CN114395757B - Preparation method of multi-element oxide coating titanium anode plate - Google Patents
Preparation method of multi-element oxide coating titanium anode plate Download PDFInfo
- Publication number
- CN114395757B CN114395757B CN202111457237.9A CN202111457237A CN114395757B CN 114395757 B CN114395757 B CN 114395757B CN 202111457237 A CN202111457237 A CN 202111457237A CN 114395757 B CN114395757 B CN 114395757B
- Authority
- CN
- China
- Prior art keywords
- oxide
- coating
- titanium
- anode plate
- acid
- 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.)
- Active
Links
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 84
- 239000010936 titanium Substances 0.000 title claims abstract description 84
- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- 238000000576 coating method Methods 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- -1 iridium tantalum molybdenum samarium Chemical compound 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 24
- 238000005530 etching Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000009835 boiling Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 18
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 16
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 12
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 239000000084 colloidal system Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000005238 degreasing Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 10
- 238000007781 pre-processing Methods 0.000 claims description 10
- 238000005488 sandblasting Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 9
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 9
- 229940075630 samarium oxide Drugs 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 6
- 239000011733 molybdenum Substances 0.000 abstract description 6
- 238000003980 solgel method Methods 0.000 abstract description 5
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical compound [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 18
- ULFQGKXWKFZMLH-UHFFFAOYSA-N iridium tantalum Chemical compound [Ta].[Ir] ULFQGKXWKFZMLH-UHFFFAOYSA-N 0.000 description 12
- 229910052761 rare earth metal Inorganic materials 0.000 description 7
- 229910052772 Samarium Inorganic materials 0.000 description 6
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 3
- VONLASUMRVUZLY-UHFFFAOYSA-N [Ir].[Ti].[Ta] Chemical compound [Ir].[Ti].[Ta] VONLASUMRVUZLY-UHFFFAOYSA-N 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
-
- 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
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
- C23C18/127—Preformed particles
-
- 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
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
-
- 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
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
-
- 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
-
- 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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Nanotechnology (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention provides a preparation method of a titanium anode plate with a multi-element oxide coating, which takes a pure titanium plate as a substrate, and a surface active layer is a multi-element oxide of iridium tantalum molybdenum samarium mixed oxide. The transition metal molybdenum is introduced, so that the compactness of the surface coating can be increased, the permeation of external active oxygen and electrolyte to a titanium base can be avoided or slowed down, and the service life of the electrode is prolonged. Meanwhile, the preparation process of the sol-gel method is improved, a surfactant is added into a solvent, the dispersion effect of metal ions is increased, part of precursor chloroiridium acid is replaced by nano IrO 2 powder and is directly fused into a colloidal solution, and the coating structure can be improved, so that the coating has more excellent electrocatalytic activity and stability.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a preparation method of a titanium anode plate with a titanium-based coating.
Background
The metal oxide coating anode is mainly applied to two major industries of electrometallurgical and electrochemistry, and the application fields relate to sewage and wastewater treatment, chemical industry, metallurgy, electroplating, organic synthesis and the like, wherein noble metal iridium has high electrochemical activity and corrosion resistance, is widely paid attention to as an electrode material, and has great success in many electrochemical industries, wherein the iridium tantalum coating titanium anode is recognized as an ideal anode material in an acidic oxygen evolution environment. However, the electrochemical performance and stability of a single iridium tantalum titanium anode can not meet the current application requirements of the electrode, and other elements are generally doped to form a titanium anode with a multi-element oxide active coating.
In the existing preparation method of the titanium anode plate, the thermal oxidative decomposition process is the most common preparation method of the titanium anode with the noble metal active coating at present due to simple preparation flow and lower equipment cost, but the required sintering temperature is higher, and the prepared electrode has the defects of uneven surface, poor density, easy falling off and unsatisfactory service life and activation performance.
Disclosure of Invention
In order to solve the problems, rare earth elements and transition metal elements are introduced into an active layer on the basis of an iridium tantalum coated titanium anode, the active coated titanium anode is prepared by adopting a sol-gel method, and meanwhile, the preparation process of the sol-gel method is improved, a multi-oxide coated titanium anode plate (Ti-IrO 2+Ta2O5+MoO3+Sm2O3) is disclosed, a titanium plate is taken as a substrate, the surface of the substrate is covered with a surface active layer of iridium tantalum molybdenum samarium mixed oxide, and the surface active layer is the iridium tantalum molybdenum samarium mixed oxide and comprises the following components in percentage by mass (30.7-32.1): (12.6-13.4): (18.5-19.7): (1.6-2.2) iridium dioxide, tantalum pentoxide, molybdenum trioxide, samarium trioxide.
The preparation method of the multi-oxide coating titanium anode plate comprises the following steps:
S1, preprocessing a titanium substrate: firstly, sand blasting is performed on the roughened surface, the primary metal color is exposed, then the roughened surface is put into a micro-boiling sodium carbonate solution for degreasing, after clean water is washed clean, the roughened surface is put into a micro-boiling oxalic acid solution for etching, and after the etching is finished, the cleaned clean water is put into ethanol for standby;
S2, preparing a sol-gel solvent: adding citric acid and a surfactant into an ethylene glycol solution, and carrying out ultrasonic treatment to uniformly mix;
s3, preparing a sol-gel coating liquid: adding chloroiridic acid, tantalum pentachloride and phosphomolybdic acid into the solvent in S2, heating and stirring to obtain a viscous colloid solution, adding samarium oxide and nano iridium oxide, and uniformly mixing;
And S4, uniformly coating the sol coating liquid in the step S3 on the titanium substrate pretreated in the step S1, drying, placing into a heat treatment furnace, sintering at high temperature, taking out the titanium plate after sintering, cooling to room temperature by air, repeating the steps in the step S2, coating, drying and sintering for a plurality of times, and annealing at the same temperature to obtain the multi-oxide coated titanium anode plate (Ti-IrO 2+Ta2O5+MoO3+Sm2O3).
Preferably, in step S1: the sodium carbonate content in the sodium carbonate solution is 5-10%, the oil removal time is 1-2h, the oxalic acid content in the oxalic acid solution is 10-15%, and the etching time is 2-3h.
Preferably, in step S2: the addition amount of the citric acid is 19-24% of the total mass of the glycol, the surfactant is one or more of sulfonate type anionic surfactants, and the surfactant mainly comprises sodium alkylbenzenesulfonate, alkyl sulfonate and alpha-sulfo monocarboxylic acid ester. The addition amount of the surfactant is 7-15% of the total mass of the glycol, and the ultrasonic treatment time is 10-15min.
Preferably, in step S3: the stirring heating temperature is 70-80 ℃, the stirring time is 20-40min, the total mass of chloroiridic acid (H 4Cl6 IrO), tantalum pentachloride (TaCl 5), phosphomolybdic acid (H 3PO4·12MoO3), samarium oxide (Sm 2O3) and nano iridium oxide (IrO 2) is 21-29% of glycol, and the mass ratio of chloroiridic acid, nano iridium oxide, tantalum pentachloride, phosphomolybdic acid and samarium oxide is (21.1-21.5): (4.2-4.7): (10.2-10.9): (9.8-10.4): (0.8-1.1).
Preferably, in step S4: the drying temperature is 100-130 ℃, the drying time is 5-10min, the sintering temperature is 400-450 ℃, the sintering time is 10-15min, the repetition times are 6-10 times, and the annealing time is 40-80min.
The invention has the beneficial effects that:
1. Compared with the traditional thermal decomposition method, the sol-gel method can uniformly disperse various metal ions in the sol, and the invention adds the surfactant, so that the effect can be improved, when the titanium anode oxide coating is prepared, the required sintering temperature is low, the colloid is uniformly dispersed, the surface particles of the finished product are uniform, the number of active points on the surface is increased, and the electrocatalytic activity of the titanium anode is improved to a certain extent.
2. The nano IrO 2 powder is used for replacing part of precursor chloroiridic acid to be directly fused into a colloid solution, and iridium element is introduced into the coating, so that the coating structure can be improved, and the coating has more excellent electrocatalytic activity and stability.
3. The rare earth element samarium can effectively reduce the interface resistance between the anodic oxide coating and the electrolytic solution after being introduced, and improve the conductivity, thereby improving the electrocatalytic performance of the electrode, reducing the cracking of the coating and increasing the binding force between the coating and the matrix.
4. The density of the surface coating can be increased after the transition metal molybdenum is introduced, so that the permeation of external active oxygen and electrolyte to the titanium base is avoided or slowed down, the passivation of the titanium base is avoided or slowed down, and the service life of the electrode is prolonged.
Detailed Description
The invention will now be further illustrated by the following comparative examples 1-5 and examples 1-3. Comparative example 1 is a single iridium tantalum titanium anode prepared by a general sol-gel method under the condition parameters and the component formula ratio provided by the invention; comparative examples 2-5 based on the component of comparative example 1, comparative example 2 was a surfactant addition, comparative example 3 was a nano IrO 2 substitution of part of chloroiridium acid, comparative example 4 was doped with the rare earth element samarium, and comparative example 5 was doped with the transition metal element molybdenum; examples 1-3 are methods of preparation provided by the present invention. The composition formula is shown in Table 1.
Table 1:
Comparative example 1:
The comparative example used the following steps to prepare iridium tantalum coated titanium anode plate a:
S1, preprocessing a titanium substrate: firstly, sand blasting is performed on the roughened surface, the primary metal color is exposed, then the roughened surface is put into a slightly boiling 7% sodium carbonate solution for degreasing for 1.5 hours, after the cleaned by clean water, the roughened surface is put into a slightly boiling 12% oxalic acid solution for etching for 2.5 hours, and after the etching is finished, the cleaned surface is put into ethanol for standby.
S2, preparing a sol-gel solvent: 44 parts of citric acid are added into 200 parts of glycol solution, and ultrasonic treatment is carried out for 12min, so that the mixture is uniform.
S3, preparing a sol-gel coating liquid: 31.7 parts of chloroiridic acid and 13 parts of tantalum pentachloride are added into the solvent in the step S2, and the mixture is heated and stirred at the temperature of 75 ℃ for 30 minutes to obtain a viscous colloid solution.
S4, uniformly coating the sol coating liquid in the step S3 on the titanium substrate pretreated in the step S1, drying at 120 ℃ for 7min, placing into a heat treatment furnace, sintering at high temperature for 12min, taking out the titanium plate, air-cooling to room temperature, repeating the steps in the step S2, coating, drying and sintering for 8 times, and annealing at 420 ℃ for 60min to obtain the iridium-tantalum coated titanium anode plate (Ti-IrO 2+Ta2O5).
Comparative example 2:
The comparative example prepares an iridium tantalum coating titanium anode plate B prepared by adding a surfactant according to the following steps:
S1, preprocessing a titanium substrate: firstly, sand blasting is performed on the roughened surface, the primary metal color is exposed, then the roughened surface is put into a slightly boiling 7% sodium carbonate solution for degreasing for 1.5 hours, after the cleaned by clean water, the roughened surface is put into a slightly boiling 12% oxalic acid solution for etching for 2.5 hours, and after the etching is finished, the cleaned surface is put into ethanol for standby.
S2, preparing a sol-gel solvent: 44 parts of citric acid and 20 parts of alkyl sulfonate are added into 200 parts of glycol solution, and ultrasonic treatment is carried out for 12min, so that the mixture is uniform.
S3, preparing a sol-gel coating liquid: 31.7 parts of chloroiridic acid and 13 parts of tantalum pentachloride are added into the solvent in the step S2, and the mixture is heated and stirred at the temperature of 75 ℃ for 30 minutes to obtain a viscous colloid solution.
S4, uniformly coating the sol coating liquid in the step S3 on the titanium substrate pretreated in the step S1, drying at 120 ℃ for 7min, placing into a heat treatment furnace, sintering at high temperature for 12min, taking out the titanium plate, air-cooling to room temperature, repeating the steps in the step S2, coating, drying and sintering for 8 times, and annealing at 420 ℃ for 60min to obtain the iridium-tantalum coating titanium anode plate (Ti-IrO 2+Ta2O5) prepared by adding the surfactant.
Comparative example 3:
The comparative example prepares an iridium tantalum coating titanium anode plate C prepared by replacing part of chloroiridium acid with nano IrO 2 according to the following steps:
S1, preprocessing a titanium substrate: firstly, sand blasting is performed on the roughened surface, the primary metal color is exposed, then the roughened surface is put into a slightly boiling 7% sodium carbonate solution for degreasing for 1.5 hours, after the cleaned by clean water, the roughened surface is put into a slightly boiling 12% oxalic acid solution for etching for 2.5 hours, and after the etching is finished, the cleaned surface is put into ethanol for standby.
S2, preparing a sol-gel solvent: 44 parts of citric acid are added into 200 parts of glycol solution, and ultrasonic treatment is carried out for 12min, so that the mixture is uniform.
S3, preparing a sol-gel coating liquid: and (2) adding 26.9 parts of chloroiridic acid and 13 parts of tantalum pentachloride into the solvent in the step (S2), heating and stirring for 30min at 75 ℃ to obtain a viscous colloidal solution, adding 4.8 parts of nano iridium oxide, and uniformly mixing.
S4, uniformly coating the sol coating liquid in the step S3 on the titanium substrate pretreated in the step S1, drying at 120 ℃ for 7min, placing into a heat treatment furnace, sintering at high temperature for 12min, taking out the titanium plate, air-cooling to room temperature, repeating the steps in the step S2, coating, drying and sintering for 8 times, and annealing at 420 ℃ for 60min to obtain the iridium tantalum coating titanium anode plate (Ti-IrO 2+Ta2O5) prepared by replacing part of chloroiridic acid with nano IrO 2.
Comparative example 4:
The comparative example prepares an iridium tantalum coating titanium anode plate D prepared by doping rare earth elements samarium according to the following steps:
S1, preprocessing a titanium substrate: firstly, sand blasting is performed on the roughened surface, the primary metal color is exposed, then the roughened surface is put into a slightly boiling 7% sodium carbonate solution for degreasing for 1.5 hours, after the cleaned by clean water, the roughened surface is put into a slightly boiling 12% oxalic acid solution for etching for 2.5 hours, and after the etching is finished, the cleaned surface is put into ethanol for standby.
S2, preparing a sol-gel solvent: 44 parts of citric acid are added into 200 parts of glycol solution, and ultrasonic treatment is carried out for 12min, so that the mixture is uniform.
S3, preparing a sol-gel coating liquid: 31.7 parts of chloroiridic acid and 13 parts of tantalum pentachloride are added into the solvent in the step S2, heated and stirred at 75 ℃ for 30min to obtain a viscous colloid solution, and then 1 part of samarium oxide is added and mixed uniformly.
S4, uniformly coating the sol coating liquid in the step S3 on the titanium substrate pretreated in the step S1, drying at 120 ℃ for 7min, placing into a heat treatment furnace, sintering at high temperature for 12min, taking out the titanium plate, air-cooling to room temperature, repeating the steps in the step S2, coating, drying and sintering for 8 times, and annealing at 420 ℃ for 60min to obtain the iridium-tantalum coating titanium anode plate (Ti-IrO 2+Ta2O5+Sm2O3) doped with the rare earth element samarium.
Comparative example 5:
The comparative example prepares an iridium tantalum coating titanium anode plate E doped with transition metal element molybdenum according to the following steps:
S1, preprocessing a titanium substrate: firstly, sand blasting is performed on the roughened surface, the primary metal color is exposed, then the roughened surface is put into a slightly boiling 7% sodium carbonate solution for degreasing for 1.5 hours, after the cleaned by clean water, the roughened surface is put into a slightly boiling 12% oxalic acid solution for etching for 2.5 hours, and after the etching is finished, the cleaned surface is put into ethanol for standby.
S2, preparing a sol-gel solvent: 44 parts of citric acid are added into 200 parts of glycol solution, and ultrasonic treatment is carried out for 12min, so that the mixture is uniform.
S3, preparing a sol-gel coating liquid: 27.6 parts of chloroiridic acid, 11.2 parts of tantalum pentachloride and 10.7 parts of phosphomolybdic acid are added into the solvent in the step S2, and the mixture is heated and stirred at the temperature of 75 ℃ for 30 minutes to obtain a viscous colloid solution.
S4, uniformly coating the sol coating liquid in the step S3 on the titanium substrate pretreated in the step S1, drying at 120 ℃ for 7min, placing into a heat treatment furnace, sintering at high temperature for 12min, taking out the titanium plate, air-cooling to room temperature, repeating the steps in the step S2, coating, drying and sintering for 8 times, and annealing at 420 ℃ for 60min to obtain the iridium-tantalum coated titanium anode plate (Ti-IrO 2+Ta2O5+MoO3) doped with transition metal element molybdenum.
Example 1:
The present example employs the following steps to prepare a first set of polyoxide-coated titanium anode plates F:
S1, preprocessing a titanium substrate: firstly, sand blasting is performed on the roughened surface, the primary metal color is exposed, then the roughened surface is put into a slightly boiling 7% sodium carbonate solution for degreasing for 1.5 hours, after the cleaned by clean water, the roughened surface is put into a slightly boiling 12% oxalic acid solution for etching for 2.5 hours, and after the etching is finished, the cleaned surface is put into ethanol for standby.
S2, preparing a sol-gel solvent: 44 parts of citric acid and 20 parts of alkyl sulfonate are added into 200 parts of glycol solution, and ultrasonic treatment is carried out for 12min, so that the mixture is uniform.
S3, preparing a sol-gel coating liquid: and (2) adding 22.8 parts of chloroiridic acid, 11.2 parts of tantalum pentachloride and 10.7 parts of phosphomolybdic acid into the solvent in S2, heating and stirring for 30min at 75 ℃ to obtain a viscous colloid solution, adding 1 part of samarium oxide and 4.8 parts of nano iridium oxide, and uniformly mixing.
S4, uniformly coating the sol coating liquid in the step S3 on the titanium substrate pretreated in the step S1, drying at 120 ℃ for 7min, placing into a heat treatment furnace, sintering at high temperature for 12min, taking out the titanium plate, air-cooling to room temperature, repeating the steps in the step S2, coating, drying and sintering for 8 times, and annealing at 420 ℃ for 60min to obtain the first group of multi-oxide coated titanium anode plates (Ti-IrO 2+Ta2O5+MoO3+Sm2O3).
Example 2:
The present example employs the following steps to prepare a second set of polyoxide-coated titanium anode plates G:
s1, preprocessing a titanium substrate: firstly, sand blasting is performed on the roughened surface, the primary metal color is exposed, then the roughened surface is put into a slightly boiling 5% sodium carbonate solution for degreasing for 2 hours, after the cleaned water is washed clean, the roughened surface is put into a slightly boiling 10% oxalic acid solution for etching for 3 hours, and after the etching is finished, the cleaned water is washed clean and then put into ethanol for standby.
S2, preparing a sol-gel solvent: 39 parts of citric acid and 16 parts of sodium alkylbenzenesulfonate are added into 200 parts of glycol solution, and ultrasonic treatment is carried out for 10 minutes, so that the mixture is uniform.
S3, preparing a sol-gel coating liquid: and (2) adding 20.1 parts of chloroiridic acid, 9.7 parts of tantalum pentachloride and 9.3 parts of phosphomolybdic acid into the solvent in the step (S2), heating and stirring for 40min at 70 ℃ to obtain a viscous colloid solution, adding 0.8 part of samarium oxide and 4.1 parts of nano iridium oxide, and uniformly mixing.
S4, uniformly coating the sol coating liquid in the step S3 on the titanium substrate pretreated in the step S1, drying at 100 ℃ for 10min, placing the titanium substrate into a heat treatment furnace, sintering at 400 ℃ for 15min, taking out the titanium plate, air-cooling to room temperature, repeating the steps in the step S2, coating, drying and sintering for 10 times, and annealing at 400 ℃ for 40min to obtain a second group of multi-oxide coated titanium anode plates (Ti-IrO 2+Ta2O5+MoO3+Sm2O3).
Example 3:
The third set of polyoxide-coated titanium anode plates H were prepared in this example using the following steps:
S1, preprocessing a titanium substrate: firstly, sand blasting is performed on the roughened surface, the primary metal color is exposed, then the roughened surface is put into a micro-boiling 10% sodium carbonate solution for degreasing for 1h, after the cleaned water is washed clean, the roughened surface is put into a micro-boiling 15% oxalic acid solution for etching for 2h, and after the etching is finished, the cleaned water is washed clean and then put into ethanol for standby.
S2, preparing a sol-gel solvent: 48 parts of citric acid and 28 parts of alpha-sulfomonocarboxylic acid ester are added into 200 parts of glycol solution, and ultrasonic treatment is carried out for 15 minutes, so that the mixture is uniform.
S3, preparing a sol-gel coating liquid: and (2) adding 24.8 parts of chloroiridic acid, 12.5 parts of tantalum pentachloride and 12.1 parts of phosphomolybdic acid into the solvent in the step (S2), heating and stirring for 20min at 80 ℃ to obtain a viscous colloid solution, adding 1.3 parts of samarium oxide and 5.5 parts of nano iridium oxide, and uniformly mixing.
S4, uniformly coating the sol coating liquid in the step S3 on the titanium substrate pretreated in the step S1, drying at 130 ℃ for 5min, placing into a heat treatment furnace, sintering at high temperature for 10min, taking out the titanium plate, air-cooling to room temperature, repeating the steps in the step S2, coating, drying and sintering for 6 times, and annealing at 450 ℃ for 80min to obtain a third group of multi-oxide coated titanium anode plates (Ti-IrO 2+Ta2O5+MoO3+Sm2O3).
The following tests were performed on A, B, C, D, E, F, G, H above.
Electrochemical performance test: on an electrochemical workstation, a platinum sheet is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, and the working electrode is a product in the embodiment. The anodic polarization curve and cyclic voltammogram of the electrode were measured by linear scanning technique in 0.5mol/L H 2SO4 electrolytic solution with a controlled temperature of 25 ℃. The resulting anodic polarization curve is shown in FIG. 1 and the resulting cyclic voltammetry curve is shown in FIG. 2.
Enhanced electrolysis life measurement: the product in the embodiment is processed into a sample with the electrode area of 1cm 2, a pure titanium sheet is used as a cathode, the electrode distance is 2cm, the current density is 20mA/cm 2, the temperature is controlled to be 40 ℃, in an electrolytic solution of 0.5mol/H 2SO4, the time for the electrolytic voltage to rise by 10V relative to the initial value of electrolysis is the strengthening service life of the electrode. The resulting enhanced electrolysis lifetimes are shown in Table 2.
Table 2:
| Product(s) | A | B | C | D | E | F | G | H |
| Enhanced electrolysis life/h | 320 | 304 | 422 | 402 | 619 | 627 | 624 | 629 |
From table 2 above, it can be seen that adding the surfactant into the solvent of the precursor slightly reduces the service life of the titanium anode, and the introduction of the transition metal molybdenum significantly improves the service life of the titanium anode, and the product F, G, H obtained by the preparation method provided by the invention has excellent service life, and the product F has an improvement of 95.9% compared with the enhanced electrolysis service life of a.
The main information reflected by the polarization curve is the electrocatalytic activity of the electrode, and the smaller the potential corresponding to the polarization curve at the same current density is, the higher the electrocatalytic activity is, namely, the higher the oxygen evolution current density is under the same oxygen evolution potential, which indicates that the prepared oxide coating titanium anode has higher oxygen evolution electrocatalytic activity. As can be seen from FIG. 1, the product F, G, H prepared by the preparation method provided by the invention has higher oxygen evolution electrocatalytic activity than the product A, B, C, D, E, and the product D can be seen from the comparison with the product A, and the introduction of the rare earth element samarium can effectively improve the electrocatalytic activity of the titanium anode.
The voltammetric area surrounded by the cyclic voltammetry curve is in direct proportion to the charge capacity of the surface of the titanium anode coating, and the larger the area surrounded by the cyclic voltammetry curve is, the larger the voltammetric electric quantity of the surface of the oxide anode is, the larger the number of active points on the surface is, the larger the electrochemical effective surface area is, and the electrocatalytic activity of the electrode is stable. As can be seen from FIG. 2, the substitution of nano IrO 2 and the introduction of rare earth samarium can both improve the electrocatalytic stability of the titanium anode under the combined action of the surfactant in the solvent, and the product F, G, H prepared by the preparation method provided by the invention has more stable electrocatalytic activity than the product A, B, C, D, E.
Claims (5)
1. The preparation method of the multi-oxide coating titanium anode plate is characterized by comprising the following steps of:
S1, preprocessing a titanium substrate: firstly, sand blasting is performed on the roughened surface, the primary metal color is exposed, then the roughened surface is put into a micro-boiling sodium carbonate solution for degreasing, after clean water is washed clean, the roughened surface is put into a micro-boiling oxalic acid solution for etching, and after the etching is finished, the cleaned clean water is put into ethanol for standby;
S2, preparing a sol-gel solvent: adding citric acid and a surfactant into an ethylene glycol solution, and carrying out ultrasonic treatment to uniformly mix;
The surfactant is one or more of sulfonate type anionic surfactants, and mainly comprises sodium alkylbenzenesulfonate, alkyl sulfonate and alpha-sulfo monocarboxylic acid ester, wherein the addition amount of the surfactant is 7% -15% of the total mass of ethylene glycol;
s3, preparing a sol-gel coating liquid: adding chloroiridic acid, tantalum pentachloride and phosphomolybdic acid into the solvent in S2, heating and stirring to obtain a viscous colloid solution, adding samarium oxide and nano iridium oxide, and uniformly mixing;
s4, uniformly coating the sol coating liquid in the step S3 on the titanium substrate pretreated in the step S1, drying, placing the titanium substrate into a heat treatment furnace for high-temperature sintering, taking out the titanium substrate for air cooling to room temperature after sintering, repeating the steps in the step S2, coating, drying and sintering for a plurality of times, and annealing at the same temperature to obtain the multi-oxide coating titanium anode plate;
The obtained multi-oxide coating titanium anode plate takes a titanium plate as a substrate, and the surface of the substrate is covered with a surface active layer of iridium tantalum molybdenum samarium mixed oxide, wherein the surface active layer comprises the following components in percentage by mass (30.7-32.1): (12.6-13.4): (18.5-19.7): (1.6-2.2) iridium dioxide, tantalum pentoxide, molybdenum trioxide, samarium trioxide.
2. The method for preparing a multi-oxide coated titanium anode plate according to claim 1, wherein in the step S1: the sodium carbonate content in the sodium carbonate solution is 5-10%, the oil removal time is 1-2h, the oxalic acid content in the oxalic acid solution is 10-15%, and the etching time is 2-3h.
3. The method for preparing a multi-oxide coated titanium anode plate according to claim 1, wherein in the step S2: the addition amount of the citric acid is 19-24% of the total mass of the glycol, and the ultrasonic treatment time is 10-15min.
4. The method for preparing a multi-oxide coated titanium anode plate according to claim 1, wherein in the step S3: the stirring and heating temperature is 70-80 ℃, the stirring time is 20-40min, the total mass of chloroiridic acid, tantalum pentachloride, phosphomolybdic acid, samarium oxide and nano iridium oxide is 21-29% of glycol, and the mass ratio of chloroiridic acid, nano iridium oxide, tantalum pentachloride, phosphomolybdic acid and samarium oxide is (21.1-21.5): (4.2-4.7): (10.2-10.9): (9.8-10.4): (0.8-1.1).
5. The multi-oxide coated titanium anode plate and the preparation method thereof according to claim 1, wherein in the step S4: the drying temperature is 100-130 ℃, the drying time is 5-10min, the sintering temperature is 400-450 ℃, the sintering time is 10-15min, the repetition times are 6-10 times, and the annealing time is 40-80min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111457237.9A CN114395757B (en) | 2021-12-02 | 2021-12-02 | Preparation method of multi-element oxide coating titanium anode plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111457237.9A CN114395757B (en) | 2021-12-02 | 2021-12-02 | Preparation method of multi-element oxide coating titanium anode plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114395757A CN114395757A (en) | 2022-04-26 |
| CN114395757B true CN114395757B (en) | 2024-04-26 |
Family
ID=81225508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111457237.9A Active CN114395757B (en) | 2021-12-02 | 2021-12-02 | Preparation method of multi-element oxide coating titanium anode plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114395757B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030080536A (en) * | 2002-04-09 | 2003-10-17 | 한국수질개발 주식회사 | Electrode and its manufacturing method using rare earth element |
| CN1995464A (en) * | 2006-11-28 | 2007-07-11 | 北京科技大学 | Nanocrystalline iridium series oxide coating electrode preparation method |
| CN106367777A (en) * | 2016-12-14 | 2017-02-01 | 青岛双瑞海洋环境工程股份有限公司 | Oxide anode material suitable for low salinity seawater environment and preparation process thereof |
| CN109763149A (en) * | 2019-03-12 | 2019-05-17 | 江阴安诺电极有限公司 | Iridium tantalum coated anode plate |
-
2021
- 2021-12-02 CN CN202111457237.9A patent/CN114395757B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030080536A (en) * | 2002-04-09 | 2003-10-17 | 한국수질개발 주식회사 | Electrode and its manufacturing method using rare earth element |
| CN1995464A (en) * | 2006-11-28 | 2007-07-11 | 北京科技大学 | Nanocrystalline iridium series oxide coating electrode preparation method |
| CN106367777A (en) * | 2016-12-14 | 2017-02-01 | 青岛双瑞海洋环境工程股份有限公司 | Oxide anode material suitable for low salinity seawater environment and preparation process thereof |
| CN109763149A (en) * | 2019-03-12 | 2019-05-17 | 江阴安诺电极有限公司 | Iridium tantalum coated anode plate |
Non-Patent Citations (1)
| Title |
|---|
| 添加纳米IrO_2的新型涂层IrO_2-Ta_2O_5钛阳极的制备及性能;白少金;魏宗平;王欣;邵艳群;唐电;;中国有色金属学报(03);第211-216页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114395757A (en) | 2022-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Corrosion resistance mechanism of a novel porous Ti/Sn-Sb-RuOx/β-PbO2 anode for zinc electrowinning | |
| CN113629255B (en) | Anti-reversal catalyst for battery and preparation method and application thereof | |
| CN1900368A (en) | Titanium anode containing ruthenium coating of high cerium content and its preparing method | |
| CN109775813B (en) | Composite intermediate layer for titanium-based oxide electrode, titanium-based oxide electrode and preparation method thereof | |
| CN104386785B (en) | The preparation method of molybdenum, antimony codope titanium base tin ash electro catalytic electrode | |
| CN113816468B (en) | DSA electrode and preparation method and application thereof | |
| CN108505083A (en) | A kind of addition modified manganese dioxide middle layer preparation titanium-based β-PbO2The method of anode | |
| CN113690455A (en) | Long-life anode electrode material and preparation method thereof | |
| CN114182307A (en) | Preparation method of noble metal anode for electrolytic copper foil | |
| CN114395757B (en) | Preparation method of multi-element oxide coating titanium anode plate | |
| CN106757248B (en) | The preparation facilities and method of lead dioxide electrode | |
| CN113716658B (en) | Preparation method of ruthenium, iridium and titanium ternary metal mesh electrode containing nano tip structure | |
| CN111137953A (en) | Preparation process of titanium-based tin iridium oxide coating electrode | |
| CN112663124B (en) | Preparation method of precious metal anode for horizontal electroplating of PCB | |
| CN113881962A (en) | Preparation method of high-conductivity Ir-Ta-Mn composite oxide coating anode | |
| CN112850787A (en) | Catalyst carrier for fuel cell, catalyst and preparation method thereof | |
| CN108155391A (en) | A kind of efficient nickel-base catalyst for promoting sodium borohydride direct oxidation | |
| CN114351179A (en) | Iridium tantalum manganese coating titanium anode plate with intermediate layer and preparation method thereof | |
| Liu et al. | Crystallization behavior-dependent electrocatalytic activity and stability of Ti/IrO2RuO2SiO2 anodes for oxygen evolution reaction | |
| CN110938856A (en) | Novel anodic oxidation process of nickel-based thin film energy storage material | |
| CN114164419B (en) | Method for preparing platinum active layer on anode plate by thermal decomposition method | |
| Xu et al. | Antimony doped tin oxide nanoparticles deposited onto Nb− TiO2 nanotubes for electrochemical degradation of bio‐refractory pollutions | |
| CN107723743B (en) | Preparation method of ternary composite oxide anode | |
| CN114318403B (en) | Method for preparing platinum monoatomic material by adopting alkyl imidazole ionic liquid | |
| CN106521610B (en) | A kind of hexavalent chromium plating combination Ni―Ti anode and preparation method thereof |
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 |