CN1680625A - Production of coating anode for electrolysis - Google Patents

Production of coating anode for electrolysis Download PDF

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Publication number
CN1680625A
CN1680625A CN 200510023583 CN200510023583A CN1680625A CN 1680625 A CN1680625 A CN 1680625A CN 200510023583 CN200510023583 CN 200510023583 CN 200510023583 A CN200510023583 A CN 200510023583A CN 1680625 A CN1680625 A CN 1680625A
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CN
China
Prior art keywords
titanium
tio
coated anode
manufacture method
oxide
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.)
Granted
Application number
CN 200510023583
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Chinese (zh)
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CN100359046C (en
Inventor
姚书典
沈嘉年
孙娟
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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
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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/en
Publication of CN1680625A publication Critical patent/CN1680625A/en
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    • 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

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  • 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

A process of preparing coating positive pole for electrolyzation. The coating positive pole bases Ti. Middle layer is oxide Ti. Outside layer is Pt or Pt-Ru oxidate. The coat can be obtained by way of electrochemical oxidation or heat decomposition.

Description

A kind of electrolysis manufacture method of coated anode
Technical field
The present invention relates to the manufacture method of a kind of electrolysis, belong to electrochemical electrode manufacturing technology field with coated anode.
Background technology
Ti metal or its alloy, application as aspects such as anodes in electrochemical industry increases day by day, particularly with the Ti metal be matrix and the anode of coated metal oxide more receive much concern and pay attention to, be widely used in chlorine industry, water electrolysis, sewage disposal, organism is synthetic and galvanic deposit industry in.
Ti base precious metal oxide compound has the good electric catalytic activity, is widely used and studies.Particularly successfully develop Ti base RuO from the nineteen sixty-five Dutch 2Since the coated anode, the extensive work of anode research just launches round metal oxide.
Anode generally should possess following requirement: have good electrical conductivity as key part in the electrochemical industry; Erosion resistance is strong; Physical strength and machining property are good; Life-span is long, expense is low; The antianode reaction has good catalytic action.
U.S. Pat Patent 5,593, and 556 have introduced Ti base sputter Ta, Zr, Nb film or its mixture film carries out process for surface modification is analysed oxygen anodes with raising wearing quality.The special public clear 60-22704 of Japanese Patent introduces the mixed oxide that oxide compound that the oxide compound that applies Ti and/or Sn and Ta and/or Nb are set before Ti base and the catalytically active coatings is formed, the special public clear 60-22705 of Japanese Patent is development on patent documentation (special public clear 60-22704) basis, add Pt in oxide compound that is provided with in the middle layer or the mixed oxide, with the electroconductibility in further raising middle layer.
Studies show that the inefficacy of Ti base oxide anode is mainly reflected in the loss of activating oxide and the passivation of Ti base.The passivation of Ti base precious metal is non-conductive layer TiO between coating and Ti base 2Formation, so high durability coated anode key is to resolve the problem of passivation of Ti base.
Because above-mentioned patented technology is failed fine processing metal oxide middle layer, fail to control the pattern of this oxide compound, and it not the in-situ preparing oxide compound, this has also influenced the bonding force problem that exists between Ti metal and middle layer oxide compound.
Summary of the invention
The object of the present invention is to provide a kind of ti-based coating anodic manufacture method.Another purpose of the present invention is the problem of passivation that solves titanium-based metal, and promptly titanium-based metal surface energy original position generates titanium oxide, and controls its pattern, thickness and electroconductibility.
The objective of the invention is to realize by following technique means:
A kind of electrolysis is characterized in that with the manufacture method of coated anode this method is is matrix with the metal titanium, is intermediate layer material and applies platinum again at skin and constitute coated anode with generated in-situ titanium oxide; The process and the step of its manufacture method are as follows: earlier pure titanium plate is polished, use ultrasonic cleaning subsequently, use aluminum oxide mechanical polishing then, with the H of 0.5M 2SO 4Carry out the titanium anodic oxidation under 25 ℃, the current density during oxidation is: i=5-50mA cm 2, make its original position generate titanium dioxide, containing Pt (NH then 3) 2(NO 2) 2H 2SO 4In the solution, adopt electrochemical deposition method,, finally make Ti/TiO in constant potential Power Supplies Condition deposit metal platinum coating 2/ Pt coated electrode.
A kind of electrolysis is characterized in that with the manufacture method of coated anode this method is is matrix with the metal titanium, is intermediate layer material and applies platinum again at skin and constitute coated anode with generated in-situ titanium oxide; The process and the step of its manufacture method are as follows: earlier with titanium plate ultrasonic cleaning, again through sandblasting, 90 ~ 100 ℃ of following etchings 2 hours in 10% oxalic acid solution were carried out anodic oxidation 2 minutes at titanium-based surface with sulfuric acid then, made its original position generation TiO 2, prepare Ti/TiO in advance 2Then with containing H 2IrCl 6χ H 2The Virahol of O and the mixing solutions of propyl carbinol toasted 12 hours down in 80 ℃, the proportioning of Virahol and propyl carbinol is 1: 1, then with this mixed solution brushing on the titanium-base. each brushing back is 100 ℃ of bakings 5 minutes down in baking oven, then 300 ℃ of following sintering in box heat treatment furnace 10 minutes, air cooling then, so repeat to brush 10 times, 650 ℃ of sintering temperatures 1 hour, finally make Ti/TiO at last 2/ IrO 2Coated anode.
Coated anode by the inventive method preparation, in electrolysis process, show and have good electrical conductivity, characteristics of the present invention are to prepare the titanium oxide middle layer in position, and can control thickness, pattern and the electroconductibility of this oxide compound in technology, have prevented the problem of passivation of titanium base.
Embodiment
Implement one: the employing metal titanium is a matrix, is the middle layer with generated in-situ titanium oxide, and applies platinum formation coated anode at skin.Adopt 99.99% pure titanium plate,, using ultrasonic cleaning then, use aluminum oxide mechanical polishing then, at 0.5MH at first with its polishing 2SO 4In 25 ℃ of following anodic oxidations, the current density during oxidation is: i=5-50mA cm 2, make its original position generate titanium dioxide, containing Pt (NH then 3) 2(NO 2) 2H 2SO 4In the solution, adopt electrochemical process, make Ti/TiO in constant potential Power Supplies Condition deposit metal platinum 2/ Pt electrode.
This electrode is owing to effect in the anode of eleetrotinplate is fine.
Implement two: the employing metal titanium is a matrix, is the middle layer with generated in-situ titanium oxide, and constitutes coated anode in outer coated with iridium oxide.With titanium plate ultrasonic cleaning, the titanium plate can be used ASTM2 level titanium plate, carries out sandblasting with the 46# white fused alumina earlier, and sandblast rear surface roughness is Ra3.0-3.5 μ m; Etching 2 hours under 100 ℃ of temperature in 10% oxalic acid solution is carried out titanium anodic oxidation 2 minutes then in sulfuric acid then, makes its original position generate titanium dioxide, prepares Ti/TiO in advance 2Use H then 2IrCl 6χ H 2The Virahol of O and the mixing solutions of propyl carbinol toasted 12 hours under 80 ℃ of temperature, and the proportioning of Virahol and propyl carbinol is 1: 1; Then with this mixed solution brushing on titanium-base; In the mixed solution, the concentration of Ir metal ion is: 0.3moldm -3Brush with banister brush, each brushing back is 100 ℃ of bakings 5 minutes down in baking oven, then 300 ℃ of following sintering in box heat treatment furnace 10 minutes, and air cooling then, brushing one deck down applies 10 times so repeatedly again, makes that deposition reaches W in the coating i=5g/m 2, sintering 1 hour in box heat treatment furnace at last.Sintering temperature is 650 ℃.Finally make Ti/TiO 2/ IrO 2Coated anode.
Coated anode in the present embodiment can be used for containing the degradation treatment of chlorophenol, can improve the cracking productive rate of chlorophenol.
The present invention is not subjected to the restriction of above these embodiment.In the inventive method, the amount of coating of intermediate layer material in the metal scaled value, is 0.1 * 10 -2～10 * 10 -2Mol/m 2Scope be advisable.
The inventive method is the electrode matrix except adopting titanium, also can adopt the alloy of erosion resistance conducting metal such as Ta, Nb, Zr or these metals to do electrode matrix.
Being provided with on the matrix in middle layer, can apply the material that other have electrochemical activity, make it become the coated anode that needs.These coating substances are the mixed oxide of platinum metals or its oxide compound, this oxide compound and titanium, tantalum metal oxide, as: IrO 2, IrO 2+ Ta 2O 5, RuO 2+ TiO 2, IrO 2+ TiO 2Deng.

Claims (2)

1. an electrolysis is characterized in that with the manufacture method of coated anode this method is is matrix with the metal titanium, is intermediate layer material and applies platinum again at skin and constitute coated anode with generated in-situ titanium oxide; The process and the step of its manufacture method are as follows: earlier pure titanium plate is polished, use ultrasonic cleaning subsequently, use aluminum oxide mechanical polishing then, with the H of 0.5M 2SO 4Carry out the titanium anodic oxidation under 25 ℃, the current density during oxidation is: i=5-50mAcm 2, make its original position generate titanium dioxide, containing Pt (NH then 3) 2(NO 2) 2H 2SO 4In the solution, adopt electrochemical oxidation process,, finally make Ti/TiO in constant potential Power Supplies Condition deposit metal platinum coating 2/ Pt coated electrode.
2. an electrolysis is characterized in that with the manufacture method of coated anode this method is is matrix with the metal titanium, is intermediate layer material and applies platinum again at skin and constitute coated anode with generated in-situ titanium oxide; The process and the step of its manufacture method are as follows: earlier with titanium plate ultrasonic cleaning, again through sandblasting, 90 ~ 100 ℃ of following etchings 2 hours in 10% oxalic acid solution were carried out anodic oxidation 2 minutes at titanium-based surface with sulfuric acid then, made its original position generation TiO 2, prepare Ti/TiO in advance 2Then with containing H 2IrCl 6XH 2The Virahol of O and the mixing solutions of propyl carbinol toasted 12 hours down in 80 ℃, the proportioning of Virahol and propyl carbinol is 1: 1, then with this mixed solution brushing on the titanium-base. each brushing back is 100 ℃ of bakings 5 minutes down in baking oven, then 300 ℃ of following sintering in box heat treatment furnace 10 minutes, air cooling then, so repeat to brush 10 times, 650 ℃ of sintering temperatures 1 hour, finally make Ti/TiO at last 2/ IrO 2Coated anode.
CNB2005100235830A 2005-01-26 2005-01-26 Production of coating anode for electrolysis Expired - Fee Related CN100359046C (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101550558B (en) * 2008-03-31 2012-07-18 培尔梅烈克电极股份有限公司 Manufacturing process of electrodes for electrolysis
CN102677092A (en) * 2012-05-30 2012-09-19 浙江大学 Preparation method of titanium anode
CN104011264A (en) * 2011-12-26 2014-08-27 培尔梅烈克电极股份有限公司 Anode for oxygen generation and manufacturing method for the same
CN104011263A (en) * 2011-12-26 2014-08-27 培尔梅烈克电极股份有限公司 Anode For Oxygen Generation And Manufacturing Method For The Same
CN109763146A (en) * 2019-03-27 2019-05-17 贵州省过程工业技术研究中心 A kind of titanium composite material anode preparation method used for aluminium electrolysis
CN110387558A (en) * 2019-07-26 2019-10-29 浙江工业大学 A kind of ruthenium tantalum analysis chloride electrode and preparation method thereof and test method
CN112853352A (en) * 2020-12-31 2021-05-28 西安泰金工业电化学技术有限公司 Preparation method of titanium-based insoluble anode
CN114197005A (en) * 2021-12-27 2022-03-18 苏州市枫港钛材设备制造有限公司 Gas diffusion anode plate for producing hydrogen by electrolyzing water and platinum gold electroplating method thereof
CN114892237A (en) * 2022-03-25 2022-08-12 西安泰金工业电化学技术有限公司 Method for improving performance of titanium electrode by improving pretreatment process

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL161817C (en) * 1972-08-03 Marston Excelsior Ltd PROCESS FOR THE MANUFACTURE OF ELECTRODES.
NL178429C (en) * 1974-10-29 1986-03-17 Diamond Shamrock Techn METHOD OF MANUFACTURING AN ELECTRODE SUITABLE FOR USE IN ELECTROLYTIC PROCESSES
JPS6022075B2 (en) * 1983-01-31 1985-05-30 ペルメレック電極株式会社 Durable electrolytic electrode and its manufacturing method
CN1174495C (en) * 2002-04-27 2004-11-03 江汉石油钻头股份有限公司 Composite titanium-base film photoelectrode and its making process

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101550558B (en) * 2008-03-31 2012-07-18 培尔梅烈克电极股份有限公司 Manufacturing process of electrodes for electrolysis
CN104011264A (en) * 2011-12-26 2014-08-27 培尔梅烈克电极股份有限公司 Anode for oxygen generation and manufacturing method for the same
CN104011263A (en) * 2011-12-26 2014-08-27 培尔梅烈克电极股份有限公司 Anode For Oxygen Generation And Manufacturing Method For The Same
CN104011264B (en) * 2011-12-26 2016-12-07 培尔梅烈克电极股份有限公司 Oxygen generation anode and manufacture method thereof
CN102677092A (en) * 2012-05-30 2012-09-19 浙江大学 Preparation method of titanium anode
CN102677092B (en) * 2012-05-30 2015-01-14 浙江大学 Preparation method of titanium anode
CN109763146A (en) * 2019-03-27 2019-05-17 贵州省过程工业技术研究中心 A kind of titanium composite material anode preparation method used for aluminium electrolysis
CN109763146B (en) * 2019-03-27 2021-03-26 贵州省过程工业技术研究中心 Preparation method of titanium-based composite material anode for aluminum electrolysis
CN110387558A (en) * 2019-07-26 2019-10-29 浙江工业大学 A kind of ruthenium tantalum analysis chloride electrode and preparation method thereof and test method
CN112853352A (en) * 2020-12-31 2021-05-28 西安泰金工业电化学技术有限公司 Preparation method of titanium-based insoluble anode
CN114197005A (en) * 2021-12-27 2022-03-18 苏州市枫港钛材设备制造有限公司 Gas diffusion anode plate for producing hydrogen by electrolyzing water and platinum gold electroplating method thereof
CN114197005B (en) * 2021-12-27 2023-09-26 苏州市枫港钛材设备制造有限公司 Hydrogen production gas diffusion anode plate by water electrolysis and platinum electroplating method thereof
CN114892237A (en) * 2022-03-25 2022-08-12 西安泰金工业电化学技术有限公司 Method for improving performance of titanium electrode by improving pretreatment process

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