CN118241242A - Ruthenium iridium tin cobalt mixed noble metal coating anode material and preparation method thereof - Google Patents
Ruthenium iridium tin cobalt mixed noble metal coating anode material and preparation method thereof Download PDFInfo
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- CN118241242A CN118241242A CN202410335311.7A CN202410335311A CN118241242A CN 118241242 A CN118241242 A CN 118241242A CN 202410335311 A CN202410335311 A CN 202410335311A CN 118241242 A CN118241242 A CN 118241242A
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- ruthenium
- tin
- iridium
- cobalt
- heat treatment
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- 239000011248 coating agent Substances 0.000 title claims abstract description 52
- 238000000576 coating method Methods 0.000 title claims abstract description 52
- -1 Ruthenium iridium tin cobalt Chemical compound 0.000 title claims abstract description 27
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 27
- 239000010405 anode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 65
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 239000002184 metal Substances 0.000 claims abstract description 54
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052718 tin Inorganic materials 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 35
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 30
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 30
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 27
- 239000010941 cobalt Substances 0.000 claims abstract description 27
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000012266 salt solution Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 55
- 239000002253 acid Substances 0.000 claims description 43
- 238000005530 etching Methods 0.000 claims description 33
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000010306 acid treatment Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 3
- GSNZLGXNWYUHMI-UHFFFAOYSA-N iridium(3+);trinitrate Chemical compound [Ir+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GSNZLGXNWYUHMI-UHFFFAOYSA-N 0.000 claims description 3
- VNVQLDDPGAWSSB-UHFFFAOYSA-H iridium(3+);trisulfate Chemical compound [Ir+3].[Ir+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNVQLDDPGAWSSB-UHFFFAOYSA-H 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 3
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 claims description 3
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 3
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 3
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 239000010936 titanium Substances 0.000 abstract description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052719 titanium Inorganic materials 0.000 abstract description 22
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 13
- 239000000460 chlorine Substances 0.000 description 13
- 229910052801 chlorine Inorganic materials 0.000 description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/089—Alloys
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
- C25B11/063—Valve metal, e.g. titanium
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention provides a ruthenium iridium tin cobalt mixed noble metal coating anode material and a preparation method thereof, and relates to the technical field of titanium anode materials. According to the invention, the mixed metal salt solution of ruthenium, iridium, tin and cobalt is coated on the titanium substrate, and then stepwise heat treatment is carried out, so that a combined coating is formed, the performance and stability of the electrode are improved, and the service life of the material is prolonged.
Description
Technical Field
The invention relates to the technical field of titanium anode materials, in particular to a ruthenium iridium tin cobalt mixed noble metal coating anode material and a preparation method thereof.
Background
The titanium anode is an insoluble anode widely applied in the electrolysis industry, consists of a titanium substrate and a noble metal oxide coating, and has the advantages of stable size, corrosion resistance, low electric energy consumption, long service life and the like. The performance of titanium anodes is largely dependent on the type, structure and thickness of the coating, and different electrolytic conditions require different coating designs. The application field of the titanium anode relates to a plurality of industries such as chemical industry, metallurgy, water treatment, environmental protection, electroplating, electrolytic organic synthesis, electrodialysis, cathode protection and the like.
Although titanium anodes have many advantages, the titanium anode has serious corrosion to the coating of the titanium anode due to the high concentration of chloride ions and sulfate ions in the electrolyte in a mixed system of chloride and sulfate, so that the coating is detached or destroyed, the performance and stability of the electrode are affected, and the service life of the anode is very short. Meanwhile, the potential mismatch problem of the titanium anode in the oxygen and chlorine separation reaction results in the decrease of the electrode performance and the increase of the energy consumption. The problems mainly occur in the process of electrolyzing water or chlorine-containing water, and the coating of the titanium anode is difficult to meet the electrocatalytic requirements of the two reactions at the same time due to the large potential difference of the oxygen evolution reaction and the chlorine evolution reaction, so that the electrochemical activity and the efficiency of the electrode are reduced, and the cell voltage and the electric energy consumption of the electrolysis are increased.
At present, a coating containing noble metal ruthenium and iridium is generally adopted to improve the performance of the titanium anode, but with the rising price of the noble metal ruthenium and iridium, the production cost of the coated titanium electrode is increased increasingly, the cost of producing and using the coated titanium electrode by enterprises is increased, and the cost performance is reduced.
Therefore, developing an anode material with low cost, good electrode performance and stability and long service life is a major development trend in the current industry.
Disclosure of Invention
The invention provides a ruthenium iridium tin cobalt mixed noble metal coating anode material, which is prepared by coating a mixed metal salt solution of ruthenium, iridium, tin and cobalt on a titanium substrate and then performing heat treatment to form a combined coating, so that the performance and stability of an electrode are improved, and the service life of the material is prolonged.
The preparation method of the ruthenium iridium tin cobalt mixed noble metal coating anode material comprises the following steps:
S1, sequentially carrying out acid treatment and alkali treatment on a base material to remove impurities such as oxides, grease and the like on the surface of the base material;
S2, immersing the treated substrate in an acid solution for acid etching;
And S3, preparing a mixed metal salt solution containing ruthenium, iridium, tin and cobalt, uniformly coating the metal salt solution on the base material subjected to acid etching, performing heat treatment on the base material, and repeating the coating-heat treatment steps for 6-8 times to obtain the ruthenium-iridium-tin-cobalt mixed noble metal coating anode material.
Further, the substrate is titanium or titanium alloy material.
Further, the acid treatment is performed by immersing the substrate in an acid treatment agent.
Further, the acid treatment agent is nitric acid solution, and the concentration of nitric acid in the solution is 100-120 g/L.
Further, the alkali treatment is performed by immersing the substrate in an alkali treatment agent.
Further, the alkali treatment agent is sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 15% -30%.
Further, the acid treatment and the alkali treatment are performed under heating or ultrasonic conditions, wherein the heating temperature is 50-100 ℃, and the ultrasonic frequency is 20-40 kHz.
Further, the acid solution is one or more of sulfuric acid solution, hydrochloric acid solution, oxalic acid solution and hydrogen fluoride solution. Preferably, the acid solution is one or more of sulfuric acid solution, hydrochloric acid solution and oxalic acid solution.
Further, the concentration of the acid solution is 5-50%, the etching temperature is 20-100 ℃, and the etching time is 5 min-12 h.
Further, the metal salt is one or more of metal acetate, metal sulfate, metal nitrate and metal chloride.
Further, the ruthenium-containing metal salt is one or more of ruthenium nitrate, ruthenium trichloride, ruthenium sulfate and ruthenium acetate; the iridium-containing metal salt is one or more of iridium nitrate, iridium chloride and iridium sulfate; the cobalt-containing metal salt is one or more of cobalt nitrate, cobalt chloride, cobalt sulfate and cobalt acetate; the tin-containing metal salt is one or more of tin tetrachloride, stannous chloride and tin sulfate.
Preferably, the ruthenium-containing metal salt is ruthenium trichloride, the iridium-containing metal salt is iridium chloride, the cobalt-containing metal salt is cobalt chloride, and the tin-containing metal salt is stannous chloride.
Further, the concentration of ruthenium, iridium and tin in the metal salt solution is 0.1-2.0 mg/mL. Preferably, the concentration of ruthenium is 0.1-0.8 mg/mL, the concentration of iridium is 0.1-1.5 mg/mL, and the concentration of tin is 0.1-0.5 mg/mL. Further preferably, the concentration of ruthenium is 0.5mg/mL, the concentration of iridium is 1.0mg/mL, and the concentration of tin is 0.35mg/mL.
Further, the content of cobalt is 30% -50% of tin.
Further, the heat treatment temperature is 300-1200 ℃, and the heat treatment time is 15 min-30 h.
Further, the heat treatment is carried out in two steps, wherein the heat treatment temperature in the first step is 300-800 ℃, the heat treatment time is 2-30 h, the heat treatment temperature in the second step is 800-1200 ℃, and the heat treatment time is 15 min-12 h.
The invention also provides a ruthenium iridium tin cobalt mixed noble metal coating anode material prepared by the method.
Compared with the prior art, the invention has the beneficial technical effects that:
According to the invention, the ruthenium-iridium-tin-cobalt mixed noble metal coating is coated on the titanium substrate, so that the combined coating is formed, and the electrochemical activity and stability of the electrode are improved.
According to the invention, the acid etching and the alkali treatment are carried out on the base material, so that the surface morphology and the structure of the base material are improved, and the bonding strength and the corrosion resistance of the base material and the coating are improved.
The invention controls the thickness and structure of the coating and improves the uniformity and quality of the coating by optimizing the proportion and concentration of the metal salt solution and the temperature and time of heat treatment.
Drawings
The invention is further described with reference to the following description of the drawings.
FIG. 1 is a schematic view of the current efficiency of the sample of example 1 of the present invention;
FIG. 2 is a schematic view of the enhanced electrolytic life of the sample of example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a ruthenium iridium tin cobalt mixed noble metal coating anode material, which comprises the following steps:
S1, sequentially carrying out acid treatment and alkali treatment on a base material to remove impurities such as oxides, grease and the like on the surface of the base material;
S2, immersing the treated substrate in an acid solution for acid etching;
And S3, preparing a mixed metal salt solution containing ruthenium, iridium, tin and cobalt, uniformly coating the metal salt solution on the base material subjected to acid etching, performing heat treatment on the base material, and repeating the coating-heat treatment steps for 6-8 times to obtain the ruthenium-iridium-tin-cobalt mixed noble metal coating anode material.
In one embodiment, the metal salt is one or more of metal acetate, metal sulfate, metal nitrate and metal chloride.
In one embodiment, the ruthenium-containing metal salt is one or more of ruthenium nitrate, ruthenium trichloride, ruthenium sulfate and ruthenium acetate; the iridium-containing metal salt is one or more of iridium nitrate, iridium chloride and iridium sulfate; the cobalt-containing metal salt is one or more of cobalt nitrate, cobalt chloride, cobalt sulfate and cobalt acetate; the tin-containing metal salt is one or more of tin tetrachloride, stannous chloride and tin sulfate.
Preferably, the ruthenium-containing metal salt is ruthenium trichloride, the iridium-containing metal salt is iridium chloride, the cobalt-containing metal salt is cobalt chloride, and the tin-containing metal salt is stannous chloride.
In one embodiment, the substrate is a titanium or titanium alloy material.
In one embodiment, the acid treatment is performed by immersing the substrate in an acid treatment agent.
In one embodiment, the acid treatment agent is a nitric acid solution, and the concentration of nitric acid in the solution is 100-120 g/L.
In one embodiment, the alkali treatment is performed by immersing the substrate in an alkali treatment agent.
In one embodiment, the alkali treatment agent is sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 15-30%.
In the process of alkali treatment of the base material, a proper amount of surfactant and silicate can be added to ensure that alkali liquor is uniformly distributed, and impurities are easy to remove. The invention does not strictly limit the use of surfactants and silicates and the types of surfactants and silicates, and generally, common anionic surfactants, nonionic surfactants and silicates can achieve the effects.
In one embodiment, the acid treatment and the base treatment are performed under heating or ultrasonic conditions, the heating temperature is 50 ℃ to 100 ℃, and the ultrasonic frequency is 20 kHz to 40kHz.
In one embodiment, the acid solution is one or more of sulfuric acid solution, hydrochloric acid solution, oxalic acid solution and hydrogen fluoride solution. Preferably, the acid solution is one or more of sulfuric acid solution, hydrochloric acid solution and oxalic acid solution.
In one embodiment, the acid solution concentration is 5% -50%, the etching temperature is 20 ℃ -100 ℃ and the etching time is 5 min-12 h.
In one embodiment, the concentration of ruthenium, iridium, tin in the metal salt solution is 0.1-2.0 mg/mL. Preferably, the concentration of ruthenium is 0.1-0.8 mg/mL, the concentration of iridium is 0.1-1.5 mg/mL, and the concentration of tin is 0.1-0.5 mg/mL. Further preferably, the concentration of ruthenium is 0.5mg/mL, the concentration of iridium is 1.0mg/mL, and the concentration of tin is 0.35mg/mL.
In one embodiment, the cobalt is present in an amount of 30% to 50% of tin.
In one embodiment, the heat treatment temperature is 300-1200 ℃ and the heat treatment time is 15 min-30 h.
In one embodiment, the heat treatment is performed in two steps, the first heat treatment temperature is 300-800 ℃, the heat treatment time is 2-30 hours, the second heat treatment temperature is 800-1200 ℃, and the heat treatment time is 15 min-12 hours.
The invention is not strictly limited to the coating mode used, as long as the metal salt solution can be uniformly coated on the substrate, and the specific coating mode can be rolling coating, brushing or electrostatic spraying.
The invention adopts a step-by-step heat treatment process, wherein the first step of heat treatment is to enable ruthenium, iridium, tin, cobalt and other metals in a metal salt solution to form a uniform oxide layer on the surface of a substrate, so as to improve the adhesive force and corrosion resistance of the coating, and the second step of heat treatment is to improve the electrochemical activity and stability of the coating.
The invention improves the surface appearance, structure and performance of the titanium-based material by acid etching, increases the surface roughness and specific surface area of the titanium-based material, and improves the bonding strength and corrosion resistance of the titanium-based material and the coating. Generally, hydrogen fluoride has the fastest corrosion rate, but generates toxic fluoride, so the present invention does not use hydrogen fluoride for acid etching except for some necessity. In addition, sulfuric acid and hydrochloric acid have slower corrosion rates but form a uniform pitted surface structure, while oxalic acid has a corrosion rate between that of hydrogen fluoride and sulfuric acid, but form larger pores and cracks.
The acid etching conditions of the invention mainly comprise acid concentration, temperature, time, stirring and the like, and the acid etching conditions influence the dynamics and mechanism of the acid etching. Generally, the higher the acid concentration, the higher the temperature, the longer the time, the stronger the agitation, and the greater the rate and depth of acid etching, but also increases the power consumption and cost. The invention limits the acid concentration, temperature and time, but whether stirring is carried out or not, and how violent the stirring can be selected according to specific conditions.
The technical scheme provided by the invention is further described below by combining with the embodiment.
Example 1
The preparation method of the ruthenium iridium tin cobalt mixed noble metal coating anode material comprises the following steps:
Immersing pure Ti in a nitric acid solution with the concentration of 150g/L, treating for 15min at 65 ℃, washing with deionized water, immersing in a 15% sodium hydroxide solution, and treating for 15min at 50 ℃;
Immersing the treated substrate in a sulfuric acid solution with the concentration of 20%, and treating at 50 ℃ for 3 hours to carry out acid etching;
Preparing a mixed metal salt solution containing ruthenium, iridium, tin and cobalt, wherein the concentration of ruthenium is 0.5mg/mL, the concentration of iridium is 1.0mg/mL, the concentration of tin is 0.35mg/mL, the content of cobalt is 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% and 60% of tin respectively, uniformly coating the metal salt solution on a base material subjected to acid etching, performing two-step heat treatment on the base material, wherein the first-step heat treatment temperature is 350 ℃, the heat treatment time is 3.5h, the second-step heat treatment temperature is 850 ℃, the heat treatment time is 1h, and repeating the coating-heat treatment steps for 8 times to obtain the ruthenium iridium tin cobalt mixed noble metal coating anode material.
Test example 1
The electrode material prepared in example 1 was tested for chlorine evolution potential relative to calomel electrode in saturated sodium chloride solution and the results are shown in table 1.
TABLE 1 potential for chlorine evolution of samples
As is clear from table 1, the cobalt content was between 30% and 50% of tin, respectively, and the chlorine evolution potential showed a decreasing trend, whereas the chlorine evolution potential showed a slight increasing trend as the cobalt content was further increased. Therefore, the cobalt content is preferably 30% to 50% of tin, both from the cost and effect point of view.
Test example 2
The current efficiency of the electrode material prepared in example 1 was measured (refer to the analysis method of effective chlorine concentration of GB 12176-90), the test temperature was 10 ℃, the reference electrode was a saturated calomel electrode, the applied current density was 0.5A/m 2, and the results are shown in Table 2 and FIG. 1:
Table 2 current efficiency of samples
Test example 3
The enhanced electrolytic life of the electrode material prepared in example 1 was measured, and the measurement was conducted in seawater at a temperature of 10℃and a current density of 5000A/m 2, and the measurement results are shown in Table 3 and FIG. 2, to simulate the actual use of the electrode more truly.
TABLE 3 enhanced electrolytic life of samples
Example 2
The preparation method of the ruthenium iridium tin cobalt mixed noble metal coating anode material comprises the following steps:
Immersing pure Ti in a nitric acid solution with the concentration of 150g/L, treating for 15min at 65 ℃, washing with deionized water, immersing in a 15% sodium hydroxide solution, and treating for 15min at 50 ℃;
Immersing the treated base material into an oxalic acid solution with the concentration of 35%, and treating at 50 ℃ for 1h to carry out acid etching;
Preparing a mixed metal salt solution containing ruthenium, iridium, tin and cobalt, wherein the concentration of ruthenium is 0.5mg/mL, the concentration of iridium is 1.0mg/mL, the concentration of tin is 0.35mg/mL, the content of cobalt is 35% of tin, uniformly coating the metal salt solution on a base material subjected to acid etching, performing two-step heat treatment on the base material, wherein the first-step heat treatment temperature is 350 ℃, the heat treatment time is 3.5h, the second-step heat treatment temperature is 850 ℃, the heat treatment time is 1h, and repeating the coating-heat treatment steps for 6 times to obtain the ruthenium iridium tin cobalt mixed noble metal coating anode material.
Through detection (the detection method is the same as that of the test examples 1-3), the chlorine evolution potential of the sample at 4kA/m 2、6kA/m2、8kA/m2 is 1.093, 1.105 and 1.122 respectively, the current efficiency is 82.5%, and the intensified electrolysis life is 223h.
Example 3
The preparation method of the ruthenium iridium tin cobalt mixed noble metal coating anode material comprises the following steps:
immersing pure Ti in a nitric acid solution with the concentration of 100g/L, treating for 20min at the temperature of 100 ℃, washing with deionized water, immersing in a 30% sodium hydroxide solution, and treating for 8min at the temperature of 50 ℃ and ultrasonic wave at 30 kHz;
Immersing the treated base material into an oxalic acid solution with the concentration of 35%, and treating at 50 ℃ for 1h to carry out acid etching;
Preparing a mixed metal salt solution containing ruthenium, iridium, tin and cobalt, wherein the concentration of ruthenium is 0.1mg/mL, the concentration of iridium is 1.5mg/mL, the concentration of tin is 0.5mg/mL, the content of cobalt is 35% of tin, uniformly coating the metal salt solution on a base material subjected to acid etching, performing two-step heat treatment on the base material, wherein the first-step heat treatment temperature is 550 ℃, the heat treatment time is 3h, the second-step heat treatment temperature is 1050 ℃, the heat treatment time is 1.5h, and repeating the coating-heat treatment steps for 6 times to obtain the ruthenium iridium tin cobalt mixed noble metal coating anode material.
Through detection (the detection method is the same as that of the test examples 1-3), the chlorine evolution potential of the sample at 4kA/m 2、6kA/m2、8kA/m2 is 1.092, 1.110 and 1.118 respectively, the current efficiency is 82.8%, and the intensified electrolysis life is 220h.
Example 4
The preparation method of the ruthenium iridium tin cobalt mixed noble metal coating anode material comprises the following steps:
immersing pure Ti in a nitric acid solution with the concentration of 100g/L, treating for 20min at the temperature of 100 ℃, washing with deionized water, immersing in a 30% sodium hydroxide solution, and treating for 8min at the temperature of 50 ℃ and ultrasonic wave at 30 kHz;
Immersing the treated base material into an oxalic acid solution with the concentration of 35%, and treating at 50 ℃ for 1h to carry out acid etching;
Preparing a mixed metal salt solution containing ruthenium, iridium, tin and cobalt, wherein the concentration of ruthenium is 2.0mg/mL, the concentration of iridium is 0.25mg/mL, the concentration of tin is 0.2mg/mL, the content of cobalt is 50% of tin, uniformly coating the metal salt solution on a base material subjected to acid etching, performing two-step heat treatment on the base material, wherein the heat treatment temperature of the first step is 500 ℃, the heat treatment time is 3h, the heat treatment temperature of the second step is 950 ℃, the heat treatment time is 1.5h, and repeating the coating-heat treatment steps for 6 times to obtain the ruthenium iridium tin cobalt mixed noble metal coating anode material.
Through detection (the detection method is the same as that of the test examples 1-3), the chlorine evolution potential of the sample at 4kA/m 2、6kA/m2、8kA/m2 is 1.083, 1.105 and 1.115, the current efficiency is 87.0%, and the intensified electrolysis life is 249h.
As can be seen from examples 1-4, some parameters in the preparation process of the product have little influence on the performance of the product, and can be adjusted within a certain range. Therefore, the preparation conditions can be optimized according to actual conditions, and the quality and the efficiency of the product are improved. For example, if the acid etching rate of the acid solution is too high during the acid etching step, the product performance may be affected. To avoid this, the acid etching rate can be slowed down by lowering the concentration of the acid solution and the temperature of the treatment to obtain a good acid etching effect. Similarly, other processing factors, such as time, temperature, concentration, etc., can be properly adjusted as required to achieve the best preparation effect.
Comparative example 1
The preparation method of the ruthenium iridium tin cobalt mixed noble metal coating anode material comprises the following steps:
Immersing pure Ti in a nitric acid solution with the concentration of 150g/L, treating for 15min at 65 ℃, washing with deionized water, immersing in a 15% sodium hydroxide solution, and treating for 15min at 50 ℃;
Immersing the treated substrate in a sulfuric acid solution with the concentration of 20%, and treating at 50 ℃ for 3 hours to carry out acid etching;
Preparing a mixed metal salt solution containing ruthenium, iridium, tin and cobalt, wherein the concentration of ruthenium is 0.5mg/mL, the concentration of iridium is 1.0mg/mL, the concentration of tin is 0.35mg/mL, the content of cobalt is 35% of that of tin, uniformly coating the metal salt solution on a base material subjected to acid etching, carrying out heat treatment for 3.5h at 350 ℃, and repeating the coating-heat treatment step for 8 times to obtain the ruthenium iridium tin cobalt mixed noble metal coating anode material.
Through detection (the detection method is the same as that of the test examples 1-3), the chlorine evolution potential of the sample at 4kA/m 2、6kA/m2、8kA/m2 is 1.115, 1.203 and 1.254 respectively, the current efficiency is 80.0%, and the intensified electrolysis life is 207h.
It can be seen that the second heat treatment provides a significant improvement in the electrochemical properties of the material. Particularly has great influence on reducing the chlorine evolution potential of the material under high current density. In addition, it was found in the study that 1200 ℃ is the upper temperature limit of the second heat treatment, and further temperature increase can lead to the destruction of the oxide layer structure, and the electrochemical performance and the service life of the product can be obviously reduced.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to assist in understanding the methods of the present invention and the core ideas thereof; also, it is within the scope of the present invention to be modified by those of ordinary skill in the art in light of the present teachings. In view of the foregoing, this description should not be construed as limiting the invention.
Claims (10)
1. The preparation method of the ruthenium iridium tin cobalt mixed noble metal coating anode material is characterized by comprising the following steps of:
S1, sequentially carrying out acid treatment and alkali treatment on a base material to remove impurities such as oxides, grease and the like on the surface of the base material;
S2, immersing the treated substrate in an acid solution for acid etching;
And S3, preparing a mixed metal salt solution containing ruthenium, iridium, tin and cobalt, uniformly coating the metal salt solution on the base material subjected to acid etching, performing heat treatment on the base material, and repeating the coating-heat treatment steps for 6-8 times to obtain the ruthenium-iridium-tin-cobalt mixed noble metal coating anode material.
2. The method according to claim 1, wherein the acid solution is one or more of sulfuric acid solution, hydrochloric acid solution, oxalic acid solution and hydrogen fluoride solution.
3. The preparation method according to claim 1, wherein the acid solution concentration is 5% -50%, the etching temperature is 20 ℃ -100 ℃ and the etching time is 5 min-12 h.
4. The preparation method according to claim 1, wherein the metal salt is one or more of metal acetate, metal sulfate, metal nitrate and metal chloride.
5. The preparation method according to claim 1, wherein the ruthenium-containing metal salt is one or more of ruthenium nitrate, ruthenium trichloride, ruthenium sulfate and ruthenium acetate; the iridium-containing metal salt is one or more of iridium nitrate, iridium chloride and iridium sulfate; the cobalt-containing metal salt is one or more of cobalt nitrate, cobalt chloride, cobalt sulfate and cobalt acetate; the tin-containing metal salt is one or more of tin tetrachloride, stannous chloride and tin sulfate.
6. The preparation method according to claim 1, wherein the concentration of ruthenium, iridium and tin in the metal salt solution is 0.1-2.0 mg/mL.
7. The method according to claim 1, wherein the cobalt content is 30% to 50% of tin.
8. The method according to claim 1, wherein the heat treatment temperature is 300 ℃ to 1200 ℃ and the heat treatment time is 15min to 30h.
9. The method according to claim 9, wherein the heat treatment is performed in two steps, the first heat treatment temperature is 300 to 800 ℃, the heat treatment time is 2 to 30 hours, the second heat treatment temperature is 800 to 1200 ℃, and the heat treatment time is 15 minutes to 12 hours.
10. An anode material of ruthenium iridium tin cobalt mixed noble metal coating, which is characterized by being prepared by the method of any one of claims 1 to 8.
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| US4213843A (en) * | 1978-03-24 | 1980-07-22 | Permelec Electrode Ltd. | Electrolysis electrodes and method of making same |
| CN110158113A (en) * | 2019-06-24 | 2019-08-23 | 蓝星(北京)化工机械有限公司 | Gas evolution electrode and preparation method thereof |
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| CN113072138A (en) * | 2021-03-22 | 2021-07-06 | 浙江大学 | Preparation method of long-life DSA electrode capable of being used for frequently reversing cathode and anode |
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| US4213843A (en) * | 1978-03-24 | 1980-07-22 | Permelec Electrode Ltd. | Electrolysis electrodes and method of making same |
| CN110158113A (en) * | 2019-06-24 | 2019-08-23 | 蓝星(北京)化工机械有限公司 | Gas evolution electrode and preparation method thereof |
| CN111137953A (en) * | 2020-01-09 | 2020-05-12 | 江苏安凯特科技股份有限公司 | Preparation process of titanium-based tin iridium oxide coating electrode |
| CN113072138A (en) * | 2021-03-22 | 2021-07-06 | 浙江大学 | Preparation method of long-life DSA electrode capable of being used for frequently reversing cathode and anode |
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