CN116905058A - Preparation method of titanium-based inert anode - Google Patents
Preparation method of titanium-based inert anode Download PDFInfo
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- CN116905058A CN116905058A CN202310682498.3A CN202310682498A CN116905058A CN 116905058 A CN116905058 A CN 116905058A CN 202310682498 A CN202310682498 A CN 202310682498A CN 116905058 A CN116905058 A CN 116905058A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000010936 titanium Substances 0.000 title claims abstract description 69
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 82
- 239000002184 metal Substances 0.000 claims abstract description 82
- 238000000576 coating method Methods 0.000 claims abstract description 67
- 239000011248 coating agent Substances 0.000 claims abstract description 65
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 238000004070 electrodeposition Methods 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 15
- 229910052718 tin Inorganic materials 0.000 claims description 15
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- AKEUNCKRJATALU-UHFFFAOYSA-N 2,6-dihydroxybenzoic acid Chemical compound OC(=O)C1=C(O)C=CC=C1O AKEUNCKRJATALU-UHFFFAOYSA-N 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- XDZAKVWAWKCHGM-UHFFFAOYSA-N 2,2-dimethyl-3-oxobutanedioic acid Chemical compound OC(=O)C(C)(C)C(=O)C(O)=O XDZAKVWAWKCHGM-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 238000010306 acid treatment Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- BZCOSCNPHJNQBP-UPHRSURJSA-N (z)-2,3-dihydroxybut-2-enedioic acid Chemical compound OC(=O)C(\O)=C(\O)C(O)=O BZCOSCNPHJNQBP-UPHRSURJSA-N 0.000 claims description 2
- XHWHHMNORMIBBB-UHFFFAOYSA-N 2,2,3,3-tetrahydroxybutanedioic acid Chemical compound OC(=O)C(O)(O)C(O)(O)C(O)=O XHWHHMNORMIBBB-UHFFFAOYSA-N 0.000 claims description 2
- VYWYYJYRVSBHJQ-UHFFFAOYSA-N 3,5-dinitrobenzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 VYWYYJYRVSBHJQ-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229960005215 dichloroacetic acid Drugs 0.000 claims description 2
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 44
- 229910045601 alloy Inorganic materials 0.000 description 20
- 239000000956 alloy Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 239000010953 base metal Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 230000001133 acceleration Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002346 layers by function Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- MINVSWONZWKMDC-UHFFFAOYSA-L mercuriooxysulfonyloxymercury Chemical compound [Hg+].[Hg+].[O-]S([O-])(=O)=O MINVSWONZWKMDC-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910000370 mercury sulfate Inorganic materials 0.000 description 1
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a preparation method of a titanium-based inert anode, which comprises the steps of carrying out first electrodeposition on the surface of a titanium substrate to obtain an electrode A containing a first metal coating, carrying out second electrodeposition on the surface of the electrode A to obtain an electrode B containing a double metal coating, soaking the electrode B in an acidified oxidant solution for reaction to obtain an electrode C with a metal oxide layer, and arranging a manganese dioxide layer on the surface of the electrode C to obtain the titanium-based inert anode. The titanium-based inert anode can be used as an inert anode in an acidic medium, and has the advantages of low oxygen evolution overpotential, long service life and the like.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a preparation method of a titanium-based inert anode.
Background
In the metal electrodeposition and other electrochemical industries, in order to reduce energy consumption and reduce the amount of electrodeposited productsThe development and adoption of lead-free anodes to replace lead-based anodes has been a general trend in terms of lead content to meet environmental requirements. Among lead-free anodes, titanium-based Dimensionally Stable Anodes (DSAs) are a type of electrode that is currently being studied in relatively large numbers. The electrode mainly uses titanium plate as base material, and the surface is coated with oxide containing platinum group metal and TiO 2 And (3) coating the active components and curing at high temperature. Due to RuO of the electrode surface 2 The active components have unique electronic conductivity and electrocatalytic activity, have obvious electrocatalytic performance on the precipitation of anodic oxygen, and can obviously reduce the precipitation potential of oxygen, thereby reducing the cell voltage in the processes of metal electrodeposition and the like, but the electrode has high preparation cost due to the need of coating noble metal oxide on the surface, and meanwhile, the service life and the like cannot completely meet the requirements of hydrometallurgy.
In order to reduce the preparation cost of the anode, in recent years, a great deal of research is carried out on preparing a functional layer on a titanium substrate by adopting base metal oxide to replace noble metal oxide at home and abroad. Due to MnO in the base metal oxide 2 、SnO 2 And PbO 2 And the like have better corrosion resistance and better electrocatalytic activity, are widely used as an active layer or an intermediate layer of an anode material, but most researches are carried out when preparing the oxide electrode, namely, preparing the intermediate layer or the surface active layer, a brush coating decomposable salt solution-thermal decomposition process is still adopted. In such electrodes, mnO on the titanium surface during processing and use is present due to the difference in lattice structure and coefficient of thermal expansion between the oxide and the titanium metal matrix 2 A large number of cracks can occur, resulting in the coating falling off and passivation of the titanium substrate.
To solve the problem, the main method is to use a titanium metal matrix and MnO 2 A middle oxide layer is brushed between the two layers. However, from the use effect, the problem of the falling-off of the surface active layer can only be relieved to a certain extent, but the electron transfer resistance between the surface functional layer and the base metal is also increased.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a titanium-based inert anode with long service life and high catalytic activity.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention relates to a preparation method of a titanium-based inert anode, which comprises the steps of carrying out first electrodeposition on the surface of a titanium substrate to obtain an electrode A containing a first metal coating, carrying out second electrodeposition on the surface of the electrode A to obtain an electrode B of a double metal coating, soaking the electrode B in an acidified oxidant solution for reaction to obtain an electrode C with a metal oxide layer, and arranging a manganese dioxide layer on the surface of the electrode C to obtain the titanium-based inert anode.
According to the preparation method, two metal coatings are electrodeposited on a titanium substrate in sequence, the second metal coating is oxidized in situ and then serves as an intermediate layer of an inert anode, and finally, the active manganese dioxide layer is coated on the surface of the electrode with the intermediate oxide layer, so that the titanium-based inert anode with good electronic conductivity and electrocatalytic activity and good combination among the functional layer, the intermediate layer and the metal substrate is obtained.
Preferably, the titanium substrate is subjected to surface acid treatment prior to the acid solution.
The titanium substrate with pitting surface is obtained by carrying out surface acid treatment on the titanium substrate in an acid solution, so that the binding force between the subsequent plating layer and the titanium substrate is increased.
Further preferably, the acid solution is one or more of dihydroxytartaric acid, maleic acid, dimethyloxaloacetic acid, dihydroxymaleic acid, oxalic acid, dichloroacetic acid, dinitrobenzoic acid, 2-ethylmalonic acid, 2, 6-dihydroxybenzoic acid; in the acid solution, H + The concentration of (C) is 0.1 to 1mol/L, preferably 0.1 to 0.50mol/L.
Preferably, the metal in the first metal coating layer is at least one selected from nickel, cobalt and copper metal, and contains nickel, and the mass fraction of the nickel in the first metal coating layer is 70-100%, preferably 80-90%.
The first metal coating contains nickel, and the nickel content is required to be more than 70%, and the nickel is mainly good in combination property with titanium and tin, so that the combination property of the first metal coating and the second metal coating with a matrix is improved; the nickel coating is doped with cobalt and copper alloy components to improve the corrosion resistance of the metal layer, so that the aim of jointly protecting the base metal with the intermediate layer is fulfilled.
Preferably, the thickness of the first metal coating layer is 1-30 μm, preferably 3-15 μm. The inventor finds that the thickness of the first metal coating is controlled within the range, the performance of the finally obtained anode is optimal, and if the thickness of the first metal coating is too thin, the first metal coating can hardly achieve the purposes of improving the bonding performance of each metal layer and the matrix and protecting the matrix metal; the excessively thick first alloy coating is easy to crack and even the coating is brittle and falls off from the substrate.
Preferably, the metal in the second metal coating layer is selected from at least one of tin, antimony, bismuth, nickel and cobalt, and comprises tin, and the mass fraction of the tin in the second metal coating layer is 80-100%, preferably 90-98%.
In the invention, the tin content in the second metal coating is more than 80 percent, and the tin content is mainly characterized in that the second metal coating can be converted into SnO with semiconductor property after being fully oxidized 2 The metal such as antimony, bismuth, nickel and cobalt is oxidized and then converted into SnO 2 Increasing SnO 2 And the electron conductivity of the carrier is improved.
Preferably, the thickness of the second metal coating layer is 10-100 μm, preferably 10-60 μm, more preferably 10-20 μm.
In the invention, the thickness of the second metal coating is controlled within the range, the anode performance is optimal, the purpose of protecting the first coating metal and the base metal cannot be met after the second metal coating which is too thin is oxidized, and an excessively thick intermediate oxide semiconductor layer is formed after the second metal coating is oxidized, so that the electronic conductivity of the whole electrode is affected.
In a preferred scheme, in the acidified oxidant solution, the oxidant is at least one selected from potassium permanganate solution, potassium dichromate solution and sodium persulfate, and the acid is at least one selected from sulfuric acid, hydrochloric acid and nitric acid.
Further preferably, in the acidified oxidant solution, the concentration of oxidantThe degree is 0.02 to 0.5mol/L, preferably 0.05 to 0.2mol/L, H + Is at a concentration of 10 -5 About 1mol/L, preferably 10 -5 ～0.1mol/L。
In a preferred scheme, the electrode B is soaked in an acidified oxidant solution for reaction for more than or equal to 20 hours.
The inventors found that immersing electrode B in an acidified oxidant solution for a period of time of 20 hours or more resulted in sufficient conversion of the second metal coating to metal oxide.
Preferably, electrode C is placed in a manganese-containing solution to grow a manganese dioxide layer by cathodic reduction or anodic oxidation.
In the preferred scheme, manganese nitrate solution is uniformly coated on the surface of an electrode C to obtain a manganese nitrate coating, then the manganese nitrate coating is converted into a manganese dioxide layer by heat treatment at 300-600 ℃, preferably 300-400 ℃, and the coating-heat treatment is repeated for 10-20 times to obtain the titanium-based inert anode.
Further preferably, in the manganese nitrate solution, the mass fraction of manganese nitrate is 30% -50%.
Advantageous effects
The invention provides a method for preparing a titanium-based inert anode, which mainly comprises the steps of electrodepositing two metal coatings on a titanium substrate, oxidizing a second metal coating in situ to serve as an intermediate layer of the inert anode, and finally coating an active manganese dioxide layer on the surface of an electrode with an intermediate oxide layer to obtain the titanium-based inert anode with good electronic conductivity and electrocatalytic activity, wherein the functional layer, the intermediate layer and the metal substrate are well combined.
Compared with the existing preparation process, the technical thought and the process principle of the invention have obvious characteristics and technical advantages, and are specifically expressed in:
(1) The invention provides that two metal/alloy layers are firstly electroplated on the surface of a titanium matrix through electrodeposition, wherein the first metal layer has good corrosion resistance and can be matched with the expansion and contraction performance between the second metal layer and the titanium matrix in the process of converting the second metal layer into oxide and using the oxide, so that firm combination performance between the middle oxide layer and the metal matrix is ensured, and the titanium matrix is prevented from being corroded or passivated when the outer oxide layer is damaged;
(2) The intermediate oxide layer of the inert electrode is obtained through the second metal coating obtained through in-situ oxidation electrodeposition, so that the tight combination property between the intermediate layer and the first metal coating can be ensured, meanwhile, the composition of the second metal layer can be adjusted, the intermediate oxide obtained after oxidation is doped oxide, and the concentration of carriers in an oxide semiconductor is improved, so that the electron conductivity of the oxide semiconductor is improved;
(3) The intermediate oxide layer of the titanium-based inert anode prepared by the method can avoid repeated solution/sol brush coating-thermal decomposition process, so that the preparation process is simple and is beneficial to reducing energy consumption.
Drawings
FIG. 1 is a graph of linear voltammetric scans of a titanium-based inert anode prepared using an embodiment of the present invention, from which the oxygen evolution potential of the electrode material can be calculated.
FIG. 2 is a graph showing constant current polarization of a titanium-based inert anode prepared according to example I of the present invention, from which accelerated lifetime of the electrode material can be obtained.
Detailed Description
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
The various reagents and materials used in the present invention are commercially available or may be prepared by known methods unless otherwise specified.
The specific embodiments of the present invention are as follows:
example 1
The titanium sheet was cut into a shape having an area of 10X 50mm as an electrode substrate, and the surface oxide layer was polished off, washed with sodium hydroxide and absolute ethyl alcohol in this order, and then dried. And (3) placing the treated titanium sheet in 0.1mol/L oxalic acid solution, boiling for 1h, and etching the surface of the titanium sheet into pitted surfaces.
At the siteThe surface of the treated titanium sheet is reserved with a working area of 10 multiplied by 10mm, and the rest parts are subjected to insulation treatment. The titanium sheet is used as a cathode, the platinum sheet electrode is used as an anode, and the anode contains Ni 2+ 0.5mol/L、Co 2+ Electrodepositing in 0.08mol/L sulfate plating solution with cathode current density of 5mA/cm 2 Taking out and cleaning after 15 minutes of deposition to obtain an electrode with a first metal/alloy coating, and using SnSO 4 0.3mol/L、BiCl 3 Electrodepositing with 0.02 mol/plating solution as electrolyte, and cathode current density of 5mA/cm 2 The deposition time was 10 minutes, resulting in an electrode with a second metal/alloy coating. Analyzing the alloy layer by using SEM and EDS, wherein the thickness of the first metal/alloy coating is 3.8 micrometers, and the mass percentage of nickel and cobalt is 88% and 12% respectively; the thickness of the second metal/alloy coating was 10.4 microns, with tin and bismuth being 94% and 6% by mass, respectively.
The electrode was immersed in a potassium permanganate solution (sulfuric acid-containing 0.05 mol/L) of 0.05mol/L for 20 hours, and then taken out for washing and drying.
And uniformly coating 50% manganese nitrate solution on the surface of the electrode, performing heat treatment at 300 ℃ for 30min, and repeating 10 times to obtain the electrode with the tin dioxide intermediate layer and the manganese dioxide surface layer.
At 1mol/L Na 2 SO 4 ，0.25mol/L H 2 SO 4 The prepared titanium-based manganese dioxide inert electrode is used as a working electrode, a titanium mesh is used as a counter electrode, a mercury/mercurous sulfate electrode is used as a reference electrode to form a three-electrode system, a linear volt-ampere scanning test is carried out, the potential range is 0.6-1.4V, the scanning speed is 2mV/s, and the obtained result is shown in figure 1. From this curve, an oxygen evolution current of 10mA/cm was calculated 2 The oxygen evolution overpotential of the electrode was 483mV.
At 0.5mol/L H 2 SO 4 The prepared titanium-based inert anode is a working electrode, and the titanium mesh is a counter electrode, so that a two-electrode system is formed, constant-current polarization reinforcement life test is carried out, and the current density is 250mA/cm 2 The resulting constant current polarization curve is shown in figure 2. The acceleration lifetime of the electrode was found to be 76.3h from this curve.
Example two
The procedure is as in example one, except that maleic acid is used instead of oxalic acid, the acid concentration is 0.5mol/L, cu is used 2+ Instead of Co 2+ ,Cu 2+ The concentration is 0.05mol/L, sbCl 3 Replacing BiCl 3 ,SbCl 3 The concentration was 0.01mol/L, the time for electrodepositing the first metal/alloy coating was 55 minutes, the time for electrodepositing the second metal/alloy coating was 20 minutes, sodium persulfate was used in place of potassium permanganate, and the sodium persulfate concentration was 0.2mol/L (sulfuric acid containing 0.025 mol/L). The thickness of the first metal/alloy coating was measured to be 14.3 microns, wherein the mass percentages of nickel and copper were 81% and 19%, respectively; the thickness of the second metal/alloy coating is 20.5 micrometers, wherein the mass percentages of tin and antimony are 98 percent and 2 percent respectively; the oxygen evolution overpotential of the titanium-based inert anode is 598mV, and the accelerated life is 80.4h.
Example III
The procedure is as in example one, except that dimethyl oxaloacetic acid is used instead of oxalic acid, the acid concentration is 0.3mol/L, co 2+ At a concentration of 0.1mol/L with CoCl 2 Replacing BiCl 3 And CoCl 2 The concentration was 0.04mol/, the time for electrodepositing the first metal/alloy coating was 30 minutes, the time for electrodepositing the second metal/alloy coating was 15 minutes, potassium dichromate was used in place of potassium permanganate, and the concentration of potassium dichromate was 0.1mol/L (pH was adjusted to 5 with sulfuric acid). The thickness of the first metal/alloy coating was measured to be 9.2 microns, wherein the mass percentages of nickel and cobalt were 86% and 14%, respectively; the thickness of the second metal/alloy coating is 16.3 microns, wherein the mass percentages of tin and cobalt are 91% and 9% respectively; the oxygen evolution overpotential of the titanium-based inert anode is 510mV, and the acceleration life is 76.8h.
Example IV
The procedure is as in example one, except that NiCl is used 2 Replacing BiCl 3 And NiCl 2 The concentration is 0.02mol/L, the time for electrodepositing the first metal/alloy coating is 20 minutes, the time for electrodepositing the second metal/alloy coating is 12 minutes, the obtained electrode with the intermediate oxide layer is used as a working electrode, the platinum sheet electrode is used as a counter electrode, and the surface II is obtained by cathodic electrodeposition in 0.1mol/L potassium permanganate solutionA manganese oxide active layer with a current density of 5mA/cm 2 The deposition time was 10 minutes. The thickness of the first metal/alloy coating was measured to be 4.3 microns, wherein the mass percentages of nickel and cobalt are 88% and 12% respectively; the thickness of the second metal/alloy coating is 11.8 micrometers, wherein the mass percentages of tin and nickel are 95% and 5%, respectively; the oxygen evolution overpotential of the titanium-based inert anode is 588mV, and the accelerated lifetime is 77.1h.
Comparative example one
The titanium sheet was cut into a shape having an area of 10X 50mm as an electrode substrate, and the surface oxide layer was polished off, washed with sodium hydroxide and absolute ethyl alcohol in this order, and then dried. And (3) placing the treated titanium sheet in 0.1mol/L oxalic acid solution, boiling for 1h, and etching the surface of the titanium sheet into pitted surfaces.
The mass ratio of citric acid, glycol and stannic chloride is 1:5:0.5, uniformly coating the prepared solution on the titanium sheet, drying at 75 ℃ and then decomposing for 10 minutes at 450 ℃, repeating the operation for 10 times, wherein the last decomposition time is 1 hour, obtaining a tin dioxide intermediate layer on the titanium substrate, and measuring the thickness of the intermediate layer by SEM (scanning electron microscope) to be 31.8 microns.
And uniformly smearing 50% manganese nitrate solution on the middle layer of the titanium matrix, and performing heat treatment at 300 ℃ for 30min and repeating 10 times to obtain the electrode with the tin dioxide middle layer and the manganese dioxide surface layer. The test method of example one was used to conduct linear voltammetry scanning and enhanced lifetime test on the electrodeposit to determine that the oxygen evolution overpotential of the titanium-based inert anode was 667mV and the accelerated lifetime was 38.5h
Comparative example two
The procedure was as in example one except that the second metal coating was electrodeposited for 5 minutes, the thickness of the second metal/alloy coating was measured to be 4.8 microns, wherein the mass percent of tin and bismuth were 92% and 8%, respectively; the oxygen evolution overpotential of the titanium-based inert anode is 558mV, and the acceleration life is 42.1h.
Comparative example three
The procedure was as in example one except that the second metal deposit was electrodeposited for 60 minutes, the thickness of the second metal deposit was measured to be 62.4 microns, wherein the mass percentages of tin and bismuth were 93% and 7%, respectively; the oxygen evolution overpotential of the titanium-based inert anode is 687mV, and the accelerated life is 80.1h.
Comparative example four
The procedure was as in example one except that the time for electrodepositing the first metal coating was 5 minutes, the thickness of the first metal coating was measured to be about 2 microns, and a portion of the surface had a discontinuous porous morphology; the oxygen evolution overpotential of the titanium-based inert anode is 558mV, and the acceleration life is 32.4h.
Claims (10)
1. A preparation method of a titanium-based inert anode is characterized by comprising the following steps: and (3) performing first electrodeposition on the surface of the titanium substrate to obtain an electrode A containing the first metal coating, performing second electrodeposition on the surface of the electrode A to obtain an electrode B containing the double metal coating, soaking the electrode B in an acidified oxidant solution for reaction to obtain an electrode C with a metal oxide layer, and arranging a manganese dioxide layer on the surface of the electrode C to obtain the titanium-based inert anode.
2. The method for preparing a titanium-based inert anode according to claim 1, wherein: the titanium matrix is subjected to surface acid treatment in advance of an acid solution;
the acid solution is more than one of dihydroxytartaric acid, maleic acid, dimethyl oxaloacetic acid, dihydroxymaleic acid, oxalic acid, dichloroacetic acid, dinitrobenzoic acid, 2-ethylmalonic acid, 2, 6 dihydroxybenzoic acid; in the acid solution, H + The concentration of (C) is 0.1 to 1mol/L, preferably 0.1 to 0.50mol/L.
3. The method for preparing a titanium-based inert anode according to claim 1, wherein: the metal in the first metal coating is selected from at least one of nickel, cobalt and copper metal, and comprises nickel, wherein the mass fraction of the nickel in the first metal coating is 70-100%.
4. A process for the preparation of a titanium-based inert anode according to claim 1 or 3, characterized in that: the thickness of the first metal coating is 1-30 mu m.
5. The method for preparing a titanium-based inert anode according to claim 1, wherein: the metal in the second metal coating is selected from at least one of tin, antimony, bismuth, nickel and cobalt, and comprises tin, wherein the mass fraction of the tin in the second metal coating is 80-100%.
6. The method for preparing a titanium-based inert anode according to claim 1, wherein: the thickness of the second metal coating is 10-100 mu m.
7. The method for preparing a titanium-based inert anode according to claim 1, wherein: the oxidant in the acidified oxidant solution is at least one selected from potassium permanganate solution, potassium dichromate solution and sodium persulfate, and the acid is at least one selected from sulfuric acid, hydrochloric acid and nitric acid
In the acidified oxidant solution, the concentration of the oxidant is 0.02-0.5 mol/L.
8. The method for preparing a titanium-based inert anode according to claim 1, wherein: and immersing the electrode B in the acidified oxidant solution, and reacting for more than or equal to 20 hours.
9. The method for preparing a titanium-based inert anode according to claim 1, wherein: electrode C is placed in a manganese-containing solution and a manganese dioxide layer is grown by cathodic reduction or anodic oxidation.
10. The method for preparing a titanium-based inert anode according to claim 1, wherein: uniformly coating a manganese nitrate solution on the surface of an electrode C to obtain a manganese nitrate coating, then performing heat treatment at 300-600 ℃ to convert the manganese nitrate coating into a manganese dioxide layer, and repeatedly coating and performing heat treatment for 10-20 times to obtain a titanium-based inert anode;
in the manganese nitrate solution, the mass fraction of the manganese nitrate is 30% -50%.
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