CN113832503A - Composite additive for improving modulus of lithium-ion battery copper foil and electrolytic copper foil production method - Google Patents
Composite additive for improving modulus of lithium-ion battery copper foil and electrolytic copper foil production method Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000011889 copper foil Substances 0.000 title claims abstract description 64
- 239000000654 additive Substances 0.000 title claims abstract description 28
- 230000000996 additive effect Effects 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 70
- 239000003792 electrolyte Substances 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 20
- 229920000570 polyether Polymers 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 12
- 229910001431 copper ion Inorganic materials 0.000 claims description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 9
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 102000008186 Collagen Human genes 0.000 claims description 2
- 108010035532 Collagen Proteins 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- WWQQXASVQCLOKF-UHFFFAOYSA-N [Na].C(C)(CC)S Chemical compound [Na].C(C)(CC)S WWQQXASVQCLOKF-UHFFFAOYSA-N 0.000 claims description 2
- YPKOTWSAVCIFAM-UHFFFAOYSA-N [Na].CCC Chemical compound [Na].CCC YPKOTWSAVCIFAM-UHFFFAOYSA-N 0.000 claims description 2
- MDVSLIZPMLVHRW-UHFFFAOYSA-N [Na].CCC.SC=1NC=CN1 Chemical compound [Na].CCC.SC=1NC=CN1 MDVSLIZPMLVHRW-UHFFFAOYSA-N 0.000 claims description 2
- 229920001436 collagen Polymers 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000002265 prevention Effects 0.000 claims description 2
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052744 lithium Inorganic materials 0.000 abstract description 19
- 230000005489 elastic deformation Effects 0.000 abstract description 4
- 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 description 8
- 239000013078 crystal Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000006073 displacement reaction Methods 0.000 description 6
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 5
- VWDLZWWPEBXHAI-UHFFFAOYSA-N C(CC)S(=O)(=O)O.SC=1NC=CN1 Chemical compound C(CC)S(=O)(=O)O.SC=1NC=CN1 VWDLZWWPEBXHAI-UHFFFAOYSA-N 0.000 description 4
- -1 amine ethoxy sulfonate Chemical class 0.000 description 4
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical compound SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- YFDKVXNMRLLVSL-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid;sodium Chemical compound [Na].CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O YFDKVXNMRLLVSL-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- RZVJXLSUGBRXFB-UHFFFAOYSA-M sodium 3-(5-sulfanyl-1H-imidazol-2-yl)propane-1-sulfonate Chemical compound SC=1N=C(NC1)CCCS(=O)(=O)[O-].[Na+] RZVJXLSUGBRXFB-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a composite additive for improving the modulus of a lithium-ion electrolytic copper foil and a production method of an electrolytic copper foil. The copper foil manufactured by the composite additive and the electrolytic copper foil production method has the advantages that the elastic modulus is obviously improved, the tensile strength is more than or equal to 370Mpa under 0.2% elastic deformation at normal temperature, and the tensile strength is more than or equal to 330Mpa under 0.2% elastic deformation after being baked at 130 ℃ for 10 minutes, so that the problem of bag expansion or strip breakage in the manufacturing process of lithium batteries, particularly soft package type lithium batteries, is effectively solved.
Description
Technical Field
The invention relates to the technical field of electrolytic copper foil, in particular to a composite additive for improving the modulus of lithium electrolytic copper foil and a production method of electrolytic copper foil.
Background
The electrolytic copper foil is a necessary basic material for manufacturing the lithium ion battery. The copper foil that the modulus is high, the rigidity is big, and is flexible strong, is difficult for the package that rises or fracture in soft packet class lithium cell production process, and secondly because of the copper foil is thinner, has saved the space, can increase coating material's coating volume, and then promotes the energy density of battery. Because of the characteristics, the high-modulus copper foil can meet the requirements of further improving the energy density and prolonging the service life of the lithium battery, particularly the soft package lithium battery. The use of the electrolyte additive is a core link for improving the modulus of the lithium battery copper foil, and the properties of the copper foil, particularly the modulus of the copper foil, are often determined by the formula components of the additive and the proportional relationship among the components.
In general, the formulation of the lithium-ion electrolytic copper foil additive needs to include three main components, namely, a brightener, a leveling agent and a displacement agent, which are matched with each other, so as to obtain the electrolytic copper foil with excellent mechanical properties. The brightener can accelerate nucleation and reduce the size of crystal grains, and the smaller the crystal grains are, the stronger the dislocation slip resistance is, and the stronger the recovery capability of the copper foil is. The leveling agent is a kind of agent for promoting the growth of the surface center of the copper foil crystal grains, such as protein with different molecular weights, and is adsorbed on the convex points of the cathode, so that the tip effect is reduced, the convex points in the copper foil can be effectively reduced, and the copper foil is more flat. The displacement agent is a kind of auxiliary additive which helps other functional additives to move to the surface of the cathode roller, and has a very large function and plays a role of a basic structure, and the effective concentration content of the displacement agent determines the basic position of the additive in the electrolyte.
Research shows that some molecules containing a sulfur structure can be used as an electrolytic copper foil brightener to perform the function of grain refinement in electrolyte, and can be used together with some nitrogen-containing polymer leveling agents to effectively improve the tensile strength in plastic deformation, and the copper foil has a certain elongation and can be quickly restored after local deformation. The reason for this is that the fine copper foil has a more compact crystal structure and a strong dislocation slip resistance. The complexing action formed by the displacement agent and the chloride ions can block the deposition speed of the copper ions, so that the copper crystals are more uniform, and the elastic modulus of the copper foil can be improved due to the uniform and compact structure.
The high-modulus lithium-ion copper foil is manufactured by adopting a composite additive mode in combination with the work (110629257A, CN 108677224B) of the company in the improvement of the tensile strength of the lithium-ion copper foil, the effective concentration of a displacement agent in electrolyte is controlled by determining the complexing action of the displacement agent and chloride ions, and then the effective concentration of a brightening agent and a leveling agent is controlled, so that the surface of the copper foil presents the characteristic of dull light.
Disclosure of Invention
Aiming at the technical problems in the related art, the invention provides a composite additive for improving the modulus of a lithium-ion electrolytic copper foil and a production method of the electrolytic copper foil, which can overcome the defects in the prior art.
In order to achieve the technical purpose, the technical scheme of the invention is realized as follows:
the utility model provides a promote compound additive of lithium electricity copper foil modulus, includes A agent, B agent, C agent, D agent, A agent is one or more in thiazolinyl dithio propane sodium sulfonate, dodecylbenzene sulfonic acid sodium, mercapto imidazole propane sodium sulfonate, the methyl mercapto propane sodium sulfonate, A agent concentration is 8-40mg/l in the electrolyte, B agent is one or more in collagen, polyethyleneimine, the polyetheramine, B agent concentration is 4-20mg/l in the electrolyte, C agent is one or more in the block polyether series, C agent concentration is 5-20mg/l in the electrolyte, D agent is one or more in HCl, NaCl, D agent concentration is 9-40ppm in the electrolyte.
A method for producing an electrolytic copper foil using the composite additive according to claim 1, comprising the steps of:
s1, reacting the copper rod or the copper block with pure water and dilute sulfuric acid to prepare copper sulfate electrolyte;
s2, adjusting the concentration of the copper sulfate electrolyte obtained in S1, and heating;
s3, the copper sulfate electrolyte obtained in the step S2 is subjected to multi-stage filtration and then is added into an electrolytic bath together with the composite additive, and meanwhile, the electrolytic bath is electrified for electrodeposition to obtain the copper foil.
Further, in the step S2, the copper ion content in the copper sulfate electrolyte is adjusted to 80-110g/L, the sulfuric acid content is adjusted to 80-110g/L, and the heating temperature of the electrolyte is adjusted to 35-65 ℃.
Further, the electric current electrodeposited in S3Density of 1800-2The flow rate of the electrolyte is 45-50m3/h。
Further, the method comprises S4 subjecting the copper foil obtained in S3 to oxidation prevention treatment.
The invention has the beneficial effects that: the copper foil manufactured by the composite additive and the electrolytic copper foil manufacturing method has the advantages that the elastic modulus is obviously improved, the tensile strength under 0.2% elastic deformation at normal temperature is more than or equal to 370Mpa, the tensile strength under 0.2% elastic deformation is more than or equal to 330Mpa after being baked at 130 ℃ for 10 minutes, the traditional tensile strength at normal temperature is more than or equal to 600Mpa, and the traditional tensile strength is more than or equal to 500Mpa after being baked at 130 ℃ for 10 minutes, so that the problem of bag expansion or belt breakage in the manufacturing process of lithium batteries, particularly soft package type lithium batteries, is effectively solved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Example 1
The prepared composite additive for improving the modulus of the copper foil contains the following components in electrolyte per liter: the copper ion content is 80g/L, the sulfuric acid content is 100g/L, an A agent of thiazolidinethione 10mg/L, a B agent of 3-mercapto-1-propane sodium sulfonate 6mg/L, a C agent of block polyether L3510 mg/L and a D agent of HCl 25ppm are respectively added, and the temperature and the flow rate of the electrolyte solution are 50m at 55 ℃, the3H, current density 1800A/m2Under conditions of (4) to thereby produce an electrolytic copper foil having a thickness of 6 μm.
Example 2
The composite additive for preparing the copper foil modulus contains the following components in each liter of electrolyte: the copper ion content is 95g/L, the sulfuric acid content is 120g/L, an A agent of thiazolidinethione 8mg/L, a B agent of 3-mercapto-1-propane sodium sulfonate 4mg/L, a C agent of block polyether L458 mg/L and a D agent of HCl 20ppm are respectively added, and the temperature and the flow rate of the electrolyte solution are 50m at 55 DEG C3H, current density, 2500A/m2Electrodeposition of 6 μm lithium electrodeposited copper foil under the conditions of (1).
Example 3
The prepared composite additive for improving the modulus of the copper foil contains the following components in electrolyte per liter: the copper ion content is 80g/L, the sulfuric acid content is 100g/L, an A agent of fatty amine ethoxy sulfonate 15mg/L, a B agent of sodium polydithio-dipropyl sulfonate 10mg/L and 2-mercaptobenzimidazole are respectively added, a C agent of block polyether L6115 mg/L and a D agent of HCl 25ppm are respectively added, the temperature of the electrolyte is 55 ℃, the flow rate is 45m3In the case of/h, a current density of 3000A/m is used26 micron lithium electrolytic copper foil is electrodeposited.
Example 4
The prepared composite additive for improving the modulus of the copper foil contains the following components in electrolyte per liter: the copper ion content is 95g/L, the sulfuric acid content is 130g/L, 18mg/L of mercaptoimidazole propanesulfonic acid (MESS) serving as an A agent, 20mg/L of sodium polydithio-dipropanesulfonate (SPS) serving as a B agent, 618 mg/L of C block polyether L618 and 18ppm of NaCl serving as a D agent are respectively added, and the current density is 1800A/m under the conditions that the temperature is 55 ℃ and the flow rate is 45m3/h2And performing electrodeposition on 5-micron lithium electrolytic copper foil.
Example 5
The composite additive for improving the modulus of the copper foil is prepared from the following electrolyte components: the copper ion content is 80g/L, the sulfuric acid content is 100g/L, 15mg/L of A agent of fatty amine ethoxy sulfonate, 10mg/L of B agent of sodium polydithio-dipropyl sulfonate, 10mg/L of C agent of block polyether L3510 mg, 12 block polyether L45 4512 mg/L, 9ppm of D agent of NaCl and 9ppm of HCl are respectively added, the temperature is 50 ℃, the flow rate is 50m3In the case of/h, a current density of 2500A/m is used2And electrodepositing 5-micron lithium electrolytic copper foil.
Example 6
The prepared composite additive for improving the modulus of the copper foil contains the following components in electrolyte per liter: the copper ion content is 80g/L, the sulfuric acid content is 100g/L, 18mg/L of agent A of mercaptoimidazole propanesulfonic acid (MESS), 20mg/L of agent B of sodium polydithio-dipropanesulfonate (SPS), 5mg/L of 2-mercaptobenzimidazole, agent C of block polyether L3520 mg/L, block polyether L4510 mg/L, block polyether L6110 mg/L and agent D of NaCl 30ppm are respectively added, and the flow rate is 45m at the temperature of 50 DEG C3In the case of/h, a current density of 3000A/m is used2And performing electrodeposition on 5-micron lithium electrolytic copper foil.
Example 7
The prepared composite additive for improving the modulus of the copper foil contains the following components in electrolyte per liter: the copper ion content is 80g/L, the sulfuric acid content is 100g/L, 40mg/L of agent A of mercaptoimidazole propanesulfonic acid (MESS), 20mg/L of agent B of sodium polydithio-dipropanesulfonate (SPS), 10mg/L of 2-mercaptobenzimidazole, L355 mg/L of agent C, L455 mg/L of block polyether, L6110 mg/L of block polyether and 20ppm of NaCl D are respectively added, and the flow rate is 45m at the temperature of 50 DEG C3In the case of/h, a current density of 2000A/m is used2And performing electrodeposition on 4.5 micron lithium electrolytic copper foil.
Example 8
The prepared composite additive for improving the modulus of the copper foil contains the following components in electrolyte per liter: the copper ion content is 80g/L, the sulfuric acid content is 100g/L, 30mg/L of agent A of sodium Mercaptoimidazolepropanesulfonate (MESS), 20mg/L of agent B of Sodium Polydithiodipropanesulfonate (SPS), 15mg/L of 2-mercaptobenzimidazole, agent C of block polyether L355 mg/L, block polyether L4510 mg/L, block polyether L6110 mg/L and agent D of HCl 30ppm are respectively added, and the flow rate is 45m at the temperature of 50 DEG C3In the case of/h, a current density of 2500A/m is used2And performing electrodeposition on 4.5 micron lithium electrolytic copper foil.
Example 9
The prepared composite additive for improving the modulus of the copper foil contains the following components in electrolyte per liter: the copper ion content is 80g/L, the sulfuric acid content is 100g/L, 30mg/L of agent A of mercaptoimidazole propanesulfonic acid (MESS), 15mg/L of agent B of 2-mercaptobenzimidazole, 15mg/L of agent C of block polyether L3510 mg/L, block polyether L4510 mg/L, block polyether L6110 mg/L and 40ppm of agent D of NaCl are respectively added, and the flow rate is 45m at the temperature of 50 DEG C3In the case of/h, a current density of 3000A/m is used2And performing electrodeposition on 4.5 micron lithium electrolytic copper foil.
The physical properties of the electrolytic copper foils prepared in examples 1 to 9 are shown in Table 1.
Table 1 high modulus lithium electrolytic copper foil performance test results
| Physical Properties | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 |
| Thickness of | 6 | 6 | 6 | 5 | 5 | 5 | 4.5 | 4.5 | 4.5 |
| 0.2% tensile Strength (MPa) | 353 | 346 | 370 | 349 | 376 | 377 | 380 | 382 | 371 |
| 0.2% tensile Strength (MPa) after baking | 320 | 325 | 340 | 310 | 346 | 349 | 348 | 351 | 341 |
| Elongation (%) | 5.6 | 4.7 | 3.5 | 5.3 | 4.5 | 4.3 | 4.2 | 3.8 | 3.3 |
In conclusion, by means of the technical scheme, crystal grains can be effectively refined, crystal dislocation is improved, the dislocation slip resistance of the crystal grains is improved, and the composite additive and the electrolytic copper foil are particularly suitable for producing 4.5-6 micron ultrathin copper foils.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. The composite additive is characterized by comprising an agent A, an agent B, an agent C and an agent D, wherein the agent A is one or more of thiazolinyl dithio propane sodium sulfonate, dodecyl benzene sodium sulfonate, mercapto imidazole propane sodium sulfonate and methyl mercapto propane sodium sulfonate, the concentration of the agent A in electrolyte is 8-40mg/l, the agent B is one or more of collagen, polyethyleneimine and polyether amine, the concentration of the agent B in electrolyte is 4-20mg/l, the agent C is one or more of block polyether series, the concentration of the agent C in electrolyte is 5-20mg/l, the agent D is one or more of HCl and NaCl, and the concentration of the agent D in electrolyte is 9-40 ppm.
2. A method for producing an electrolytic copper foil using the composite additive according to claim 1, comprising the steps of:
s1, reacting the copper rod or the copper block with pure water and dilute sulfuric acid to prepare copper sulfate electrolyte;
s2, adjusting the concentration of the copper sulfate electrolyte obtained in S1, and heating;
s3, the copper sulfate electrolyte obtained by the treatment of S2 is added into an electrolytic bath together with the compound additive after multi-stage filtration, and the electrolytic bath is electrified for electrodeposition to obtain the copper foil.
3. The production method as claimed in claim 2, wherein the copper ion content of the copper sulfate electrolyte is adjusted to 80-110g/L, the sulfuric acid content is adjusted to 80-110g/L, and the electrolyte heating temperature is adjusted to 35-65 ℃ in S2.
4. The method as claimed in claim 2, wherein the electrodeposition current density in S3 is 1800-4000A/m2The flow rate of the electrolyte is 45-50m3/h。
5. The production method according to claim 2, characterized by further comprising:
s4 the copper foil obtained in S3 is subjected to oxidation prevention treatment.
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| CN202111036789.2A CN113832503A (en) | 2021-09-06 | 2021-09-06 | Composite additive for improving modulus of lithium-ion battery copper foil and electrolytic copper foil production method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111910222A (en) * | 2020-08-21 | 2020-11-10 | 九江德福科技股份有限公司 | Electrolytic copper foil additive with brightening and leveling functions and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008101267A (en) * | 2006-04-28 | 2008-05-01 | Mitsui Mining & Smelting Co Ltd | Electrolytic copper foil, surface treated copper foil using the electrolytic copper foil, copper-clad laminated plate using the surface treated copper foil, and method for manufacturing the electrolytic copper foil |
| CN107099823A (en) * | 2017-04-25 | 2017-08-29 | 佛冈建滔实业有限公司 | Compound additive and its depositing operation for electrolytic copper foil |
| CN112501661A (en) * | 2020-11-30 | 2021-03-16 | 九江德福科技股份有限公司 | High-modulus lithium electrolytic copper foil composite additive |
| 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 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008101267A (en) * | 2006-04-28 | 2008-05-01 | Mitsui Mining & Smelting Co Ltd | Electrolytic copper foil, surface treated copper foil using the electrolytic copper foil, copper-clad laminated plate using the surface treated copper foil, and method for manufacturing the electrolytic copper foil |
| CN107099823A (en) * | 2017-04-25 | 2017-08-29 | 佛冈建滔实业有限公司 | Compound additive and its depositing operation for electrolytic copper foil |
| 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 |
| CN112501661A (en) * | 2020-11-30 | 2021-03-16 | 九江德福科技股份有限公司 | High-modulus lithium electrolytic copper foil composite additive |
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| CN111910222A (en) * | 2020-08-21 | 2020-11-10 | 九江德福科技股份有限公司 | Electrolytic copper foil additive with brightening and leveling functions and application thereof |
| CN111910222B (en) * | 2020-08-21 | 2022-08-23 | 九江德福科技股份有限公司 | Electrolytic copper foil additive with brightening and leveling functions and application thereof |
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