CN108624920A - A kind of preparation method of iridium tin Zr ternary compound oxides inert anode - Google Patents

A kind of preparation method of iridium tin Zr ternary compound oxides inert anode Download PDF

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CN108624920A
CN108624920A CN201810385366.3A CN201810385366A CN108624920A CN 108624920 A CN108624920 A CN 108624920A CN 201810385366 A CN201810385366 A CN 201810385366A CN 108624920 A CN108624920 A CN 108624920A
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anode
iridium
tin
ternary compound
preparation
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王成彦
刘宝
陈永强
王硕
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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Priority to CN201810385366.3A priority Critical patent/CN108624920A/en
Publication of CN108624920A publication Critical patent/CN108624920A/en
Priority to CN201910302460.2A priority patent/CN109972177B/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
    • 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
    • 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
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • 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

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a kind of hydrometallurgy preparation methods of iridium tin Zr ternary compound oxides anode, belong to field of hydrometallurgy.Obtained anode is made of Titanium base and oxide coating, iridium dioxide and stannic oxide are Rutile Type in coating, zirconium dioxide is amorphous phase, part stannic oxide and iridium dioxide can form rutile-type solid solution in being sintered preparation process, with conventional Ti/IrO2Anode is compared, and the addition of zirconium promotes oxygen evolution activity substance IrO2The precipitation of crystal, effectively raises the oxygen evolution activity surface area of anode, and the addition of tin improves active component IrO2Corrosion resistance in sulfuric acid system extends the service life of anode.Preparation flow of the present invention is simple, obtained anode has preferable analysis oxygen catalytic activity and service life, further, since the precious metal element in coating is replaced by zirconium and tin, the production cost for effectively reducing anode is a kind of very hydrometallurgy anode with prospect of the application.

Description

A kind of preparation method of iridium tin Zr ternary compound oxides inert anode
Technical field
The present invention relates to a kind of technical field of wet metallurgy more particularly to a kind of iridium tin Zr ternary compound oxides inertia sun The preparation method of pole.
Background technology
In recent ten years, the coloured industry development in China is rapid, and the increase of production of the especially metals such as copper, zinc is rapid.With fire Method smelting is compared, and hydrometallurgy is with production capacity is big, efficient, operating condition is good, pollution is relatively light and valuable metal integrates back The advantages of high income, currently, in the world 80% or so zinc and 20% or so copper by hydrometallurgy extract.Anode is as wet Core main body in method metallurgical process and important equipment have the title of hydrometallurgical " heart ", and the quality of anode performance is not Electrochemical reaction speed in wet smelting process is only influenced, cathode product quality can also be impacted.
Currently, the anode that hydrometallurgy industry uses is mostly pure Pb anodes and Pb alloy anodes, such as：Pb-Ag、Pb-Ag- Sn and Pb-Sb-Sn-Ag etc..Though it is with corrosion-resistant in easy processing molding, low manufacture cost, sulfuric acid electrolyte, service life is long The advantages that, but there is also big in oxygen overpotential on anode height, electrolytic process anode Pb dissolving pollutions cathode product, electrolytic process The shortcomings of generation of the amount earth of positive pole can increase labour cost.According to statistics, overpotential for oxygen evolution of the pure Pb anodes in electrolytic process can Up to 860mV, and the overpotential for oxygen evolution of Pb-Ag alloy anodes, 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.
Titanium is referred to as valve metal, has stable oxide layer protection, there is good durability and dimensional stability under electrolysis conditions. Compared with pure Pb anodes and Pb alloy anodes, coated titanium anode is with appearance and size is stable, overpotential for oxygen evolution is low, electrolytic process The advantages that Anodic will not pollute cathode product has obtained making extensively in the electrolysis production process of high purity product in recent years With.Ruthenic oxide (RuO2) and iridium dioxide (IrO2) due to its good analysis oxygen catalytic performance, it is chiefly used in coated titanium anode It prepares.And it finds in use, Ti/RuO2Though anode shows excellent analysis oxygen catalytic performance, preferably reduce The overpotential for oxygen evolution of electrolytic process Anodic, but in sulfuric acid system, Ti/RuO2The service life of anode is shorter, about 100 days, Constrain its application in hydrometallurgy process.Ti/IrO2Though the analysis oxygen catalytic performance slightly worse than Ti/RuO of anode2Anode, but It shows preferable corrosion resistance in sulfuric acid system, and service life was up to 1 year or more, but iridium is expensive, Ti/ IrO2The cost of manufacture of anode is higher, limits its large-scale application.Therefore, it is high to prepare a kind of oxygen evolution activity, service life Long and cheap cost of manufacture analysis oxygen anodes, have a very important significance the energy-saving of nonferrous metallurgy industry.
Invention content
The object of the present invention is to provide a kind of preparation method of iridium tin Zr ternary compound oxides inert anode, the preparation sides Method flow is simple, and obtained anode has preferable analysis oxygen catalytic activity, long service life and cheap manufacturing cost.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of preparation method of iridium tin Zr ternary compound oxides inert anode, the method includes：
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, is cleaned by ultrasonic and dries；
Step 2, by SnCl4、H2IrCl6It is miscible with tetrabutyl zirconate progress, obtain the solute needed for configuration coating solution；
Step 3, by volume ratio be 1:1 n-butanol and the mixed solvent of isopropanol are added in matched solute, are obtained Coating solution；
The coating solution prepared is coated in pretreated Titanium base surface by step 4, through drying Iridium tin Zr ternary compound oxides inert anode is obtained after dry, sintering processes.
In obtained coating solution, the molar concentration of tin and iridium is 0.01-0.10mol/L, and the molar concentration of zirconium is 0.05-0.15mol/L。
In the step 4：
Coating is applied to 10-40 layers, and drying temperature is 100-200 DEG C, and drying time is 10-15 minutes；
Sintering temperature is 400-600 DEG C, and sintering time is 10-15 minutes, and it is 1 hour to burn the time eventually.
In the step 4：
Iridium dioxide and stannic oxide are Rutile Type in the coating, and zirconium dioxide is amorphous phase, in sintering process Stannic oxide can form rutile-type solid solution with iridium dioxide.
As seen from the above technical solution provided by the invention, simple, the obtained anode of above-mentioned preparation method flow It is a kind of very hydrometallurgy anode with prospect of the application with preferable analysis oxygen catalytic activity and service life.
Description of the drawings
Fig. 1 is Ti/IrO of the present invention2-SnO2-ZrO2The preparation flow figure of ternary compound oxides inert anode.
Specific implementation mode
Embodiment one：
It is first that the titanium plate of 10mm × 10mm × 1mm is small through 10% oxalic acid etching 2.5 at 60 DEG C of alkali cleanings 30 minutes, 90 DEG C When, deionized water is cleaned by ultrasonic after ten minutes, drying for standby.
Weigh the SnCl of certain mass4、H2IrCl6It is miscible with tetrabutyl zirconate.
SnCl after will be miscible4、H2IrCl6It is dissolved in by 1 with the mixed solution of tetrabutyl zirconate:The positive fourth of 1 proportioning mixing The in the mixed solvent of alcohol and isopropanol, obtains coating solution.SnCl in coating solution4、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, postcooling is taken out to room temperature.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 tin containing iridium.
Further, the ternary compound oxides anode prepared can be placed in the sulfuric acid solution of 0.5mol/L, is adopted The oxygen evolution potential of anode is determined with three-electrode system, is platinum electrode to electrode, saturated calomel electrode is reference electrode, When current density is 50mA/cm2, the oxygen evolution potential of anode is 1.40V vs.SCE.It is to assess anode in sulfuric acid system Service life in current density is 2A/cm to the anode for preparing2Under conditions of carried out accelerated life test, work as tank voltage Judgement anode failure when rising 5V compared with testing initial voltage.It is calculated according to experiment measurement result and empirical equation, it is obtained Its true service life of the Zr ternary compound oxides of tin containing iridium anode is expected to be higher than 3 years.
Embodiment two：
First by the titanium plate of 10mm × 10mm × 1mm through 60 DEG C of alkali cleanings 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 SnCl of certain mass4、H2IrCl6It is miscible with tetrabutyl zirconate.
By the SnCl after standing4、H2IrCl6It is dissolved in by 1 with the mixed solution of tetrabutyl zirconate:The positive fourth of 1 proportioning mixing The in the mixed solvent of alcohol and isopropanol, obtains coating solution.SnCl in coating solution4、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, postcooling is taken out to room temperature.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 tin 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 in current density is 2A/cm to the anode for preparing2Under conditions of carried out accelerated life test, when tank voltage and reality Initial voltage is tested compared to judgement anode failure when rising 5V.It is calculated according to experiment measurement result and empirical equation, it is obtained to contain iridium Its true service life of tin Zr ternary compound oxides anode is expected to be higher than 3 years.
Embodiment three：
First by the titanium plate of 10mm × 10mm × 1mm through 60 DEG C of alkali cleanings 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 SnCl of certain mass4、、H2IrCl6It is miscible with tetrabutyl zirconate.
By the SnCl after standing4、H2IrCl6It is dissolved in by 1 with the mixed solution of tetrabutyl zirconate:The positive fourth of 1 proportioning mixing The in the mixed solvent of alcohol and isopropanol, obtains coating solution.SnCl in coating solution4、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, postcooling is taken out to room temperature.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 tin 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 in current density is 2A/cm to the anode for preparing2Under conditions of carried out accelerated life test, when tank voltage and reality Initial voltage is tested compared to judgement anode failure when rising 5V.It is calculated according to experiment measurement result and empirical equation, it is obtained to contain iridium Its true service life of tin Zr ternary compound oxides anode is expected to be higher than 2 years.
Embodiment four：
First by the titanium plate of 10mm × 10mm × 1mm through 60 DEG C of alkali cleanings 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 SnCl of certain mass4、H2IrCl6It is miscible with tetrabutyl zirconate.
By the SnCl after standing4、H2IrCl6It is dissolved in by 1 with the mixed solution of tetrabutyl zirconate:The positive fourth of 1 proportioning mixing The in the mixed solvent of alcohol and isopropanol, obtains coating solution.SnCl in coating solution4、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, postcooling is taken out to room temperature.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 tin 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 1.44V vs.SCE.For use of the assessment anode in sulfuric acid system Service life in current density is 2A/cm to the anode for preparing2Under conditions of carried out accelerated life test, when tank voltage and reality Initial voltage is tested compared to judgement anode failure when rising 5V.It is calculated according to experiment measurement result and empirical equation, it is obtained to contain iridium Its true service life of tin Zr ternary compound oxides anode is expected to be higher than 3 years.
It is worth noting that, the content not being described in detail in the embodiment of the present invention belongs to professional and technical personnel in the field's public affairs The prior art known.
The anode prepared according to the method for the invention has following features compared with existing anode：
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)ZrO2Incorporation promote active material IrO2The precipitation of crystal, makes gained ternary compound oxides anode and passes Unite IrO2Oxide anode compares the specific surface area active with bigger, improves the analysis oxygen catalytic activity of anode；
3) inertia constituent element ZrO2And SnO2Incorporation, reduce the usage amount of precious metal iridium, significantly reduce the production of anode Cost；
4) active component IrO2With inertia constituent element SnO2Solid solution effect, improve active component IrO2It is resistance in sulfuric acid system Corrosive nature.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, Any one skilled in the art is in the technical scope of present disclosure, the change or replacement that can be readily occurred in, 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 (4)

1. a kind of preparation method of iridium tin Zr ternary compound oxides inert anode, which is characterized in that the method includes：
Step 1 first pre-processes Titanium base, specifically includes alkali cleaning, oxalic acid etching, is cleaned by ultrasonic and dries；
Step 2, by SnCl4、H2IrCl6It is miscible with tetrabutyl zirconate progress, obtain the solute needed for configuration coating solution；
Step 3, by volume ratio be 1:1 n-butanol and the mixed solvent of isopropanol are added in matched solute, are coated Solution；
The coating solution prepared is coated in pretreated Titanium base surface, drying, burning by step 4 Iridium tin Zr ternary compound oxides inert anode is obtained after knot processing.
2. the preparation method of iridium tin Zr ternary compound oxides inert anode according to claim 1, which is characterized in that In obtained coating solution, the molar concentration of iridium and tin is 0.01-0.10mol/L, and the molar concentration of zirconium is 0.05- 0.15mol/L。
3. the preparation method of iridium tin Zr ternary compound oxides inert anode according to claim 1, which is characterized in that step Rapid 4 coating is applied to 10-40 layers, and drying temperature is 100~200 DEG C, and drying time is 10-15 minutes；Sintering temperature is 400-600 DEG C, sintering time is 10-15 minutes, and it is 1 hour to burn the time eventually.
4. the preparation method of iridium tin Zr ternary compound oxides inert anode according to claim 1, which is characterized in that step Stannic oxide and iridium dioxide are Rutile Type in rapid 4 coating, and zirconium dioxide is amorphous phase, part stannic oxide and dioxy Rutile-type solid solution can be formed in being sintered preparation process by changing iridium.
CN201810385366.3A 2018-04-26 2018-04-26 A kind of preparation method of iridium tin Zr ternary compound oxides inert anode Withdrawn CN108624920A (en)

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CN201810385366.3A CN108624920A (en) 2018-04-26 2018-04-26 A kind of preparation method of iridium tin Zr ternary compound oxides inert anode
CN201910302460.2A CN109972177B (en) 2018-04-26 2019-04-16 Preparation method of long-life iridium-zirconium composite oxide inert anode

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CN201810385366.3A CN108624920A (en) 2018-04-26 2018-04-26 A kind of preparation method of iridium tin Zr ternary compound oxides inert anode

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113767068A (en) * 2019-09-26 2021-12-07 株式会社Lg化学 Tin oxide forming composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113767068A (en) * 2019-09-26 2021-12-07 株式会社Lg化学 Tin oxide forming composition

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