CN117568878B - Production equipment of titanium anode and electrolytic copper foil - Google Patents
Production equipment of titanium anode and electrolytic copper foil Download PDFInfo
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- CN117568878B CN117568878B CN202410051440.3A CN202410051440A CN117568878B CN 117568878 B CN117568878 B CN 117568878B CN 202410051440 A CN202410051440 A CN 202410051440A CN 117568878 B CN117568878 B CN 117568878B
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- titanium
- titanium anode
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- anode
- tantalum
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000010936 titanium Substances 0.000 title claims abstract description 114
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 114
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000011889 copper foil Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 50
- 230000000996 additive effect Effects 0.000 claims abstract description 48
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 18
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 17
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 14
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- -1 hydroxyalkyl ethylenediamine Chemical compound 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 7
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 claims description 6
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- BYACHAOCSIPLCM-UHFFFAOYSA-N 2-[2-[bis(2-hydroxyethyl)amino]ethyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)CCN(CCO)CCO BYACHAOCSIPLCM-UHFFFAOYSA-N 0.000 claims description 3
- CYOIAXUAIXVWMU-UHFFFAOYSA-N 2-[2-aminoethyl(2-hydroxyethyl)amino]ethanol Chemical compound NCCN(CCO)CCO CYOIAXUAIXVWMU-UHFFFAOYSA-N 0.000 claims description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 claims description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 claims 1
- 241000270708 Testudinidae Species 0.000 abstract description 8
- 230000002035 prolonged effect Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 23
- 238000000576 coating method Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 20
- 239000002987 primer (paints) Substances 0.000 description 19
- 239000002253 acid Substances 0.000 description 17
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 17
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- 239000011159 matrix material Substances 0.000 description 15
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 12
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical compound [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 description 11
- 238000005245 sintering Methods 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 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 description 5
- ULFQGKXWKFZMLH-UHFFFAOYSA-N iridium tantalum Chemical compound [Ta].[Ir] ULFQGKXWKFZMLH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 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 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013528 artificial neural network Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The application relates to the technical field of electrolytic copper foil, in particular to a titanium anode and production equipment of the electrolytic copper foil. The titanium anode comprises a titanium substrate and an active layer on the surface of the titanium substrate, wherein the active layer comprises noble metal oxide and an additive; noble metal oxides include oxides of iridium and tantalum; the additive comprises a hydroxyalkyl ethylenediamine additive. After the hydroxyalkyl ethylenediamine additive is introduced into the active layer, the tortoise cracks on the surface of the titanium anode can be reduced, the durability of the titanium anode can be improved, and the service life of the titanium anode can be prolonged.
Description
Technical Field
The application relates to the technical field of electrolytic copper foil, in particular to a titanium anode and production equipment of the electrolytic copper foil.
Background
The electrolytic copper foil is an important material for manufacturing copper-clad plates, printed circuit boards and lithium ion batteries. In the current high-speed development of the electronic information industry, the electrolytic copper foil is called a 'neural network' for transmitting and communicating signals and power of electronic products. The electrolytic copper foil is produced by reducing copper ions to copper metal by means of electrolysis, thereby obtaining a high-purity copper foil. In this process, the anode acts as an oxidation to convert copper ions to copper, thereby maintaining the concentration of copper ions in the electrolyte.
The electrolytic copper foil anode is an indispensable part of the electrolytic copper foil production process. The quality and stability of the copper foil directly affect the quality and production efficiency of the copper foil. The titanium anode for the electrolytic copper foil has higher electrocatalytic performance, less anode slag, more stable electrode spacing and longer service life, and plays a key role in uniformity of copper foil products and stability of an electrolytic process.
Currently, titanium anodes generally comprise a titanium substrate, and an active layer containing iridium (Ir), tantalum (Ta) applied to the surface thereof. The preparation method comprises the steps of dissolving a metal solution with a molar ratio of Ir:Ta=7:3 in an organic solvent, and preparing the IrO 2-Ta2O5 electrode through coating and high-temperature calcination. However, the titanium anode prepared by the method has larger cracks, and electrolyte with large flow is easy to fall off due to impact, so that the anode fails.
Disclosure of Invention
In view of this, the present invention provides a production facility for titanium anodes and electrolytic copper foil. After the hydroxyalkyl ethylenediamine additive is introduced into the active layer, the tortoise cracks on the surface of the titanium anode can be reduced, the durability of the titanium anode can be improved, and the service life of the titanium anode can be prolonged.
In order to achieve the above object, the present invention provides the following technical solutions:
In a first aspect, the present invention provides a titanium anode comprising a titanium substrate and an active layer on a surface thereof, the active layer comprising a noble metal oxide and an additive;
Noble metal oxides include oxides of iridium and tantalum;
the additive comprises at least one of the following compounds:
Wherein each R 1、R2、R3、R4 is independently selected from H, C 1-4 alkyl, C 1-4 hydroxyalkyl; at least one of R 1、R2、R3、R4 is C 1-4 hydroxyalkyl.
For the conventional titanium anode, the surface tortoise crack is larger, and the active layer is easy to fall off due to the impact of a large flow of electrolyte, so that the anode is invalid. After the hydroxyalkyl ethylenediamine additive shown in the general formula is introduced into the active layer, the invention can reduce tortoise cracks on the surface of the titanium anode, improve the durability of the titanium anode, particularly the durability under complex working conditions, and prolong the service life of the titanium anode.
In an embodiment of the invention, the C 1-4 hydroxyalkyl group is selected from hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl or 4-hydroxybutyl.
In an embodiment of the invention, the C 1-4 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
In particular embodiments of the present invention, the additive includes, but is not limited to, at least one of N, N, N ', N' -tetrakis (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) ethylenediamine, N, N, N ', N' -tetrakis (2-hydroxypropyl) ethylenediamine, N, N-bis (2-hydroxyethyl) ethylenediamine.
In an embodiment of the invention, the oxide of iridium comprises at least one of IrO 2、IrO3、Ir2O3、Ir2O4. IrO 2 is preferred.
In an embodiment of the invention, the oxide of tantalum comprises Ta 2O5.
Preferably, the molar ratio of the additive to the noble metal oxide is (0.01 to 0.2): 1. The molar ratio of additive to noble metal oxide is illustratively any one of the values of 0.01:1, 0.03:1, 0.05:1, 0.08:1, 0.1:1, 0.13:1, 0.15:1, 0.18:1, 0.2:1 or any one of the values in the range of values.
Preferably, the noble metal oxide further comprises an oxide of cobalt. For the conventional titanium anode, the content of noble metal is relatively large, and the cost is high. According to the invention, non-noble metal cobalt is introduced and doped, so that the consumption of noble metal is reduced, and the production cost is reduced.
In an embodiment of the invention, the cobalt oxide comprises at least one of CoO, co 2O3、Co3O4.
Preferably, the molar ratio of iridium element, tantalum element and cobalt element is (0.8-1.2): (0-0.06). The invention can enhance the conductivity of the electrode by adjusting the molar ratio of iridium to tantalum. More preferably, the molar ratio of iridium element, tantalum element and cobalt element is (0.8-1.2): (0.04-0.06).
Preferably, the thickness of the active layer is 4 to 12 μm (micrometers). The thickness of the active layer is exemplified by any one of 4 μm,5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm or any one of the range values of the two values.
Preferably, a primer layer is also included between the titanium substrate and the active layer. The arrangement of the bottom coating can protect the titanium matrix and prevent the passivation of the titanium anode caused by the exposure of the titanium matrix.
Preferably, the primer layer comprises an oxide of tantalum. Wherein the oxide of tantalum comprises Ta 2O5.
Preferably, the thickness of the primer layer is 1 to 3 μm (micrometers). The thickness of the undercoat layer is exemplified by any one of 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm or any one of the range values composed of the two values.
Preferably, the titanium substrate has a roughness Rz of 50 to 70 μm (micrometers) and a Ra of 8 to 15 μm (micrometers). Rz is exemplified by any one of 50 μm, 52 μm, 54 μm, 56 μm, 58 μm, 60 μm, 61 μm, 62 μm, 63 μm, 64 μm, 65 μm, 66 μm, 67 μm, 68 μm, 69 μm, 70 μm or any one of the range values of the two-by-two values. Ra is exemplified by any one of 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm or any one of the range values of the above two-by-two values.
For the titanium matrix with the roughness Rz smaller than 50 mu m and the Ra smaller than 8 mu m, the binding force between the active layer, the base coat and other coatings and the titanium matrix is poor, and the coating is easy to fall off due to the impact of high acid, high current density and high flow due to the fact that the electrolytic copper foil anode is poor in use working condition, the titanium matrix is exposed, the anode is passivated, the service life of the anode is short, and the continuous production of the copper foil is affected. According to the invention, the roughness Rz of the titanium matrix is adjusted to be 50-70 mu m, the Ra is adjusted to be 8-15 mu m, so that the adhesive force of the coating is enhanced, the problem of poor adhesive force between the coating and the titanium matrix is solved, and the service life of the anode is prolonged.
In a specific embodiment of the invention, the titanium substrate has a roughness Rz of 65 μm and a Ra of 12 μm.
The invention also provides a preparation method of the titanium anode, which comprises the following steps:
Pretreatment: pretreating the surface of a titanium matrix;
Preparation of active liquid: mixing an iridium source, a tantalum source and an additive with a proper amount of organic solvent to obtain an active liquid;
Coating and sintering an active liquid: and (3) coating the active liquid on the surface of the titanium substrate, and sintering to obtain the titanium anode.
In an embodiment of the present invention, the pretreatment includes a blasting treatment and a cleaning treatment.
In the embodiment of the invention, the roughness Rz of the titanium substrate after the sand blasting treatment is 50-70 mu m, and the Ra is 8-15 mu m. Preferably, the roughness Rz is 60 to 70 μm and the Ra is 10 to 15 μm.
In an embodiment of the invention, the iridium source comprises at least one of chloroiridic acid, iridium trichloride, bromoiridic acid.
In an embodiment of the invention, the tantalum source comprises at least one of tantalum n-butanol pentachloride solution, tantalum butanediol, tantalum ethoxide.
In an embodiment of the invention, when the noble metal oxide comprises an oxide of cobalt, the active liquid is prepared by: and mixing the iridium source, the tantalum source, the cobalt source and the additive with an organic solvent to obtain an active liquid.
In an embodiment of the invention, the cobalt source comprises at least one of cobalt chloride, cobalt nitrate, cobalt oxalate.
In an embodiment of the present invention, the organic solvent includes any one of n-butanol, isopropanol, ethanol or a mixture thereof.
In the embodiment of the invention, the sintering temperature is 450-550 ℃ and the sintering time is 10-15 h.
In an embodiment of the present invention, when a primer layer is further included between the titanium substrate and the active layer, preparation of a primer solution, primer solution coating, and sintering are further included.
In an embodiment of the invention, the preparation method of the primer solution comprises the following steps: and mixing the tantalum source with a proper amount of organic solvent to obtain the primer solution. The organic solvent in the primer liquid comprises any one or a mixture of n-butanol, isopropanol and ethanol.
In an embodiment of the present invention, the method of primer coating and sintering is: and (3) coating the primer on the surface of the titanium matrix, and sintering to obtain the titanium matrix coated with the primer. At this time, the steps of active liquid coating and sintering are as follows: and (3) coating the active liquid on the surface of the titanium substrate coated with the bottom coating, and sintering to obtain the titanium anode.
The invention also provides application of the titanium anode in preparing electrolytic copper foil.
In a second aspect, the present invention provides an electrolytic copper foil production apparatus comprising the above titanium anode.
Compared with the prior art, the invention has the following beneficial effects:
After the hydroxyalkyl ethylenediamine additive is introduced into the active layer, the invention can reduce tortoise cracks on the surface of the titanium anode, improve the durability of the titanium anode, especially under complex working conditions, and prolong the service life of the titanium anode.
Furthermore, according to the invention, through adjusting the molar ratio of iridium to tantalum, non-noble metal cobalt is introduced and doped, so that the conductivity of the electrode is enhanced, the consumption of noble metal is reduced, and the production cost is reduced.
Further, the arrangement of the bottom coating can protect the titanium matrix and prevent the passivation of the titanium anode caused by the exposure of the titanium matrix.
Furthermore, the invention enhances the adhesive force of the coating by adjusting the roughness Rz of the titanium matrix to 50-70 mu m and the Ra to 8-15 mu m, solves the problem of poor adhesive force between the coating and the titanium matrix, and prolongs the service life of the anode.
Drawings
FIG. 1 is a schematic view of a titanium anode structure according to the present invention, wherein 1 is a titanium substrate, 2 is a primer layer, and 3 is an active layer.
FIG. 2 is an SEM image (with additives) of a titanium anode (Co 3O4/IrO2-Ta2O5 electrode) of example 1.
Fig. 3 is an SEM image (no additive) of the titanium anode of comparative example 1 (IrO 2-Ta2O5 electrode).
Fig. 4 is an SEM image (no additive) of the titanium anode (Co 3O4/IrO2-Ta2O5 electrode) of comparative example 2.
FIG. 5 is a graph showing oxygen evolution potential of different electrodes in example 1, comparative example 1 and comparative example 2; wherein the titanium anode of comparative example 1 is labeled "IrO 2-Ta2O5" in the figure, the titanium anode of comparative example 2 is labeled "Co 3O4/IrO2-Ta2O5 without additive in the figure, and the titanium anode of example 1 is labeled" Co 3O4/IrO2-Ta2O5 with additive in the figure.
FIG. 6 is a graph comparing Cyclic Voltammograms (CV) of different electrodes of example 1, comparative example 1 and comparative example 2; wherein the titanium anode of comparative example 1 is labeled "IrO 2-Ta2O5" in the figure, the titanium anode of comparative example 2 is labeled "Co 3O4/IrO2-Ta2O5 without additive in the figure, and the titanium anode of example 1 is labeled" Co 3O4/IrO2-Ta2O5 with additive in the figure.
FIG. 7 is a graph showing the comparison of electrolytic life of different electrodes in example 1, comparative example 1 and comparative example 2; wherein the titanium anode of comparative example 1 is labeled "IrO 2-Ta2O5" in the figure, the titanium anode of comparative example 2 is labeled "Co 3O4/IrO2-Ta2O5 without additive in the figure, and the titanium anode of example 1 is labeled" Co 3O4/IrO2-Ta2O5 with additive in the figure.
Detailed Description
The invention discloses production equipment of a titanium anode and an electrolytic copper foil, and a person skilled in the art can properly improve the technological parameters by referring to the content of the invention. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention.
Term interpretation:
the surface roughness (surface roughness) refers to the small pitch and the unevenness of the minute peaks and valleys of the processed surface. The distance (wave distance) between two wave crests or wave troughs is very small and is generally below 1mm, and the wave crests or wave troughs are difficult to distinguish by naked eyes, and belong to microscopic geometric errors. The smaller the surface roughness, the smoother the surface.
The surface roughness is expressed as follows:
rz represents the microscopic unevenness ten-point height: the sum of the average of the maximum profile peak heights and the average of the five maximum profile valley depths over the sampling length;
Ra represents the arithmetic mean deviation of the profile: the arithmetic mean of the absolute value of the profile offset over the sampling length.
The reagents, instruments, materials, etc. used in the present invention are commercially available.
The invention is further illustrated by the following examples:
example 1
1. Titanium substrate 1 treatment:
The surface of the titanium matrix 1 is subjected to sand blasting treatment by adopting steel grit until the roughness Rz reaches 65 micrometers and the Ra reaches 12 micrometers. Etching with 10% boiling oxalic acid for 2 hr to remove oil and impurities on the surface. And (3) cleaning the pickled titanium plate by ultrasonic for 1 hour, then repeatedly cleaning the titanium plate by pure water for 2 times, and drying for later use.
2. Preparation of primer layer 2:
1mL of 0.588 mol/L tantalum pentachloride n-butanol solution is weighed and dissolved in 8.58 mL n-butanol, 2mL of hydrochloric acid is added, and finally the concentration of the obtained tantalum pentachloride n-butanol solution is 0.065 mol/L, so that a primer solution is obtained.
The primer solution was applied to the treated titanium substrate 1 by brushing, calcining at 500℃for 20 min times, and repeating this step 6 times, to obtain a primer layer 2 comprising tricobalt tetraoxide and having a thickness of about 2. Mu.m.
3. Preparation of active layer 3:
0.77g of 35% chloroiridium acid solution is weighed and dissolved in 3mL of isopropanol, the concentration of the chloroiridium acid solution is 0.175 mol/L (solution A), 1mL of 0.588 mol/L of tantalum pentachloride n-butanol solution is weighed and dissolved in 3.19mL of n-butanol, the concentration of the obtained tantalum pentachloride n-butanol solution is 0.175 mol/L (solution B), the solution A and the solution B are mixed according to the volume ratio of 1:1, and meanwhile 0.003g of cobalt chloride is added to obtain a mixed solution; and hydrochloric acid corresponding to 1/10 volume of the mixed solution was added thereto, and the above was sufficiently stirred for dissolution. After dissolution, 0.0093g of additive N, N, N ', N' -tetra (2-hydroxyethyl) ethylenediamine is added, the molar ratio of chloroiridium acid, tantalum pentachloride, cobalt chloride and additive is 1:1:0.05: and 0.2, stirring and dissolving to obtain an active liquid for standby.
The active liquid was applied on the titanium substrate 1 coated with the undercoat layer 2 by brushing, and the procedure was repeated 30 times at 500 c for 20min hours, and the last calcination was performed for 2 hours, to obtain the active layer 3 comprising iridium dioxide, tantalum pentoxide, and tricobalt tetraoxide, having a thickness of about 6 μm, to obtain a titanium anode having a structure shown in fig. 1, the scanning electron microscope view of which is shown in fig. 2. As can be seen from fig. 2, the SEM of the titanium anode (Co 3O4/IrO2-Ta2O5 electrode, with additive) of this example has few cracks in the coating, the surface of the coating is smoother, and the iridium oxide is uniformly distributed on the surface of the electrode in the form of spinel-like clusters, which indicates that the precipitated iridium oxide is uniformly distributed.
Example 2 group
The preparation process was essentially the same as in example 1, the only difference being the type of additive.
Example 2a: n- (2-hydroxyethyl) ethylenediamine;
Example 2b: n, N' -tetrakis (2-hydroxypropyl) ethylenediamine;
example 2c: n, N-bis (2-hydroxyethyl) ethylenediamine.
Example 3 group
The preparation is essentially the same as in example 1, the only difference being the amount of additive used.
Example 3a: the mol ratio of the chloroiridium acid, the tantalum pentachloride, the cobalt chloride and the additive is 1:1:0.05:0.02;
example 3b: the mol ratio of the chloroiridium acid, the tantalum pentachloride, the cobalt chloride and the additive is 1:1:0.05:0.4;
example 3c: the mol ratio of the chloroiridium acid, the tantalum pentachloride, the cobalt chloride and the additive is 1:1:0.05:0.01;
example 3d: the mol ratio of the chloroiridium acid, the tantalum pentachloride, the cobalt chloride and the additive is 1:1:0.05:0.5.
Example 4 group
The preparation was essentially the same as in example 1, with the only difference being the molar ratio of iridium to tantalum.
Example 4a: the molar ratio of the chloroiridic acid, the tantalum pentachloride, the cobalt chloride and the additive is 0.8:1.2:0.05:0.2;
Example 4b: the mol ratio of the chloroiridium acid, the tantalum pentachloride, the cobalt chloride and the additive is 1.2:0.8:0.05:0.2;
Example 4c: the molar ratio of the chloroiridic acid, the tantalum pentachloride, the cobalt chloride and the additive is 0.6:1.4:0.05:0.2;
example 4c: the mol ratio of the chloroiridium acid, the tantalum pentachloride, the cobalt chloride and the additive is 1.4:0.6:0.05:0.2.
Example 5 group
The preparation process was essentially the same as in example 1, the only difference being the amount of cobalt chloride in the active solution.
Example 5a: cobalt chloride is not added;
example 5b: the molar ratio of the chloroiridic acid, the tantalum pentachloride, the cobalt chloride and the additive is 0.8:1.2:0.04:0.2;
example 5c: the mol ratio of the chloroiridium acid, the tantalum pentachloride, the cobalt chloride and the additive is 1.2:0.8:0.06:0.2;
example 5d: the mol ratio of the chloroiridium acid, the tantalum pentachloride, the cobalt chloride and the additive is 1:1:0.08:0.2.
Example 6 group
The preparation process is essentially the same as in example 1, the only difference being that: the active layers 3 with different thicknesses are obtained through the brushing times and the calcining times of the active liquid.
Example 6a:4 μm;
example 6b:8 μm;
example 6c:0.5 μm;
Example 6d:12 μm.
Example 7 group
The preparation process is essentially the same as in example 1, the only difference being that: the primer layers 2 of different thicknesses are obtained by the number of brushing and the number of calcining of the primer liquid.
Example 7a:1 μm;
example 7b:3 μm;
example 7c:0 μm;
example 7d:5 μm.
Example 8 group
The preparation process is essentially the same as in example 1, the only difference being the roughness of the titanium substrate 1.
Example 8a: rz is 60 μm and Ra is 10 μm;
Example 8b: rz is 70 μm and Ra is 15 μm;
example 8c: rz is 50 μm and Ra is 8 μm;
example 8d: rz is 80 μm and Ra is 17 μm;
example 8e: rz is 40 μm and Ra is 6 μm.
Comparative example 1
The preparation process was essentially the same as in example 1, except that no additive was added and no cobalt chloride was added to the active solution.
See fig. 3 for a scanning electron microscope image of the titanium anode of this comparative example. As can be seen from FIG. 3, the SEM of the titanium anode (IrO 2-Ta2O5 electrode, without additive) of this comparative example showed that the surface tortoise cracks were large and the surface was rough, and that no spinel-like clusters were distributed on the electrode surface in the SEM, indicating that no iridium oxide was precipitated on the electrode surface.
Comparative example 2
The preparation was essentially the same as in example 1, except that no additives were added.
See fig. 4 for a scanning electron microscope image of the titanium anode of this comparative example. As can be seen from fig. 4, the SEM of the titanium anode (Co 3O4/IrO2-Ta2O5 electrode, without additive) of the comparative example had a large surface crack, uneven surface, protrusions, and the anode of this structure had a poor life, and no sharp cone-shaped clusters were distributed on the electrode surface in the SEM image, indicating that iridium oxide was not precipitated on the electrode surface, and thus the conductivity of the electrode was poor.
Test case
1. Oxygen evolution potential test:
Test conditions: the platinum electrode was used as a counter electrode, the titanium anodes of examples and comparative examples were used as working electrodes, and the Ag/AgCl electrode was used as a reference electrode, and scanning was performed at a sweep rate of 10mV/s in an aqueous solution of 1mol/LH 2SO4, and oxygen evolution potentials at an oxygen evolution current density of 10A/dm 2 were recorded, respectively.
2. Electrode activity test:
test conditions: the electrochemical cyclic voltammetry test is adopted, the bias scanning range is 0.16-1.16V, and the scanning speed is 0.05V/s in 1mol/L H 2SO4 of aqueous solution.
3. Reinforced life test:
Test conditions: to verify the durability of the titanium anode, the titanium anodes of the above examples and comparative examples were respectively subjected to a life-strengthening test in a sulfuric acid electrolyte of 1mol/L, with a current density of 30000A/square meter and a polar spacing of 1.5cm.
The test results are shown in FIGS. 5-7 and the following tables:
TABLE 1 oxygen evolution potential, electrode Activity and enhanced lifetime test results
As can be seen from the test results of example 1 and comparative examples 1-2, after the hydroxyalkyl ethylenediamine additive is added to the active layer 3, the tortoise cracks on the surface of the titanium anode can be significantly reduced, the durability of the titanium anode can be improved, and the service life of the titanium anode can be prolonged.
The test results of the example 2 show that the tortoise cracks on the surface of the titanium anode can be obviously reduced, the durability of the titanium anode can be improved, and the service life of the titanium anode can be prolonged for different hydroxyalkyl ethylenediamine additive types.
As shown by the test results of the group 3, when the additive amount is within the limited range, the iridium tantalum coating liquid is slowly deposited on the surface of the titanium substrate 1, and has good dispersibility and uniform deposition. Above or below the limit range of the invention, the iridium tantalum coating liquid has poor agglomeration and dispersion on the surface of the titanium substrate 1 and uneven deposition.
The test results of the group 4 show that the iridium-tantalum molar ratio is within a limited range (0.8-1.2), and the catalyst has good catalytic activity and strong conductivity. When the catalyst is higher or lower than the limit range of the invention, the catalyst is poor, the oxygen evolution reaction is poor and the cost is high.
As shown by the test results of the group 5, when the molar ratio of iridium to tantalum to cobalt is within a limited range of (0.8-1.2): (0.04-0.06), grains of the material can be thinned, and the electrode activity can be improved. Above or below the limits defined in the present invention, cobalt metal may affect the formation of iridium tantalum solid solutions.
As shown by the test results of the group 6, when the thickness of the active layer 3 is within the limited range of 4-12 μm, the catalytic activity is good, the cost is low, and the service life of the electrode is long. If the thickness is less than the defined range, the electrode activity is poor; if the thickness is larger than the limit range, the cost is high.
As is clear from the test results of the group 7, when the thickness of the undercoat layer 2 is within the limited range of 1 to 3. Mu.m, the titanium substrate 1 can be well protected from passivation. If the amount is outside the defined range, the formation of solid solution of the coating layer and the bonding force between the undercoat layer 2 and the active coating layer are affected.
As shown by the test results of the group 8, when the roughness of the titanium substrate 1 is within the limit range Rz of 50-70 μm and Ra of 8-15 μm, the adhesion between the undercoat layer 2 and the titanium substrate 1 can be enhanced, and when the roughness is smaller than the limit range, the adhesion between the undercoat layer 2 and the titanium substrate 1 is deteriorated, and the service life of the titanium anode is reduced; when the roughness is increased, thicker iridium tantalum coating liquid is needed to cover the substrate, and the cost is high.
Example 9
The embodiment provides production equipment of electrolytic copper foil, which comprises any one of the titanium anodes in the embodiments 1-8.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A titanium anode, characterized in that the titanium anode comprises a titanium substrate and an active layer on the surface of the titanium substrate, wherein the active layer comprises noble metal oxide and an additive;
the noble metal oxide comprises iridium oxide, tantalum oxide and cobalt oxide, wherein the molar ratio of iridium element to tantalum element to cobalt element in the noble metal oxide is (0.8-1.2) (0-0.06);
the additive comprises at least one of the following compounds having the general formula:
Wherein each R 1、R2、R3、R4 is independently selected from H, C 1-4 alkyl, C 1-4 hydroxyalkyl; at least one of R 1、R2、R3、R4 is C 1-4 hydroxyalkyl;
an undercoat layer is also included between the titanium substrate and the active layer, the undercoat layer comprising an oxide of tantalum.
2. The titanium anode according to claim 1, wherein said C 1-4 hydroxyalkyl is selected from hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl or 4-hydroxybutyl;
the C 1-4 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
3. The titanium anode according to claim 1, wherein the additive comprises N, N, N ', N' -tetrakis (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) ethylenediamine, N, at least one of N, N ', N' -tetra (2-hydroxypropyl) ethylenediamine and N, N-bis (2-hydroxyethyl) ethylenediamine.
4. The titanium anode of claim 1, wherein the molar ratio of the additive to noble metal oxide is (0.01-0.2): 1.
5. The titanium anode of claim 1, wherein the active layer has a thickness of 4-12 μm.
6. The titanium anode of claim 1, wherein the primer layer has a thickness of 1 to 3 μm.
7. The titanium anode according to any one of claims 1 to 6, wherein the titanium substrate has a roughness Rz of 50 to 70 μm and a Ra of 8 to 15 μm.
8. An electrolytic copper foil production apparatus comprising the titanium anode according to any one of claims 1 to 7.
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