CN117305919B - Preparation method of double-light copper foil for high-heat-resistance lithium battery - Google Patents
Preparation method of double-light copper foil for high-heat-resistance lithium battery Download PDFInfo
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- CN117305919B CN117305919B CN202311239243.6A CN202311239243A CN117305919B CN 117305919 B CN117305919 B CN 117305919B CN 202311239243 A CN202311239243 A CN 202311239243A CN 117305919 B CN117305919 B CN 117305919B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000011889 copper foil Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 34
- 229910052744 lithium Inorganic materials 0.000 title abstract description 34
- 239000003792 electrolyte Substances 0.000 claims abstract description 129
- 239000010949 copper Substances 0.000 claims abstract description 60
- 239000011888 foil Substances 0.000 claims abstract description 51
- 229910052802 copper Inorganic materials 0.000 claims abstract description 48
- 239000000654 additive Substances 0.000 claims abstract description 40
- 230000000996 additive effect Effects 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 27
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 23
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims abstract description 19
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims abstract description 19
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims abstract description 19
- JWYUFVNJZUSCSM-UHFFFAOYSA-N 2-aminobenzimidazole Chemical compound C1=CC=C2NC(N)=NC2=C1 JWYUFVNJZUSCSM-UHFFFAOYSA-N 0.000 claims abstract description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 16
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 16
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 15
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 238000005096 rolling process Methods 0.000 claims abstract description 13
- 125000002769 thiazolinyl group Chemical group 0.000 claims abstract description 7
- 239000001294 propane Substances 0.000 claims abstract description 5
- 238000002161 passivation Methods 0.000 claims description 93
- 238000005868 electrolysis reaction Methods 0.000 claims description 37
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 28
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 claims description 26
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 26
- 239000004280 Sodium formate Substances 0.000 claims description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 14
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 14
- 235000019254 sodium formate Nutrition 0.000 claims description 14
- 235000015393 sodium molybdate Nutrition 0.000 claims description 14
- 239000011684 sodium molybdate Substances 0.000 claims description 14
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 230000035515 penetration Effects 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 62
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 44
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000007664 blowing Methods 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 11
- UBILRPVXFRDZQT-UHFFFAOYSA-M sodium 1-(4,5-dihydro-1,3-thiazol-2-yl)propyl-oxido-bis(sulfanylidene)-lambda6-sulfane Chemical compound S1C(=NCC1)C(CC)S(=S)(=S)[O-].[Na+] UBILRPVXFRDZQT-UHFFFAOYSA-M 0.000 description 11
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 229910021642 ultra pure water Inorganic materials 0.000 description 10
- 239000012498 ultrapure water Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 5
- -1 polydithio-dipropyl Polymers 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- XPSQRFGOPLDGPO-UHFFFAOYSA-N sodium;dimethylazanide Chemical compound [Na+].C[N-]C XPSQRFGOPLDGPO-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 230000037303 wrinkles Effects 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention provides a preparation method of a double-light copper foil for a high heat-resistant lithium battery, which relates to the technical field of manufacturing of lithium electric copper foil, and the preparation method of the electrolytic copper foil comprises the following steps: (1) preparation of electrolyte: adding sulfuric acid into a copper simple substance source to obtain primary copper sulfate electrolyte, filtering, adding Cl ‑ to obtain secondary electrolyte, and mixing with an additive solution to obtain electrolyte; the additive solution comprises: thiazolinyl dithiopropane sodium sulfonate, 3-mercapto-1-propane sodium sulfonate, hydroxyethyl cellulose, polyethylene glycol, polyethylene imine, 2-aminobenzimidazole; (2) electrolytic preparation of green foil: electrolyzing the electrolyte to obtain a green foil; (3) And washing the raw foil with water, passivating, drying and rolling to obtain the double-light copper foil. The double-light copper foil has excellent tensile strength and elongation, avoids the use of toxic metal ions, reduces the emission of pollutants, is beneficial to environmental protection, and also avoids the resistance rise caused by surface impurity penetration.
Description
Technical Field
The invention relates to the technical field of manufacturing of lithium battery copper foil, in particular to a preparation method of a double-light copper foil for a high heat-resistant lithium battery.
Background
The electrolytic copper foil is used as a negative electrode current collector of the lithium battery, plays a role in supporting a negative electrode active material in the lithium battery and plays a role in collecting and conducting electrons passing through the negative electrode material of the lithium battery. In the process of preparing the lithium battery, the electrolytic copper foil is required to be subjected to the steps of surface coating with an active negative electrode material, lamination, cutting, encapsulation and the like, and after the electrolytic copper foil is manufactured into the lithium battery, the negative electrode material expands and contracts to generate deformation and transfer the deformation to the electrolytic copper foil in the charge and discharge process of the lithium battery, and the electrolytic copper foil for the lithium battery is required to have better tensile strength and elongation rate in all the processes so as to avoid wrinkles and cracks of the electrolytic copper foil. Meanwhile, in order to firmly bond the anode active material, which is easily deformed during charge and discharge, with the anode current collector, an adhesive is generally required, and in the curing process of the adhesive, the electrolytic copper foil is subjected to high-temperature hot pressing at about 200 ℃ for 3 hours. When the electrolytic copper foil is hot pressed at high temperature, a copper oxide layer is easily formed on the surface of the electrolytic copper foil. The binding force between the copper oxide layer on the surface and the copper layer inside is weak, so that the copper oxide layer is easily stripped and falls off to enable the electrolytic copper foil to be rolled, and meanwhile, the active negative electrode material coated on the electrolytic copper foil is also easily stripped and falls off from the surface of the electrolytic copper foil, so that problems are easily caused in the aspects of durability and service life of the lithium battery.
The prior art, such as patent CN115198321a, discloses a production process of a double-light copper foil for a lithium battery, which uses an additive and electrolyte to carry out electrolysis to obtain the copper foil; wherein the additive comprises sodium polydithio-dipropyl sulfonate, collagen, hydroxyethyl cellulose, polyethylene glycol, N-dimethyl-dithio carbonyl sodium propane sulfonate, vanillin and dimethylamino sodium barrenate. The invention improves the production process of the double-light copper foil for the lithium battery, can improve the elongation percentage and the tensile strength of the 4.5-micrometer double-light copper foil, reduces the generation of pinholes, improves the safety of the lithium battery, and has the advantages of less additive consumption and low cost.
And as further disclosed in patent CN115287715A, a production process of a double-light copper foil for a lithium battery with medium tensile strength is disclosed, wherein a pre-additive and electrolyte are used for electrolysis to prepare a foil, and when the tensile strength of the copper foil reaches a fixed value, a post-additive is added for continuous electrolysis to obtain the copper foil. According to the invention, through the addition of the early-stage additive and the later-stage additive, the tensile strength of the copper foil is improved, the roughness of the smooth surface and the rough surface is reduced, and meanwhile, the problem of warping of the ultrathin copper foil is effectively avoided.
However, the tensile strength and the elongation of the double-gloss copper foil of the two patents still have room for improvement, and the quality resistivity level of the copper foil is not explored in the patents. Aiming at the problems existing in the prior art, a preparation method of the double-light copper foil for the high-heat-resistance lithium battery with more excellent tensile and elongation properties needs to be found.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation method of a double-light copper foil for a high heat-resistant lithium battery, and the prepared double-light copper foil has excellent tensile strength and elongation, avoids the use of toxic metal ions, reduces the emission of pollutants, is beneficial to environmental protection, and also avoids the resistance rise caused by surface impurity penetration.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The invention provides a preparation method of a double-light copper foil, which comprises the following steps:
(1) Preparing an electrolyte: adding sulfuric acid into a copper simple substance source to obtain primary copper sulfate electrolyte, filtering, adding Cl - to obtain secondary electrolyte, and mixing with an additive solution to obtain electrolyte;
The additive solution comprises: thiazolinyl dithiopropane sodium sulfonate, 3-mercapto-1-propane sodium sulfonate, hydroxyethyl cellulose, polyethylene glycol, polyethylene imine, 2-aminobenzimidazole;
(2) Preparing raw foil by electrolysis: electrolyzing the electrolyte to obtain a green foil;
(3) And washing the raw foil with water, passivating, drying and rolling to obtain the double-light copper foil.
Further, the additive solution in step (1) includes: 16-20mg/L of thiazolinyl dithiopropane sodium sulfonate, 8-10mg/L of 3-mercapto-1-propane sodium sulfonate, 12-15mg/L of hydroxyethyl cellulose, 12-15mg/L of polyethylene glycol, 12-15mg/L of polyethyleneimine and 12-15mg/L of 2-aminobenzimidazole.
Further, the thiazolinyl dithiopropane sodium sulfonate and 3-mercapto-1-propane sodium sulfonate in the additive are taken as brightening agents, and have the function of refining grains; hydroxyethyl cellulose and polyethylene glycol are used as wetting agents, so that the surface tension of the electrolyte can be reduced, and the plating layer is crystallized and compacted; the polyethyleneimine and the 2-aminobenzimidazole are used as leveling agents, so that the microscopic profile of the surface of the copper foil can be smoothed, and the surface roughness can be reduced.
Further, the Cl - content in the step (1) is 1.0-2.0mg/L, and the product is obtained by preparing an aqueous solution from 36-38 wt% of concentrated hydrochloric acid (HCl).
Further, the preparation of the electrolyte in the step (1) specifically includes: putting a copper simple substance source into a copper dissolving tank, adding sulfuric acid from top to bottom of the copper simple substance source, and blowing high-temperature air into the bottom of the copper simple substance source from bottom to top by using a blower to obtain a primary copper sulfate electrolyte; filtering the primary copper sulfate electrolyte, adding Cl -, and mixing to obtain a secondary electrolyte; the secondary electrolyte is conveyed to a high-level tank to be uniformly mixed with the additive solution after the temperature of the secondary electrolyte is maintained at 49-51 ℃ by a heat exchanger, so that the electrolyte is obtained, and the electrolyte is pumped into an electrolytic tank for electrolysis.
Further, the weight ratio of the thiazolinyl dithiopropane sodium sulfonate, the hydroxyethyl cellulose and the 2-aminobenzimidazole in the step (1) is (16-20): 12-15.
Further, the electrolyte in the step (1) comprises 80-100g/L Cu 2+ and 110-120g/L H 2SO4.
Further, the electrolysis in step (2) is specifically carried out at a current density of from 49 to 51℃and from 60 to 70A/dm 2.
Further, the temperature of the water washing in the step (3) is 25-35 ℃, and the flow is 2-3L/min.
Further, the passivation solution used in the passivation in the step (3) comprises 40-60mg/L of hydroxybenzotriazole, 20-30mg/L of silver nitrate, 0.4-0.6g/L of sodium molybdate, 2.0-3.0g/L of sodium formate and water; ph=3.5-4.5 of the passivation solution.
Further, the passivation temperature in the step (3) is 30-34 ℃, the treatment time is 10-15s, and the circulation flow rate of the passivation solution is 20-24m 3/h.
Further, the temperature of the drying in the step (3) is 260-300 ℃ and the time is 5-10s.
Further, the invention also provides the double-gloss copper foil prepared by the preparation method.
The invention has the technical effects that:
The invention provides a double-light copper foil for a high heat-resistant lithium battery, which has the thickness of 4.5-8.0 mu m, the normal-temperature tensile strength of more than or equal to 450MPa, the normal-temperature elongation of more than or equal to 4.0 percent, and no oxidative discoloration on the surface after being heated for 3 hours at 200 ℃, and the mass resistivity of less than or equal to 0.166 omega-g/m 2 by referring to the test method in the electrolytic copper foil for a GB/T5230-2020 printed board. According to the invention, the double-gloss copper foil with excellent performance parameters is finally obtained through optimizing additive components in the electrolytic process and the synergistic cooperation of raw foil preparation and passivation treatment; the invention does not use chromium ions, reduces harm to human body and environment, and reduces water treatment cost; meanwhile, zinc metal is not used, so that the problem of resistance rise caused by taking zinc as an oxidation prevention layer is avoided.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Before the embodiments of the invention are explained in further detail, it is to be understood that the invention is not limited in its scope to the particular embodiments described below; it is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It should be noted that the raw materials used in the present invention are all common commercial products, and therefore the sources thereof are not particularly limited.
Example 1
The preparation method of the double-light copper foil for the high heat-resistant lithium battery comprises the following steps:
(1) Preparing an electrolyte: putting a copper simple substance source into a copper dissolving tank, adding sulfuric acid from top to bottom of the copper simple substance source, and blowing high-temperature air into the bottom of the copper simple substance source from bottom to top by using a blower to obtain a primary copper sulfate electrolyte; filtering the primary copper sulfate electrolyte, adding Cl -, and mixing to obtain a secondary electrolyte; the temperature of the secondary electrolyte is maintained at 49 ℃ through a heat exchanger, the secondary electrolyte is conveyed to a high-level tank and then is uniformly mixed with the additive solution to obtain the electrolyte, and the electrolyte is pumped into an electrolytic tank for electrolysis.
Wherein the Cl - content is 1.0mg/L, and the aqueous solution is prepared from 36-38wt% of concentrated hydrochloric acid (HCl).
The additive comprises: 16mg/L of sodium thiazolinyl dithiopropane sulfonate, 8mg/L of sodium 3-mercapto-1-propane sulfonate, 12mg/L of hydroxyethyl cellulose, 12mg/L of polyethylene glycol, 12mg/L of polyethyleneimine, 12mg/L of 2-aminobenzimidazole.
The electrolyte contains 80g/L of Cu 2+ and 110g/L of H 2SO4, and the solvent in the electrolyte is ultrapure water.
(2) Preparing raw foil by electrolysis: the green foil was prepared electrolytically in an electrolytic cell at 49℃and a current density of 70A/dm 2.
(3) Washing: washing with RO water at 25deg.C at flow rate of 3L/min to remove excessive electrolyte on the surface of the green foil;
And (3) surface passivation treatment of raw foil: the passivation solution comprises 40mg/L of Hydroxybenzotriazole (HBTA), 20mg/L of silver nitrate, 0.4g/L of sodium molybdate, 2.0g/L of sodium formate and the balance of RO water, the pH value of the passivation solution is=3.5-4.5, the passivation treatment temperature is 30 ℃, the passivation treatment time is 15s, the circulation flow of the passivation solution is 20m 3/h, so that the passivation solution is ensured to be uniformly attached to the surface of the electrolytic copper foil, and the energy is not wasted;
And (3) drying: oven temperature 260 ℃, oven drying for 10s, so as to make the passivation layer more compact;
And (3) rolling: thus obtaining the double-gloss copper foil for the high heat-resistant lithium battery without cutting.
Example 2
The preparation method of the double-light copper foil for the high heat-resistant lithium battery comprises the following steps:
(1) Preparing an electrolyte: putting a copper simple substance source into a copper dissolving tank, adding sulfuric acid from top to bottom of the copper simple substance source, and blowing high-temperature air into the bottom of the copper simple substance source from bottom to top by using a blower to obtain a primary copper sulfate electrolyte; filtering the primary copper sulfate electrolyte, adding Cl -, and mixing to obtain a secondary electrolyte; the secondary electrolyte is conveyed to a high-level tank after being conveyed to the heat exchanger to be uniformly mixed with the additive solution to obtain the electrolyte, and the electrolyte is pumped into an electrolytic tank for electrolysis.
Wherein the Cl - content is 2.0mg/L, and is obtained by preparing an aqueous solution from 36-38wt% of concentrated hydrochloric acid (HCl).
The additive comprises: 20mg/L of sodium thiazolinyl dithiopropane sulfonate, 10mg/L of sodium 3-mercapto-1-propane sulfonate, 15mg/L of hydroxyethyl cellulose, 15mg/L of polyethylene glycol, 15mg/L of polyethyleneimine, 15mg/L of 2-aminobenzimidazole.
The electrolyte contains 100g/L of Cu 2+ and 120g/L of H 2SO4, and the solvent in the electrolyte is ultrapure water.
(2) Preparing raw foil by electrolysis: the green foil was prepared by electrolysis in an electrolytic cell at a temperature of 51℃and a current density of 60A/dm 2.
(3) Washing: washing with RO water at 35deg.C at flow rate of 2L/min to remove excessive electrolyte on the surface of the green foil;
And (3) surface passivation treatment of raw foil: the passivation solution comprises 60mg/L of Hydroxybenzotriazole (HBTA), 30mg/L of silver nitrate, 0.6g/L of sodium molybdate, 3.0g/L of sodium formate and the balance RO water, the pH value of the passivation solution is=3.5-4.5, the passivation treatment temperature is 34 ℃, the passivation treatment time is 10 seconds, the circulation flow rate of the passivation solution is 24m 3/h, so that the passivation solution is ensured to be uniformly attached to the surface of the electrolytic copper foil, and the energy is not wasted;
and (3) drying: oven temperature 300 deg.c and stoving for 5s to densify the passivation layer;
And (3) rolling: thus obtaining the double-gloss copper foil for the high heat-resistant lithium battery without cutting.
Example 3
The preparation method of the double-light copper foil for the high heat-resistant lithium battery comprises the following steps:
(1) Preparing an electrolyte: putting a copper simple substance source into a copper dissolving tank, adding sulfuric acid from top to bottom of the copper simple substance source, and blowing high-temperature air into the bottom of the copper simple substance source from bottom to top by using a blower to obtain a primary copper sulfate electrolyte; filtering the primary copper sulfate electrolyte, adding Cl -, and mixing to obtain a secondary electrolyte; the secondary electrolyte is conveyed to a high-level tank after being conveyed to the heat exchanger to be uniformly mixed with the additive solution to obtain the electrolyte, and the electrolyte is pumped into an electrolytic tank for electrolysis.
Wherein the Cl - content is 1.5mg/L, and the aqueous solution is prepared from 36-38wt% of concentrated hydrochloric acid (HCl).
The additive comprises: 18mg/L of sodium thiazolinyl dithiopropane sulfonate, 9mg/L of sodium 3-mercapto-1-propane sulfonate, 14mg/L of hydroxyethyl cellulose, 14mg/L of polyethylene glycol, 14mg/L of polyethyleneimine, 14mg/L of 2-aminobenzimidazole.
The electrolyte contains 90g/L of Cu 2+ and 115g/L of H 2SO4, and the solvent in the electrolyte is ultrapure water.
(2) Preparing raw foil by electrolysis: the green foil was prepared by electrolysis in an electrolytic cell at 50℃and a current density of 65A/dm 2.
(3) Washing: washing with RO water at 30deg.C at a flow rate of 2.5L/min to remove excessive electrolyte on the surface of the green foil;
And (3) surface passivation treatment of raw foil: the passivation solution comprises 50mg/L of Hydroxybenzotriazole (HBTA), 25mg/L of silver nitrate, 0.5g/L of sodium molybdate, 2.5g/L of sodium formate and the balance of RO water, the pH value of the passivation solution is=3.5-4.5, the passivation treatment temperature is 32 ℃, the passivation treatment time is 12s, the circulation flow rate of the passivation solution is 22m 3/h, so that the passivation solution is ensured to be uniformly attached to the surface of the electrolytic copper foil, and energy is not wasted;
And (3) drying: oven temperature 280 ℃, drying for 8s to make passivation layer more compact;
And (3) rolling: thus obtaining the double-gloss copper foil for the high heat-resistant lithium battery without cutting.
Comparative example 1
The only difference from example 3 is that the sodium thiazolinyl dithiopropane sulfonate, hydroxyethyl cellulose in the additive is replaced by an equivalent amount of 2-aminobenzimidazole; namely, the method comprises the following steps:
(1) Preparing an electrolyte: putting a copper simple substance source into a copper dissolving tank, adding sulfuric acid from top to bottom of the copper simple substance source, and blowing high-temperature air into the bottom of the copper simple substance source from bottom to top by using a blower to obtain a primary copper sulfate electrolyte; filtering the primary copper sulfate electrolyte, adding Cl -, and mixing to obtain a secondary electrolyte; the secondary electrolyte is conveyed to a high-level tank after being conveyed to the heat exchanger to be uniformly mixed with the additive solution to obtain the electrolyte, and the electrolyte is pumped into an electrolytic tank for electrolysis.
Wherein the Cl - content is 1.5mg/L, and the aqueous solution is prepared from 36-38wt% of concentrated hydrochloric acid (HCl).
The additive comprises: 9mg/L of sodium 3-mercapto-1-propanesulfonate, 14mg/L of polyethylene glycol, 14mg/L of polyethyleneimine and 46mg/L of 2-aminobenzimidazole.
The electrolyte contains 90g/L of Cu 2+ and 115g/L of H 2SO4, and the solvent in the electrolyte is ultrapure water.
(2) Preparing raw foil by electrolysis: the green foil was prepared by electrolysis in an electrolytic cell at 50℃and a current density of 65A/dm 2.
(3) Washing: washing with RO water at 30deg.C at a flow rate of 2.5L/min to remove excessive electrolyte on the surface of the green foil;
And (3) surface passivation treatment of raw foil: the passivation solution comprises 50mg/L of Hydroxybenzotriazole (HBTA), 25mg/L of silver nitrate, 0.5g/L of sodium molybdate, 2.5g/L of sodium formate and the balance of RO water, the pH value of the passivation solution is=3.5-4.5, the passivation treatment temperature is 32 ℃, the passivation treatment time is 12s, the circulation flow rate of the passivation solution is 22m 3/h, so that the passivation solution is ensured to be uniformly attached to the surface of the electrolytic copper foil, and energy is not wasted;
And (3) drying: oven temperature 280 ℃, drying for 8s to make passivation layer more compact;
And (3) rolling: thus obtaining the double-gloss copper foil for the high heat-resistant lithium battery without cutting.
Comparative example 2
The only difference from example 3 is that the hydroxyethylcellulose, 2-aminobenzimidazole in the additive is replaced by an equivalent amount of sodium thiazolinyl dithiopropane sulfonate; namely, the method comprises the following steps:
(1) Preparing an electrolyte: putting a copper simple substance source into a copper dissolving tank, adding sulfuric acid from top to bottom of the copper simple substance source, and blowing high-temperature air into the bottom of the copper simple substance source from bottom to top by using a blower to obtain a primary copper sulfate electrolyte; filtering the primary copper sulfate electrolyte, adding Cl -, and mixing to obtain a secondary electrolyte; the secondary electrolyte is conveyed to a high-level tank after being conveyed to the heat exchanger to be uniformly mixed with the additive solution to obtain the electrolyte, and the electrolyte is pumped into an electrolytic tank for electrolysis.
Wherein the Cl - content is 1.5mg/L, and the aqueous solution is prepared from 36-38wt% of concentrated hydrochloric acid (HCl).
The additive comprises: 46mg/L of sodium thiazolinyl dithiopropane sulfonate, 9mg/L of sodium 3-mercapto-1-propane sulfonate, 14mg/L of polyethylene glycol, 14mg/L of polyethyleneimine.
The electrolyte contains 90g/L of Cu 2+ and 115g/L of H 2SO4, and the solvent in the electrolyte is ultrapure water.
(2) Preparing raw foil by electrolysis: the green foil was prepared by electrolysis in an electrolytic cell at 50℃and a current density of 65A/dm 2.
(3) Washing: washing with RO water at 30deg.C at a flow rate of 2.5L/min to remove excessive electrolyte on the surface of the green foil;
And (3) surface passivation treatment of raw foil: the passivation solution comprises 50mg/L of Hydroxybenzotriazole (HBTA), 25mg/L of silver nitrate, 0.5g/L of sodium molybdate, 2.5g/L of sodium formate and the balance of RO water, the pH value of the passivation solution is=3.5-4.5, the passivation treatment temperature is 32 ℃, the passivation treatment time is 12s, the circulation flow rate of the passivation solution is 22m 3/h, so that the passivation solution is ensured to be uniformly attached to the surface of the electrolytic copper foil, and energy is not wasted;
And (3) drying: oven temperature 280 ℃, drying for 8s to make passivation layer more compact;
And (3) rolling: thus obtaining the double-gloss copper foil for the high heat-resistant lithium battery without cutting.
Comparative example 3
The only difference from example 3 is that the sodium thiazolinyl dithiopropane sulfonate, 2-aminobenzimidazole in the additive is replaced by an equivalent amount of hydroxyethylcellulose; namely, the method comprises the following steps:
(1) Preparing an electrolyte: putting a copper simple substance source into a copper dissolving tank, adding sulfuric acid from top to bottom of the copper simple substance source, and blowing high-temperature air into the bottom of the copper simple substance source from bottom to top by using a blower to obtain a primary copper sulfate electrolyte; filtering the primary copper sulfate electrolyte, adding Cl -, and mixing to obtain a secondary electrolyte; the secondary electrolyte is conveyed to a high-level tank after being conveyed to the heat exchanger to be uniformly mixed with the additive solution to obtain the electrolyte, and the electrolyte is pumped into an electrolytic tank for electrolysis.
Wherein the Cl - content is 1.5mg/L, and the aqueous solution is prepared from 36-38wt% of concentrated hydrochloric acid (HCl).
The additive comprises: 9mg/L of sodium 3-mercapto-1-propanesulfonate, 46mg/L of hydroxyethyl cellulose, 14mg/L of polyethylene glycol and 14mg/L of polyethyleneimine.
The electrolyte contains 90g/L of Cu 2+ and 115g/L of H 2SO4, and the solvent in the electrolyte is ultrapure water.
(2) Preparing raw foil by electrolysis: the green foil was prepared by electrolysis in an electrolytic cell at 50℃and a current density of 65A/dm 2.
(3) Washing: washing with RO water at 30deg.C at a flow rate of 2.5L/min to remove excessive electrolyte on the surface of the green foil;
And (3) surface passivation treatment of raw foil: the passivation solution comprises 50mg/L of Hydroxybenzotriazole (HBTA), 25mg/L of silver nitrate, 0.5g/L of sodium molybdate, 2.5g/L of sodium formate and the balance of RO water, the pH value of the passivation solution is=3.5-4.5, the passivation treatment temperature is 32 ℃, the passivation treatment time is 12s, the circulation flow rate of the passivation solution is 22m 3/h, so that the passivation solution is ensured to be uniformly attached to the surface of the electrolytic copper foil, and energy is not wasted;
And (3) drying: oven temperature 280 ℃, drying for 8s to make passivation layer more compact;
And (3) rolling: thus obtaining the double-gloss copper foil for the high heat-resistant lithium battery without cutting.
Comparative example 4
The only difference from example 3 is that 18mg/L of sodium thiazolinyl dithiopropane sulfonate is replaced by 18mg/L of sodium polydithio-dipropyl sulfonate, 9mg/L of sodium 3-mercapto-1-propane sulfonate is replaced by 9mg/L N, N-dimethyl-dithioformamide propane sulfonate.
Namely, the method comprises the following steps:
(1) Preparing an electrolyte: putting a copper simple substance source into a copper dissolving tank, adding sulfuric acid from top to bottom of the copper simple substance source, and blowing high-temperature air into the bottom of the copper simple substance source from bottom to top by using a blower to obtain a primary copper sulfate electrolyte; filtering the primary copper sulfate electrolyte, adding Cl -, and mixing to obtain a secondary electrolyte; the secondary electrolyte is conveyed to a high-level tank after being conveyed to the heat exchanger to be uniformly mixed with the additive solution to obtain the electrolyte, and the electrolyte is pumped into an electrolytic tank for electrolysis.
Wherein the Cl - content is 1.5mg/L, and the aqueous solution is prepared from 36-38wt% of concentrated hydrochloric acid (HCl).
The additive comprises: 18mg/L sodium polydithio-dipropyl sulfonate, 9mg/L N, sodium N-dimethyl-dithioformamide propane sulfonate, 14mg/L hydroxyethyl cellulose, 14mg/L polyethylene glycol, 14mg/L polyethylenimine, 14 mg/L2-aminobenzimidazole.
The electrolyte contains 90g/L of Cu 2+ and 115g/L of H 2SO4, and the solvent in the electrolyte is ultrapure water.
(2) Preparing raw foil by electrolysis: the green foil was prepared by electrolysis in an electrolytic cell at 50℃and a current density of 65A/dm 2.
(3) Washing: washing with RO water at 30deg.C at a flow rate of 2.5L/min to remove excessive electrolyte on the surface of the green foil;
And (3) surface passivation treatment of raw foil: the passivation solution comprises 50mg/L of Hydroxybenzotriazole (HBTA), 25mg/L of silver nitrate, 0.5g/L of sodium molybdate, 2.5g/L of sodium formate and the balance of RO water, the pH value of the passivation solution is=3.5-4.5, the passivation treatment temperature is 32 ℃, the passivation treatment time is 12s, the circulation flow rate of the passivation solution is 22m 3/h, so that the passivation solution is ensured to be uniformly attached to the surface of the electrolytic copper foil, and energy is not wasted;
And (3) drying: oven temperature 280 ℃, drying for 8s to make passivation layer more compact;
And (3) rolling: thus obtaining the double-gloss copper foil for the high heat-resistant lithium battery without cutting.
Comparative example 5
The only difference from example 3 is that the passivation solution contains 30mg/L of Hydroxybenzotriazole (HBTA), 15mg/L of silver nitrate, 0.3g/L of sodium molybdate, and 1.5g/L of sodium formate.
Namely, the method comprises the following steps:
(1) Preparing an electrolyte: putting a copper simple substance source into a copper dissolving tank, adding sulfuric acid from top to bottom of the copper simple substance source, and blowing high-temperature air into the bottom of the copper simple substance source from bottom to top by using a blower to obtain a primary copper sulfate electrolyte; filtering the primary copper sulfate electrolyte, adding Cl -, and mixing to obtain a secondary electrolyte; the secondary electrolyte is conveyed to a high-level tank after being conveyed to the heat exchanger to be uniformly mixed with the additive solution to obtain the electrolyte, and the electrolyte is pumped into an electrolytic tank for electrolysis.
Wherein the Cl - content is 1.5mg/L, and the aqueous solution is prepared from 36-38wt% of concentrated hydrochloric acid (HCl).
The additive comprises: 18mg/L of sodium thiazolinyl dithiopropane sulfonate, 9mg/L of sodium 3-mercapto-1-propane sulfonate, 14mg/L of hydroxyethyl cellulose, 14mg/L of polyethylene glycol, 14mg/L of polyethyleneimine, 14mg/L of 2-aminobenzimidazole.
The electrolyte contains 90g/L of Cu 2+ and 115g/L of H 2SO4, and the solvent in the electrolyte is ultrapure water.
(2) Preparing raw foil by electrolysis: the green foil was prepared by electrolysis in an electrolytic cell at 50℃and a current density of 65A/dm 2.
(3) Washing: washing with RO water at 30deg.C at a flow rate of 2.5L/min to remove excessive electrolyte on the surface of the green foil;
and (3) surface passivation treatment of raw foil: the passivation solution comprises 30mg/L of Hydroxybenzotriazole (HBTA), 15mg/L of silver nitrate, 0.3g/L of sodium molybdate, 1.5g/L of sodium formate and the balance of RO water, the pH value of the passivation solution is=3.5-4.5, the passivation treatment temperature is 32 ℃, the passivation treatment time is 12s, the circulation flow rate of the passivation solution is 22m 3/h, so that the passivation solution is ensured to be uniformly attached to the surface of the electrolytic copper foil, and energy is not wasted;
And (3) drying: oven temperature 280 ℃, drying for 8s to make passivation layer more compact;
And (3) rolling: thus obtaining the double-gloss copper foil for the high heat-resistant lithium battery without cutting.
Comparative example 6
The only difference from example 3 is that the passivation solution contains 70mg/L of Hydroxybenzotriazole (HBTA), 40mg/L of silver nitrate, 0.7g/L of sodium molybdate, 3.5g/L of sodium formate.
Namely, the method comprises the following steps:
(1) Preparing an electrolyte: putting a copper simple substance source into a copper dissolving tank, adding sulfuric acid from top to bottom of the copper simple substance source, and blowing high-temperature air into the bottom of the copper simple substance source from bottom to top by using a blower to obtain a primary copper sulfate electrolyte; filtering the primary copper sulfate electrolyte, adding Cl -, and mixing to obtain a secondary electrolyte; the secondary electrolyte is conveyed to a high-level tank after being conveyed to the heat exchanger to be uniformly mixed with the additive solution to obtain the electrolyte, and the electrolyte is pumped into an electrolytic tank for electrolysis.
Wherein the Cl - content is 1.5mg/L, and the aqueous solution is prepared from 36-38wt% of concentrated hydrochloric acid (HCl).
The additive comprises: 18mg/L of sodium thiazolinyl dithiopropane sulfonate, 9mg/L of sodium 3-mercapto-1-propane sulfonate, 14mg/L of hydroxyethyl cellulose, 14mg/L of polyethylene glycol, 14mg/L of polyethyleneimine, 14mg/L of 2-aminobenzimidazole.
The electrolyte contains 90g/L of Cu 2+ and 115g/L of H 2SO4, and the solvent in the electrolyte is ultrapure water.
(2) Preparing raw foil by electrolysis: the green foil was prepared by electrolysis in an electrolytic cell at 50℃and a current density of 65A/dm 2.
(3) Washing: washing with RO water at 30deg.C at a flow rate of 2.5L/min to remove excessive electrolyte on the surface of the green foil;
And (3) surface passivation treatment of raw foil: the passivation solution comprises 70mg/L of Hydroxybenzotriazole (HBTA), 40mg/L of silver nitrate, 0.7g/L of sodium molybdate, 3.5g/L of sodium formate and the balance of RO water, the pH value of the passivation solution is=3.5-4.5, the passivation treatment temperature is 32 ℃, the passivation treatment time is 12s, the circulation flow rate of the passivation solution is 22m 3/h, so that the passivation solution is ensured to be uniformly attached to the surface of the electrolytic copper foil, and energy is not wasted;
And (3) drying: oven temperature 280 ℃, drying for 8s to make passivation layer more compact;
And (3) rolling: thus obtaining the double-gloss copper foil for the high heat-resistant lithium battery without cutting.
Comparative example 7
The only difference from example 3 is that silver nitrate is replaced with an equal amount of copper sulfate and sodium formate is replaced with an equal amount of sodium acetate.
Namely, the method comprises the following steps:
(1) Preparing an electrolyte: putting a copper simple substance source into a copper dissolving tank, adding sulfuric acid from top to bottom of the copper simple substance source, and blowing high-temperature air into the bottom of the copper simple substance source from bottom to top by using a blower to obtain a primary copper sulfate electrolyte; filtering the primary copper sulfate electrolyte, adding Cl -, and mixing to obtain a secondary electrolyte; the secondary electrolyte is conveyed to a high-level tank after being conveyed to the heat exchanger to be uniformly mixed with the additive solution to obtain the electrolyte, and the electrolyte is pumped into an electrolytic tank for electrolysis.
Wherein the Cl - content is 1.5mg/L, and the aqueous solution is prepared from 36-38wt% of concentrated hydrochloric acid (HCl).
The additive comprises: 18mg/L of sodium thiazolinyl dithiopropane sulfonate, 9mg/L of sodium 3-mercapto-1-propane sulfonate, 14mg/L of hydroxyethyl cellulose, 14mg/L of polyethylene glycol, 14mg/L of polyethyleneimine, 14mg/L of 2-aminobenzimidazole.
The electrolyte contains 90g/L of Cu 2+ and 115g/L of H 2SO4, and the solvent in the electrolyte is ultrapure water.
(2) Preparing raw foil by electrolysis: the green foil was prepared by electrolysis in an electrolytic cell at 50℃and a current density of 65A/dm 2.
(3) Washing: washing with RO water at 30deg.C at a flow rate of 2.5L/min to remove excessive electrolyte on the surface of the green foil;
And (3) surface passivation treatment of raw foil: the passivation solution comprises 50mg/L of Hydroxybenzotriazole (HBTA), 25mg/L of copper sulfate, 0.5g/L of sodium molybdate, 2.5g/L of sodium acetate and the balance RO water, the pH value of the passivation solution is=3.5-4.5, the passivation treatment temperature is 32 ℃, the passivation treatment time is 12s, and the circulation flow rate of the passivation solution is 22m 3/h so as to ensure that the passivation solution is uniformly attached to the surface of the electrolytic copper foil and the energy is not wasted;
And (3) drying: oven temperature 280 ℃, drying for 8s to make passivation layer more compact;
And (3) rolling: thus obtaining the double-gloss copper foil for the high heat-resistant lithium battery without cutting.
Performance test of double-gloss copper foil
The performance test results of the double-light copper foil of each example in the invention are shown in table 1, wherein the surface discoloration is that the surface of the sample is free from oxidative discoloration after being heated for 3 hours at 200 ℃; the tensile strength, the elongation and the mass resistivity are all detected by referring to the test method in the electrolytic copper foil for printed boards of GB/T5230-2020.
Table 1 performance parameters of the double-gloss copper foil in each example
According to the results in Table 1 of the present invention, the double-gloss copper foil of the present invention has good warpage, tensile strength and elongation, and the surface of the copper foil is free from oxidative discoloration after heating at 200 ℃ for 3 hours, and at the same time, the mass resistivity of the double-gloss copper foil is also low.
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. A preparation method of a double-light copper foil is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparing an electrolyte: adding sulfuric acid into a copper simple substance source to obtain primary copper sulfate electrolyte, filtering, adding Cl - to obtain secondary electrolyte, and mixing with an additive solution to obtain electrolyte;
The additive solution comprises: 16-20mg/L of thiazolinyl dithiopropane sodium sulfonate, 8-10mg/L of 3-mercapto-1-propane sodium sulfonate, 12-15mg/L of hydroxyethyl cellulose, 12-15mg/L of polyethylene glycol, 12-15mg/L of polyethyleneimine and 12-15mg/L of 2-aminobenzimidazole;
(2) Preparing raw foil by electrolysis: electrolyzing the electrolyte to obtain a green foil;
(3) Washing, passivating, drying and rolling the raw foil to obtain a double-light copper foil;
the passivation solution used in the passivation in the step (3) comprises 40-60mg/L of hydroxybenzotriazole, 20-30mg/L of silver nitrate, 0.4-0.6g/L of sodium molybdate, 2.0-3.0g/L of sodium formate and water.
2. The method of manufacturing according to claim 1, characterized in that: the weight ratio of the thiazolinyl dithiopropane sodium sulfonate, the hydroxyethyl cellulose and the 2-aminobenzimidazole in the step (1) is (16-20): 12-15.
3. The method of manufacturing according to claim 1, characterized in that: the electrolyte in the step (1) comprises 80-100g/L Cu 2+ and 110-120g/L H 2SO4.
4. The method of manufacturing according to claim 1, characterized in that: the electrolysis in step (2) is carried out in particular at a current density of from 49 to 51℃and from 60 to 70A/dm 2.
5. The method of manufacturing according to claim 1, characterized in that: the temperature of the water washing in the step (3) is 25-35 ℃, and the flow is 2-3L/min.
6. The method of manufacturing according to claim 1, characterized in that: the pH of the passivation solution in step (3) is=3.5-4.5.
7. The method of manufacturing according to claim 1, characterized in that: the passivation temperature in the step (3) is 30-34 ℃, the treatment time is 10-15s, and the circulation flow of the passivation solution is 20-24m 3/h.
8. The method of manufacturing according to claim 1, characterized in that: the temperature of the drying in the step (3) is 260-300 ℃ and the time is 5-10s.
9. The matte copper foil produced by the production method according to any one of claims 1 to 8.
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| CN109161946A (en) * | 2018-08-17 | 2019-01-08 | 厦门大学 | A kind of oxidation resistant electrochemical process for treating of copper product |
| CN110904473A (en) * | 2019-12-04 | 2020-03-24 | 中山美力特环保科技有限公司 | 5G antenna environment-friendly copper plating process |
| CN115478306A (en) * | 2022-09-30 | 2022-12-16 | 江苏梦得新材料科技有限公司 | High-elongation high-tensile additive and preparation method and use method thereof |
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| KR20190025418A (en) * | 2017-09-01 | 2019-03-11 | 케이씨에프테크놀로지스 주식회사 | Copper foil capable of manufacturing high capacity secondary battery, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same |
| CN111058063B (en) * | 2018-10-16 | 2021-02-02 | 长春石油化学股份有限公司 | Electrolytic copper foil, electrode comprising same, and lithium ion battery comprising same |
| CN110760897B (en) * | 2019-10-11 | 2021-03-23 | 广州盛门新材料科技有限公司 | Copper-based graphene heat conduction and dissipation film and preparation method thereof |
| CN112553659A (en) * | 2020-11-09 | 2021-03-26 | 九江德福科技股份有限公司 | Manufacturing method of high-modulus copper foil |
| CN116377527A (en) * | 2023-05-06 | 2023-07-04 | 江苏铭丰电子材料科技有限公司 | High-ductility electrolytic copper foil and preparation method thereof |
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| CN109161946A (en) * | 2018-08-17 | 2019-01-08 | 厦门大学 | A kind of oxidation resistant electrochemical process for treating of copper product |
| CN110904473A (en) * | 2019-12-04 | 2020-03-24 | 中山美力特环保科技有限公司 | 5G antenna environment-friendly copper plating process |
| CN115478306A (en) * | 2022-09-30 | 2022-12-16 | 江苏梦得新材料科技有限公司 | High-elongation high-tensile additive and preparation method and use method thereof |
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