CN116641044A - Copper electrodeposition coating titanium anode and preparation method and application thereof - Google Patents
Copper electrodeposition coating titanium anode and preparation method and application thereof Download PDFInfo
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- CN116641044A CN116641044A CN202310438177.9A CN202310438177A CN116641044A CN 116641044 A CN116641044 A CN 116641044A CN 202310438177 A CN202310438177 A CN 202310438177A CN 116641044 A CN116641044 A CN 116641044A
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- titanium
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- strontium
- copper
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 223
- 239000010936 titanium Substances 0.000 title claims abstract description 223
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 223
- 238000000576 coating method Methods 0.000 title claims abstract description 164
- 239000011248 coating agent Substances 0.000 title claims abstract description 156
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000010949 copper Substances 0.000 title claims abstract description 88
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000004070 electrodeposition Methods 0.000 title claims description 10
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 59
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000758 substrate Substances 0.000 claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 22
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 230000001680 brushing effect Effects 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 5
- 238000005530 etching Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 229910004116 SrO 2 Inorganic materials 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 25
- 238000004321 preservation Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 34
- 239000002184 metal Substances 0.000 description 34
- -1 iridium tantalum strontium oxide copper Chemical compound 0.000 description 29
- 238000007792 addition Methods 0.000 description 26
- 230000003197 catalytic effect Effects 0.000 description 15
- 238000010586 diagram Methods 0.000 description 15
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 15
- 239000011889 copper foil Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000002659 electrodeposit Substances 0.000 description 3
- ULFQGKXWKFZMLH-UHFFFAOYSA-N iridium tantalum Chemical compound [Ta].[Ir] ULFQGKXWKFZMLH-UHFFFAOYSA-N 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000001453 impedance spectrum Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VONLASUMRVUZLY-UHFFFAOYSA-N [Ir].[Ti].[Ta] Chemical compound [Ir].[Ti].[Ta] VONLASUMRVUZLY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- JVOQKOIQWNPOMI-UHFFFAOYSA-N ethanol;tantalum Chemical compound [Ta].CCO JVOQKOIQWNPOMI-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000001075 voltammogram 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- 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
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/08—Etching of refractory metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a copper electrodeposited coating titanium anode and a preparation method and application thereof, wherein the preparation method comprises the following steps: iridium source compound, tantalum source compound and strontium source compound are prepared according to Ir: ta: sr= (70-x): 30: adding the mole percentage of x into organic alcohol, and preparing coating liquid after ultrasonic dispersion; brushing the coating liquid on the surface of the rough titanium substrate, and then baking to obtain a dry titanium substrate; heating the dry titanium substrate to 400-600 ℃ in an air atmosphere, and preserving heat for a first preset time to finish the coating of the primary coating; and (3) after repeated coating for a plurality of times, placing the titanium substrate coated for the last time in a muffle furnace, and heating to 400-600 ℃ in an air atmosphere for heat preservation for a second preset time to obtain the copper electrodeposited coating titanium anode. According to the invention, strontium is added into the coating liquid, iridium with equivalent molar mass is reduced, the electrocatalytic activity of the prepared copper electrodeposited coating titanium anode is improved when the molar mass ratio of strontium addition is 10%, and the voltammetric electric quantity is increased along with the increase of the strontium addition.
Description
Technical Field
The invention relates to the technical field of titanium anodes, in particular to a copper electrodeposited coating titanium anode and a preparation method and application thereof.
Background
The titanium anode comprises a titanium substrate serving as a current collector and an oxide coating which plays a role in catalytic activity, and the performance of the copper electrodeposited anode in electrolytic copper foil, electronic copper plating, copper electrodeposited recovery and the like is closely related to the surface morphology structure, coating components and the like of the substrate. Titanium anodes generally have electrocatalytic activity derived from surface mixed oxides, but since titanium substrates are easily corroded by acidic electrolytes, active oxide coatings are required to have high stability in addition to good catalytic activity.
Most of the research on insoluble anodes in acidic copper electrodeposition systems is carried out around noble metals iridium and ruthenium, but in order to control the cost and facilitate commercialization and popularization, the reduction of the noble metal content and the cost of the coating is very important. In an acidic electrolyte, electrocatalytically active RuO 2 >IrO 2 But IrO in stability 2 >RuO 2 . Therefore, when preparing the titanium anode, researchers often find a proper proportion of iridium oxide to ruthenium oxide on one hand; on the other hand, researchers have sought to add new oxide components while taking iridium oxide as the primary active material to increase their catalytic activity while controlling costs. The addition of inert components to the coating can even function to increase its service life in high current density or high temperature operating environments. Therefore, the preparation of the multi-element oxide coating has high research value whether to improve the catalytic activity and the service life or reduce the cost of the coating.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the defects in the prior art, the invention aims to provide a copper electrodeposited coating titanium anode and a preparation method and application thereof, and aims to solve the problems of poor electrocatalytic activity, poor stability, high cost and the like of the conventional copper electrodeposited coating titanium anode.
The technical scheme of the invention is as follows:
a method for preparing a titanium anode with a copper electrodeposition coating, comprising the following steps:
etching the initial titanium sheet to obtain a rough titanium substrate;
iridium source compound, tantalum source compound and strontium source compound are prepared according to Ir: ta: sr= (70-x): 30: adding the mole percentage of x into organic alcohol, and carrying out ultrasonic dispersion to obtain coating liquid, wherein x is more than or equal to 10 and less than or equal to 15;
uniformly brushing the coating liquid on the surface of the rough titanium substrate, and then baking to obtain a dry titanium substrate;
transferring the dry titanium substrate into a muffle furnace, heating to 400-600 ℃ in an air atmosphere, and preserving heat for a first preset time to finish the coating of a primary coating;
repeating the coating for several times, placing the titanium substrate coated for the last time in a muffle furnace, heating to 400-600 ℃ under the air atmosphere, and preserving heat for a second preset time to obtain the IrO (Infrared radiation) surface coating 2 -Ta 2 O 5 -SrO 2 A copper electrodeposited coated titanium anode.
The preparation method of the copper electrodeposited coating titanium anode comprises the following steps of 2 IrCl 6 ·6H 2 O, wherein the tantalum source compound is tantalum ethoxide, the strontium source compound is strontium acetate, and the organic alcohol is one or more of n-butanol, ethanol and propanol.
The preparation method of the copper electrodeposited coating titanium anode comprises the steps of uniformly brushing the coating liquid on the surface of the rough titanium substrate, and then baking the coating liquid, wherein the preparation method comprises the following steps:
dipping the coating liquid by a brush, uniformly brushing the coating liquid on the surface of the rough titanium substrate, and baking the brushed rough titanium substrate under an infrared lamp for 30 seconds to remove most of the solvent;
and then placing the brushed rough titanium substrate in a drying box at 100 ℃ for fully drying for 10min to obtain the dry titanium substrate.
The preparation method of the copper electrodeposited coating titanium anode comprises the steps of enabling the first preset time to be 10min and enabling the second preset time to be 60min.
The preparation method of the copper electrodeposited coating titanium anode comprises the steps of performing etching treatment on an initial titanium sheet to obtain a rough titanium substrate, wherein the preparation method comprises the following steps:
cutting the initial titanium sheet, and then performing alkali washing and degreasing treatment to obtain a cut titanium sheet;
NaBr is used as electrolyte, the cut titanium sheet is used as a working electrode, an initial titanium sheet is used as a counter electrode to form a double-electrode system, the double-electrode system is electrified, and a constant current of 180mA cm is used first -2 Etching the cut titanium sheet once, and then carrying out constant current of 500 mA.cm -2 And (3) performing secondary etching on the cut titanium sheet to obtain the coarse titanium substrate.
The preparation method of the copper electrodeposited coating titanium anode comprises the steps of cutting an initial titanium sheet, and then performing alkaline washing oil removal treatment, wherein the preparation method comprises the following steps:
na is mixed with 3 PO 4 ·12H 2 O、Na 2 CO 3 NaOH is dissolved in deionized water according to the mass ratio of 105:25:4 to prepare 0.3% alkali wash oil liquid, and the alkali wash oil liquid is heated to be boiled for standby;
cutting an initial titanium sheet, adding the cut initial titanium sheet into boiling alkaline washing oil liquid, and keeping for a preset time;
and taking out the initial titanium sheet, flushing with deionized water, and performing ultrasonic cleaning treatment in the deionized water to complete the alkaline cleaning process, so as to obtain the cut titanium sheet.
The invention relates to a copper electrodeposited coating titanium anode, which is prepared by adopting the preparation method of the copper electrodeposited coating titanium anode.
The invention relates to an application of a copper electrodeposited coating titanium anode, wherein the copper electrodeposited coating titanium anode is used for electrolytic copper foil or wastewater treatment.
The beneficial effects are that: the invention introduces metallic strontium into the coating liquid, reduces the usage amount of noble metal iridium according to the same proportion, and prepares IrO 2 -Ta 2 O 5 -SrO 2 Copper electrodeposited coated titanium anode and comparative wherein Ir: sr=70: 0. ir: sr=65: 5. ir:sr=60: 10. ir: sr=55: 15 The electrochemical performance, phase morphology analysis and the like of the titanium anode in equal proportion (mol%) lead to the following conclusion: the comparative electrochemical performance test shows that the electrochemical performance is similar to that at 0% when the strontium addition is 5%, whereas the IrO is 10% when the strontium addition is 5% 2 -Ta 2 O 5 -SrO 2 The titanium anode with copper electrodeposited coating can obtain specific IrO 2 -Ta 2 O 5 The better catalytic activity of the copper electrodeposited coating titanium anode is deduced by combining an SEM image and an electrochemical test, and the addition of strontium is favorable for the increase of the surface active sites of the copper electrodeposited coating titanium anode, so that the real area of the copper electrodeposited coating titanium anode is increased, and the electrocatalytic activity of the copper electrodeposited coating titanium anode is improved.
Drawings
FIG. 1 is a flow chart of a method for preparing a titanium anode with a copper electrodeposit coating according to the present invention.
A, b, c, d in FIG. 2 is a SEM topography of the surface of a titanium anode of a copper electrodeposited coating with 0%, 5%, 10%, 15% (mol%) strontium added, respectively.
FIG. 3 is an EDS diagram of a titanium anode with a 10% strontium mole ratio iridium tantalum strontium oxide copper electrodeposited coating, wherein b-e are elemental profiles.
FIG. 4 is a XRD pattern for a titanium anode of a copper electrodeposited coating of iridium tantalum strontium oxide with different metal molar ratios.
Fig. 5a is a LSV activity graph of titanium anodes with iridium tantalum strontium oxide copper electrodeposited coatings with different metal molar ratios, and b is a tafel graph of titanium anodes with iridium tantalum strontium oxide copper electrodeposited coatings with different metal molar ratios.
Fig. 6 a is a CV graph of titanium anodes with iridium tantalum strontium oxide copper electrodeposited coatings with different metal molar ratios, and b is a cyclic voltammetry charge graph of titanium anodes with iridium tantalum strontium oxide copper electrodeposited coatings with different metal molar ratios.
FIG. 7 is a graph of the chronoamperometric current of a copper electrodeposited coating titanium anode of iridium tantalum strontium oxide with varying metal molar ratios.
Fig. 8 a is an EIS diagram of an iridium tantalum strontium oxide copper electrodeposited coating titanium anode with different metal molar ratios, and b is an EIS fitting diagram and an equivalent circuit diagram of the iridium tantalum strontium copper electrodeposited coating titanium anode with a strontium addition of 10%.
FIG. 9 is a graph showing the cell pressure of Ir-Ta-Sr oxide copper electrodeposited coated titanium anodes with varying metal mole ratios as a function of electrolysis time.
FIG. 10 is a bar graph of enhanced electrolytic life of iridium tantalum strontium oxide copper electrodeposited coated titanium anodes with varying metal molar ratios.
In FIG. 11, a is a failure chart of the Sr0/Ir70 electrode, b is a failure chart of the Sr5/Ir65 electrode, c is a failure chart of the Sr10/Ir60 electrode, and d is a failure chart of the Sr15/Ir55 electrode.
In fig. 12, a is a bonding surface micro-morphology diagram of a pure titanium cathode, and b is a surface micro-morphology diagram of grain growth in solution.
Fig. 13 is a stress-strain curve of the electrolytic copper foil.
Detailed Description
The invention provides a copper electrodeposited coating titanium anode and a preparation method and application thereof, and the invention is further described in detail below for making the purpose, technical scheme and effect of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
FIG. 1 is a flow chart of a method for preparing a titanium anode with a copper electrodeposition coating, which comprises the following steps:
s10, performing electrochemical etching treatment on an initial titanium sheet to obtain a rough titanium substrate;
s20, iridium source compound, tantalum source compound and strontium source compound are prepared according to Ir: ta: sr= (70-x): 30: adding the mole percentage of x into organic alcohol, and carrying out ultrasonic dispersion to obtain coating liquid, wherein x is more than or equal to 10 and less than or equal to 15;
s30, uniformly brushing the coating liquid on the surface of the rough titanium substrate, and then baking to obtain a dry titanium substrate;
s40, transferring the dry titanium substrate into a muffle furnace, heating to 400-600 ℃ under an air atmosphere, and preserving heat for a first preset time to finish the coating of a primary coating;
s50, repeating the coating for several timesThen, the titanium substrate coated for the last time is placed in a muffle furnace, and is heated to 400-600 ℃ for heat preservation for a second preset time in the air atmosphere, and the surface coating is IrO 2 -Ta 2 O 5 -SrO 2 A copper electrodeposited coated titanium anode.
In this example, in order to reduce the amount of noble iridium used, a certain molar mass of strontium was added to the coating solution based on the iridium tantalum coating oxide anode, and the equivalent molar mass of iridium was reduced. Preliminary studies have found that IrO prepared by thermal decomposition 2 -Ta 2 O 5 -SrO 2 The electrocatalytic activity of the titanium anode with the copper electrodeposited coating is improved when the molar mass ratio of strontium addition is 10 percent, and the voltammetric electric quantity of the titanium anode with the increase of the strontium addition is also increased.
Specifically, the embodiment prepares IrO by introducing strontium metal into the coating liquid and reducing the use amount of iridium noble metal according to the same proportion 2 -Ta 2 O 5 -SrO 2 Copper electrodeposited coated titanium anode and comparative wherein Ir: sr=70: 0. ir: sr=65: 5. ir: sr=60: 10. ir: sr=55: 15 The electrochemical performance, phase morphology analysis and the like of the titanium anode in equal proportion (mol%) lead to the following conclusion: the comparative electrochemical performance test shows that the electrochemical performance is similar to that at 0% when the strontium addition is 5%, whereas the IrO is 10% when the strontium addition is 5% 2 -Ta 2 O 5 -SrO 2 The titanium anode with copper electrodeposited coating can obtain specific IrO 2 -Ta 2 O 5 The better catalytic activity of the copper electrodeposited coating titanium anode is deduced by combining an SEM image and an electrochemical test, and the addition of strontium is favorable for the increase of the surface active sites of the copper electrodeposited coating titanium anode, so that the real area of the copper electrodeposited coating titanium anode is increased, and the electrocatalytic activity of the copper electrodeposited coating titanium anode is improved.
In some embodiments, the iridium source compound is H 2 IrCl 6 ·6H 2 O, wherein the tantalum source compound is tantalum ethoxide, the strontium source compound is strontium acetate, and the organic alcohol is one or more of n-butanol, ethanol and propanol.
In some embodiments, the baking treatment is performed after the coating liquid is uniformly brushed on the surface of the rough titanium substrate, and the baking treatment comprises the following steps: dipping the coating liquid by a brush, uniformly brushing the coating liquid on the surface of the rough titanium substrate, and baking the brushed rough titanium substrate under an infrared lamp for 30 seconds to remove most of the solvent; and then placing the brushed rough titanium substrate in a drying box at 100 ℃ for fully drying for 10min to obtain the dry titanium substrate.
In some embodiments, the first predetermined time is 10 minutes and the second predetermined time is 60 minutes.
In some embodiments, the electrochemical etching treatment is performed on the initial titanium sheet to obtain a rough titanium substrate, including: cutting the initial titanium sheet, and then performing alkali washing and degreasing treatment to obtain a cut titanium sheet; naBr is used as electrolyte, the cut titanium sheet is used as a working electrode, an initial titanium sheet is used as a counter electrode to form a double-electrode system, the double-electrode system is electrified, and a constant current of 180mA cm is used first -2 Etching the cut titanium sheet once, and then carrying out constant current of 500 mA.cm -2 And (3) performing secondary etching on the cut titanium sheet to obtain the coarse titanium substrate.
In this embodiment, the alkaline washing degreasing treatment is performed after the initial titanium sheet is cut, and includes: na is mixed with 3 PO 4 ·12H 2 O、Na 2 CO 3 NaOH is dissolved in deionized water according to the mass ratio of 105:25:4 to prepare 0.3% alkali wash oil liquid, and the alkali wash oil liquid is heated to be boiled for standby; cutting an initial titanium sheet, adding the cut initial titanium sheet into boiling alkaline washing oil liquid, and keeping for a preset time; and taking out the initial titanium sheet, flushing with deionized water, and performing ultrasonic cleaning treatment in the deionized water to complete the alkaline cleaning process, so as to obtain the cut titanium sheet.
The rough titanium substrate obtained by electrochemical etching has higher electrocatalytic activity and electrochemical active area under the condition of the same active oxide load; through the experiment of the enhanced electrolytic life and the electrode failure graph, the service life of the electrode is directly influenced by proper etching, wherein the large hilly fluctuation and high roughness of the EE electrode surface can keep longer enhanced electrolytic life, which proves that the electrochemical etching is more beneficial to the adhesion of the coating and the stability of the electrode.
In some embodiments, there is also provided a copper electrodeposited coated titanium anode made using the method of making a copper electrodeposited coated titanium anode of the present invention.
In some embodiments, there is also provided the use of a copper electrodeposited coated titanium anode, wherein the copper electrodeposited coated titanium anode of the present invention is used for the electrolysis of copper.
Specifically, the electrolytic copper plating solution mainly comprises a base plating solution, which is generally composed of copper sulfate and sulfuric acid, and an additive mainly comprising an inorganic additive (Cl - ) And organic additives (levelers, accelerators, suppressors), the plating environment of strong acids requires development of high performance stable anode materials; the electric energy efficiency in the copper electroplating process is very low and is generally difficult to exceed 40%, and the application of the titanium anode with the copper electrodeposit coating can improve the electric energy efficiency and the performance of the copper electroplating.
The invention is further illustrated by the following examples:
example 1
The preparation of the titanium anode with the copper electrodeposition coating comprises the following steps:
a rough titanium substrate: the electrochemical etching adopts 1 mol.L -1 NaBr is used as electrolyte, and an intelligent N8352D direct current power supply is adopted as a power supply; the cut titanium sheet is used as a working electrode, a double-electrode system consisting of large-area titanium sheets is adopted as a counter electrode, and the magnetic stirring speed is 800rpm; the constant current is 180mA cm -2 After a period of time, 500 mA.cm is adopted -2 After etching for a period of time, completing two sections of electric etching; removing flocculent impurities on the surface by using an ultrasonic cleaner, and then adopting acid etching solution (1% HF+10% HNO) 3 ) Washing for 1-2 min, washing with deionized water for 3-4 times, washing with ethanol for one time, and storing the washed coarse titanium substrate in absolute ethanol for later use;
copper electrodeposited coating titanium anode: the tantalum source of the coating liquid adopts ethanol tantalum solution, and the iridium source adopts H 2 IrCl 6 ·6H 2 The O, strontium source adopts strontium nitrate and the solvent adoptsN-butanol, configured into Ir according to a certain proportion: ta: sr= (70-x): 30: x (mol%) coating liquid is subjected to ultrasonic dispersion for 60min for standby; preparing an iridium tantalum strontium ternary oxide copper electrodeposition coating titanium anode by using the particle-free coating liquid and the titanium substrate prepared by electrochemical etching, firstly taking out the roughened titanium substrate from absolute ethyl alcohol, and drying absolute ethyl alcohol remained on the surface of the titanium substrate; dipping the coating liquid by a brush, uniformly brushing the coating liquid on the surface of a titanium substrate, immediately baking the brushed titanium sheet under an infrared lamp for 30 seconds to remove most of the solvent, and then placing the titanium sheet in a 100 ℃ drying box for fully drying for 10 minutes; transferring the dried titanium sheet to a muffle furnace, and setting the temperature to be 10 ℃ for min under the air atmosphere -1 Heating to 500 ℃, and preserving heat for 10min at the temperature to finish the coating work of the primary coating; repeating the coating operation for several times until the coating liquid is exhausted, placing the titanium sheet coated for the last time in a muffle furnace, and fully treating at 500 ℃ for 60min under the same heating rate to finish the preparation of the iridium tantalum strontium oxide copper electrodeposited coating titanium anode. IrO prepared 2 -Ta 2 O 5 -SrO 2 The copper electrodeposited coated titanium anode was named as in table 1 below, with the difference in molar mass of strontium added and iridium reduced.
TABLE 1 naming of Iridium tantalum strontium oxide copper electrodeposited coated titanium anodes with different metal molar ratios
Performance test was performed on the copper electrodeposited coating titanium anode prepared in this example:
1. phase and microscopic morphology:
IrO with different metal mole ratios of the coating liquid is prepared by adjusting the proportion of the coating liquid 2 -Ta 2 O 5 -SrO 2 Copper electrodeposits coating titanium anodes. By comparing the electrochemical properties between them, andenhancing the electrolytic life, attempts were made to explore the most suitable addition of strontium as a third component. Firstly we study the effect of ternary oxide anode with different metal mole ratios on the microscopic morphology of the coating by SEM, a, b, c, d in FIG. 2 is a graph of anode surface morphology with 0%, 5%, 10% and 15% (mol%) strontium addition, respectively, as can be seen from the graph, when strontium is not added, binary IrO 2 -Ta 2 O 5 The surface of the titanium anode with the copper electrodeposited coating has larger oxide cracks and is continuous deep cracks, and the appearance is typical of the surface appearance of the titanium anode with the iridium tantalum oxide copper electrodeposited coating. As the metal strontium is added in the coating liquid proportion, the crack depth of the oxide film on the b-d surface in fig. 2 is reduced and finer. And at a molar ratio of strontium metal of 10%, it can be seen that the crack depth is significantly reduced while retaining the presence of many cracks, which would be beneficial to increase the actual surface area of the electrode, providing more active sites. In the anode with the strontium mol ratio of 15%, the deeper and larger cracks almost disappear, the cracks show discontinuous fine gaps, and the coating is flat.
In summary, SEM images can find that the addition of the metal element strontium can have a significant effect on the morphology of the active layer, and when the addition of the strontium is 10%, the ideal microscopic surface morphology can be prepared. In order to explore the coating composition of the prepared iridium tantalum strontium copper oxide electrodeposited coating titanium anode, EDS is adopted to carry out elemental analysis on the surface of the titanium anode. Fig. 3 is an EDS diagram of a titanium anode of an iridium tantalum strontium oxide copper electrodeposited coating with a strontium mole ratio of 10%, and fig. 3 b-e are elemental profiles wherein it can be seen that all elements of Sr, ir, ta, O are uniformly distributed on the coating. And then adopting a roughness test to further test the surface roughness of the titanium anode and researching the influence of the change of the proportion of the coating metal on the roughness. The surface roughness of the substrate and the coating of the iridium tantalum strontium oxide anode with different metal molar ratios is shown in table 2.
TABLE 2 surface roughness of Iridium tantalum strontium oxide copper electrodeposited coated titanium anodes with different metal molar ratios
It is evident from table 2 that the roughness decreases after the application of the coating, because the coating liquid is more likely to accumulate at the lower pits during the brushing process, thereby decreasing the roughness value. Anodes with 10% and 15% strontium added therein had a significant change in roughness values before and after application of the coating. In combination with SEM images, the patterns of Sr10/Ir60 are also mutated compared with the patterns of Sr0/Ir70 and Sr5/Ir65, so that the roughness change before and after the electrolysis is applied is larger, and the oxygen evolution activity of the titanium anode of the copper electrodeposited coating is affected.
The phase composition of the iridium tantalum strontium oxide copper electrodeposited coating titanium anode prepared in this section was detected by XRD. FIG. 4 is an XRD pattern of a titanium anode of a copper electrodeposited coating of iridium tantalum strontium oxide with different metal molar ratios, wherein a clear diffraction peak of titanium appears in the XRD pattern because the thickness of the metal oxide coating is about 5 μm, and the XRD test depth is generally more than 10 μm and can completely penetrate the coating to reach the titanium substrate. As can be seen by comparison with JCPDS cards, the XRD patterns have IrO in addition to the titanium base peaks 2 Diffraction peaks appear at 27.5 °, 34.6 ° and 53.6 ° of 2θ, respectively, and IrO can be known through analysis and literature review 2 Is rutile type. Ta does not appear in XRD patterns 2 O 5 In the coating prepared at the sintering temperature of 500 ℃, ta exists in an amorphous state and does not generate beta-Ta 2 O 5 Thus, there is no diffraction peak information in the XRD pattern.
2. Polarization curve:
the potential of the titanium anode applied to the electrolytic copper foil industry is detected by carrying out OER performance and stability tests on the titanium anode. In FIG. 5a is IrO 2 -Ta 2 O 5 -SrO 2 The LSV activity curve graph of the copper electrodeposited coating titanium anode can reflect the electrocatalytic activity of different metal oxide coatings under a certain potential. The trend of the activity curves for the different strontium additions in fig. 5a is substantially consistent, indicating that similar anodic reactions occur. However, in the potential range of 1.4V-2V, the Sr10/Ir60 electrode has the highest current density, and the Sr15/Ir55 electrode has the highest current densityThe current density in the interval is relatively lowest, in the potential interval of 1.4V-1.65V, the oxygen evolution activities of the two electrodes of Sr0/Ir70 and Sr5/Ir65 are similar, and the current density of Sr0/Ir70 is higher than that of Sr5/Ir65 under the potential higher than 1.65V. In summary, when the addition of strontium is 10% of the total metal amount, the catalytic activity of the ternary copper electrodeposited coating titanium anode is improved compared with that of iridium tantalum binary copper electrodeposited coating titanium anode without metal strontium while the iridium dosage can be reduced. And further reduces the iridium metal ratio, and when the strontium duty ratio is increased, the current density of the Sr15/Ir55 electrode is reduced again. Based on this graph, it can be found that the highest oxygen evolution activity is possessed in the higher potential range of 1.4V to 2.0V at the strontium addition amount of 10%.
In fig. 5 b is a tafel slope curve obtained by linear fitting, wherein the tafel slope is positively correlated with the oxygen absorption difficulty of the electrode, and the larger the tafel slope, the slower the electron transfer when the reaction occurs, and the worse the catalytic activity. The slopes of the Tafel of the Sr5/Ir65 and Sr10/Ir60 electrodes of the anode prepared into the ternary oxide coating are smaller than those of the Sr0/Ir70 electrode, and the slope of the Tafel curve becomes smaller, which shows that the oxygen evolution overpotential of the anode can be slowly increased along with the increase of the current density, and shows that the Sr10/Ir60 coating has good electrocatalytic activity. The oxygen evolution activity reflected in Tafel curve in FIG. 5 b is Sr10/Ir60> Sr5/Ir65> Sr0/Ir70> Sr15/Ir55, which is consistent with the trend of LSV curve in FIG. 5a, and is more visual by the magnitude of slope values. Wherein, the Tafel slope of the Sr10/Ir60 electrode with the molar content of added metal strontium of 10 percent is the lowest, and the electrode has the highest electrocatalytic activity.
3. Cyclic voltammogram
The cyclic voltammogram can reflect the catalytic activity of the coated anode to a certain extent, but mainly reflects the number of catalytic active sites and the voltammogram of the titanium anode. As shown in fig. 6 a, the cyclic voltammetry coverage area shows an ascending trend with the increase of the strontium addition, and also explains that the activity of the copper electrodeposited coating titanium anode after the third component strontium is introduced in the oxygen evolution curve can be higher than that of the common iridium tantalum copper electrodeposited coating titanium anode. The magnitude of the voltammetric charge for each sample, calculated from the cyclic voltammetric curve integral, is shown in fig. 6 b, where the voltammetric charge Q is capable of providing a more convincing magnitude of active area from an electrochemical perspective. The Q value is increased along with the increase of the mole ratio of added strontium, the mole ratio of strontium between Sr0/Ir70 and Sr5/Ir65 is increased to 5%, and the maximum volt-ampere electric quantity between the two electrodes is increased (74.8%), which proves that the introduction of the third component strontium into the iridium tantalum binary oxide copper electrodeposited coating titanium anode can be beneficial to the increase of the surface active sites and the promotion of the catalytic activity. The addition of the third component strontium is beneficial to the increase of the active area sites on the surface of the titanium anode of the iridium tantalum copper electrodeposited coating and the improvement of the catalytic activity of the electrode.
4. Timing current
The current density value is continuously recorded under constant potential by adopting a timing current test, so that the electrochemical stability of the titanium anode of the iridium tantalum strontium oxide copper electrodeposited coating with different metal mole ratios is explored. FIG. 7 is a graph of the timed current for titanium anodes of iridium tantalum strontium oxide copper electrodeposited coatings with varying metal molar ratios, as can be readily seen, with each titanium anode having a substantially uniform decay trend, a rapid drop in current density centered between 0 and 150 seconds, and stabilizing after 300 seconds of decay. The timing current curves of Sr0/Ir70 and Sr05/Ir65 samples have small fluctuation after 700s, mainly because a large amount of oxygen bubbles separated out from the anode in the test process cannot be removed in time, active sites are blocked to form a bubble shielding effect, and the current density at 1.4V is 2.3 mA.cm -2 The current density fluctuates around. Similar chronoamperometric curves indicate that iridium tantalum strontium coatings with different metal molar ratios have no significant effect on the chronoamperometric stability of the electrode for 1800 s.
5. Electrochemical ac impedance spectroscopy
The electrochemical alternating current impedance spectrum can reflect the electron transfer rate of the titanium anode of the iridium tantalum strontium oxide copper electrodeposited coating with different metal mole ratios. In FIG. 8, a is a precursor solution with different metal molar mass ratios, and the prepared iridium tantalum strontium copper electrodeposited coating titanium anode is 0.5 mol.L -1 H 2 SO 4 In solution, 4.7b is an impedance fit of a Sr10/Ir60 sample measured at 1.35V. We can blockThe anti-graph further shows that the electrocatalytic performance of titanium anodes, the nyquist graph of all the electrodes is a semi-arc capacitive arc, and the radius of the arc is positively correlated with the OER reaction charge transfer resistance. The equivalent circuit diagram used for fitting is shown in fig. 8 b, and as can be seen in the EIS fitting map, experimental data of the Sr10/Ir60 electrode can be very fit with fitting data when the equivalent circuit is used, and the fitting result is very good.
Table 3 shows the fitting results of electrochemical impedance spectra of titanium substrates with different pretreatment modes
| Sample of | R s /Ω·cm 2 | R ct /Ω·cm 2 | Q dl /mF·cm 2 | nl |
| Sr0/Ir70 | 1.914 | 1.944 | 105.3 | 0.8348 |
| Sr5/Ir65 | 1.939 | 1.405 | 90.9 | 0.8551 |
| Sr10/Ir60 | 2.144 | 1.070 | 105.0 | 0.8370 |
| Sr15/Ir55 | 1.911 | 0.987 | 109.61 | 0.8292 |
As can be seen from Table 3, Q dl The data relate to the number of active sites on the surface of the coating, Q for Sr15/Ir55 samples dl The highest, it shows that the coating contains more surface active sites and has better catalytic activity. R is R ct The resistance value of the oxide coating is reflected, and the lower the value is, the more favorable the anode reaction is. Wherein R of Sr10/Ir60 ct The value is the lowest, which is favorable for the electrochemical reaction, and the addition amount is continuously increased to 15 percent, R of Sr15/Ir55 ct The value again starts to rise, so that the coating resistance value is the lowest at an addition of 10%. Q of Sr10/Ir60 at the same time dl The value is 105mF cm 2 Is higher than Sr0/Ir70 and Sr5/Ir65, is more favorable for OER reaction when the molar ratio of strontium is 10 percent, and has the highest catalytic activity.
6. Enhanced electrolysis life test and failure analysis
The reinforced electrolytic life line graph can reflect the change trend of the cell pressure of the iridium tantalum strontium oxide copper electrodeposited coating titanium anode with different metal mole ratios, so as to analyze the failure process of the electrode. It can be seen from the fold line change law in fig. 9 that the line graph of the cell pressure versus time of the Sr0/Ir70 electrode has a wider flat region than the other electrodes when the iridium content is highest and no strontium is added. Both the Sr5/Ir65 and Sr10/Ir60 electrodes have sudden rise in cell pressure and fail immediately after the cell pressure rises to 7V, while the cell pressure of the Sr15/Ir55 electrode has sudden rise at 6.5V, and the intensified electrolytic life of the Sr15/Ir55 electrode is only 176 hours. As can be seen in fig. 10, the enhanced electrolytic life of the titanium anode is decreasing with decreasing iridium content in the anode, wherein the life time duration Sr0/Ir70> Sr5/Ir65> Sr10/Ir60> Sr15/Ir55. There have been many studies showing that the lifetime of iridium tantalum titanium anodes is related to the amount of iridium metal in the coating, i.e., the greater the amount of iridium metal applied over a range, the longer the enhanced electrolysis lifetime. In combination with the stability test in the electrochemical test, chronoamperometric curve, the four samples, although not exhibiting a significant difference in electrochemical stability within 1800s of the chronoamperometric curve, have a continuously decreasing electrolytic life as the amount of strontium added increases. It is shown that adding strontium and reducing the amount of noble iridium in a severe high-current acidic system will have an effect on the lifetime of the iridium tantalum strontium ternary oxide copper electrodeposited coating titanium anode, and the enhanced electrolysis lifetime of Sr15/Ir55 is greatly reduced (48.2%) by only half of the lifetime of the Sr0/Ir70 sample without strontium addition.
And carrying out surface microscopic morphology analysis on the failure titanium anode to infer failure behavior. FIG. 11 is a failure morphology diagram of an Ir Ta-Sr oxide Cu electrodeposited coating titanium anode with different metal mole ratios, a is a failure diagram of an Sr0/Ir70 electrode, b is a failure diagram of an Sr5/Ir65 electrode, c is a failure diagram of an Sr10/Ir60 electrode, and d is a failure diagram of an Sr15/Ir55 electrode. From the failure map, it can be speculated that the Sr0/Ir70 and Sr5/Ir65 electrode failure process is that the cracks deepen due to the massive dissolution at the cracks of the coating. The Sr10/Ir60 electrode coating is seriously peeled off, and the shallower cracks do not have obvious deepening. When the strontium addition is increased to 15%, the Sr15/Ir55 electrode is obviously different from the failure diagrams of the first three electrolysis modes, and a large amount of coating falling off does not occur on the failure diagrams. It is speculated from the failure SEM images that the electrode coating layer is peeled off and cracks deepen, which will lead to corrosion of the titanium substrate by the immersed electrolyte, eventually leading to electrode failure.
7. Electrolytic copper foil
IrO of a platinum-containing intermediate layer of 10mm by 15mm by 0.5mm 2 -Ta 2 O 5 -SrO 2 The size of the copper electrodeposited coating titanium anode is enlarged for practical application of electrolytic copper foil, and the coating titanium electrodeposited coating of 40mm multiplied by 30mm multiplied by 0.5mm is prepared under the same preparation conditionsAnd (3) taking a self-made titanium electrode as an anode, taking a purchased polished pure titanium plate as a cathode, putting the pure titanium cathode into a mixed solution of 5% hydrogen peroxide and 10% sulfuric acid for activation for 5min before use, putting the cathode plate and the anode plate into an electrolytic tank, and controlling the distance between the two electrode plates to be 1cm.
Related testing of copper foil: fig. 12 shows the microscopic morphology of an electrolytic copper foil, wherein a is the bonding surface of a pure titanium cathode, which is commonly known as a smooth surface, and the scratch-shaped microscopic surface is a rubbing of scratches polished on the surface of the pure titanium cathode, which is macroscopically brighter and smoother overall. b is the surface of grain growth in solution, commonly known as the matte surface, the surface of which consists of uniform copper bump crystals. Wherein the roughness of the a-gloss surface is measured to be 0.071 μm and Rz is 0.510 μm; b pitting surface Ra is 0.577 μm and Rz is 3.098 μm. FIG. 13 shows a tensile test of a homemade copper foil, the test specimen being bone-shaped, having a width of 0.2cm and a thickness of 31.3 μm and 29.4. Mu.m. It can be seen in fig. 13 that the tensile strength thereof reaches 303MPa and 286MPa.
In conclusion, the invention introduces the metal strontium into the coating liquid, reduces the use amount of the noble metal iridium according to the same proportion, and prepares the IrO 2 -Ta 2 O 5 -SrO 2 Copper electrodeposited coated titanium anode and comparative wherein Ir: sr=70: 0. ir: sr=65: 5. ir: sr=60: 10. ir: sr=55: 15 The electrochemical performance, phase morphology analysis and the like of the titanium anode in equal proportion (mol%) lead to the following conclusion: the comparative electrochemical performance test shows that the electrochemical performance is similar to that at 0% when the strontium addition is 5%, whereas the IrO is 10% when the strontium addition is 5% 2 -Ta 2 O 5 -SrO 2 The titanium anode with copper electrodeposited coating can obtain specific IrO 2 -Ta 2 O 5 The better catalytic activity of the copper electrodeposited coating titanium anode is deduced by combining an SEM image and an electrochemical test, and the addition of strontium is favorable for the increase of the surface active sites of the copper electrodeposited coating titanium anode, so that the real area of the copper electrodeposited coating titanium anode is increased, and the electrocatalytic activity of the copper electrodeposited coating titanium anode is improved.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (8)
1. The preparation method of the copper electrodeposited coating titanium anode is characterized by comprising the following steps:
etching the initial titanium sheet to obtain a rough titanium substrate;
iridium source compound, tantalum source compound and strontium source compound are prepared according to Ir: ta: sr= (70-x): 30: adding the mole percentage of x into organic alcohol, and carrying out ultrasonic dispersion to obtain coating liquid, wherein x is more than or equal to 10 and less than or equal to 15;
uniformly brushing the coating liquid on the surface of the rough titanium substrate, and then baking to obtain a dry titanium substrate;
transferring the dry titanium substrate into a muffle furnace, heating to 400-600 ℃ in an air atmosphere, and preserving heat for a first preset time to finish the coating of a primary coating;
repeating the coating for several times, placing the titanium substrate coated for the last time in a muffle furnace, heating to 400-600 ℃ under the air atmosphere, and preserving heat for a second preset time to obtain the IrO (Infrared radiation) surface coating 2 -Ta 2 O 5 -SrO 2 A copper electrodeposited coated titanium anode.
2. The method for producing a copper electrodeposited coated titanium anode according to claim 1, wherein said iridium source compound is H 2 IrCl 6 ·6H 2 O, wherein the tantalum source compound is tantalum ethoxide, the strontium source compound is strontium acetate, and the organic alcohol is one or more of n-butanol, ethanol and propanol.
3. The method for preparing a titanium anode for copper electrodeposition coating according to claim 1, wherein the baking treatment is performed after the coating liquid is uniformly brushed on the surface of the rough titanium substrate, comprising:
dipping the coating liquid by a brush, uniformly brushing the coating liquid on the surface of the rough titanium substrate, and baking the brushed rough titanium substrate under an infrared lamp for 30 seconds to remove most of the solvent;
and then placing the brushed rough titanium substrate in a drying box at 100 ℃ for fully drying for 10min to obtain the dry titanium substrate.
4. The method of producing a copper electrodeposited coated titanium anode according to claim 1, wherein said first predetermined time is 10 minutes and said second predetermined time is 60 minutes.
5. The method for preparing a titanium anode for copper electrodeposition coating according to claim 1, wherein the initial titanium sheet is subjected to etching treatment to prepare a rough titanium substrate, comprising:
cutting the initial titanium sheet, and then performing alkali washing and degreasing treatment to obtain a cut titanium sheet;
NaBr is used as electrolyte, the cut titanium sheet is used as a working electrode, an initial titanium sheet is used as a counter electrode to form a double-electrode system, the double-electrode system is electrified, and a constant current of 180mA cm is used first -2 Etching the cut titanium sheet once, and then carrying out constant current of 500 mA.cm -2 And (3) performing secondary etching on the cut titanium sheet to obtain the coarse titanium substrate.
6. The method for preparing the titanium anode with the copper electrodeposition coating according to claim 5, wherein the cutting of the initial titanium sheet and the alkaline washing degreasing treatment are carried out, and the method comprises the following steps:
na is mixed with 3 PO 4 ·12H 2 O、Na 2 CO 3 NaOH is dissolved in deionized water according to the mass ratio of 105:25:4 to prepare 0.3% alkali wash oil liquid, and the alkali wash oil liquid is heated to be boiled for standby;
cutting an initial titanium sheet, adding the cut initial titanium sheet into boiling alkaline washing oil liquid, and keeping for a preset time;
and taking out the initial titanium sheet, flushing with deionized water, and performing ultrasonic cleaning treatment in the deionized water to complete the alkaline cleaning process, so as to obtain the cut titanium sheet.
7. A copper electrodeposited coated titanium anode produced by the process for producing a copper electrodeposited coated titanium anode according to any one of claims 1 to 6.
8. Use of a copper electrodeposited coated titanium anode according to claim 7 for electrolysis of copper.
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