CN114875458B - Noble metal anode for electrolytic copper foil and preparation method thereof - Google Patents
Noble metal anode for electrolytic copper foil and preparation method thereof Download PDFInfo
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- CN114875458B CN114875458B CN202210543507.6A CN202210543507A CN114875458B CN 114875458 B CN114875458 B CN 114875458B CN 202210543507 A CN202210543507 A CN 202210543507A CN 114875458 B CN114875458 B CN 114875458B
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000011889 copper foil Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000010936 titanium Substances 0.000 claims abstract description 75
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 75
- 239000011248 coating agent Substances 0.000 claims abstract description 64
- 238000000576 coating method Methods 0.000 claims abstract description 64
- 239000000758 substrate Substances 0.000 claims abstract description 53
- 238000005245 sintering Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 21
- ULFQGKXWKFZMLH-UHFFFAOYSA-N iridium tantalum Chemical compound [Ta].[Ir] ULFQGKXWKFZMLH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 15
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 58
- 239000010410 layer Substances 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000011159 matrix material Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 238000005488 sandblasting Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 claims description 10
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- -1 tantalum butanediol Chemical compound 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 5
- 238000004513 sizing Methods 0.000 claims description 5
- 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 4
- OPZULYDYSMWNFK-UHFFFAOYSA-I butan-1-ol tantalum(5+) pentachloride Chemical compound [Cl-].C(CCC)O.[Ta+5].[Cl-].[Cl-].[Cl-].[Cl-] OPZULYDYSMWNFK-UHFFFAOYSA-I 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000011363 dried mixture Substances 0.000 claims description 2
- 230000003746 surface roughness Effects 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 150000004706 metal oxides Chemical class 0.000 abstract description 8
- 238000010422 painting Methods 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 239000002585 base Substances 0.000 description 16
- 239000002253 acid Substances 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000005303 weighing Methods 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BPNRRQFZIBQRMK-UHFFFAOYSA-N [O-2].[Ta+5].[Ir+3].[O-2].[O-2].[O-2] Chemical compound [O-2].[Ta+5].[Ir+3].[O-2].[O-2].[O-2] BPNRRQFZIBQRMK-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ZIPLUEXSCPLCEI-UHFFFAOYSA-N cyanamide group Chemical group C(#N)[NH-] ZIPLUEXSCPLCEI-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/30—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W)
- B05D2202/35—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W) based on Ti
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Abstract
A noble metal anode for electrolytic copper foil and its preparing process, wherein the noble metal anode comprises titanium substrate sintered with g-C 3 N 4 An intermediate layer, and g-C 3 N 4 The iridium-tantalum system coating on the intermediate layer comprises the following preparation methods: the method comprises the following steps of (1) pretreating the surface of a titanium substrate; (2) Preparation of g-C by pyrolysis 3 N 4 (ii) a (3) preparing a base solution: 30 to 100mg of g-C 3 N 4 Dissolving in 5ml of organic solvent, and stirring at room temperature to form a base solution; preparing an active solution: mixing and dissolving 70 mol percent of iridium source and 30 mol percent of tantalum source in an organic solvent, and stirring at room temperature to form active liquid; (5) painting and sintering; the invention introduces g-C with two-dimensional layered structure into the traditional iridium-tantalum system coating 3 N 4 The intermediate layer is prepared, so that the effective catalytic activity area of the coating can be effectively increased, and the electrochemical performance of the noble metal oxide titanium electrode can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of electrolytic copper foil, and particularly relates to a noble metal anode for electrolytic copper foil and a preparation method thereof.
Background
In the electrolytic copper foil production equipment, the anode material is one of the key components; after a series of changes of a traditional soluble anode, a lead anode and the like are carried out on the selection of anode materials, the noble metal coated titanium anode with dimensional stability shows more excellent service performance. The preparation method of the electrolytic copper foil anode plate with the patent application number of CN201810529420.7 comprises the following steps: (1) selecting a titanium plate as a raw material; (6) preparing a noble metal solution; (7) Coating the noble metal solution on the surface of the titanium plate substrate subjected to heat treatment for multiple times to form a coating with the thickness of 6-10 mu m; the product obtained by coating the noble metal solution on the surface of the matrix has low electric energy efficiency caused by overhigh anode potential required by copper deposition in the copper foil electrolysis process, and the cost is increased, which is an important problem in production. DSA with iridium tantalum oxide coating system has higher oxygen evolution electrocatalytic activity in an acid medium, keeps higher stability, can obtain lower overpotential in production, and is a popular anode at present. At present, because the current density required under the working condition of the electrolytic copper foil is higher, oxygen permeation is easy to occur in the iridium-tantalum system anode, so that the titanium matrix is oxidized, and the abnormal failure of the anode is caused.
Disclosure of Invention
In order to overcome the above-mentioned disadvantages of the prior art, it is an object of the present invention to provide a noble metal anode for electrolytic copper foil and a method for preparing the same, incorporating g-C having a two-dimensional layered structure 3 N 4 The intermediate layer is prepared, so that the effective catalytic active area of the coating can be effectively increased, the electrochemical performance of the noble metal oxide titanium electrode can be effectively improved, the service life of the electrolytic copper foil anode can be prolonged, and lower electrolytic voltage can be obtained.
In order to achieve the purpose, the invention provides the following technical scheme:
a noble metal anode for electrolytic copper foil comprises a titanium substrate sintered with g-C 3 N 4 An intermediate layer, and g-C 3 N 4 An iridium tantalum system coating over the intermediate layer.
Said g-C 3 N 4 g-C in the intermediate layer 3 N 4 One selected from melamine, cyanuric chloride, cyanamide, dicyanodiamine and urea is obtained by thermal decomposition.
The iridium-tantalum system coating comprises the following raw materials in a molar ratio: 60% -90% of iridium source and 10% -40% of tantalum source, wherein the tantalum source is selected from any one of tantalum pentachloride n-butyl alcohol solution, tantalum butanediol and tantalum ethoxide.
Said g-C 3 N 4 Thermal decomposition, in particular: heating to 510-610 ℃ at the heating rate of 1-10 ℃/min, calcining at constant temperature for 1-4 h, naturally cooling, and grindingTo obtain g-C 3 N 4 。
The g to C 3 N 4 The thickness of the intermediate layer is 0.5-1 μm.
In the intermediate layer, g-C 3 N 4 The loading amount of the catalyst is 0.3-2.5 mg cm -2 。
The thickness of the catalytic active layer is 6-10 μm, and IrO is added in the catalytic active layer 2 The loading amount of the element Ir in the form is 0.5-3 mg cm -2 。
A preparation method of a noble metal anode for electrolytic copper foil specifically comprises the following steps:
(1) Pretreating the surface of the titanium substrate;
(2) Preparing a base solution: 30mg to 100mg of g-C 3 N 4 Dissolving in 5ml of organic solvent A, and stirring at room temperature to form a base solution;
(3) Preparing an active solution: mixing and dissolving 60-90 mol percent of iridium source and 10-40 mol percent of tantalum source in an organic solvent B, and stirring at room temperature to form active liquid;
(4) Coating and sintering: and (2) coating and sintering the surface of the titanium substrate pretreated in the step (1) with a base solution, and coating and sintering with an active solution.
The step (1) of pretreating the surface of the titanium substrate specifically comprises the following steps:
(1.1) carrying out surface oil removal and sand blasting treatment on the titanium matrix until the surface roughness Ra is less than 15 mu m;
(1.2) carrying out thermal shape correction treatment on the titanium matrix subjected to sand blasting;
(1.3) soaking the titanium substrate with good shape correction in dilute hydrochloric acid with the mass concentration of 3-15% for 8-24 h, and then boiling in oxalic acid solution with the mass concentration of 5-10% for 0.5-3 h;
and (1.4) cleaning and airing the titanium substrate.
G to C in the step (2) 3 N 4 One selected from melamine, cyanuric chloride, cyanamide, dicyanodiamine and urea is obtained by thermal decomposition.
The organic solvent A in the step (2) is any one of n-butyl alcohol, ethylene glycol, dimethylformamide, nitrogen and nitrogen-dimethyl pyrrolidone or a mixture of n-butyl alcohol, ethylene glycol, dimethylformamide and nitrogen-dimethyl pyrrolidone in any proportion.
The tantalum source in the step (3) is selected from any one of tantalum pentachloride n-butyl alcohol solution, tantalum butanediol and tantalum ethoxide.
The organic solvent B in the step (3) is any one of n-butyl alcohol, isopropanol and ethanol or a mixture of n-butyl alcohol, isopropanol and ethanol in any proportion.
The step (4) of coating and sintering comprises the following steps:
(4.1) coating the base solution prepared in the step (2) on the pretreated titanium substrate not less than twice, wherein the total thickness is 0.5-1 mu m, and g-C 3 N 4 The loading amount of the catalyst is 0.3-2.5 mg cm -2 Naturally drying the mixture, and putting the dried mixture in an oven at 60-100 ℃ to completely volatilize the solvent;
(4.2) placing the titanium substrate treated in the step (4.1) in a muffle furnace at 450-520 ℃ for sintering for 10-25 min, taking out, and cooling to room temperature;
(4.3) repeating the step (4.1), placing the treated titanium substrate in a muffle furnace at the temperature of 450-520 ℃ for sintering for 50-75 min, taking out, and cooling to room temperature;
(4.4) brushing the active liquid prepared in the step (3) on the titanium substrate treated in the step (4.3) for more than 15 times, wherein the thickness is 6-10 mu m, and the loading amount of element Ir in the form of IrO2 is 0.5-3 mg cm < -2 >; naturally drying, and putting the dried product in an oven at 60-100 ℃ to completely volatilize the solvent;
(4.5) placing the titanium substrate treated in the step (4.4) in a muffle furnace at the temperature of 450-520 ℃ for sintering for 10-25 min, taking out, and cooling to room temperature;
(4.6) repeating the steps (4.4) and (4.5) until the active solution is brushed for more than 15 times;
(4.7) preserving the temperature of the coated titanium substrate in a muffle furnace at 450-500 ℃ for 30-90min, taking out, and naturally cooling to room temperature.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects: graphite-like phase carbon nitride (g-C) 3 N 4 ) Is a two-dimensional plane structure similar to graphene, and has the advantages of no toxicity, no metal, low density and room temperatureHigh thermal stability and chemical stability, acid and alkali resistance, low cost and the like. Introduction of g-C with good conductivity into traditional iridium-tantalum system coating 3 N 4 The intermediate layer has better electron conduction capability, so that an effective charge conduction channel exists between the titanium matrix and the oxide coating, the voltage is reduced, and the passivation of the titanium matrix caused by the unfavorable charge conduction is inhibited; in addition, two-dimensional lamellar g-C in priming solution 3 N 4 The attachment area of the noble metal oxide is greatly increased, so that the effective catalytic activity area is increased, and the catalytic activity of the electrode is improved.
Drawings
FIG. 1 shows g-C prepared by thermal decomposition according to the present invention 3 N 4 X-ray electron diffraction pattern of (a).
FIG. 2 is a scanning electron microscope photograph of an anode of an electrodeposited copper foil prepared in accordance with an embodiment of the present invention.
FIG. 3 is a scanning electron microscope photograph of an anode of an electrolytic copper foil prepared in example two of the present invention.
FIG. 4 is a scanning electron microscope photograph of an anode of an electrolytic copper foil prepared in example three of the present invention.
FIG. 5 is a scanning electron microscope photograph of an anode of an electrolytic copper foil according to comparative example of the present invention.
FIG. 6 is a graph showing electrocatalytic properties of anodes of electrolytic copper foils prepared by the preparation methods provided in example 2 and comparative example one.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example one
A noble metal anode for electrolytic copper foil comprises a titanium substrate sintered with g-C 3 N 4 An intermediate layer, and an iridium tantalum system coating.
G to C 3 N 4 g-C in the intermediate layer 3 N 4 Selected from melamine, and is obtained by thermal decomposition of melamine at 600 ℃ for 2 h.
The iridium-tantalum system coating comprises the following raw materials in a molar ratio: 70% of an iridium source selected from chloroiridic acid and 30% of a tantalum source; the tantalum source is selected from tantalum pentachloride n-butanol solution.
The preparation method of the noble metal anode of the embodiment specifically includes:
s1, pretreating the surface of a titanium substrate:
s1.1, carrying out surface oil removal and sand blasting treatment on a titanium matrix;
s1.2, carrying out thermal sizing treatment on the titanium matrix subjected to sand blasting;
s1.3, soaking the titanium substrate with the corrected shape in dilute hydrochloric acid with the mass concentration of 10% for 15 hours, and then boiling the titanium substrate in oxalic acid solution with the mass concentration of 8% for 2 hours;
s1.4, cleaning and airing the titanium substrate;
s2, preparation of g-C 3 N 4 :: weighing a certain amount of melamine, placing the melamine in a crucible, placing the crucible in a muffle furnace, heating to 600 ℃ at a heating rate of 1 ℃/min, preserving heat for 2 hours, and cooling with the furnace to obtain the required g-C 3 N 4 (ii) a Referring to FIG. 1, FIG. 1 is a graph showing g-C prepared by a thermal decomposition method 3 N 4 X-ray electron diffraction pattern of (a).
S3, preparing a base solution A: weighing 30mg g-C 3 N 4 Dissolving in 2.5ml of ethylene glycol and 2.5ml of DMF solution, stirring at room temperature until the mixture is completely dissolved to form a base solution A, and storing for later use;
s4, preparing active liquid B: weighing chloroiridic acid and tantalum pentachloride n-butyl alcohol solution according to the molar ratio of Ir to Ta =7:3, mixing and dissolving the chloroiridic acid and the tantalum pentachloride n-butyl alcohol solution in the n-butyl alcohol solvent, stirring the mixture at room temperature until the chloroiridic acid and the tantalum pentachloride n-butyl alcohol solution are completely dissolved to form active liquid B, and storing the active liquid B for later use;
s5, coating and sintering: uniformly coating the prepared base solution A on a titanium substrate, drying, sintering in a muffle furnace at 450-480 ℃ for 15min, taking out, cooling, coating in the next step, drying, sintering at 450-480 ℃ for 60min, coating a g-C3N4 layer to a thickness of 0.5 mu m; taking out and cooling, then uniformly coating the prepared active liquid B on a titanium substrate, baking for 15min in a muffle furnace at 450-500 ℃ after drying, taking out and cooling to room temperature for next coating, repeating the step for 16 times, wherein the coating thickness is 6 mu m, and finally preserving the heat in the muffle furnace at 480-520 ℃ for 60min to prepare the Ir-Ta system noble metal oxide anode with the g-C3N 4-containing intermediate layer. A scanning electron micrograph of the obtained electrolytic copper foil anode is shown in FIG. 2.
Example two
The embodiment of the noble metal anode for the electrolytic copper foil comprises a titanium substrate, wherein g-C is sintered on the titanium substrate 3 N 4 An intermediate layer, and an iridium tantalum system coating.
Said g-C 3 N 4 g-C in the intermediate layer 3 N 4 Selected from cyanamide, and is obtained by thermal decomposition of cyanamide at 600 ℃ for 2 h.
The iridium-tantalum system coating comprises the following raw materials in a molar ratio: 60% of an iridium source selected from chloroiridic acid and 40% of a tantalum source; the tantalum source is selected from tantalum pentachloride n-butanol solution.
Referring to fig. 3, a scanning electron microscope image of an anode of an electrolytic copper foil prepared by the method for preparing a noble metal anode for electrolytic copper foil, in this example, a coating of a titanium anode is an Ir-Ta system noble metal coating with a platinum interlayer added thereto, and the preparation method specifically includes:
s1, pretreating the surface of a titanium substrate:
s1.1, carrying out surface oil removal and sand blasting treatment on a titanium matrix;
s1.2, carrying out thermal sizing treatment on the titanium matrix subjected to sand blasting;
s1.3, soaking the titanium substrate with the corrected shape in dilute hydrochloric acid with the mass concentration of 3% for 8 hours, and then boiling in oxalic acid solution with the mass concentration of 5% for 0.5 hour;
s1.4, cleaning and airing the titanium substrate;
s2, preparation of g-C 3 N 4 Weighing a certain amount of cyanamide, placing into a crucible, placing into a muffle furnace, heating to 600 deg.C at a heating rate of 1 deg.C/min, maintaining for 2 hr, and cooling to obtain the required g-C 3 N 4 ；
S3, preparing a base solution A: accurately weighing 50mg g-C 3 N 4 Dissolving in 2.5ml of ethylene glycol and 2.5ml of DMF solution, stirring at room temperature until the mixture is completely dissolved to form a base solution A, and storing for later use;
s4, preparing active liquid B: weighing chloroiridic acid and tantalum pentachloride n-butyl alcohol solution according to the molar ratio of Ir to Ta =6:4, mixing and dissolving in a n-butyl alcohol solvent, stirring at room temperature until the chloroiridic acid and the tantalum pentachloride n-butyl alcohol solution are completely dissolved to form an active liquid B, and storing for later use;
s5, coating and sintering: uniformly coating the prepared base solution A on a titanium substrate, drying, sintering in a muffle furnace at 480-520 ℃ for 10min, taking out, cooling, coating, drying, sintering at 480-520 ℃ for 60min, and coating a g-C3N4 layer to a thickness of 1 mu m; taking out and cooling, then uniformly coating the prepared active liquid B on a titanium substrate, baking for 10min in a muffle furnace at 450-500 ℃ after drying, taking out and cooling to room temperature for next coating, repeating the coating step of the active liquid B for 20 times, wherein the coating thickness is 10 mu m, and finally preserving the heat in the muffle furnace at 450-480 ℃ for 60min to prepare the Ir-Ta system noble metal oxide anode with the platinum-containing intermediate layer.
EXAMPLE III
The embodiment of the noble metal anode for the electrolytic copper foil comprises a titanium substrate, wherein g-C is sintered on the titanium substrate 3 N 4 An intermediate layer, and an iridium tantalum system coating.
Said g-C 3 N 4 g-C in the intermediate layer 3 N 4 Selected from urea, and is obtained by thermal decomposition of urea at 600 ℃ for 2 h.
The iridium-tantalum system coating comprises the following raw materials in a molar ratio: 90% of an iridium source selected from chloroiridic acid and 10% of a tantalum source; the tantalum source is selected from tantalum pentachloride n-butanol solution.
In this example, referring to fig. 4, a scanning electron microscope image of an anode of an electrolytic copper foil prepared by the method for preparing a noble metal anode for electrolytic copper foil, a coating of a titanium anode is an Ir-Ta system noble metal coating added with a platinum interlayer, and the preparation method specifically includes:
s1, pretreating the surface of a titanium substrate:
s1.1, carrying out surface oil removal and sand blasting treatment on a titanium matrix;
s1.2, carrying out thermal sizing treatment on the titanium matrix subjected to sand blasting;
s1.3, soaking the titanium substrate with good shape correction in dilute hydrochloric acid with the mass concentration of 15% for 24 hours, and then boiling in oxalic acid solution with the mass concentration of 10% for 3 hours;
s1.4, cleaning and airing the titanium substrate;
s2, preparation of g-C 3 N 4 Weighing a certain amount of urea, placing into a crucible, placing into a muffle furnace, heating to 600 deg.C at a heating rate of 1 deg.C/min, maintaining for 2 hr, and cooling to obtain the required g-C 3 N 4 ；
S3, preparing a base solution A: accurately weighing 100mg g-C 3 N 4 Dissolving in 2.5ml of ethylene glycol and 2.5ml of DMF solution, stirring at room temperature until the mixture is completely dissolved to form a base solution A, and storing for later use;
s4, preparing active liquid B: accurately weighing a certain amount of chloroiridic acid and tantalum pentachloride n-butyl alcohol solution according to the molar ratio of Ir to Ta =9:1, mixing and dissolving in a n-butyl alcohol solvent, stirring at room temperature until the solution is completely dissolved to form an active liquid B, and storing for later use;
s5, coating and sintering: uniformly coating the prepared base solution A on a titanium substrate, drying, sintering in a muffle furnace at 460-500 ℃ for 25min, taking out, cooling, coating, drying, sintering at 480-520 ℃ for 1h, coating a g-C3N4 layer with the thickness of 0.8 mu m, and loading the g-C3N4 layer with 1.5mg cm < -2 >; taking out and cooling, then uniformly coating the prepared active liquid B on a titanium substrate, baking for 25min in a muffle furnace at the temperature of 450-520 ℃, taking out and cooling to room temperature for next coating, repeating the coating step of the active liquid B for 18 times, wherein the coating thickness is 8 mu m, and finally preserving the heat in the muffle furnace at the temperature of 450-480 ℃ for 60min to prepare the Ir-Ta system noble metal oxide anode with the platinum-containing intermediate layer.
Comparative example 1
The comparative example shows a scanning electron microscope image of an anode of electrolytic copper foil prepared by the method for preparing a noble metal anode for electrolytic copper foil, referring to fig. 5, a coating of a titanium anode is an Ir-Ta system noble metal coating added with a platinum interlayer, and the preparation method specifically comprises the following steps:
s1, pretreating the surface of a titanium substrate:
s1.1, carrying out surface oil removal and sand blasting treatment on a titanium matrix;
s1.2, carrying out thermal sizing treatment on the titanium matrix subjected to sand blasting;
s1.3, soaking the titanium substrate with good shape correction in dilute hydrochloric acid with the concentration of 3-15% for 8-24 h, and then boiling in oxalic acid solution with the concentration of 5-10% for 0.5-3 h;
s1.4, cleaning and airing the titanium substrate;
s2, preparing a base solution A: 2.5ml of ethylene glycol and 2.5ml of DMF are mixed evenly to form a base solution A which is stored for standby, and the difference from the invention lies in that g-C in the invention is not added 3 N 4 ；
S3, preparing active liquid: accurately weighing a certain amount of chloroiridic acid and tantalum pentachloride n-butyl alcohol solution according to the molar ratio of Ir to Ta =7:3, mixing and dissolving in a n-butyl alcohol solvent, stirring at room temperature until the solution is completely dissolved to form an active liquid B, and storing for later use;
s4, coating and sintering: uniformly coating the prepared base solution A on a titanium substrate, drying, sintering in a muffle furnace at 450-520 ℃ for 10-25 min, taking out, cooling, coating, drying, and sintering at 450-520 ℃ for 60min; taking out and cooling, then uniformly coating the prepared active liquid B on a titanium substrate, baking for 10-25 min in a muffle furnace at 450-520 ℃, taking out and cooling to room temperature for next coating, repeating the steps until the active liquid B is used up, and finally preserving the heat in the muffle furnace at 450-520 ℃ for 60min to prepare the Ir-Ta system noble metal oxide anode with the platinum-containing interlayer.
And (3) performance testing: h in the electrolyte is 0.5mol/L 2 SO 4 The electrolytic copper foil anode prepared by the preparation method provided by the second embodiment and the first embodiment is a working electrode, and the electro-catalysis performance of the sample is tested in an electrochemical workstation under a three-electrode system. As can be seen from FIG. 6, 50mg g-C was added to the intermediate layer 3 N 4 The catalytic activity of the electrode can be effectively improved, and the overpotential of the OER reaction is reduced. Meanwhile, as can be seen from FIGS. 2 to 5, g-C 3 N 4 The addition of (A) significantly affects the surface morphology of the noble metal oxide catalyst, showing moreThe needle shape solves the precipitation, which is beneficial to improving the catalytic performance of the electrode.
In summary, the present invention employs pyrogenically prepared g-C 3 N 4 Method for preparing iridium-tantalum system noble metal coating layer for intermediate layer g-C 3 N 4 Has a graphite-like layered structure, good thermal stability and chemical stability, no toxicity, rich sources and simple preparation and molding process. The two-dimensional layered structure is used as the middle layer, so that the catalytic activity area can be effectively improved, the electrochemical performance of the noble metal anode is optimized, and the service life is prolonged.
Claims (8)
1. A preparation method of a noble metal anode for electrolytic copper foil is characterized by comprising the following steps:
(1) Pretreating the surface of the titanium substrate;
(1.1) carrying out surface oil removal and sand blasting treatment on the titanium matrix until the surface roughness Ra is less than 15 mu m;
(1.2) carrying out thermal sizing treatment on the titanium matrix subjected to sand blasting;
(1.3) soaking the titanium substrate with good shape correction in dilute hydrochloric acid with the mass concentration of 3-15% for 8-24 h, and then boiling in oxalic acid solution with the mass concentration of 5-10% for 0.5-3 h;
(1.4) cleaning and airing the titanium substrate;
(2) Preparing a base solution: 30mg to 100mg of g-C 3 N 4 Dissolving in 5ml of organic solvent A, and stirring at room temperature to form a base solution;
(3) Preparing an active solution: mixing and dissolving 60-90 mol percent of iridium source and 10-40 mol percent of tantalum source in an organic solvent B, and stirring at room temperature to form active liquid;
(4) And coating and sintering: coating base solution on the surface of the titanium substrate pretreated in the step (1) for coating and sintering, and then coating and sintering active solution;
(4.1) coating the base solution prepared in the step (2) on the pretreated titanium substrate not less than twice, wherein the total thickness is 0.5-1 mu m, and g-C 3 N 4 The supported amount of (A) is 0.3-2.5 mg·cm -2 Naturally drying the mixture, and putting the dried mixture in an oven at 60-100 ℃ to completely volatilize the solvent;
(4.2) placing the titanium substrate treated in the step (4.1) in a muffle furnace at the temperature of 450-520 ℃ for sintering for 10-25 min, taking out, and cooling to room temperature;
(4.3) repeating the step (4.1), placing the treated titanium substrate in a muffle furnace at the temperature of 450-520 ℃ for sintering for 50-75 min, taking out, and cooling to room temperature;
(4.4) coating the active liquid prepared in the step (3) on the titanium substrate treated in the step (4.3), wherein the total thickness is 6-10 mu m and IrO is used 2 The loading amount of the element Ir in the form is 0.5-3 mg cm -2 (ii) a Naturally drying, and putting the dried product in an oven at 60-100 ℃ to completely volatilize the solvent;
(4.5) placing the titanium substrate treated in the step (4.4) in a muffle furnace at 450-520 ℃ for sintering for 10-25 min, taking out, and cooling to room temperature;
(4.6) repeating the steps (4.4) and (4.5) until the active solution is brushed for more than 15 times;
(4.7) keeping the coated titanium substrate in a muffle furnace at 450-500 ℃ for 30-90min, taking out, naturally cooling to room temperature, and obtaining the noble metal anode for the electrolytic copper foil, which comprises the titanium substrate, wherein g-C is sintered on the titanium substrate 3 N 4 An intermediate layer, and g-C 3 N 4 An iridium tantalum system coating over the intermediate layer.
2. The method of manufacturing a noble metal anode for electrolytic copper foil according to claim 1, wherein the iridium-tantalum system coating layer is prepared by using the following raw materials in a molar ratio: 60% -90% of iridium source and 10% -40% of tantalum source, wherein the tantalum source is selected from any one of tantalum pentachloride n-butyl alcohol solution, tantalum butanediol and tantalum ethoxide.
3. The method for preparing a noble metal anode for electrolytic copper foil according to claim 1, wherein the g-C is 3 N 4 The thickness of the middle layer is 0.5-1 μm; in the intermediate layer, g-C 3 N 4 The loading amount of the catalyst is 0.3-2.5 mg cm -2 。
4. The method for preparing a noble metal anode for electrolytic copper foil according to claim 1, wherein the iridium-tantalum system coating layer has a thickness of 6 to 10 μm, and IrO is used in the iridium-tantalum system coating layer 2 The loading amount of the element Ir in the form is 0.5-3 mg cm -2 。
5. The method for preparing a noble metal anode for electrolytic copper foil according to claim 1, wherein g-C in the step (2) 3 N 4 One selected from melamine, cyanuric chloride, cyanamide, dicyanodiamine and urea is obtained by thermal decomposition; g to C 3 N 4 Thermal decomposition, in particular: heating to 510-610 ℃ at the heating rate of 1-10 ℃/min, calcining at constant temperature for 1-4 h, naturally cooling, and grinding to obtain g-C 3 N 4 。
6. The method for preparing a noble metal anode for electrolytic copper foil according to claim 1, wherein the organic solvent A in the step (2) is selected from n-butanol, ethylene glycol, dimethylformamide, nitrogen-dimethyl pyrrolidone or a mixture thereof in any ratio.
7. The method for preparing a noble metal anode for electrolytic copper foil according to claim 1, wherein the tantalum source of the step (3) is selected from any one of tantalum pentachloride n-butanol solution, tantalum butanediol, tantalum ethoxide.
8. The method for preparing a noble metal anode for electrolytic copper foil according to claim 1, wherein the organic solvent B in the step (3) is selected from n-butanol, isopropanol, ethanol or a mixture thereof in any proportion.
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