CN109972178A - A kind of preparation method of high activity iridium zirconium composite oxides inert anode - Google Patents

A kind of preparation method of high activity iridium zirconium composite oxides inert anode Download PDF

Info

Publication number
CN109972178A
CN109972178A CN201910302487.1A CN201910302487A CN109972178A CN 109972178 A CN109972178 A CN 109972178A CN 201910302487 A CN201910302487 A CN 201910302487A CN 109972178 A CN109972178 A CN 109972178A
Authority
CN
China
Prior art keywords
iridium
anode
zirconium
inert anode
drying
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
CN201910302487.1A
Other languages
Chinese (zh)
Other versions
CN109972178B (en
Inventor
王成彦
刘宝
陈永强
王硕
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.)
University of Science and Technology Beijing USTB
Original Assignee
University of Science and Technology Beijing USTB
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
Priority claimed from CN201810385376.7A external-priority patent/CN108486614A/en
Priority claimed from CN201810384787.4A external-priority patent/CN108505074A/en
Priority claimed from CN201810385367.8A external-priority patent/CN108330513A/en
Priority claimed from CN201810384759.2A external-priority patent/CN108486613A/en
Priority claimed from CN201810384760.5A external-priority patent/CN108330511A/en
Priority claimed from CN201810385071.6A external-priority patent/CN108330512A/en
Application filed by University of Science and Technology Beijing USTB filed Critical University of Science and Technology Beijing USTB
Publication of CN109972178A publication Critical patent/CN109972178A/en
Application granted granted Critical
Publication of CN109972178B publication Critical patent/CN109972178B/en
Active 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof

Abstract

A kind of preparation method of hydrometallurgy high activity iridium zirconium composite oxides anode, including iridium zirconium binary composite oxides inert anode, iridium ruthenium Zr ternary compound oxides inert anode, iridium cobalt Zr ternary compound oxides inert anode, iridium molybdenum Zr ternary compound oxides inert anode, iridium rubidium Zr ternary compound oxides inert anode and iridium ruthenium rubidium zirconium quaternary composite oxides inert anode.Obtained anode is made of Titanium base and oxide coating, and zirconium dioxide and rubidium oxide are amorphous phase in coating, and iridium dioxide and ruthenic oxide are Rutile Type, and cobaltosic oxide is Spinel, and molybdenum trioxide is α phase.The addition of zirconium or ruthenium or cobalt improves the oxygen evolution activity surface area of anode, improves anode activity, and the addition of rubidium or molybdenum enhances the electric conductivity of anode.Preparation flow of the present invention is simple, and obtained anode has preferable analysis oxygen catalytic activity and service life, since the precious metal iridium element in coating is replaced base metal, reduces the production cost of anode.

Description

A kind of preparation method of high activity iridium zirconium composite oxides inert anode
Technical field
The invention belongs to technical field of wet metallurgy more particularly to a kind of high activity iridium zirconium composite oxides inert anodes Preparation method, including iridium zirconium binary composite oxides inert anode, iridium ruthenium Zr ternary compound oxides inert anode, iridium cobalt zirconium Ternary compound oxides inert anode, iridium molybdenum Zr ternary compound oxides inert anode, iridium rubidium Zr ternary compound oxides inertia Anode and iridium ruthenium rubidium zirconium quaternary composite oxides inert anode.
Background technique
With being constantly progressive for society, have in industrial production to the consuming of the pollution of environment and the energy more stringent It is required that energy-saving and emission-reduction have become the theme of 21 century social development.In recent ten years, the coloured industry development in China is rapid, copper, The increase of production of the metals such as zinc is rapid.Compared with pyrometallurgical smelting, hydrometallurgy big, high-efficient, operating condition with production capacity It is good, pollute compared with light and high valuable metal comprehensive recovery advantage, currently, 80% or so zinc and 20% or so in the world Copper is extracted by hydrometallurgy.Anode has hydrometallurgical as core main body and important equipment in hydrometallurgy process The title of " heart ".The superiority and inferiority of anode performance will have a direct impact on energy consumption and cathode product quality in wet smelting process.
Currently, the anode that hydrometallurgy industry uses is mostly pure Pb anode and Pb alloy anode, such as: Pb-Ag, Pb-Ag- Sn and Pb-Sb-Sn-Ag etc..Though it is with corrosion-resistant, long service life in easy processing molding, low manufacture cost, sulfuric acid electrolyte The advantages that, but there is also big in oxygen overpotential on anode height, electrolytic process anode Pb dissolution pollution cathode product, electrolytic process The disadvantages of generation of the amount earth of positive pole will increase labour cost.According to statistics, overpotential for oxygen evolution of the pure Pb anode in electrolytic process can Up to 860mV, and the overpotential for oxygen evolution of Pb-Ag alloy anode, also in 600mV or so, thus increased useless power consumption accounts for about Zinc electrolysis 30% or so of total energy consumption, therefore, exploitation and the application of high oxygen separated active anode have received widespread attention.
40~fifties of 20th century, as titanium production makes a breakthrough, global titanium yield is continuously increased, It lays a good foundation for the development of coated titanium anode.Titanium is referred to as valve metal, has stable oxide layer protection, under electrolysis conditions There are good durability and dimensional stability.Compared with pure Pb anode and Pb alloy anode, coated titanium anode has outer dimension steady Calmly, the advantages that overpotential for oxygen evolution is low, electrolytic process Anodic will not pollute cathode product, in recent years in high purity product Electrolysis production process is widely used.Ruthenic oxide (RuO2) and iridium dioxide (IrO2) due to its good analysis oxygen catalysis Performance is chiefly used in the preparation of coated titanium anode.And it finds in use, Ti/RuO2Though anode shows excellent Oxygen catalytic performance is analysed, preferably reduces the overpotential for oxygen evolution of electrolytic process Anodic, but in sulfuric acid system, Ti/RuO2Sun The service life of pole is shorter, about 100 days, constrains its application in hydrometallurgy process.Ti/IrO2The analysis oxygen of anode is catalyzed Though performance slightly worse than Ti/RuO2Anode, but it shows preferable corrosion resistance in sulfuric acid system, and service life can Up to 1 year or more, but iridium was expensive, Ti/IrO2The cost of manufacture of anode is higher, limits its large-scale application.Therefore, it makes A kind of standby oxygen evolution activity is high, long service life and the cheap analysis oxygen anodes of cost of manufacture, to the energy-saving of nonferrous metallurgy industry It has a very important significance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high activity iridium zirconium composite oxides inert anode, the preparations Method flow is simple, and obtained anode has preferable analysis oxygen catalytic activity, long service life and cheap is prepared into This.
A kind of preparation method of high activity iridium zirconium composite oxides inert anode, including iridium zirconium binary composite oxides are lazy Property anode, iridium ruthenium Zr ternary compound oxides inert anode, iridium cobalt Zr ternary compound oxides inert anode, iridium molybdenum zirconium ternary it is multiple Close oxide inert anode, iridium rubidium Zr ternary compound oxides inert anode and iridium ruthenium rubidium zirconium quaternary composite oxides inertia sun Pole.
The wherein preparation method of iridium zirconium binary composite oxides inert anode, preparation step are as follows:
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, ultrasonic cleaning and drying；
Step 2, by H2IrCl6Miscible, solute needed for obtaining configuration coating solution is carried out with tetrabutyl zirconate.
Volume ratio is added in the solute matched by step 3 by the n-butanol of 1:1 and the mixed solvent of isopropanol, is obtained Coating solution；In coating solution, the molar concentration of iridium is 0.05-0.20mol/L, and the molar concentration of zirconium is 0.01-0.15mol/ L。
The coating solution prepared is coated in pretreated Titanium base surface by step 4, through drying Iridium zirconium binary composite oxides inert anode is obtained after dry, sintering processes.Coating is applied to 10-40 layers, drying temperature 100- 200 DEG C, drying time is 10-15 minutes；Sintering temperature is 400-600 DEG C, and sintering time is 10-15 minutes, and burning the time eventually is 1 Hour.Iridium dioxide is Rutile Type in the coating, and zirconium dioxide is amorphous phase, and part zirconium dioxide can be with iridium dioxide shape At solid solution.
Further, the preparation step of the iridium ruthenium Zr ternary compound oxides inert anode includes:
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, ultrasonic cleaning and drying；
Step 2, by RuCl3、H2IrCl6Miscible, solute needed for obtaining configuration coating solution is carried out with tetrabutyl zirconate；
Volume ratio is added in the solute matched by step 3 by the n-butanol of 1:1 and the mixed solvent of isopropanol, is obtained Coating solution；In coating solution, the molar concentration of ruthenium and iridium is 0.01-0.10mol/L, and the molar concentration of zirconium is 0.05- 0.15mol/L。
The coating solution prepared is coated in pretreated Titanium base surface by step 4, through drying Ternary compound oxides inert anode is obtained after dry, sintering processes.Coating is applied to 10-40 layers, drying temperature 100-200 DEG C, drying time is 10-15 minutes；Sintering temperature is 400-600 DEG C, and sintering time is 10-15 minutes, and burning the time eventually is 1 small When.Iridium dioxide and ruthenic oxide are Rutile Type in the coating, and zirconium dioxide is amorphous phase.
Further, the preparation step of the iridium cobalt Zr ternary compound oxides inert anode is as follows:
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, ultrasonic cleaning and drying；
Step 2, by Co (NO3)2、H2IrCl6It is miscible with tetrabutyl zirconate progress, it obtains molten needed for configuration coating solution Matter；
Volume ratio is added in the solute matched by step 3 by the n-butanol of 1:1 and the mixed solvent of isopropanol, is obtained Coating solution；In coating solution, the molar concentration of cobalt and iridium is 0.01-0.10mol/L, and the molar concentration of zirconium is 0.05- 0.15mol/L。
The coating solution prepared is coated in pretreated Titanium base surface by step 4, through drying Iridium cobalt Zr ternary compound oxides inert anode is obtained after dry, sintering processes.Coating is applied to 10-40 layers, and drying temperature is 100-200 DEG C, drying time is 10-15 minutes；Sintering temperature is 400-600 DEG C, and sintering time is 10-15 minutes, when burning eventually Between be 1 hour.Iridium dioxide is Rutile Type in the coating, and zirconium dioxide is amorphous phase, and cobaltosic oxide is Spinel.
Further, the preparation step of iridium molybdenum Zr ternary compound oxides inert anode is as follows:
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, ultrasonic cleaning and drying；
Step 2, by MoCl5、H2IrCl6Miscible, solute needed for obtaining configuration coating solution is carried out with tetrabutyl zirconate；
Volume ratio is added in the solute matched by step 3 by the n-butanol of 1:1 and the mixed solvent of isopropanol, is obtained Coating solution；In coating solution, the molar concentration of molybdenum and iridium is 0.01-0.10mol/L, and the molar concentration of zirconium is 0.05- 0.15mol/L。
The coating solution prepared is coated in pretreated Titanium base surface by step 4, through drying Iridium molybdenum Zr ternary compound oxides inert anode is obtained after dry, sintering processes.Coating is applied to 10-40 layers, and drying temperature is 100-200 DEG C, drying time is 10-15 minutes；Sintering temperature is 400-600 DEG C, and sintering time is 10-15 minutes, when burning eventually Between be 1 hour.Iridium dioxide is Rutile Type in the coating, and zirconium dioxide is amorphous phase, and molybdenum trioxide is α phase.
Further, the preparation step of iridium rubidium Zr ternary compound oxides inert anode is as follows:
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, ultrasonic cleaning and drying；
Step 2, by RbCl, H2IrCl6Miscible, solute needed for obtaining configuration coating solution is carried out with tetrabutyl zirconate；
Volume ratio is added in the solute matched by step 3 by the n-butanol of 1:1 and the mixed solvent of isopropanol, is obtained Coating solution；In coating solution, the molar concentration of iridium and rubidium is 0.01-0.10mol/L, and the molar concentration of zirconium is 0.05- 0.15mol/L。
The coating solution prepared is coated in pretreated Titanium base surface by step 4, through drying Iridium rubidium Zr ternary compound oxides inert anode is obtained after dry, sintering processes.Coating is applied to 10-40 layers, and drying temperature is 100-200 DEG C, drying time is 10-15 minutes；Sintering temperature is 400-600 DEG C, and sintering time is 10-15 minutes, when burning eventually Between be 1 hour.Iridium dioxide is Rutile Type in the coating, and zirconium dioxide and rubidium oxide are amorphous phase.
Further, the preparation step of iridium ruthenium rubidium zirconium quaternary composite oxides inert anode is as follows:
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, ultrasonic cleaning and drying；
Step 2, by RbCl, RuCl3、H2IrCl6It is miscible with tetrabutyl zirconate progress, it obtains needed for configuration coating solution Solute；
Volume ratio is added in the solute matched by step 3 by the n-butanol of 1:1 and the mixed solvent of isopropanol, is obtained Coating solution；In coating solution, the molar concentration of iridium, ruthenium and rubidium is 0.01-0.10mol/L, and the molar concentration of zirconium is 0.05- 0.15mol/L。
The coating solution prepared is coated in pretreated Titanium base surface by step 4, through drying Iridium ruthenium rubidium zirconium quaternary composite oxides inert anode is obtained after dry, sintering processes.Coating is applied to 10-40 layers, and drying temperature is 100-200 DEG C, drying time is 10-15 minutes；Sintering temperature is 400-600 DEG C, and sintering time is 10-15 minutes, when burning eventually Between be 1 hour.Iridium dioxide and ruthenic oxide are Rutile Type in the coating, and zirconium dioxide and rubidium oxide are amorphous phase.
It is had a characteristic that compared with existing anode according to anode prepared by the method for the invention
1) preparation flow is succinct, and required equipment is few and simple, and equipment investment is low, and easy to operate, technology is easily promoted；
2) iridium zirconium binary composite oxides inert anode, ZrO are used as2Incorporation promote active material IrO2The analysis of crystal Out, make gained binary composite oxides anode and tradition IrO2Oxide anode, which is compared, has bigger specific surface area active, mentions The high analysis oxygen catalytic activity of anode；
As iridium ruthenium Zr ternary compound oxides inert anode, RuO2Incorporation to improve iridium zirconium binary composite oxides lazy The analysis oxygen catalytic performance of property anode, due to active component IrO2With RuO2Solid solution effect, active component RuO not only can be improved2 The corrosion resistance in sulfuric acid system, while also improving active component IrO2Analyse oxygen catalytic performance；
As iridium cobalt Zr ternary compound oxides inert anode, Co3O4Incorporation to improve iridium zirconium binary composite oxides lazy The analysis oxygen catalytic activity of property anode, reduces the overpotential for oxygen evolution of anode；
As iridium molybdenum Zr ternary compound oxides inert anode, MoO3Incorporation improve the electric conductivity of anode, improve The service performance of iridium zirconium binary composite oxides inert anode, reduces the overpotential for oxygen evolution of anode；
As iridium rubidium Zr ternary compound oxides inert anode, Rb2The incorporation of O improves the electric conductivity of anode, improves The service performance of iridium zirconium binary composite oxides inert anode, reduces the overpotential for oxygen evolution of anode；
As iridium ruthenium rubidium zirconium quaternary composite oxides inert anode, RuO2And Rb2The incorporation of O can play improvement Oxygen anodic evolution The double goal of catalytic activity and electric conductivity effectively reduces the overpotential for oxygen evolution of anode.
3) constituent element ZrO2、RuO2、Co3O4、MoO3Or Rb2The incorporation of O reduces the usage amount of precious metal iridium, significantly reduces The production cost of anode.
Detailed description of the invention
Fig. 1 is Ti/IrO of the present invention2-ZrO2The preparation flow figure of binary composite oxides inert anode.
Fig. 2 is Ti/IrO of the present invention2-RuO2-ZrO2The preparation flow figure of ternary compound oxides inert anode.
Fig. 3 is Ti/IrO of the present invention2-Co3O4-ZrO2The preparation flow figure of ternary compound oxides inert anode.
Fig. 4 is Ti/IrO of the present invention2-MoO3-ZrO2The preparation flow figure of ternary compound oxides inert anode.
Fig. 5 is Ti/IrO of the present invention2-Rb2O-ZrO2The preparation flow figure of ternary compound oxides inert anode.
Fig. 6 is Ti/IrO of the present invention2-RuO2-Rb2O-ZrO2The preparation flow figure of quaternary composite oxides inert anode.
Specific embodiment
Embodiment one:
It is first that 10mm × 10mm × 1mm titanium plate is small through 60 DEG C of etchings 2.5 of 10% oxalic acid at alkali cleaning 30 minutes, 90 DEG C When, deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the H of certain mass2IrCl6It is miscible with tetrabutyl zirconate.
H after will be miscible2IrCl6With the mixed solution of tetrabutyl zirconate be dissolved in by 1:1 match mixed n-butanol with it is different The in the mixed solvent of propyl alcohol, obtains coating solution.H in coating solution2IrCl6Molar concentration with tetrabutyl zirconate is respectively 0.18 and 0.02mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 10 minutes, then be sintered 10 minutes at 450 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 450 DEG C, obtains the binary composite oxides anode of the zirconium containing iridium.
Further, the binary composite oxides anode prepared can be placed in the sulfuric acid solution of 0.5mol/L, is adopted It being determined with oxygen evolution potential of the three-electrode system to anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, When current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.38V vs.SCE.It is assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, work as tank voltage Anode failure is determined when rising 5V compared with testing initial voltage.It is calculated according to test measurement result and empirical equation, it is obtained Its true service life expection of the binary composite oxides of zirconium containing iridium anode can be higher than 3 years.
Embodiment two:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the H of certain mass2IrCl6It is miscible with tetrabutyl zirconate.
By the H after standing2IrCl6With the mixed solution of tetrabutyl zirconate be dissolved in by the mixed n-butanol of 1:1 proportion with it is different The in the mixed solvent of propyl alcohol, obtains coating solution.H in coating solution2IrCl6Molar concentration with tetrabutyl zirconate is respectively 0.14 and 0.06mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 15 minutes, then be sintered 15 minutes at 500 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 500 DEG C, obtains the binary composite oxides anode of the zirconium containing iridium.
Further, the binary composite oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.37V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of zirconium binary composite oxides anode can be higher than 4 years.
Embodiment three:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the H of certain mass2IrCl6It is miscible with tetrabutyl zirconate.
By the H after standing2IrCl6With the mixed solution of tetrabutyl zirconate be dissolved in by the mixed n-butanol of 1:1 proportion with it is different The in the mixed solvent of propyl alcohol, obtains coating solution.H in coating solution2IrCl6Molar concentration with tetrabutyl zirconate is 0.10mol/L。
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 15 minutes, then be sintered 15 minutes at 400 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 400 DEG C, obtains the binary composite oxides anode of zirconium containing iridium.
Further, the binary composite oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.31V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of zirconium binary composite oxides anode can be higher than 2 years.
Embodiment four:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the H of certain mass2IrCl6It is miscible with tetrabutyl zirconate.
By the H after standing2IrCl6With the mixed solution of tetrabutyl zirconate be dissolved in by the mixed n-butanol of 1:1 proportion with it is different The in the mixed solvent of propyl alcohol, obtains coating solution.H in coating solution2IrCl6Molar concentration with tetrabutyl zirconate is respectively 0.06 and 0.14mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 10 minutes, then be sintered 10 minutes at 600 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 30 times, anode plate is existed It is sintered 1 hour at 600 DEG C, obtains the binary composite oxides anode of zirconium containing iridium.
Further, the binary composite oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.40V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of zirconium binary composite oxides anode can be higher than 2 years.
Embodiment five:
It is first that 10mm × 10mm × 1mm titanium plate is small through 60 DEG C of etchings 2.5 of 10% oxalic acid at alkali cleaning 30 minutes, 90 DEG C When, deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the RuCl of certain mass3、H2IrCl6It is miscible with tetrabutyl zirconate.
RuCl after will be miscible3、H2IrCl6The positive fourth by 1:1 proportion mixing is dissolved in the mixed solution of tetrabutyl zirconate The in the mixed solvent of alcohol and isopropanol, obtains coating solution.RuCl in coating solution3、H2IrCl6With mole of tetrabutyl zirconate Concentration is respectively 0.098,0.042 and 0.060mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 10 minutes, then be sintered 10 minutes at 450 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 450 DEG C, obtains the ternary compound oxides anode of the zirconium of ruthenium containing iridium.
Further, the ternary compound oxides anode prepared can be placed in the sulfuric acid solution of 0.5mol/L, is adopted It being determined with oxygen evolution potential of the three-electrode system to anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, When current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.28V vs.SCE.It is assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, work as tank voltage Anode failure is determined when rising 5V compared with testing initial voltage.It is calculated according to test measurement result and empirical equation, it is obtained Its true service life expection of the Zr ternary compound oxides of ruthenium containing iridium anode can be higher than 2 years.
Embodiment six:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the RuCl of certain mass3、H2IrCl6It is miscible with tetrabutyl zirconate.
By the RuCl after standing3、H2IrCl6It is dissolved in the mixed solution of tetrabutyl zirconate and matches the positive fourth mixed by 1:1 The in the mixed solvent of alcohol and isopropanol, obtains coating solution.RuCl in coating solution3、H2IrCl6With mole of tetrabutyl zirconate Concentration is respectively 0.050,0.050 and 0.100mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 15 minutes, then be sintered 15 minutes at 500 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 500 DEG C, obtains the ternary compound oxides anode of the zirconium of ruthenium containing iridium.
Further, the ternary compound oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.34V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of ruthenium Zr ternary compound oxides anode can be higher than 2 years.
Embodiment seven:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the RuCl of certain mass3、H2IrCl6It is miscible with tetrabutyl zirconate.
By the RuCl after standing3、H2IrCl6It is dissolved in the mixed solution of tetrabutyl zirconate and matches the positive fourth mixed by 1:1 The in the mixed solvent of alcohol and isopropanol, obtains coating solution.RuCl in coating solution3、H2IrCl6With mole of tetrabutyl zirconate Concentration is respectively 0.042,0.098 and 0.060mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 15 minutes, then be sintered 15 minutes at 400 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 400 DEG C, obtains the ternary compound oxides anode of the zirconium of ruthenium containing iridium.
Further, the ternary compound oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.35V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of ruthenium Zr ternary compound oxides anode can be higher than 3 years.
Embodiment eight:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the RuCl of certain mass3、H2IrCl6It is miscible with tetrabutyl zirconate.
By the RuCl after standing3、H2IrCl6It is dissolved in the mixed solution of tetrabutyl zirconate and matches the positive fourth mixed by 1:1 The in the mixed solvent of alcohol and isopropanol, obtains coating solution.RuCl in coating solution3、H2IrCl6With mole of tetrabutyl zirconate Concentration is respectively 0.030,0.030 and 0.140mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 10 minutes, then be sintered 10 minutes at 600 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 30 times, anode plate is existed It is sintered 1 hour at 600 DEG C, obtains the Zr ternary compound oxides anode of ruthenium containing iridium.
Further, the ternary compound oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.39V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of ruthenium Zr ternary compound oxides anode can be higher than 3 years.
Embodiment nine:
It is first that 10mm × 10mm × 1mm titanium plate is small through 60 DEG C of etchings 2.5 of 10% oxalic acid at alkali cleaning 30 minutes, 90 DEG C When, deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the Co (NO of certain mass3)2、H2IrCl6It is miscible with tetrabutyl zirconate.
Co (NO after will be miscible3)2、H2IrCl6It is dissolved in the mixed solution of tetrabutyl zirconate by 1:1 proportion mixing The in the mixed solvent of n-butanol and isopropanol, obtains coating solution.Co (NO in coating solution3)2、H2IrCl6And tetrabutyl zirconate Molar concentration be respectively 0.098,0.042 and 0.060mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 10 minutes, then be sintered 10 minutes at 450 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 450 DEG C, obtains the ternary compound oxides anode of the zirconium of cobalt containing iridium.
Further, the ternary compound oxides anode prepared can be placed in the sulfuric acid solution of 0.5mol/L, is adopted It being determined with oxygen evolution potential of the three-electrode system to anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, When current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.35V vs.SCE.It is assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, work as tank voltage Anode failure is determined when rising 5V compared with testing initial voltage.It is calculated according to test measurement result and empirical equation, it is obtained Its true service life expection of the Zr ternary compound oxides of cobalt containing iridium anode can be higher than 2 years.
Embodiment ten:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the Co (NO of certain mass3)2、H2IrCl6It is miscible with tetrabutyl zirconate.
By the Co (NO after standing3)2、H2IrCl6It is dissolved in the mixed solution of tetrabutyl zirconate and is mixed by 1:1 proportion The in the mixed solvent of n-butanol and isopropanol, obtains coating solution.Co (NO in coating solution3)2、H2IrCl6And tetrabutyl zirconate Molar concentration be respectively 0.050,0.050 and 0.100mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 15 minutes, then be sintered 15 minutes at 500 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 500 DEG C, obtains the ternary compound oxides anode of the zirconium of cobalt containing iridium.
Further, the ternary compound oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.37V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of cobalt Zr ternary compound oxides anode can be higher than 3 years.
Embodiment 11:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the Co (NO of certain mass3)2、H2IrCl6It is miscible with tetrabutyl zirconate.
By the Co (NO after standing3)2、H2IrCl6It is dissolved in the mixed solution of tetrabutyl zirconate and is mixed by 1:1 proportion The in the mixed solvent of n-butanol and isopropanol, obtains coating solution.Co (NO in coating solution3)2、H2IrCl6And tetrabutyl zirconate Molar concentration be respectively 0.042,0.098 and 0.060mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 15 minutes, then be sintered 15 minutes at 400 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 400 DEG C, obtains the ternary compound oxides anode of the zirconium of cobalt containing iridium.
Further, the ternary compound oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.33V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of cobalt Zr ternary compound oxides anode can be higher than 1 year.
Embodiment 12:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the Co (NO of certain mass3)2、H2IrCl6It is miscible with tetrabutyl zirconate.
By the Co (NO after standing3)2、H2IrCl6It is dissolved in the mixed solution of tetrabutyl zirconate and is mixed by 1:1 proportion The in the mixed solvent of n-butanol and isopropanol, obtains coating solution.Co (NO in coating solution3)2、H2IrCl6And tetrabutyl zirconate Molar concentration be respectively 0.030,0.030 and 0.140mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 10 minutes, then be sintered 10 minutes at 600 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 30 times, anode plate is existed It is sintered 1 hour at 600 DEG C, obtains the Zr ternary compound oxides anode of cobalt containing iridium.
Further, the ternary compound oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.40V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of cobalt Zr ternary compound oxides anode can be higher than 2 years.
Embodiment 13:
It is first that 10mm × 10mm × 1mm titanium plate is small through 60 DEG C of etchings 2.5 of 10% oxalic acid at alkali cleaning 30 minutes, 90 DEG C When, deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the MoCl of certain mass5、H2IrCl6It is miscible with tetrabutyl zirconate.
MoCl after will be miscible5、H2IrCl6The positive fourth by 1:1 proportion mixing is dissolved in the mixed solution of tetrabutyl zirconate The in the mixed solvent of alcohol and isopropanol, obtains coating solution.MoCl in coating solution5、H2IrCl6With mole of tetrabutyl zirconate Concentration is respectively 0.098,0.042 and 0.060mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 10 minutes, then be sintered 10 minutes at 500 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 500 DEG C, obtains the ternary compound oxides anode of the zirconium of molybdenum containing iridium.
Further, the ternary compound oxides anode prepared can be placed in the sulfuric acid solution of 0.5mol/L, is adopted It being determined with oxygen evolution potential of the three-electrode system to anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, When current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.38V vs.SCE.It is assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, work as tank voltage Anode failure is determined when rising 5V compared with testing initial voltage.It is calculated according to test measurement result and empirical equation, it is obtained Its true service life expection of the Zr ternary compound oxides of molybdenum containing iridium anode can be higher than 2 years.
Embodiment 14:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the MoCl of certain mass5、H2IrCl6It is miscible with tetrabutyl zirconate.
By the MoCl after standing5、H2IrCl6It is dissolved in the mixed solution of tetrabutyl zirconate and matches the positive fourth mixed by 1:1 The in the mixed solvent of alcohol and isopropanol, obtains coating solution.MoCl in coating solution5、H2IrCl6With mole of tetrabutyl zirconate Concentration is respectively 0.050,0.050 and 0.100mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 15 minutes, then be sintered 15 minutes at 450 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 450 DEG C, obtains the ternary compound oxides anode of the zirconium of molybdenum containing iridium.
Further, the ternary compound oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.36V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of molybdenum Zr ternary compound oxides anode can be higher than 2 years.
Embodiment 15:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the MoCl of certain mass5、H2IrCl6It is miscible with tetrabutyl zirconate.
By the MoCl after standing5、H2IrCl6It is dissolved in the mixed solution of tetrabutyl zirconate and matches the positive fourth mixed by 1:1 The in the mixed solvent of alcohol and isopropanol, obtains coating solution.MoCl in coating solution5、H2IrCl6With mole of tetrabutyl zirconate Concentration is respectively 0.042,0.098 and 0.060mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 15 minutes, then be sintered 15 minutes at 400 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 400 DEG C, obtains the ternary compound oxides anode of the zirconium of molybdenum containing iridium.
Further, the ternary compound oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.33V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of molybdenum Zr ternary compound oxides anode can be higher than 2 years.
Embodiment 16:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the MoCl of certain mass5、H2IrCl6It is miscible with tetrabutyl zirconate.
By the MoCl after standing5、H2IrCl6It is dissolved in the mixed solution of tetrabutyl zirconate and matches the positive fourth mixed by 1:1 The in the mixed solvent of alcohol and isopropanol, obtains coating solution.MoCl in coating solution5、H2IrCl6With mole of tetrabutyl zirconate Concentration is respectively 0.030,0.030 and 0.140mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 10 minutes, then be sintered 10 minutes at 600 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 30 times, anode plate is existed It is sintered 1 hour at 600 DEG C, obtains the Zr ternary compound oxides anode of molybdenum containing iridium.
Further, the ternary compound oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.36V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of molybdenum Zr ternary compound oxides anode can be higher than 2 years.
Embodiment 17:
It is first that 10mm × 10mm × 1mm titanium plate is small through 60 DEG C of etchings 2.5 of 10% oxalic acid at alkali cleaning 30 minutes, 90 DEG C When, deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the H of certain mass2IrCl6, RbCl and tetrabutyl zirconate it is miscible.
H after will be miscible2IrCl6, RbCl and tetrabutyl zirconate mixed solution be dissolved in the positive fourth by 1:1 proportion mixing The in the mixed solvent of alcohol and isopropanol, obtains coating solution.H in coating solution2IrCl6, RbCl and tetrabutyl zirconate it is mole dense Degree is respectively 0.098,0.042 and 0.060mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 10 minutes, then be sintered 10 minutes at 450 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 450 DEG C, obtains the ternary compound oxides anode of the zirconium of rubidium containing iridium.
Further, the ternary compound oxides anode prepared can be placed in the sulfuric acid solution of 0.5mol/L, is adopted It being determined with oxygen evolution potential of the three-electrode system to anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, When current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.34V vs.SCE.It is assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, work as tank voltage Anode failure is determined when rising 5V compared with testing initial voltage.It is calculated according to test measurement result and empirical equation, it is obtained Its true service life expection of the Zr ternary compound oxides of rubidium containing iridium anode can be higher than 2 years.
Embodiment 18:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the H of certain mass2IrCl6, RbCl and tetrabutyl zirconate it is miscible.
By the H after standing2IrCl6, RbCl and the mixed solution of tetrabutyl zirconate be dissolved in and match the positive fourth mixed by 1:1 The in the mixed solvent of alcohol and isopropanol, obtains coating solution.H in coating solution2IrCl6, RbCl and tetrabutyl zirconate it is mole dense Degree is respectively 0.050,0.050 and 0.100mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 15 minutes, then be sintered 15 minutes at 500 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 500 DEG C, obtains the ternary compound oxides anode of the zirconium of rubidium containing iridium.
Further, the ternary compound oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.33V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of rubidium Zr ternary compound oxides anode can be higher than 2 years.
Embodiment 19:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the H of certain mass2IrCl6, RbCl and tetrabutyl zirconate it is miscible.
By the H after standing2IrCl6, RbCl and the mixed solution of tetrabutyl zirconate be dissolved in and match the positive fourth mixed by 1:1 The in the mixed solvent of alcohol and isopropanol, obtains coating solution.H in coating solution2IrCl6, RbCl and tetrabutyl zirconate it is mole dense Degree is respectively 0.042,0.098 and 0.060mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 15 minutes, then be sintered 15 minutes at 400 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 400 DEG C, obtains the Zr ternary compound oxides anode of rubidium containing iridium.
Further, the ternary compound oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.32V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of rubidium Zr ternary compound oxides anode can be higher than 2 years.
Embodiment 20:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the H of certain mass2IrCl6It is miscible with tetrabutyl zirconate.
By the H after standing2IrCl6With the mixed solution of tetrabutyl zirconate be dissolved in by the mixed n-butanol of 1:1 proportion with it is different The in the mixed solvent of propyl alcohol, obtains coating solution.H in coating solution2IrCl6, RbCl and tetrabutyl zirconate molar concentration difference For 0.030,0.030 and 0.140mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 10 minutes, then be sintered 10 minutes at 600 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 30 times, anode plate is existed It is sintered 1 hour at 600 DEG C, obtains the Zr ternary compound oxides anode of rubidium containing iridium.
Further, the ternary compound oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.38V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of rubidium Zr ternary compound oxides anode can be higher than 2 years.
Embodiment 21:
It is first that 10mm × 10mm × 1mm titanium plate is small through 60 DEG C of etchings 2.5 of 10% oxalic acid at alkali cleaning 30 minutes, 90 DEG C When, deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh RbCl, RuCl of certain mass3、H2IrCl6It is miscible with tetrabutyl zirconate.
RbCl, RuCl after will be miscible3、H2IrCl6It is dissolved in match by 1:1 with the mixed solution of tetrabutyl zirconate and mix N-butanol and isopropanol in the mixed solvent, obtain coating solution.RbCl, RuCl in coating solution3、H2IrCl6With zirconic acid four The molar concentration of butyl ester is respectively 0.020,0.084,0.036 and 0.060mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 10 minutes, then be sintered 10 minutes at 450 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 450 DEG C, obtains the quaternary composite oxides anode of the rubidium zirconium of ruthenium containing iridium.
Further, the quaternary composite oxides anode prepared can be placed in the sulfuric acid solution of 0.5mol/L, is adopted It being determined with oxygen evolution potential of the three-electrode system to anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, When current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.27V vs.SCE.It is assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, work as tank voltage Anode failure is determined when rising 5V compared with testing initial voltage.It is calculated according to test measurement result and empirical equation, it is obtained Its true service life expection of the rubidium zirconium quaternary composite oxides anode of ruthenium containing iridium can be higher than 2 years.
Embodiment 22:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh RbCl, RuCl of certain mass3、H2IrCl6It is miscible with tetrabutyl zirconate.
By RbCl, RuCl after standing3、H2IrCl6It is dissolved in the mixed solution of tetrabutyl zirconate and is mixed by 1:1 proportion N-butanol and isopropanol in the mixed solvent, obtain coating solution.RbCl, RuCl in coating solution3、H2IrCl6With zirconic acid four The molar concentration of butyl ester is respectively 0.040,0.030,0.030 and 0.100mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 15 minutes, then be sintered 15 minutes at 500 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 500 DEG C, obtains the quaternary composite oxides anode of the rubidium zirconium of ruthenium containing iridium.
Further, the quaternary composite oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.32V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of ruthenium rubidium zirconium quaternary composite oxides anode can be higher than 2 years.
Embodiment 23:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh RbCl, RuCl of certain mass3、H2IrCl6It is miscible with tetrabutyl zirconate.
By RbCl, RuCl after standing3、H2IrCl6It is dissolved in the mixed solution of tetrabutyl zirconate and is mixed by 1:1 proportion N-butanol and isopropanol in the mixed solvent, obtain coating solution.RbCl, RuCl in coating solution3、H2IrCl6With zirconic acid four The molar concentration of butyl ester is respectively 0.060,0.024,0.056 and 0.060mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 15 minutes, then be sintered 15 minutes at 400 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 25 times, anode plate is existed It is sintered 1 hour at 400 DEG C, obtains the quaternary composite oxides anode of the rubidium zirconium of ruthenium containing iridium.
Further, the quaternary composite oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.31V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of ruthenium rubidium zirconium quaternary composite oxides anode can be higher than 2 years.
Embodiment 24:
First by 10mm × 10mm × 1mm titanium plate through 60 DEG C alkali cleaning 30 minutes, 90 DEG C of 10% oxalic acid etches 2.5 hours, Deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh RbCl, RuCl of certain mass3、H2IrCl6It is miscible with tetrabutyl zirconate.
By RbCl, RuCl after standing3、H2IrCl6It is dissolved in the mixed solution of tetrabutyl zirconate and is mixed by 1:1 proportion N-butanol and isopropanol in the mixed solvent, obtain coating solution.RbCl, RuCl in coating solution3、H2IrCl6With zirconic acid four The molar concentration of butyl ester is respectively 0.020,0.020,0.020 and 0.140mol/L.
The coating solution prepared is coated uniformly on pretreated Titanium base surface with hairbrush, is dried at 120 DEG C 10 minutes, then be sintered 10 minutes at 600 DEG C, it is cooled to room temperature after taking-up.After above-mentioned steps repeat 30 times, anode plate is existed It is sintered 1 hour at 600 DEG C, obtains the rubidium zirconium quaternary composite oxides anode of ruthenium containing iridium.
Further, the quaternary composite oxides anode prepared is placed in the sulfuric acid solution of 0.5mol/L, using three Electrode system is determined the oxygen evolution potential of anode, is platinum electrode to electrode, saturated calomel electrode is reference electrode, works as electricity Current density is 50mA/cm2When, the oxygen evolution potential of anode is 1.38V vs.SCE.For use of the assessment anode in sulfuric acid system Service life, to the anode prepared current density be 2A/cm2Under conditions of carried out accelerated life test, when tank voltage and reality It tests initial voltage and determines that anode fails compared to when rising 5V.It is calculated according to test measurement result and empirical equation, it is obtained to contain iridium Its true service life expection of ruthenium rubidium zirconium quaternary composite oxides anode can be higher than 2 years.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art, It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims Subject to enclosing.

Claims (6)

1. a kind of preparation method of high activity iridium zirconium composite oxides inert anode, it is characterised in that high activity iridium zirconium is compound Oxide inert anode includes iridium zirconium binary composite oxides inert anode, iridium ruthenium Zr ternary compound oxides inert anode, iridium Cobalt Zr ternary compound oxides inert anode, iridium molybdenum Zr ternary compound oxides inert anode, iridium rubidium Zr ternary compound oxides Inert anode and iridium ruthenium rubidium zirconium quaternary composite oxides inert anode；
The wherein preparation method of iridium zirconium binary composite oxides inert anode, preparation step are as follows:
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, ultrasonic cleaning and drying；
Step 2, by H2IrCl6Miscible, solute needed for obtaining configuration coating solution is carried out with tetrabutyl zirconate；
Volume ratio is added in the solute matched by step 3 by the n-butanol of 1:1 and the mixed solvent of isopropanol, is coated Solution；In coating solution, the molar concentration of iridium is 0.05-0.20mol/L, and the molar concentration of zirconium is 0.01-0.15mol/L；
The coating solution prepared is coated in pretreated Titanium base surface, drying, burning by step 4 Iridium zirconium binary composite oxides inert anode is obtained after knot processing；Coating is applied to 10-40 layers, and drying temperature is 100-200 DEG C, Drying time is 10-15 minutes；Sintering temperature is 400-600 DEG C, and sintering time is 10-15 minutes, and burning the time eventually is 1 hour； Iridium dioxide is Rutile Type in the coating, and zirconium dioxide is amorphous phase, and part zirconium dioxide can form solid with iridium dioxide Solution.
2. the preparation method of high activity iridium zirconium composite oxides inert anode according to claim 1, which is characterized in that The preparation step of the iridium ruthenium Zr ternary compound oxides inert anode includes:
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, ultrasonic cleaning and drying；
Step 2, by RuCl3、H2IrCl6Miscible, solute needed for obtaining configuration coating solution is carried out with tetrabutyl zirconate；
Volume ratio is added in the solute matched by step 3 by the n-butanol of 1:1 and the mixed solvent of isopropanol, is coated Solution；In coating solution, the molar concentration of ruthenium and iridium is 0.01-0.10mol/L, and the molar concentration of zirconium is 0.05-0.15mol/ L；
The coating solution prepared is coated in pretreated Titanium base surface, drying, burning by step 4 Ternary compound oxides inert anode is obtained after knot processing；Coating is applied to 10-40 layers, and drying temperature is 100-200 DEG C, drying Time is 10-15 minutes；Sintering temperature is 400-600 DEG C, and sintering time is 10-15 minutes, and burning the time eventually is 1 hour；It is described Iridium dioxide and ruthenic oxide are Rutile Type in coating, and zirconium dioxide is amorphous phase.
3. the preparation method of high activity iridium zirconium composite oxides inert anode according to claim 1, which is characterized in that The preparation step of the iridium cobalt Zr ternary compound oxides inert anode is as follows:
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, ultrasonic cleaning and drying；
Step 2, by Co (NO3)2、H2IrCl6Miscible, solute needed for obtaining configuration coating solution is carried out with tetrabutyl zirconate；
Volume ratio is added in the solute matched by step 3 by the n-butanol of 1:1 and the mixed solvent of isopropanol, is coated Solution；In coating solution, the molar concentration of cobalt and iridium is 0.01-0.10mol/L, and the molar concentration of zirconium is 0.05-0.15mol/ L；
The coating solution prepared is coated in pretreated Titanium base surface, drying, burning by step 4 Iridium cobalt Zr ternary compound oxides inert anode is obtained after knot processing；Coating is applied to 10-40 layers, drying temperature 100-200 DEG C, drying time is 10-15 minutes；Sintering temperature is 400-600 DEG C, and sintering time is 10-15 minutes, and burning the time eventually is 1 small When；Iridium dioxide is Rutile Type in the coating, and zirconium dioxide is amorphous phase, and cobaltosic oxide is Spinel.
4. the preparation method of high activity iridium zirconium composite oxides inert anode according to claim 1, which is characterized in that The preparation step of iridium molybdenum Zr ternary compound oxides inert anode is as follows:
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, ultrasonic cleaning and drying；
Step 2, by MoCl5、H2IrCl6Miscible, solute needed for obtaining configuration coating solution is carried out with tetrabutyl zirconate；
Volume ratio is added in the solute matched by step 3 by the n-butanol of 1:1 and the mixed solvent of isopropanol, is coated Solution；In coating solution, the molar concentration of molybdenum and iridium is 0.01-0.10mol/L, and the molar concentration of zirconium is 0.05-0.15mol/ L；
The coating solution prepared is coated in pretreated Titanium base surface, drying, burning by step 4 Iridium molybdenum Zr ternary compound oxides inert anode is obtained after knot processing；Coating is applied to 10-40 layers, drying temperature 100-200 DEG C, drying time is 10-15 minutes；Sintering temperature is 400-600 DEG C, and sintering time is 10-15 minutes, and burning the time eventually is 1 small When；Iridium dioxide is Rutile Type in the coating, and zirconium dioxide is amorphous phase, and molybdenum trioxide is α phase.
5. the preparation method of high activity iridium zirconium composite oxides inert anode according to claim 1, which is characterized in that The preparation step of iridium rubidium Zr ternary compound oxides inert anode is as follows:
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, ultrasonic cleaning and drying；
Step 2, by RbCl, H2IrCl6Miscible, solute needed for obtaining configuration coating solution is carried out with tetrabutyl zirconate；
Volume ratio is added in the solute matched by step 3 by the n-butanol of 1:1 and the mixed solvent of isopropanol, is coated Solution；In coating solution, the molar concentration of iridium and rubidium is 0.01-0.10mol/L, and the molar concentration of zirconium is 0.05-0.15mol/ L；
The coating solution prepared is coated in pretreated Titanium base surface, drying, burning by step 4 Iridium rubidium Zr ternary compound oxides inert anode is obtained after knot processing；Coating is applied to 10-40 layers, drying temperature 100-200 DEG C, drying time is 10-15 minutes；Sintering temperature is 400-600 DEG C, and sintering time is 10-15 minutes, and burning the time eventually is 1 small When；Iridium dioxide is Rutile Type in the coating, and zirconium dioxide and rubidium oxide are amorphous phase.
6. the preparation method of high activity iridium zirconium composite oxides inert anode according to claim 1, which is characterized in that The preparation step of iridium ruthenium rubidium zirconium quaternary composite oxides inert anode is as follows:
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, ultrasonic cleaning and drying；
Step 2, by RbCl, RuCl3、H2IrCl6Miscible, solute needed for obtaining configuration coating solution is carried out with tetrabutyl zirconate；
Volume ratio is added in the solute matched by step 3 by the n-butanol of 1:1 and the mixed solvent of isopropanol, is coated Solution；In coating solution, the molar concentration of iridium, ruthenium and rubidium is 0.01-0.10mol/L, and the molar concentration of zirconium is 0.05- 0.15mol/L；
The coating solution prepared is coated in pretreated Titanium base surface, drying, burning by step 4 Iridium ruthenium rubidium zirconium quaternary composite oxides inert anode is obtained after knot processing；Coating is applied to 10-40 layers, drying temperature 100- 200 DEG C, drying time is 10-15 minutes；Sintering temperature is 400-600 DEG C, and sintering time is 10-15 minutes, and burning the time eventually is 1 Hour；Iridium dioxide and ruthenic oxide are Rutile Type in the coating, and zirconium dioxide and rubidium oxide are amorphous phase.
CN201910302487.1A 2018-04-26 2019-04-16 Preparation method of high-activity iridium zirconium composite oxide inert anode Active CN109972178B (en)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
CN2018103853678 2018-04-26
CN201810385376.7A CN108486614A (en) 2018-04-26 2018-04-26 A kind of preparation method of iridium molybdenum Zr ternary compound oxides inert anode
CN201810384787.4A CN108505074A (en) 2018-04-26 2018-04-26 A kind of preparation method of iridium cobalt Zr ternary compound oxides inert anode
CN2018103847874 2018-04-26
CN2018103847592 2018-04-26
CN201810385367.8A CN108330513A (en) 2018-04-26 2018-04-26 A kind of preparation method of iridium zirconium binary composite oxides inert anode
CN2018103853767 2018-04-26
CN2018103850716 2018-04-26
CN201810384759.2A CN108486613A (en) 2018-04-26 2018-04-26 A kind of preparation method of iridium rubidium Zr ternary compound oxides inert anode
CN2018103847605 2018-04-26
CN201810384760.5A CN108330511A (en) 2018-04-26 2018-04-26 A kind of preparation method of iridium ruthenium rubidium zirconium quaternary composite oxides inert anode
CN201810385071.6A CN108330512A (en) 2018-04-26 2018-04-26 A kind of preparation method of iridium ruthenium Zr ternary compound oxides inert anode

Publications (2)

Publication Number Publication Date
CN109972178A true CN109972178A (en) 2019-07-05
CN109972178B CN109972178B (en) 2021-03-16

Family

ID=67084747

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910302487.1A Active CN109972178B (en) 2018-04-26 2019-04-16 Preparation method of high-activity iridium zirconium composite oxide inert anode

Country Status (1)

Country Link
CN (1) CN109972178B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101016632A (en) * 2006-12-22 2007-08-15 扬州大学 Process of preparing metal oxide electrode by polymeric precursor thermal decomposition method
CN101469434A (en) * 2007-12-27 2009-07-01 中国蓝星（集团）股份有限公司 Active anode for hydrochloric acid electrolysis and preparation thereof
CN103981534A (en) * 2013-02-08 2014-08-13 拜耳材料科技股份有限公司 Electrocatalyst, electrode coating and electrode for the preparation of chlorine
CN107723744A (en) * 2017-09-21 2018-02-23 王成彦 A kind of preparation method of quaternary composite oxides anode

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101016632A (en) * 2006-12-22 2007-08-15 扬州大学 Process of preparing metal oxide electrode by polymeric precursor thermal decomposition method
CN101469434A (en) * 2007-12-27 2009-07-01 中国蓝星（集团）股份有限公司 Active anode for hydrochloric acid electrolysis and preparation thereof
CN103981534A (en) * 2013-02-08 2014-08-13 拜耳材料科技股份有限公司 Electrocatalyst, electrode coating and electrode for the preparation of chlorine
CN107723744A (en) * 2017-09-21 2018-02-23 王成彦 A kind of preparation method of quaternary composite oxides anode

Also Published As

Publication number Publication date
CN109972178B (en) 2021-03-16

Similar Documents

Publication Publication Date Title
CN102766882B (en) A kind of preparation method analysing chlorine DSA electro catalytic electrode of three-dimensional structure
CN104846397B (en) One kind being used for electrochemical reduction CO2The electrode and its preparation method and application of formic acid processed
CN103422116B (en) A kind of porous Ni-base ru oxide is combined the preparation method of hydrogen-precipitating electrode
CN104746097B (en) A kind of preparation method of graphene blended metal oxide anode
CN106967997B (en) A kind of efficient self-supporting catalysis electrode and its preparation method and application
CN103668342B (en) A kind of manganese electrolysis titanium based composite anode and preparation method
CN101532147A (en) Nanocrystal metal oxide composite electrode and method for preparing same
CN103924263A (en) Preparation method of high-performance nickel-based ruthenium-containing compound oxide hydrogen evolution electrode
CN109518221A (en) A kind of surface is rich in the gradient distribution Ni―Ti anode and preparation method thereof of iridium dioxide
CN107723744B (en) Preparation method of quaternary composite oxide anode
CN104562094B (en) A kind of preparation method of non-ferrous metal electrodeposition graded composite anode
CN109972177A (en) A kind of preparation method of long-life iridium zirconium composite oxides inert anode
CN104294313A (en) Electrochemical gold dissolving device and method
CN102864465B (en) A kind of preparation method of high reactivity Ti/Pr2O3-PbO2 modified electrode
CN108330512A (en) A kind of preparation method of iridium ruthenium Zr ternary compound oxides inert anode
CN104022295A (en) Direct methanol fuel cell PdAg/TiO2 nanotube electrode and preparation method thereof
CN109972178A (en) A kind of preparation method of high activity iridium zirconium composite oxides inert anode
CN108624920A (en) A kind of preparation method of iridium tin Zr ternary compound oxides inert anode
CN107723743B (en) Preparation method of ternary composite oxide anode
CN108486613A (en) A kind of preparation method of iridium rubidium Zr ternary compound oxides inert anode
CN108330511A (en) A kind of preparation method of iridium ruthenium rubidium zirconium quaternary composite oxides inert anode
CN108486614A (en) A kind of preparation method of iridium molybdenum Zr ternary compound oxides inert anode
CN108330513A (en) A kind of preparation method of iridium zirconium binary composite oxides inert anode
CN108330514A (en) A kind of preparation method of iridium tin rubidium zirconium quaternary composite oxides inert anode
CN108505074A (en) A kind of preparation method of iridium cobalt Zr ternary compound oxides inert anode

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant