CN117646270B - Titanium anode suitable for organic additive application system and manufacturing method thereof - Google Patents
Titanium anode suitable for organic additive application system and manufacturing method thereof Download PDFInfo
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- CN117646270B CN117646270B CN202410118656.7A CN202410118656A CN117646270B CN 117646270 B CN117646270 B CN 117646270B CN 202410118656 A CN202410118656 A CN 202410118656A CN 117646270 B CN117646270 B CN 117646270B
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000010936 titanium Substances 0.000 title claims abstract description 79
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 78
- 239000006259 organic additive Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 238000000576 coating method Methods 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000009713 electroplating Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 15
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 7
- 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 claims abstract description 4
- 238000000137 annealing Methods 0.000 claims abstract description 4
- 239000010406 cathode material Substances 0.000 claims abstract description 4
- 238000001953 recrystallisation Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000005868 electrolysis reaction Methods 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000007747 plating Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 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 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical compound [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 14
- 239000010410 layer Substances 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011889 copper foil Substances 0.000 abstract description 8
- 230000002035 prolonged effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 abstract 3
- 239000011247 coating layer Substances 0.000 abstract 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 abstract 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 11
- ULFQGKXWKFZMLH-UHFFFAOYSA-N iridium tantalum Chemical compound [Ta].[Ir] ULFQGKXWKFZMLH-UHFFFAOYSA-N 0.000 description 6
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 5
- 239000010405 anode material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910052741 iridium Inorganic materials 0.000 description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 241000270708 Testudinidae Species 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- CSLZEOQUCAWYDO-UHFFFAOYSA-N [O-2].[Ti+4].[Ta+5] Chemical compound [O-2].[Ti+4].[Ta+5] CSLZEOQUCAWYDO-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011900 installation process Methods 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a method for manufacturing a titanium anode suitable for an organic additive application system, which comprises the following steps: carrying out surface heat treatment, recrystallization and annealing on a titanium material, carrying out electrochemical corrosion on the titanium material cooled along with a furnace, preparing a nano sol coating solution containing chloroiridic acid and tantalum pentachloride n-butyl alcohol solution, coating the nano sol coating solution on the surface of the dried titanium material, putting the titanium material with the Ir/Ta coating layer serving as an anode plate into an electroplating solution, and electroplating a lead oxide layer with high oxygen evolution potential on the surface of the titanium anode by taking a TA1 titanium plate as a cathode material. In the electrolytic reaction process, the anode end can decompose organic matters harmful to the anode, and the condition that an organic additive is complexed with a noble metal coating is avoided, so that the service life of the titanium anode of an electrolytic copper foil lead-free system or a high organic additive system is effectively prolonged. The invention also provides a titanium anode prepared by the method.
Description
Technical Field
The invention relates to the technical field of titanium anodes, in particular to a titanium anode suitable for an organic additive application system and a manufacturing method thereof.
Background
In the production of electrolytic copper foil, the anode current is 6000-10000A/square meter, and the electrolyte contains various organic additives and trace metal impurities. During electrolysis, the anode surface noble metal oxide is easily complexed by the organic additive. For example Ir 4+ Reduced to Ir in an organic additive R (reducing) 2+ (Ir) ,IrO 2 And Ta 2 O 5 The titanium oxide is of a rutile structure, is similar to the titanium oxide, and has good stability. The organic matter is a reducing substance, and no lead oxide on the surface can cause the organic matter and oxygenThe iridium is directly reacted, and tetravalent iridium is reduced into 2-valence iridium or simple substance iridium by an organic matter, so that the coating is dissolved and falls off. Because lead oxide is not generated on the surface of the anode plate, under the condition of high-current electrolysis, the noble metal coating is in a crack shape, a large amount of oxygen is separated out from the surface of the anode, and the noble metal iridium oxide is slowly eroded after being eroded by oxygen at a high speed. The too fast consumption rate of the noble metal coating can cause the adverse effects of increased power consumption of production enterprises, uneven surface density of copper foil, reduced product qualification rate and the like. The main reason is that a lead oxide substance is not formed on the surface of the anode to protect the noble metal coating.
Aiming at the problem, at present, copper foil factories generally adopt copper raw materials with higher lead content or lead sulfate/basic lead carbonate and other modes to increase the lead content, and the purpose is to form a lead oxide layer on the surface of an anode plate to protect noble metal coating in the electrolytic process. However, due to the improvement of the requirements of copper foil products on impurity elements and the conductivity difference caused by the installation process of the anode plate, the adhesion uniformity and the binding force of lead oxide cannot be ensured.
In view of the above, it is an object of the present invention to provide a titanium anode suitable for an organic additive application system and a method for manufacturing the same.
Disclosure of Invention
The invention aims to provide a manufacturing method of a titanium anode suitable for an organic additive application system, lead dioxide plating layers are formed on the surfaces of the titanium anode, organic matters harmful to the anode can be decomposed from the anode end in the electrolytic reaction process, the condition that an organic additive is complexed with a noble metal coating is avoided, and therefore the service life of the titanium anode of an electrolytic copper foil lead-free system or a high organic additive system is effectively prolonged.
The technical scheme of the invention is as follows:
a method for manufacturing a titanium anode suitable for an organic additive application system, comprising the steps of:
step S1, carrying out surface heat treatment, recrystallization and annealing on a titanium material, wherein the heat treatment temperature is 650-680 ℃, and cooling along with a furnace after heat preservation for 2-3 hours;
step S2, carrying out electrochemical corrosion on the titanium material cooled along with the furnace, wherein the titanium material is subjected to electrochemical corrosionThe electrolyte comprises the following components: 1 to 1.05mol/L NH 4 Br,0.1-0.15mol/L NaF,0.05-0.06mol/L HCl,2-5ppm polyethylene glycol-2000; wherein the pH value of the electrolyte is 2-3, and the temperature is 25-30 ℃;
the electrolysis process comprises the following steps: the current density is 50-80A/m 2 The electrolysis time is 60-120min;
step S3, cleaning the titanium material subjected to electrochemical corrosion by distilled water after ultrasonic oscillation, and drying;
step S4, preparing a nanosol coating solution containing chloroiridic acid and tantalum pentachloride n-butanol solution, wherein the method comprises the following steps of:
88g/m 2 122ml/m of citric acid 2 Heating to 60 ℃, adding 126ml/m absolute ethanol under continuous stirring 2 Mixing with citric acid, and adding 60g/m 2 Chloroiridium acid and 85g/m 2 Tantalum pentachloride n-butanol solution, and finally adding absolute ethanol 350ml/m 2 Stirring uniformly;
step S5, coating the nano sol coating liquid on the surface of the titanium material dried in the step S3, heating the titanium material to 480-520 ℃ in an oxidation furnace, and sintering the coated titanium material in the oxidation furnace for 10-20min;
wherein, the heating temperature of the oxidation furnace can be 480 ℃, 500 ℃ or 520 ℃, and can also be other values within the range; the sintering time can be 10min, 15min or 20min, or can be other values within the range;
s6, naturally cooling, repeating the step S5, and forming an Ir/Ta coating with the thickness of 1.5-1.8 micrometers on the surface of the titanium material, wherein the final sintering time is 50-60min;
step S7, preparing a plating solution, which comprises the following components: 400g/L of lead nitrate, 50g/L of nitric acid, 44g/L of glycol, 2g/L of polyvinylpyrrolidone and 5g/L of zirconia;
step S8, heating the prepared electroplating solution to 60-65 ℃, putting the titanium material with the Ir/Ta coating formed in the step S6 into the electroplating solution as an anode plate, and taking a TA1 titanium plate as a cathode material, wherein the distance between the anode and the cathode is 10+/-0.5 cm; current density setting of 150-250A/m 2 Electroplating for 5-20min to form a layer on the surface of the titanium anodeA dense lead oxide coating; wherein, the heating temperature of the plating solution can be 60 ℃, 62 ℃ or 65 ℃, or can be other values within the range;
and S9, carrying out ultrasonic cleaning on the anode plate subjected to electroplating, and drying.
In the step S2, the electrolysis temperature is 30-50 ℃, a TA1 titanium plate is used as a cathode, and the distance between the anode and the cathode is 80-100mm.
Further, in step S2, the power used in the electrolysis process is a positive and negative pulse power, and the parameters thereof are as follows:
rated voltage: 24V, rated current: 2000A, rated power: 48kw, pulse frequency: 1000Hz, duty cycle: 20%.
Further, in step S3, the drying temperature is 110-130 ℃ and the drying time is 10-20min. Specifically, the drying temperature may be 110 ℃, 120 ℃ or 130 ℃, or may be other values within the range; the drying time may be 10min, 20min or 30min, or may be other values within this range.
Further, the titanium material is TA1, the grain size is 6-9 grade, and the Rockwell hardness is HRC50-60.
The invention also provides a titanium anode suitable for an organic additive application system, which is prepared by the method.
Compared with the prior art, the titanium anode suitable for the organic additive application system and the manufacturing method thereof have the beneficial effects that:
because the pure TA1 titanium plate belongs to valve metal, the conductivity is poor, and electroplating cannot be directly carried out, the pure titanium plate is subjected to titanium tantalum oxide pretreatment, and the conductivity is improved, so that the binding force and the efficiency of a plating layer are improved. According to the manufacturing method of the titanium anode suitable for the application system of the organic additive, provided by the invention, the lead dioxide coating with high oxygen evolution potential is formed on the surface of the titanium anode by electroplating, and the ethylene glycol organic additive in the electroplating solution in the electroplating process can improve the diffusion coefficient of lead ions in the electroplating process, so that continuous nucleation is converted into instant nucleation, and the deposition rate of the lead ions on the surface of a substrate is further improved; the existence of zirconia can inhibit the deposition of lead dioxide and help refine twoLead oxide crystal grains obviously reduce the crystal grain size of lead dioxide, improve the specific surface area and enhance the electrocatalytic efficiency; the small amount of polyvinylpyrrolidone can control PbO 2 The surface morphology, fine particle size, and increase oxygen evolution overpotential during plating. The oxygen evolution point of the lead dioxide coating is 1.93v relative to the oxygen evolution point of the saturated calomel electrode, the oxygen evolution potential of the iridium tantalum coating is 1.4v, and the high oxygen evolution potential material has stronger oxidability in the electrolysis process, can open an organic molecular chain, further oxidatively decompose the organic molecular chain into carbon dioxide and water, and effectively prevents the complexing action of the organic matters on noble metal oxides, thereby effectively prolonging the service life of the titanium anode of the electrolytic copper foil lead-free system or the high organic additive system.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern for different anode materials;
FIG. 2 is an SEM image of a different anode material;
FIG. 3 is a plot of life effects of different anode materials;
fig. 4 is a LSV plot of different anode materials.
Detailed Description
In order to better understand the technical solution in the embodiments of the present invention and make the above objects, features and advantages of the present invention more obvious and understandable, the following detailed description of the present invention will be further described.
The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1
A method for manufacturing a titanium anode suitable for an organic additive application system, comprising the steps of:
step S1, selecting a titanium material TA1, wherein the grain size of the titanium material TA1 is 6-9 grades, and the Rockwell hardness is HRC50-60; carrying out surface heat treatment, recrystallization and annealing on the titanium material, wherein the heat treatment temperature is 680 ℃, and cooling along with a furnace after heat preservation for 3 hours;
step S2, carrying out electrochemical corrosion on the titanium material cooled along with the furnace, wherein the electrolyte comprises the following components: 1.05mol/L NH 4 Br, 0.15mol/L NaF, 0.06mol/L HCl, 5ppm polyethylene glycol-2000; wherein the pH value of the electrolyte is 2-3, and the temperature is 30 ℃; the cathode is a TA1 titanium plate; the distance between the anode and the cathode is 10cm;
the electrolysis process comprises the following steps: current density 80A/m 2 The electrolysis time is 80min;
the power source used in the electrolysis process is a positive and negative pulse power source, and the parameters are as follows:
rated voltage: 24V, rated current: 2000A, rated power: 48kw, pulse frequency: 1000Hz, duty cycle: 20%.
In the invention, the arrangement of the electrochemical etching process can ensure the uniformity of the surface roughness and the bonding firmness of the anode.
Step S3, cleaning the titanium material subjected to electrochemical corrosion by distilled water after ultrasonic oscillation, and drying for 15min at 120 ℃;
step S4, preparing a nanosol coating solution containing chloroiridic acid and tantalum pentachloride n-butanol solution, which specifically comprises the following steps: 88g/m 2 122ml/m of citric acid 2 Heating to 60 ℃, adding 126ml/m absolute ethanol under continuous stirring 2 Mixing with citric acid, and adding 60g/m 2 Chloroiridium acid and 85g/m 2 Tantalum pentachloride n-butanol solution, and finally adding absolute ethanol 350ml/m 2 Stirring uniformly;
step S5, coating the nano sol coating liquid on the surface of the titanium material dried in the step S3, heating the oxidation furnace to 500 ℃, and sintering the coated titanium material in the oxidation furnace for 15min;
s6, naturally cooling, repeating the step S5, and forming a noble metal coating with the thickness of 1.5-1.8 micrometers on the surface of the titanium material, wherein the final sintering time is 60 minutes;
step S7, preparing a plating solution, which comprises the following components: 400g/L of lead nitrate, 50g/L of nitric acid, 44g/L of glycol, 2g/L of polyvinylpyrrolidone and 5g/L of zirconia;
step S8, heating the prepared electroplating solution to 65 ℃, putting the titanium material with the noble metal coating formed in the step S6 into the electroplating solution as an anode plate, and taking a TA1 titanium plate as a cathode material, wherein the distance between the anode and the cathode is 10cm; current density setting 200A/m 2 Electroplating for 5min to form a compact lead oxide coating on the surface of the titanium anode;
step S9, the electroplated anode plate is dried after ultrasonic cleaning, and the Ti-Ir/Ta-PbO is prepared 2 And an anode.
Comparative example 1
The titanium anode of comparative example 1 was prepared by omitting the step of electroplating lead oxide on the basis of example 1 and preparing a Ti-Ir/Ta anode in the same manner as in example 1.
Raw titanium plate, ti-Ir/Ta-PbO prepared in example 1 2 EDX tests are carried out on the anode and the Ti-Ir/Ta anode without lead oxide electroplating, the element content of the surface of the material is detected respectively, and the test results are shown in Table 1:
table 1: EDX test data for different anodes
As can be seen from Table 1, after the electroplating of the lead oxide layer on the Ti-Ir/Ta surface, no titanium element was detected on the surface layer of the material.
Raw titanium plate, ti-Ir/Ta-PbO prepared in example 1 2 As shown in FIG. 1, the XRD patterns of the anode and the Ti-Ir/Ta anode without electroplated lead oxide show that the weak peak of Ti-Ir/Ta-PbO2 at 26.7 degrees compared with Ti-Ir/Ta and TA1 Ti belongs to the (111) crystal face of beta-lead dioxide, the formed peak intensity is relatively weak due to the weak plating thickness and crystallinity, and 29The half-width of the lead dioxide coating was confirmed to be widened at 8 degrees (011), 36.8 degrees (020) and 56.2 degrees (310) and the peak intensities of tantalum and titanium at 40.2 degrees and 56.2 degrees were obviously weakened, which can be confirmed from the assistance of EDX.
Raw titanium plate, ti-Ir/Ta-PbO prepared in example 1 2 SEM images of the anode and the lead oxide-unplated Ti-Ir/Ta anode are shown in FIG. 2, wherein FIG. 2 (a) shows a raw material titanium plate, FIG. 2 (b) shows the lead oxide-unplated Ti-Ir/Ta anode, and FIG. 2 (c) shows the Ti-Ir/Ta-PbO prepared in example 1 2 And an anode. As can be seen from fig. 2: FIG. 2 (a) shows that the surface of the pure titanium substrate after sandblasting is relatively flat and has no active grains; FIG. 2 (b) shows that after the iridium tantalum layer is coated, a large amount of iridium tantalum solid solution crystals exist, the surface is rugged, active sites are increased, the catalytic performance is enhanced, but tortoise cracks exist, and electrolyte is easy to permeate, so that the electrode failure potential is rapidly increased; fig. 2 (c) electroplates 5min lead dioxide on the surface of the coating, the surface grains are smaller, the arrangement is compact, the permeation of electrolyte can be resisted to a certain extent, the service life of the catalyst is prolonged, the dissolution of noble metal iridium is reduced, meanwhile, the specific surface area is obviously increased, and the catalytic efficiency is improved.
Ti-Ir/Ta-PbO prepared in example 1 2 The service lives of the anode and the Ti-Ir/Ta anode without lead oxide electroplating are tested, and the testing method and the testing result are as follows:
70 mg and 144mg of protein are added every day respectively, four groups of experiments are parallel, the protein belongs to organic matters and is used for simulating actual use conditions, and the effect of accelerating life test under extreme conditions is achieved in the test. The end of life was determined when the voltage increased to 1.5 times the starting voltage. Please refer to fig. 3, which is a diagram showing the lifetime effect of different anode materials, as can be seen from fig. 3: the addition of the lead dioxide coating causes a slight increase in initial potential, but compared with the iridium tantalum active layer, the coating is more stable after lead dioxide is electroplated, and the voltage is slowly increased, which is related to the crystal structure and the compactness of the lead dioxide coating, so that the service life is obviously prolonged compared with the iridium tantalum active layer; secondly, the more protein is added, the protein and the active catalyst react chemically, the catalytic property is changed, the catalyst is deactivated/poisoned, and the service life is shortened.
Examples1 prepared Ti-Ir/Ta-PbO 2 The LSV graphs of the anode and the Ti-Ir/Ta anode without electroplated lead oxide are shown in FIG. 4, and as can be seen from FIG. 4, the lead dioxide has weak conductivity, and the lead dioxide active layer has a relatively higher potential than the iridium tantalum layer at the same current density, consistent with the life initiation test.
Comparative examples 2 to 5
By adjusting the content of the organic and inorganic additives (ethylene glycol, polyvinylpyrrolidone, zirconium oxide) in step S7 based on example 1, the current density was then 200A/m 2 The plating time was 5 minutes, the reinforced life test was performed at 65℃and the test method was the same as in example 1, and the other steps of the titanium anode manufacturing method were the same as in example 1, obtaining comparative examples 2 to 5. The life test data for comparative examples 2-5 are shown in Table 2:
table 2: life test data for different embodiments
Note that: in the table, the addition amount was 0.
As can be seen from Table 2, the addition of both organic and inorganic additives to the plating solution ensures that the noble metal coating is not easily consumed and increases the lifetime of the anode.
In summary, the titanium anode prepared by the method of the invention is electroplated on the surface of the titanium anode to form a lead dioxide coating with high oxygen evolution potential, and organic matters harmful to the anode can be decomposed at the anode end in the electrolytic reaction process, so that the condition that an organic additive is complexed with a noble metal coating is avoided, and the service life of the titanium anode of an electrolytic copper foil lead-free system or a high organic additive system is effectively prolonged.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention.
Claims (6)
1. A method for manufacturing a titanium anode suitable for an organic additive application system, comprising the steps of:
step S1, carrying out surface heat treatment, recrystallization and annealing on a titanium material, wherein the heat treatment temperature is 650-680 ℃, and cooling along with a furnace after heat preservation for 2-3 hours;
step S2, carrying out electrochemical corrosion on the titanium material cooled along with the furnace, wherein the electrolyte comprises the following components: 1 to 1.05mol/L NH 4 Br,0.1-0.15mol/L NaF,0.05-0.06mol/L HCl,2-5ppm polyethylene glycol-2000; wherein the pH value of the electrolyte is 2-3, and the temperature is 25-30 ℃;
the electrolysis process comprises the following steps: the current density is 50-80A/m 2 The electrolysis time is 60-120min;
step S3, cleaning the titanium material subjected to electrochemical corrosion by distilled water after ultrasonic oscillation, and drying;
step S4, preparing a nanosol coating solution containing chloroiridic acid and tantalum pentachloride n-butanol solution, wherein the method comprises the following steps of:
88g/m 2 122ml/m of citric acid 2 Heating to 60 ℃, adding 126ml/m absolute ethanol under continuous stirring 2 Mixing with citric acid, and adding 60g/m 2 Chloroiridium acid and 85g/m 2 Tantalum pentachloride n-butanol solution, and finally adding absolute ethanol 350ml/m 2 Stirring uniformly;
step S5, coating the nano sol coating liquid on the surface of the titanium material dried in the step S3, heating the titanium material to 480-520 ℃ in an oxidation furnace, and sintering the coated titanium material in the oxidation furnace for 10-20min;
s6, naturally cooling, repeating the step S5, and forming an Ir/Ta coating with the thickness of 1.5-1.8 micrometers on the surface of the titanium material, wherein the final sintering time is 50-60min;
step S7, preparing a plating solution, which comprises the following components: 400g/L of lead nitrate, 50g/L of nitric acid, 44g/L of glycol, 2g/L of polyvinylpyrrolidone and 5g/L of zirconia;
step S8, heating the prepared electroplating solution to 60-65 ℃, putting the titanium material with the Ir/Ta coating formed in the step S6 into the electroplating solution as an anode plate, and taking a TA1 titanium plate as a cathode material, wherein the distance between the anode and the cathode is 10+/-0.5 cm;
current density setting of 150-250A/m 2 Electroplating for 5-20min to form a compact lead oxide coating on the surface of the titanium anode;
and S9, carrying out ultrasonic cleaning on the anode plate subjected to electroplating, and drying.
2. The method according to claim 1, wherein in the step S2, the electrolysis temperature is 30-50deg.C, the TA1 titanium plate is used as the cathode, and the anode-cathode distance is 80-100mm.
3. The method for producing a titanium anode suitable for an organic additive application system according to claim 2, wherein in step S2, the power source used in the electrolysis process is a positive and negative pulse power source, and the parameters are as follows:
rated voltage: 24V, rated current: 2000A, rated power: 48kw, pulse frequency: 1000Hz, duty cycle: 20%.
4. The method for producing a titanium anode suitable for an organic additive application system according to claim 1, wherein in step S3, the drying temperature is 110-130 ℃ and the time is 10-20min.
5. The method of any one of claims 1 to 4, wherein the titanium material is TA1, has a grain size of 6 to 9 grades, and has a rockwell hardness of HRC50-60.
6. A titanium anode suitable for use in an organic additive application, prepared by the method of claim 1.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6280297A (en) * | 1985-10-02 | 1987-04-13 | Tanaka Kikinzoku Kogyo Kk | Production of electrode |
| JPH07229000A (en) * | 1993-12-24 | 1995-08-29 | Daiso Co Ltd | Oxygen generating anode |
| JPH09287096A (en) * | 1996-02-20 | 1997-11-04 | Nippon Steel Corp | Electrode for electrolysis |
| CN101608326A (en) * | 2009-04-03 | 2009-12-23 | 昆明理工大学 | The method of aluminium and aluminum alloy surface Direct Electroplating lead |
| CN102280626A (en) * | 2010-06-13 | 2011-12-14 | 宝山钢铁股份有限公司 | Composite lead dioxide electrode plate and manufacturing method thereof |
| CN114808067A (en) * | 2022-04-29 | 2022-07-29 | 中宁县宁华再生资源循环利用科技有限公司 | Titanium-based nano composite anode for zinc electrodeposition and processing technology thereof |
| CN114855105A (en) * | 2022-02-09 | 2022-08-05 | 宝鸡钛普锐斯钛阳极科技有限公司 | Pretreatment method of titanium anode base material |
| CN116240598A (en) * | 2023-02-08 | 2023-06-09 | 宝鸡钛普锐斯钛阳极科技有限公司 | Preparation method of titanium-based noble metal oxide coating electrode material |
-
2024
- 2024-01-29 CN CN202410118656.7A patent/CN117646270B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6280297A (en) * | 1985-10-02 | 1987-04-13 | Tanaka Kikinzoku Kogyo Kk | Production of electrode |
| JPH07229000A (en) * | 1993-12-24 | 1995-08-29 | Daiso Co Ltd | Oxygen generating anode |
| JPH09287096A (en) * | 1996-02-20 | 1997-11-04 | Nippon Steel Corp | Electrode for electrolysis |
| CN101608326A (en) * | 2009-04-03 | 2009-12-23 | 昆明理工大学 | The method of aluminium and aluminum alloy surface Direct Electroplating lead |
| CN102280626A (en) * | 2010-06-13 | 2011-12-14 | 宝山钢铁股份有限公司 | Composite lead dioxide electrode plate and manufacturing method thereof |
| CN114855105A (en) * | 2022-02-09 | 2022-08-05 | 宝鸡钛普锐斯钛阳极科技有限公司 | Pretreatment method of titanium anode base material |
| CN114808067A (en) * | 2022-04-29 | 2022-07-29 | 中宁县宁华再生资源循环利用科技有限公司 | Titanium-based nano composite anode for zinc electrodeposition and processing technology thereof |
| CN116240598A (en) * | 2023-02-08 | 2023-06-09 | 宝鸡钛普锐斯钛阳极科技有限公司 | Preparation method of titanium-based noble metal oxide coating electrode material |
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