CN118028918A - Copper foil composite additive and method for preparing crystal face highly oriented electrolytic copper foil - Google Patents
Copper foil composite additive and method for preparing crystal face highly oriented electrolytic copper foil Download PDFInfo
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- CN118028918A CN118028918A CN202410284722.8A CN202410284722A CN118028918A CN 118028918 A CN118028918 A CN 118028918A CN 202410284722 A CN202410284722 A CN 202410284722A CN 118028918 A CN118028918 A CN 118028918A
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- copper foil
- copper
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000000654 additive Substances 0.000 title claims abstract description 105
- 230000000996 additive effect Effects 0.000 title claims abstract description 105
- 239000011889 copper foil Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 239000013078 crystal Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 41
- 239000010949 copper Substances 0.000 claims abstract description 41
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 36
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims description 69
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 46
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000011888 foil Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- -1 hydrogen ions Chemical class 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 108010010803 Gelatin Proteins 0.000 claims description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims description 10
- 230000005587 bubbling Effects 0.000 claims description 10
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- 239000008273 gelatin Substances 0.000 claims description 10
- 229920000159 gelatin Polymers 0.000 claims description 10
- 235000019322 gelatine Nutrition 0.000 claims description 10
- 235000011852 gelatine desserts Nutrition 0.000 claims description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- 102000008186 Collagen Human genes 0.000 claims description 9
- 108010035532 Collagen Proteins 0.000 claims description 9
- 229920001436 collagen Polymers 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920001285 xanthan gum Polymers 0.000 claims description 7
- 229940082509 xanthan gum Drugs 0.000 claims description 7
- 235000010493 xanthan gum Nutrition 0.000 claims description 7
- 239000000230 xanthan gum Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 238000005282 brightening Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000080 wetting agent Substances 0.000 claims description 3
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 abstract description 13
- 238000001556 precipitation Methods 0.000 abstract description 6
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 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 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a copper foil composite additive and a method for preparing a crystal face highly oriented electrolytic copper foil, wherein the composite additive comprises the following components: an additive A, wherein the additive A is at least one of sulfonated thiacalix [4] arene, sulfonated thiacalix [6] arene and sulfonated thiacalix [8] arene; due to the rigid structure of the sulfonated thiacalixarene, the calixarene adsorbed on the cathode forms an oriented arrangement with the sulfonic acid groups upwards. The thiaaromatics can absorb water molecules in the hydrated copper ions by utilizing sulfonic acid groups and hydroxyl groups to obtain exposed copper ions. Copper ions entering the annular cavity through the upper edge can be complexed with the sulfur bridge bond of the calixarene, and the annular cavity at the lower edge of the calixarene is smaller, so that copper cannot be separated out on the cathode. Copper ions can only approach the cathode from the edge of calixarene, so that copper grains grow directionally, meanwhile, the overpotential for copper ion precipitation is increased, and according to the principle of lowest energy, the (111) crystal face precipitation of copper is facilitated, and the tensile strength of the copper foil is further improved.
Description
Technical Field
The invention relates to the technical field of copper foil production, in particular to a copper foil composite additive and a method for preparing a crystal face highly oriented electrolytic copper foil by using the same.
Background
In recent years, as the requirements of lithium batteries are higher and higher, higher requirements are put on the performance of lithium electric copper foil. For example, aiming at the requirement of high energy density, the copper foil is required to be thinned on one hand, so that the copper foil with unit mass has larger area of the coatable anode material; on the other hand, copper foil coated with more active material on a fixed coated area, copper foil coated with more negative electrode active material is required to withstand greater pressure in the rolling step in the subsequent battery process, and thus copper foil having high tensile strength is required.
The copper foil additive is commonly used at present and comprises sulfur-containing organic additives such as sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, thiourea and the like, and the tensile strength and the elongation of the copper foil are controlled by controlling the crystal nucleus formation and the growth rate of copper foil grains, so that the particle size of the copper foil and the flatness of the surface of the copper foil are controlled. However, after the conventional additive raw materials are used for preparing the additive, the tensile strength of the copper foil is generally 320-370MPa, and the tensile strength is required to be improved.
According to the literature, the higher the (111) plane ratio in the copper foil crystal grains, the higher the tensile strength of the copper foil, and therefore an additive was developed which can effectively promote highly oriented growth of the copper foil (111) plane, thereby realizing production of the high tensile strength copper foil.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a composite additive which is mixed and added into main electrolyte, so that the microstructure and morphology of a plating layer are changed by influencing the copper ion deposition reaction rate, and the high-tensile electrolytic copper foil is prepared.
In order to solve the problems, the invention adopts the following technical scheme. An electrolytic copper foil composite additive, the composite additive comprising:
An additive A which is at least one of sulfonated thiacalix [4] arene, sulfonated thiacalix [6] arene and sulfonated thiacalix [8] arene and is used as a brightening agent;
Additive B as a wetting agent;
additive C, as levelling agent.
Preferably, the additive B is at least one of ethylene glycol, polyoxyethylene ether, polyacrylamide and xanthan gum.
Preferably, the additive C is gelatin or collagen.
Preferably, in the additive B, the molecular weight of the ethylene glycol is 6000-9000Mw.
Preferably, in the additive C, the molecular weight of the gelatin or collagen is 2000-5000Mw.
The preparation method of the high-tensile electrolytic copper foil comprises the following steps:
s1, preparing electrolyte, namely adding metal copper into a copper dissolving tank containing sulfuric acid, bubbling air, and dissolving to obtain copper sulfate electrolyte;
S2, adding ammonium chloride in the step S1 to obtain a main electrolyte;
s3, adding a composite additive in the step S2;
and S4, conveying the electrolyte obtained in the step S3 to a foil producing machine to obtain the copper foil.
Preferably, the temperature of the heat exchanger in the platinum producing process of the platinum producing machine is set to be 50-55 ℃, the conveying flow is 46-58m 3/h, and the current density is 40-46A/dm 2
Preferably, after step S is completed, the concentration of additive a in the electrolyte is between 100 and 160ppm; the concentration of the additive B in the electrolyte is 20-40ppm; the concentration of the additive C in the electrolyte is 5-45ppm; the concentration of copper ions is 70-130g/L, the concentration of hydrogen ions is 80-130g/L, and the concentration of chloride ions is 15-35ppm.
Preferably, the additive A, the additive B and the additive C are respectively stirred and dissolved at 50-55 ℃ and then sequentially added into the main electrolyte.
Preferably, the metal copper is a metal copper wire, the copper content is more than or equal to 99.5%, the iron content is not more than 0.5%, and the thickness of the copper foil is 6um.
Compared with the prior art, the invention has the beneficial effects that:
the sulfonated thiacalixarene represented by water-soluble calixarene has strong inclusion coordination capability to metals and good bonding selectivity, and becomes a substitute for sps sulfur-containing chemicals. The sulfonated thiacalixarene can be adsorbed on the cathode surface by utilizing hydroxyl and sulfur functional groups, and the sulfonic acid anion at the other end adsorbs copper ions. Due to the rigid structure of the sulfonated thiacalixarene, the calixarene adsorbed on the cathode forms an oriented arrangement with the sulfonic acid groups upwards. The thiaaromatics can absorb water molecules in the hydrated copper ions by utilizing sulfonic acid groups and hydroxyl groups to obtain exposed copper ions. Copper ions entering the annular cavity through the upper edge can be complexed with the sulfur bridge bond of the calixarene, and the annular cavity at the lower edge of the calixarene is smaller, so that copper cannot be separated out on the cathode. Copper ions can only approach the cathode from the edge of calixarene, so that copper grains grow directionally, meanwhile, the overpotential for copper ion precipitation is increased, and according to the principle of lowest energy, the (111) crystal face precipitation of copper is facilitated, and the tensile strength of the copper foil is further improved.
Drawings
FIG. 1 is a diagram showing adsorption of sulfonated thiacalix [4] arene on a titanium roll and adsorption of metal ions according to the present invention
Fig. 2 is a comparative characteristic diagram of example 1 and comparative example 1 of the present invention.
The reference numerals in the figures illustrate:
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The first aspect of the embodiment of the application provides an electrolytic copper foil composite additive, which comprises the following components: an additive A which is at least one of sulfonated thiacalix [4] arene, sulfonated thiacalix [6] arene and sulfonated thiacalix [8] arene and is used as a brightening agent; additive B as a wetting agent; additive C, as levelling agent. It is understood that additive A may be a sulfonated thiacalix [4] arene alone, a sulfonated thiacalix [6] arene alone, a sulfonated thiacalix [8] arene alone; the mixture of the sulfonated thiacalix [4] arene and the sulfonated thiacalix [6] arene, the mixture of the sulfonated thiacalix [4] arene and the sulfonated thiacalix [8] arene and the mixture of the sulfonated thiacalix [6] arene and the sulfonated thiacalix [8] arene can also be used; the mixture of sulfonated thiacalix [4] arene and sulfonated thiacalix [6] arene and sulfonated thiacalix [8] arene can also be used.
In some embodiments, the additive B is at least one of ethylene glycol, polyoxyethylene ether, polyacrylamide, and xanthan gum. It can be understood that the additive B can be one of glycol, polyoxyethylene ether, polyacrylamide and xanthan gum, or can be two or three of glycol and polyoxyethylene ether, glycol and polyacrylamide, glycol and xanthan gum, polyoxyethylene ether and polyacrylamide; and can be all of ethylene glycol, polyoxyethylene ether, polyacrylamide and xanthan gum.
In some embodiments, the additive C is gelatin or collagen. It will be appreciated that since collagen is an upgrade to gelatin, additive C is either gelatin alone or collagen alone, both of which cannot be used in combination.
In some embodiments, in additive B, the molecular weight of ethylene glycol is 6000 to 9000Mw. For example: 6000Mw, 6500Mw, 7000Mw, 7500Mw, 8000Mw, 8500Mw, 9000Mw and the like.
In some embodiments, in additive C, the gelatin or collagen has a molecular weight of 2000-5000Mw. For example: 2000Mw, 2500Mw, 3000Mw, 3500Mw, 4000Mw, 4500Mw, 5000Mw, and the like.
The second aspect of the embodiment of the application provides a preparation method of a high-tensile electrolytic copper foil, which comprises the following steps:
s1, preparing electrolyte, namely adding metal copper into a copper dissolving tank containing sulfuric acid, bubbling air, and dissolving to obtain copper sulfate electrolyte;
S2, adding ammonium chloride in the step S1 to obtain a main electrolyte;
s3, adding a composite additive in the step S2;
and S4, conveying the electrolyte obtained in the step S3 to a foil producing machine to obtain the copper foil.
In some embodiments, the heat exchanger temperature during the platinum production process of the platinum producing machine is set to 50-55 ℃, for example: 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, etc.; the conveying flow rate is 46-58m 3/h, such as ：46m3/h、47m3/h、48m3/h、49m3/h、50m3/h、51m3/h、52m3/h、53m3/h、54m3/h、55m3/h、56m3/h、57m3/h、58m3/h; the current density is 40-46A/dm 2, such as ：40A/dm2、41A/dm2、42A/dm2、43A/dm2、44A/dm2、45A/dm2、46A/dm2、47A/dm2, etc.
In some embodiments, after step S is completed, the concentration of additive a in the electrolyte is 100-160ppm; for example; 100ppm, 110ppm, 120ppm, 130ppm, 140ppm, 150ppm, 160ppm, etc. The concentration of the additive B in the electrolyte is 20-40ppm; for example: 20ppm, 25, ppm, 30ppm, 35ppm, 40ppm, etc. The concentration of the additive C in the electrolyte is 5-45ppm; for example: 5ppm, 10ppm, 15ppm, 20ppm, 25ppm, 30ppm, 35ppm, 40ppm, 45ppm, etc. Copper ion concentration is 70-130g/L, for example: 70g/L, 80g/L, 90g/L, 100g/L, 110g/L, 120g/L, 130g/L, etc. The hydrogen ion concentration is 80-130g/L, for example: 80g/L, 90g/L, 100g/L, 110g/L, 120g/L, 130g/L, etc. The chloride ion concentration is 15-35ppm, for example: 15ppm, 20ppm, 25ppm, 30ppm, 35ppm, etc.
In some embodiments, the additive A, the additive B and the additive C are respectively dissolved by stirring at 50-55 ℃ and then sequentially added into the main electrolyte. It will be appreciated that in order to ensure stability, the temperature of the additive A, B, C needs to be controlled to be the same as the temperature of the main electrolyte before it is added to the main electrolyte.
In some embodiments, the metallic copper is a metallic copper wire with a copper content of 99.5% or more, for example: 99.5%, 99.6%, 99.7%, 99.8% and 100%. Iron content is not more than 0.5%, for example: 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, 0%. The copper foil thickness was 6um. It will be appreciated that copper metal may also be copper blocks, rods, sheets of copper, etc.
Example 1:
Adding metal copper into a copper dissolving tank containing sulfuric acid, bubbling air, dissolving to obtain copper sulfate electrolyte, and adding ammonium chloride to obtain main electrolyte; then, the additive A sulphonated thiacalix [4] arene and the additive B ethylene glycol are respectively stirred and dissolved at 50 ℃, and are sequentially added into a main electrolyte, and the concentrations of the additive A, the additive B and the additive C in the electrolyte are respectively 100ppm, 20ppm and 5ppm; the concentrations of copper ions, hydrogen ions and chloride ions in the electrolyte are respectively 70g/L, 80g/L and 15ppm; and finally, conveying the electrolyte to a foil producing machine, wherein the temperature of a heat exchanger of the foil producing machine is set to be 50 ℃, the conveying flow is 46m 3/h, the current density is 40A/dm 2, and the copper foil with the thickness of 6um is obtained.
Example 2:
Adding metal copper into a copper dissolving tank containing sulfuric acid, bubbling air, dissolving to obtain copper sulfate electrolyte, and adding ammonium chloride to obtain main electrolyte; then, the additive A sulphonated thiacalix [6] arene and the additive B ethylene glycol are respectively stirred and dissolved at the temperature of 51 ℃, and are sequentially added into a main electrolyte, and the concentrations of the additive A, the additive B and the additive C in the electrolyte are respectively 110ppm, 20ppm and 10ppm; the concentrations of copper ions, hydrogen ions and chloride ions in the electrolyte are respectively 80g/L, 90g/L and 20ppm; and finally, conveying the electrolyte to a foil producing machine, wherein the temperature of a heat exchanger of the foil producing machine is set to be 51 ℃, the conveying flow is 48m 3/h, the current density is 42A/dm 2, and the copper foil with the thickness of 6um is obtained.
Example 3:
Adding metal copper into a copper dissolving tank containing sulfuric acid, bubbling air, dissolving to obtain copper sulfate electrolyte, and adding ammonium chloride to obtain main electrolyte; then, the additive A sulphonated thiacalix [8] arene and the additive B ethylene glycol are respectively stirred and dissolved at 52 ℃, and are sequentially added into a main electrolyte, and the concentrations of the additive A, the additive B and the additive C in the electrolyte are respectively 120ppm, 30ppm and 15ppm; the concentrations of copper ions, hydrogen ions and chloride ions in the electrolyte are respectively 90g/L, 100g/L and 25ppm; and finally, conveying the electrolyte to a foil producing machine, wherein the temperature of a heat exchanger of the foil producing machine is set to be 52 ℃, the conveying flow is 50m 3/h, the current density is 43A/dm 2, and the copper foil with the thickness of 6um is obtained.
Example 4:
Adding metal copper into a copper dissolving tank containing sulfuric acid, bubbling air, dissolving to obtain copper sulfate electrolyte, and adding ammonium chloride to obtain main electrolyte; then mixing additive A sulfonated thiacalix [4] arene and sulfonated thiacalix [6] arene, additive B glycol and polyoxyethylene ether, stirring and dissolving additive C gelatin at 53 deg.C, and sequentially adding into main electrolyte, wherein the concentrations of additive A, additive B and additive C in the electrolyte are 130ppm, 35ppm and 25ppm respectively; the concentrations of copper ions, hydrogen ions and chloride ions in the electrolyte are respectively 100g/L, 110g/L and 30ppm; and finally, conveying the electrolyte to a foil producing machine, wherein the temperature of a heat exchanger of the foil producing machine is set to be 53 ℃, the conveying flow is 52m 3/h, the current density is 44A/dm 2, and the copper foil with the thickness of 6um is obtained.
Example 5:
Adding metal copper into a copper dissolving tank containing sulfuric acid, bubbling air, dissolving to obtain copper sulfate electrolyte, and adding ammonium chloride to obtain main electrolyte; then mixing additive A sulfonated thiacalix [4] arene and sulfonated thiacalix [8] arene, additive B glycol, polyoxyethylene ether and polyacrylamide, stirring and dissolving additive C collagen at 54 ℃ respectively, and sequentially adding the mixture into a main electrolyte, wherein the concentrations of additive A, additive B and additive C in the electrolyte are 140ppm, 35ppm and 35ppm respectively; the concentrations of copper ions, hydrogen ions and chloride ions in the electrolyte are 120g/L, 120g/L and 30ppm respectively; and finally, conveying the electrolyte to a foil producing machine, wherein the temperature of a heat exchanger of the foil producing machine is set to be 54 ℃, the conveying flow is 55m 3/h, the current density is 45A/dm 2, and the copper foil with the thickness of 6um is obtained.
Example 6:
Adding metal copper into a copper dissolving tank containing sulfuric acid, bubbling air, dissolving to obtain copper sulfate electrolyte, and adding ammonium chloride to obtain main electrolyte; then mixing and dissolving the mixture of the sulfonated thiacalix [4] arene and sulfonated thiacalix [6] arene and sulfonated thiacalix [8] arene added with the additive B, the mixture of ethylene glycol and polyoxyethylene ether added with the additive C and polyacrylamide added with xanthan gum respectively at 55 ℃, and sequentially adding the mixture into a main electrolyte, wherein the concentrations of the additive A, the additive B and the additive C in the electrolyte are 160ppm, 40ppm and 45ppm respectively; the concentrations of copper ions, hydrogen ions and chloride ions in the electrolyte are 130g/L, 130g/L and 35ppm respectively; and finally, conveying the electrolyte to a foil producing machine, wherein the temperature of a heat exchanger of the foil producing machine is set to 55 ℃, the conveying flow is 58m 3/h, the current density is 46A/dm 2, and the copper foil with the thickness of 6um is obtained.
Referring to fig. 1, calixarenes adsorbed on the cathode form an oriented arrangement with sulfonic acid groups upward due to the rigid structure of the sulfonated thiacalixarenes. The thiaaromatics can absorb water molecules in the hydrated copper ions by utilizing sulfonic acid groups and hydroxyl groups to obtain exposed copper ions. Copper ions entering the annular cavity through the upper edge can be complexed with the sulfur bridge bond of the calixarene, and the annular cavity at the lower edge of the calixarene is smaller, so that copper cannot be separated out on the cathode. Copper ions can only approach the cathode from the edge of calixarene, so that directional growth of copper grains is caused, meanwhile, the overpotential for copper ion precipitation is increased, and the (111) crystal face precipitation of copper is facilitated according to the principle of lowest energy.
Comparative example 1:
Adding metal copper into a copper dissolving tank containing sulfuric acid, bubbling air, dissolving to obtain copper sulfate electrolyte, and adding ammonium chloride to obtain main electrolyte; then SPS is taken as brightening agent and additive B glycol, additive C gelatin is respectively stirred and dissolved at 50 ℃, and is sequentially added into main electrolyte, and the concentration of SPS brightening agent, additive B and additive C in the electrolyte is respectively 100ppm, 20ppm and 5ppm; the concentrations of copper ions, hydrogen ions and chloride ions in the electrolyte are respectively 70g/L, 80g/L and 15ppm; and finally, conveying the electrolyte to a foil producing machine, wherein the temperature of a heat exchanger of the foil producing machine is set to be 50 ℃, the conveying flow is 46m 3/h, the current density is 40A/dm 2, and the copper foil with the thickness of 6um is obtained.
Referring to fig. 2, comparative example 1 is the trend curve No. 1 of fig. 2; example 1 is the trend curve No. 2 of fig. 2. 1. Sample No. 2 has a characteristic peak height ratio I (111)/I (220) of: 1.748 and 1.618, the sulfonated thiacalix [4] arene promotes the secondary oriented growth of copper grains in the copper foil and improves the crystallization degree of the copper grains. The more (111) planes in the copper grain, the higher the tensile strength of the copper foil.
The lithium electric copper foil prepared by the electrolytic copper foil composite additive has the advantages of high tensile strength and uniform thickness, and the tensile strength of the lithium electric copper foil is more than or equal to 680Mpa under the condition of 3% elastic deformation at normal temperature, and the tensile strength of the copper foil is more than or equal to 450Mpa after baking for 16 hours under the protection of nitrogen at 300 ℃.
The above description is only of the preferred embodiments of the present invention; the scope of the invention is not limited in this respect. Any person skilled in the art, within the technical scope of the present disclosure, may apply to the present invention, and the technical solution and the improvement thereof are all covered by the protection scope of the present invention.
Claims (10)
1. An electrolytic copper foil composite additive, the composite additive comprising:
An additive A which is at least one of sulfonated thiacalix [4] arene, sulfonated thiacalix [6] arene and sulfonated thiacalix [8] arene and is used as a brightening agent;
Additive B as a wetting agent;
additive C, as levelling agent.
2. An electrolytic copper foil additive according to claim 1, wherein: the additive B is at least one of ethylene glycol, polyoxyethylene ether, polyacrylamide and xanthan gum.
3. An electrolytic copper foil additive according to claim 1, wherein: the additive C is gelatin or collagen.
4. An electrolytic copper foil additive according to claim 2, wherein: in the additive B, the molecular weight of the glycol is 6000-9000Mw.
5. An electrolytic copper foil additive according to claim 3, wherein: in the additive C, the molecular weight of gelatin or collagen is 2000-5000Mw.
6. A method for producing a crystal plane highly oriented electrolytic copper foil, characterized in that an electrolytic copper foil additive according to any one of claims 1 to 5 is used, comprising the steps of:
s1, preparing electrolyte, namely adding metal copper into a copper dissolving tank containing sulfuric acid, bubbling air, and dissolving to obtain copper sulfate electrolyte;
S2, adding ammonium chloride in the step S1 to obtain a main electrolyte;
s3, adding a composite additive in the step S2;
and S4, conveying the electrolyte obtained in the step S3 to a foil producing machine to obtain the copper foil.
7. The method for producing a crystal face highly oriented electrolytic copper foil according to claim 6, wherein: the temperature of a heat exchanger in the platinum producing process of the platinum producing machine is set to be 50-55 ℃, the conveying flow is 46-58m 3/h, and the current density is 40-46A/dm 2
8. The method for producing a crystal face highly oriented electrolytic copper foil according to claim 6, wherein: after step S is completed, the concentration of the additive A in the electrolyte is 100-160ppm; the concentration of the additive B in the electrolyte is 20-40ppm; the concentration of the additive C in the electrolyte is 5-45ppm; the concentration of copper ions is 70-130g/L, the concentration of hydrogen ions is 80-130g/L, and the concentration of chloride ions is 15-35ppm.
9. The method for producing a crystal face highly oriented electrolytic copper foil according to claim 6, wherein: the additive A, the additive B and the additive C are respectively stirred and dissolved at 50-55 ℃ and then are sequentially added into the main electrolyte.
10. The method for producing a crystal face highly oriented electrolytic copper foil according to claim 6, wherein: the metal copper is a metal copper wire, the copper content is more than or equal to 99.5%, the iron content is not more than 0.5%, and the thickness of the copper foil is 6um.
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