为宜。
本发明方法除了采用钛为电极基体外，也可以采用Ta、Nb、Zr等耐腐蚀性导电金属或这些金属的合金做电极基体。
在设置了中间层的基体上，可涂覆其他具有电化学活性的物质，使其成为需要的涂覆阳极。这些涂覆物质为铂族金属或其氧化物、该氧化物与钛、钽金属氧化物的混合氧化物，如：IrO2、IrO2+Ta2O5、RuO2+TiO2、IrO2+TiO2等。

Claims (2)

1.一种电解用涂层阳极的制造方法，其特征在于该方法是以金属钛为基体，以原位生成的钛氧化物为中间层物质并在外层再涂敷铂构成涂层阳极；其制造方法的过程和步骤如下：先将纯钛板进行抛光，随后用超声波清洗，然后用氧化铝机械抛光，用0.5M的H2SO4于25℃下进行钛阳极氧化，氧化时的电流密度为：i＝5-50mA/cm2，使其原位生成二氧化钛，然后在含有Pt(NH3)2(NO2)2的H2SO4溶液中，采用电化学氧化法，在恒电位电源条件下沉积金属铂涂层，最终制成Ti/TiO2/Pt涂层电极。
2.一种电解用涂层阳极的制造方法，其特征在于该方法是以金属钛为基体，以原位生成的钛氧化物为中间层物质并在外层再涂敷氧化铱构成涂层阳极；其制造方法的过程和步骤如下：先将钛板用超声波清洗，再经喷砂处理，然后在10％草酸溶液中90～100℃下刻蚀2小时，在钛基表面用硫酸进行阳极氧化2分钟，使其原位生成TiO2，预先制备好Ti/TiO2；然后用含H2IrCl6·xH2O的异丙醇和正丁醇的混合溶液于80℃下烘烤12小时，异丙醇和正丁醇的配比为1∶1，然后将该混合液涂刷在钛基板上.每次涂刷后在烘箱中100℃下烘烤5分钟，然后在在箱式热处理炉中300℃下烧结10分钟，然后空冷，如此重复涂刷10次，最后在650℃温度下烧结1小时，最终制成Ti/TiO2/IrO2的涂层阳极。
CNB2005100235830A 2005-01-26 2005-01-26 一种电解用涂层阳极的制造方法 Expired - Fee Related CN100359046C (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2005100235830A CN100359046C (zh) 2005-01-26 2005-01-26 一种电解用涂层阳极的制造方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2005100235830A CN100359046C (zh) 2005-01-26 2005-01-26 一种电解用涂层阳极的制造方法

Publications (2)

Publication Number Publication Date
CN1680625A CN1680625A (zh) 2005-10-12
CN100359046C true CN100359046C (zh) 2008-01-02

Family

ID=35067365

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2005100235830A Expired - Fee Related CN100359046C (zh) 2005-01-26 2005-01-26 一种电解用涂层阳极的制造方法

Country Status (1)

Country Link
CN (1) CN100359046C (zh)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI453306B (zh) * 2008-03-31 2014-09-21 Permelec Electrode Ltd 電解用電極的製造方法
JP5686457B2 (ja) * 2011-12-26 2015-03-18 ペルメレック電極株式会社 酸素発生用陽極の製造方法
JP5686456B2 (ja) * 2011-12-26 2015-03-18 ペルメレック電極株式会社 酸素発生用陽極の製造方法
CN102677092B (zh) * 2012-05-30 2015-01-14 浙江大学 一种钛阳极的制备方法
CN109763146B (zh) * 2019-03-27 2021-03-26 贵州省过程工业技术研究中心 一种铝电解用钛基复合材料阳极制备方法
CN110387558B (zh) * 2019-07-26 2020-11-24 浙江工业大学 一种钌钽析氯电极及其制备方法和测试方法
CN112853352A (zh) * 2020-12-31 2021-05-28 西安泰金工业电化学技术有限公司 一种钛基不溶性阳极的制备方法
CN114197005B (zh) * 2021-12-27 2023-09-26 苏州市枫港钛材设备制造有限公司 一种电解水制氢气体扩散阳极板及其电镀铂金方法
CN114892237B (zh) * 2022-03-25 2023-05-02 西安泰金新能科技股份有限公司 一种通过改进前处理工艺来提高钛电极性能的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4979971A (zh) * 1972-08-03 1974-08-01
US4039400A (en) * 1974-10-29 1977-08-02 Marston Excelsior Limited Method of forming electrodes
GB2134544A (en) * 1983-01-31 1984-08-15 Permelec Electrode Ltd Electrolysis electrodes
CN1389932A (zh) * 2002-04-27 2003-01-08 江汉石油钻头股份有限公司 钛基复合型薄膜光电极及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4979971A (zh) * 1972-08-03 1974-08-01
US4039400A (en) * 1974-10-29 1977-08-02 Marston Excelsior Limited Method of forming electrodes
GB2134544A (en) * 1983-01-31 1984-08-15 Permelec Electrode Ltd Electrolysis electrodes
CN1389932A (zh) * 2002-04-27 2003-01-08 江汉石油钻头股份有限公司 钛基复合型薄膜光电极及其制备方法

Also Published As

Publication number Publication date
CN1680625A (zh) 2005-10-12

Similar Documents

Publication Publication Date Title
CN100359046C (zh) 一种电解用涂层阳极的制造方法
EP1616046B1 (en) Electrocatalytic coating with platinium group metals and electrode made therefrom
US7247229B2 (en) Coatings for the inhibition of undesirable oxidation in an electrochemical cell
CN101343749B (zh) 一种金属氧化物涂层电极及其制备方法
US6251254B1 (en) Electrode for chromium plating
RU2568546C2 (ru) Анод для электровыделения и способ электровыделения с его применением
JP4554542B2 (ja) 電解用電極
CN102677092A (zh) 一种钛阳极的制备方法
CN109778100B (zh) 一种延寿节能形稳PbO2阳极中间层的电弧热喷涂制备方法
JP2008050675A (ja) 電解用電極
JP2641584B2 (ja) 寸法安定性をもった陽極
CN102165102B (zh) 用于次氯酸盐电解槽的阴极部件和双极板
JP2514032B2 (ja) 金属の電解処理方法
JP2023523690A (ja) 電極を製造するための金属基材の処理のための方法
CN102560561A (zh) Dsa电极及其制作方法
JPH0790665A (ja) 酸素発生用電極
CN106835192B (zh) 一种电解二氧化锰用钛基阳极表面复合涂层的制备方法
CN113699540B (zh) 一种消毒液的制备方法
JPH07331494A (ja) 酸素発生用電極とその製造方法
JPH08199384A (ja) 電解用電極及びその製造方法
KR100770736B1 (ko) 수처리용 세라믹 전극 및 그 제조방법 그리고 이를 이용한전극구성체
JPH0417689A (ja) 水電解用電極及びその製造方法
JPH02294494A (ja) 酸素発生用陽極
JPH03253590A (ja) 水電解用電極の製造方法
JPH0925591A (ja) 電解用電極の製造方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080102

Termination date: 20110126