CN117684224A - Preparation method of electrolyte and production process of copper foil - Google Patents
Preparation method of electrolyte and production process of copper foil Download PDFInfo
- Publication number
- CN117684224A CN117684224A CN202311706582.0A CN202311706582A CN117684224A CN 117684224 A CN117684224 A CN 117684224A CN 202311706582 A CN202311706582 A CN 202311706582A CN 117684224 A CN117684224 A CN 117684224A
- Authority
- CN
- China
- Prior art keywords
- concentration
- copper
- solution
- electrolyte
- collagen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000011889 copper foil Substances 0.000 title claims abstract description 56
- 239000003792 electrolyte Substances 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 39
- 102000008186 Collagen Human genes 0.000 claims abstract description 37
- 108010035532 Collagen Proteins 0.000 claims abstract description 37
- 229920001436 collagen Polymers 0.000 claims abstract description 37
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims abstract description 30
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims abstract description 30
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims abstract description 30
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 30
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 26
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 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 22
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 22
- -1 polydithio-dipropyl Polymers 0.000 claims abstract description 22
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 22
- 239000011734 sodium Substances 0.000 claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 22
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- PGJHGXFYDZHMAV-UHFFFAOYSA-K azanium;cerium(3+);disulfate Chemical compound [NH4+].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PGJHGXFYDZHMAV-UHFFFAOYSA-K 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 53
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 27
- 229910052802 copper Inorganic materials 0.000 claims description 25
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 21
- 229910001431 copper ion Inorganic materials 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims 5
- 239000000203 mixture Substances 0.000 claims 1
- 238000004070 electrodeposition Methods 0.000 description 13
- 238000005868 electrolysis reaction Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- OKJMLYFJRFYBPS-UHFFFAOYSA-J tetraazanium;cerium(4+);tetrasulfate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OKJMLYFJRFYBPS-UHFFFAOYSA-J 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The application discloses a preparation method of electrolyte and a production process of copper foil, which relate to the field of electrolytic copper foil and comprise the following steps: preparing a mixed solution of additives; preparing a copper sulfate mixed solution; mixing the additive mixed solution with the copper sulfate mixed solution to obtain an electrolyte; wherein the additive comprises collagen, hydroxyethyl cellulose, sodium polydithio-dipropyl sulfonate, polyethylene glycol and rare earth elements; the rare earth element comprises ammonium cerium sulfate; by the method, production efficiency is improved, and copper foil quality is guaranteed.
Description
Technical Field
The application relates to the field of electrolytic copper foil, in particular to a preparation method of electrolyte and a production process of copper foil.
Background
Along with the development of new energy industry, the production requirements of the power battery are higher and higher, and the requirements of the lithium electric copper foil on the tensile strength, the elongation percentage, the surface density and the like of the lithium electric copper foil are also higher and higher in consideration of indexes such as safety, battery density and the like.
Therefore, additives are required to be added into the electrolyte to meet the quality requirement of the copper foil, but the additives are various, and the addition of the additives enables the copper foil to have relatively good quality, but the electrodeposition rate of copper ions on the cathode roller is relatively slow, so that the production efficiency of the copper foil is affected.
Disclosure of Invention
The purpose of the application is to provide a preparation method of electrolyte capable of improving production efficiency and guaranteeing copper foil quality and a production process of the copper foil.
The application discloses a preparation method of electrolyte, which comprises the following steps:
preparing a mixed solution of additives;
preparing a copper sulfate mixed solution;
mixing the additive mixed solution with the copper sulfate mixed solution to obtain an electrolyte;
wherein the additive comprises collagen, hydroxyethyl cellulose, sodium polydithio-dipropyl sulfonate, polyethylene glycol and rare earth elements; and the rare earth element comprises cerium ammonium sulfate.
Optionally, the concentration of the collagen is 7-22g/L, the concentration of the hydroxyethyl cellulose is 0.2-0.6g/L, the concentration of the sodium polydithio-dipropyl sulfonate is 10-18g/L, the concentration of the polyethylene glycol is 3.5-8.5g/L, and the concentration of the rare earth element is 60-100g/L.
Optionally, the concentration of the collagen is 15+/-0.5 g/L, the concentration of the hydroxyethyl cellulose is 0.45+/-0.15 g/L, the concentration of the sodium polydithio-dipropyl sulfonate is 16+/-0.5 g/L, the concentration of the polyethylene glycol is 5.5+/-0.5 g/L, and the concentration of the rare earth element is 100+/-10 g/L.
Optionally, the concentration of the collagen is 22g/L, the concentration of the hydroxyethyl cellulose is 0.5g/L, the concentration of the sodium polydithio-dipropyl sulfonate is 18g/L, the concentration of the polyethylene glycol is 5.5g/L, and the concentration of the rare earth element is 100g/L.
Optionally, the step of preparing the mixed solution of additives includes the steps of:
dissolving collagen with 45-55deg.C hot water to obtain collagen solution;
dissolving hydroxyethyl cellulose with hot water at 45-55deg.C to obtain hydroxyethyl cellulose solution;
mixing and stirring uniformly the sodium polydithio-dipropyl sulfonate and polyethylene glycol liquid to obtain a mixed solution;
mixing the collagen solution, the hydroxyethyl cellulose solution and the mixed solution;
adding rare earth element liquid and stirring uniformly.
Optionally, the step of preparing the copper sulfate solution includes the steps of:
adding copper wires into a copper dissolving tank;
adding sulfuric acid solution into a copper dissolving tank, and reacting with copper wires to form copper sulfate solution;
adding the hydrochloric acid solution into a copper dissolving tank, and mixing with the copper sulfate solution.
Optionally, the step of adding the hydrochloric acid solution into the copper dissolving tank and mixing the hydrochloric acid solution with the copper sulfate solution to form the electrolyte further comprises the steps of:
introducing hydrochloric acid solution into the copper sulfate solution through a liquid level metering pump, and mixing the hydrochloric acid solution with the copper sulfate solution to form electrolyte;
filtering the electrolyte;
wherein the temperature of the electrolyte is controlled to be 45-70 ℃.
Optionally, in the electrolyte, the concentration of chloride ions is 10-25ppm, the concentration of copper ions is 70-110g/L, and the concentration of sulfuric acid is 80-130g/L.
The application also discloses a copper foil production process, which adopts the electrolyte as described above and comprises the following steps:
polishing and cleaning the cathode roller;
adjusting the distance between the cathode roller and the anode plate to a preset value;
adding electrolyte into an anode tank of a foil producing machine;
and electrifying to electrolyze the electrolyte, so that copper ions are deposited on the cathode roller.
Optionally, the energizing electrolyzes the electrolyte, and in the step of depositing copper ions on the cathode roller, the energizing current density is 3500-8500A/square meter.
Compared with the scheme that the electrodeposition speed of copper ions is affected after the additive is added in the prior art, the additive comprises collagen, hydroxyethyl cellulose, sodium polydithio-dipropyl sulfonate, polyethylene glycol and rare earth elements; and the rare earth element comprises cerium ammonium sulfate; the inventor finds that the reason that the electrodeposition rate of copper ions in the production of the copper foil is low is that collagen can be adsorbed on the surface of a cathode to prevent the electrodeposition of the copper ions, especially when the copper foil with high tensile strength and high ductility is produced, the addition of the collagen is necessary, so that the inventor adds rare earth elements into the additive, thereby being beneficial to improving the movement energy and speed of ions in the electrolyte, further improving the electrodeposition rate, improving the electrodeposition rate of the copper ions by matching with the collagen, further improving the production efficiency, and ensuring the copper foil to have the performances of high tensile strength, high ductility and smoothness.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application. It is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained from these drawings without inventive faculty for a person skilled in the art. In the drawings:
FIG. 1 is a schematic illustration of a preparation flow of the electrolyte of the present application;
FIG. 2 is a schematic illustration of the production process flow of the copper foil of the present application;
FIG. 3 is a further flow chart of step S1 in FIG. 1;
FIG. 4 is a further flow chart of step S2 in FIG. 1;
FIG. 5 is a further flow chart of step S23 in FIG. 4;
FIG. 6 is a microscopic morphology diagram of the roughened surface of the lithium-ion copper foil prepared in the first embodiment of the present application under an optical microscope;
FIG. 7 is a microscopic topography of the matte surface of the lithium electrodeposited copper foil prepared in the fourth embodiment of the present application under an optical microscope;
FIG. 8 is a histogram of tensile strength provided by a fourth embodiment of the present application;
fig. 9 is a histogram of gloss provided by the fourth embodiment of the present application.
Detailed Description
It should be understood that the terminology, specific structural and functional details disclosed herein are merely representative for purposes of describing particular embodiments, but that the application may be embodied in many alternate forms and should not be construed as limited to only the embodiments set forth herein.
In the description of the present application, the terms "first", "second" are used for descriptive purposes only and are not to be construed as indicating relative importance or implicitly indicating the number of technical features indicated. Thus, unless otherwise indicated, features defining "first", "second" may include one or more such features either explicitly or implicitly; the meaning of "plurality" is two or more. In addition, terms of the azimuth or positional relationship indicated by "upper", "lower", "left", "right", "vertical", "horizontal", etc., are described based on the azimuth or relative positional relationship shown in the drawings, and are merely for convenience of description of the present application, and do not indicate that the apparatus or element referred to must have a specific azimuth, be constructed and operated in a specific azimuth, and thus should not be construed as limiting the present application. The specific meaning of the terms in this application will be understood by those of ordinary skill in the art as the case may be.
Fig. 1 is a schematic diagram of a preparation flow of an electrolyte of the present application, and as shown in fig. 1, the present application discloses a preparation method of an electrolyte, including the steps of:
s1: preparing a mixed solution of additives;
s2: preparing a copper sulfate mixed solution;
s3: mixing the additive mixed solution with the copper sulfate mixed solution to obtain an electrolyte;
wherein the additive comprises collagen, hydroxyethyl cellulose, sodium polydithio-dipropyl sulfonate, polyethylene glycol and rare earth elements; and the rare earth element comprises cerium ammonium sulfate.
Compared with the scheme that the electrodeposition speed of copper ions is affected after the additive is added in the prior art, the additive comprises collagen, hydroxyethyl cellulose, sodium polydithio-dipropyl sulfonate, polyethylene glycol and rare earth elements; and the rare earth element comprises cerium ammonium sulfate; the inventor finds that the reason that the electrodeposition rate of copper ions in the production of the copper foil is low is that collagen can be adsorbed on the surface of a cathode to prevent the electrodeposition of the copper ions, especially when the copper foil with high tensile strength and high ductility is produced, the addition of the collagen is necessary, so that the inventor adds rare earth elements into the additive, thereby being beneficial to improving the movement energy and speed of ions in the electrolyte, further improving the electrodeposition rate, improving the electrodeposition rate of the copper ions by matching with the collagen, further improving the production efficiency, and ensuring the copper foil to have the performances of high tensile strength, high ductility and smoothness.
Fig. 2 is a schematic view of a production process flow of the copper foil of the present application, and as shown in fig. 2, the present application also discloses a production process of the copper foil, wherein the electrolyte is adopted, and the method comprises the following steps:
s4: polishing and cleaning the cathode roller;
s5: adjusting the distance between the cathode roller and the anode plate to a preset value;
s6: adding electrolyte into an anode tank of a foil producing machine;
s7: and electrifying to electrolyze the electrolyte, so that copper ions are deposited on the cathode roller, and a copper foil primary product is obtained.
Wherein the current density of the electrified water is 3500-8500A/square meter.
In the preparation of the electrolyte, collagen plays a role of a leveling agent and can be adsorbed on the surface of a cathode to block electrodeposition of copper ions, and the collagen can form an adsorption complex with the copper ions in the electrolyte, so that the electrochemical polarization of the copper cathode is promoted, the deposition overpotential is increased, and copper nucleation is promoted by coupling two factors, thereby refining crystal grains, reducing the surface coarse precision, being beneficial to the copper foil to obtain good uniform deformability and realizing high extensibility; the chloride ions can react with copper ions for the second time to generate cuprous ions in the electrolysis process, so that the electrolysis is catalyzed to a certain extent, the overpotential can be increased in a proper concentration range, and nucleation is promoted; HEC (hydroxyethyl cellulose) canThe compactness of the plating layer is increased, the generation of holes is reduced, and the warping degree is improved to a certain extent; the sodium polydithio-dipropyl sulfonate refines the grains, prevents abnormal grain growth, can smooth the surface of the fine grains to increase the rough surface glossiness of the copper foil, but excessively reduces the high-temperature tensile strength and the elongation of the copper foil; polyethylene glycol in Cl - And Cu + In the presence of the catalyst, the catalyst can be adsorbed on the surface of metal, so that the surface tension of an interface is reduced, the gas generated by hydrogen evolution reaction is promoted to be discharged, and the less amount of pinhole defects is avoided; rare earth element Ce (SO) 4 ) 2 "helps to increase the kinetic energy and velocity of ions in the electrolyte, and thus increase the electrodeposition rate.
In this application: the concentration of the collagen is 7-22g/L, the concentration of the hydroxyethyl cellulose is 0.2-0.6g/L, the concentration of the sodium polydithio-dipropyl sulfonate is 10-18g/L, the concentration of the polyethylene glycol is 3.5-8.5g/L, the concentration of the rare earth element is 60-100g/L, and the flow is controlled to be 15+/-5L/h when each component is added. Wherein the concentrations of the additives are selected to be different, the quality of the copper foil will vary over the surface, and the present application will be described in detail with reference to the accompanying drawings and alternative examples.
First embodiment:
fig. 3 is a further schematic flow chart of step S1 in fig. 1, and as shown in fig. 3, in the step of preparing the mixed solution of additives, the steps include:
s11: dissolving collagen with 45-55deg.C hot water to obtain collagen solution;
s12: dissolving hydroxyethyl cellulose with hot water at 45-55deg.C to obtain hydroxyethyl cellulose solution;
s13: mixing and stirring uniformly the sodium polydithio-dipropyl sulfonate and polyethylene glycol liquid to obtain a mixed solution;
s14: mixing the collagen solution, the hydroxyethyl cellulose solution and the mixed solution;
s15: adding rare earth element liquid and stirring uniformly.
In the dissolving process of the collagen, the material is thoroughly dissolved, the solution is clear and transparent after dissolution, otherwise, if the collagen is not fully dissolved, the pipeline is blocked later; the hydroxyethyl cellulose is easy to flocculate in the dissolving process, so that the hydroxyethyl cellulose needs to be rapidly stirred in the dissolving process, otherwise, burrs are easy to generate; the sodium polydithio-dipropyl sulfonate and polyethylene glycol liquid are added into the same stirring tank for stirring, and the rare earth element liquid is added into the stirring tank independently, so that the formed additive mixed liquid is more uniform and more fully dissolved.
Fig. 4 is a further schematic flow chart of step S2 in fig. 1, and as shown in fig. 4, the step of preparing a copper sulfate solution includes the steps of:
s21: adding copper wires into a copper dissolving tank;
s22: adding sulfuric acid solution into a copper dissolving tank, and reacting with copper wires to form copper sulfate solution;
s23: adding the hydrochloric acid solution into a copper dissolving tank, and mixing with the copper sulfate solution.
Wherein, hydrochloric acid solution is added to provide chloride ions, which are adsorbed at the cathode with high coverage rate to attract copper ions to form complexes and support electron transfer. The concentration of chloride ions in the electrolyte is 10-25ppm; the concentration of copper ions is 70-110g/L; the concentration of sulfuric acid is 80-130g/L.
Fig. 5 is a schematic diagram of a further flow chart of step S23 in fig. 4, and as shown in fig. 5, the step of adding the hydrochloric acid solution into the copper dissolving tank and mixing with the copper sulfate solution to form an electrolyte further includes the steps of:
s231: introducing hydrochloric acid solution into the copper sulfate solution through a liquid level metering pump, and mixing the hydrochloric acid solution with the copper sulfate solution to form electrolyte;
s232: filtering the electrolyte;
the impurities in the electrolyte can be removed, wherein the temperature of the electrolyte is set to 45-60 ℃, and the temperature of the electrolyte is controlled to 45-70 ℃ after the electrolyte is prepared.
Specifically, electrolytic equipment is adopted for preparing copper foil, and additives are added into electrolyte, wherein the additives comprise the following components: the concentration of collagen is 12g/L, HEC, the concentration of sodium polydithio-dipropyl sulfonate is 11g/L, the concentration of polyethylene glycol is 5g/L, and the concentration of rare earth element is 50g/L. After adding the additive, electricity is generatedThe solution comprises the following components: cu ion concentration is 90g/L, H 2 SO 4 The concentration was 93g/L, the concentration of chloride ions was 18ppm, the electrolysis temperature in the electrolysis apparatus was 53 ℃, copper was separated from the cathode, and copper foil was obtained by peeling.
Fig. 6 is a microscopic morphology diagram of the matte surface of the lithium-ion copper foil prepared in the first embodiment of the application under an optical microscope, and as shown in fig. 6, the size of the copper crystal particles is smaller than 50um. The electrodeposited copper foil prepared in this example had a matte surface roughness Ra of 0.278. Mu.m, an Rz of 1.631. Mu.m, and a tensile strength of 43Kgf/mm 2 The warpage was 8mm and the gloss was 145GU. The tensile strength is low, and the method is not suitable for mass production.
Second embodiment:
preparing copper foil by electrolytic equipment, and adding additives into the electrolyte, wherein the additives comprise the following components: collagen concentration is 15g/L, HEC concentration is 0.6g/L, sodium polydithio-dipropyl sulfonate concentration is 15g/L, polyethylene glycol concentration is 6g/L, and rare earth element concentration is 80g/L. The electrolyte comprises the following components in percentage by weight: cu ion concentration is 90g/l, H 2 SO 4 The concentration was 93g/L, the concentration of chloride ions was 20ppm, the electrolysis temperature in the electrolysis apparatus was 51 ℃, copper was separated from the cathode, and copper foil was obtained by peeling. The electrodeposited copper foil prepared in this example had a matte surface roughness Ra of 0.23 μm, an Rz of 1.51 μm and a tensile strength of 47Kgf/mm 2 The warpage was 4mm and the gloss was 168GU. The prepared copper foil has the advantages of high tensile strength, low warping degree and relatively meeting the quality requirements, and can be produced in mass.
Third embodiment:
preparing copper foil by electrolytic equipment, and adding additives into the electrolyte, wherein the additives comprise the following components: the concentration of collagen is 22g/L, HEC, the concentration of sodium polydithio-dipropyl sulfonate is 18g/L, the concentration of polyethylene glycol is 5.5g/L, and the concentration of rare earth element is 100g/L. The electrolyte comprises the following components in percentage by weight: the concentration of Cu ions is 90g/L, the concentration of H2SO4 is 93g/L, the concentration of chloride ions is 20ppm, the electrolysis temperature in the electrolysis equipment is 51 ℃, copper is separated from the cathode, and the copper foil is obtained by stripping. The electrodeposited copper foil prepared in this example had a matte surface roughness Ra of 0.2113 μm, an Rz of 1.89 μm and a tensile strengthStrength of 51Kgf/mm 2 The warpage was 2mm and the gloss was 110GU. The collagen concentration of this example is higher, and the situation that the torn edge copper foil is brittle easily occurs in the preparation process.
Fourth embodiment:
preparing copper foil by electrolytic equipment, and adding additives into the electrolyte, wherein the additives comprise the following components: collagen concentration is 15g/L, HEC concentration is 0.45g/L, sodium polydithio-dipropyl sulfonate concentration is 16g/L, polyethylene glycol concentration is 5.5g/L, and rare earth element concentration is 100g/L. The electrolyte comprises the following components in percentage by weight: cu ion concentration is 95g/l, H 2 SO 4 The concentration was 98g/L, the concentration of chloride ions was 23ppm, the electrolysis temperature in the electrolysis apparatus was 51 ℃, copper was separated from the cathode, and copper foil was obtained by peeling. The electrodeposited copper foil prepared in this example had a matte surface roughness Ra of 0.23 μm, an Rz of 1.43 μm and a tensile strength of 55Kgf/mm 2 The warpage was 2mm and the gloss was 160GU. The stable production and physical properties of the copper foil in the manufacturing process of the embodiment break the problem that the traditional additive can not ensure that the copper foil has tensile property, extensibility and smooth coating at the same time.
FIG. 7 is a graph showing the microscopic morphology of the roughened surface of a lithium-ion copper foil obtained in the fourth example of the present application under an optical microscope, FIG. 8 is a histogram of tensile strength provided in the fourth example of the present application, FIG. 9 is a histogram of glossiness provided in the fourth example of the present application, wherein the X-axis is a test physical property value and the Y-axis is the frequency of occurrence of the physical property value, and in combination with FIGS. 7 to 9, it is found that the surface cells of a bump copper foil are uniformly leveled by observing SEM using a scanning electron microscope in the production of a lithium-ion copper foil by using the additive as a whole, and the copper foil is baked at 140℃for 15min by an electrothermal constant temperature blast drying oven, and the tensile strength is tested to 55Kgf/mm by an electronic universal tester 2 The elongation percentage is more than or equal to 13 percent and more than or equal to 7 percent. Therefore, the copper foil prepared by adopting the additive concentration of each component of the additive has high tensile property, high elongation, good glossiness, good control of the warping degree of the finished product and no occurrence of the condition of exceeding the standard of batchability.
It should be noted that, the limitation of each step in the present solution is not to be considered as limiting the sequence of steps on the premise of not affecting the implementation of the specific solution, and the steps written in the previous step may be executed before, may be executed after, or may even be executed simultaneously, so long as the implementation of the present solution is possible, all should be considered as falling within the protection scope of the present application.
It should be noted that, the inventive concept of the present application may form a very large number of embodiments, but the application documents have limited space and cannot be listed one by one, so that on the premise of no conflict, the above-described embodiments or technical features may be arbitrarily combined to form new embodiments, and after the embodiments or technical features are combined, the original technical effects will be enhanced.
The foregoing is a further detailed description of the present application in connection with specific alternative embodiments, and it is not intended that the practice of the present application be limited to such descriptions. It should be understood that those skilled in the art to which the present application pertains may make several simple deductions or substitutions without departing from the spirit of the present application, and all such deductions or substitutions should be considered to be within the scope of the present application.
Claims (10)
1. The preparation method of the electrolyte is characterized by comprising the following steps:
preparing a mixed solution of additives;
preparing a copper sulfate mixed solution;
mixing the additive mixed solution with the copper sulfate mixed solution to obtain an electrolyte;
wherein the additive comprises collagen, hydroxyethyl cellulose, sodium polydithio-dipropyl sulfonate, polyethylene glycol and rare earth elements; the rare earth element includes ammonium cerium sulfate.
2. The method according to claim 1, wherein the concentration of the collagen is 7 to 22g/L, the concentration of the hydroxyethyl cellulose is 0.2 to 0.6g/L, the concentration of the sodium polydithio-dipropyl sulfonate is 10 to 18g/L, the concentration of the polyethylene glycol is 3.5 to 8.5g/L, and the concentration of the rare earth element is 60 to 100g/L.
3. The method according to claim 2, wherein the concentration of collagen is 15±0.5g/L, the concentration of hydroxyethyl cellulose is 0.45±0.15g/L, the concentration of sodium polydithio-dipropyl sulfonate is 16±0.5g/L, the concentration of polyethylene glycol is 5.5±0.5g/L, and the concentration of rare earth element is 100±10g/L.
4. The method according to claim 2, wherein the concentration of the collagen is 22g/L, the concentration of the hydroxyethyl cellulose is 0.5g/L, the concentration of the sodium polydithio-dipropyl sulfonate is 18g/L, the concentration of the polyethylene glycol is 5.5g/L, and the concentration of the rare earth element is 100g/L.
5. The method for preparing an electrolyte according to claim 1, wherein the step of preparing the additive mixture comprises the steps of:
dissolving collagen with 45-55deg.C hot water to obtain collagen solution;
dissolving hydroxyethyl cellulose with hot water at 45-55deg.C to obtain hydroxyethyl cellulose solution;
mixing and stirring uniformly the sodium polydithio-dipropyl sulfonate and polyethylene glycol liquid to obtain a mixed solution;
mixing the collagen solution, the hydroxyethyl cellulose solution and the mixed solution;
adding rare earth element liquid and stirring uniformly.
6. The method for producing an electrolytic solution according to claim 1, wherein the step of producing a copper sulfate solution comprises the steps of:
adding copper wires into a copper dissolving tank;
adding sulfuric acid solution into a copper dissolving tank, and reacting with copper wires to form copper sulfate solution;
adding hydrochloric acid solution into a copper dissolving tank, and mixing with copper sulfate solution to form electrolyte.
7. The method of preparing an electrolyte according to claim 6, wherein the step of adding a hydrochloric acid solution to the copper dissolution tank and mixing the hydrochloric acid solution with a copper sulfate solution to form the electrolyte further comprises the steps of:
introducing hydrochloric acid solution into the copper sulfate solution through a liquid level metering pump, and mixing the hydrochloric acid solution with the copper sulfate solution to form electrolyte;
filtering the electrolyte;
wherein the temperature of the electrolyte is controlled to be 45-70 ℃.
8. The method for producing an electrolytic solution according to claim 7, wherein the concentration of chloride ions in the electrolytic solution is 10 to 25ppm, the concentration of copper ions is 70 to 110g/L, and the concentration of sulfuric acid is 80 to 130g/L.
9. A process for producing a copper foil using the electrolytic solution according to any one of claims 1 to 8, comprising the steps of:
polishing and cleaning the cathode roller;
adjusting the distance between the cathode roller and the anode plate to a preset value;
adding electrolyte into an anode tank of a foil producing machine;
and electrifying to electrolyze the electrolyte, so that copper ions are deposited on the cathode roller, and a copper foil primary product is obtained.
10. The method of producing copper foil according to claim 9, wherein the step of applying electricity to electrolyze the electrolytic solution to deposit copper ions on the cathode roll has an electric current density of 3500 to 8500A/square meter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311706582.0A CN117684224A (en) | 2023-12-12 | 2023-12-12 | Preparation method of electrolyte and production process of copper foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311706582.0A CN117684224A (en) | 2023-12-12 | 2023-12-12 | Preparation method of electrolyte and production process of copper foil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117684224A true CN117684224A (en) | 2024-03-12 |
Family
ID=90129753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311706582.0A Pending CN117684224A (en) | 2023-12-12 | 2023-12-12 | Preparation method of electrolyte and production process of copper foil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117684224A (en) |
-
2023
- 2023-12-12 CN CN202311706582.0A patent/CN117684224A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109267111B (en) | Additive for electrolytic copper foil and application thereof, electrolytic copper foil and preparation method and application thereof, and lithium ion battery | |
| KR101386093B1 (en) | Copper electrolysis solution for production of electrolytic copper foil, process for producing electrolytic copper foil and electrolytic copper foil | |
| US9812700B2 (en) | Method for producing porous aluminum foil, porous aluminum foil, positive electrode current collector for electrical storage devices, electrode for electrical storage devices, and electrical storage device | |
| CN110644021B (en) | 4.5-micron electrolytic copper foil for lithium ion battery, preparation method and additive | |
| CN108251869B (en) | Tin plating electrolyte and the preparation method and application thereof | |
| US3769179A (en) | Copper plating process for printed circuits | |
| CN111286765B (en) | Electrolytic copper foil and preparation method and application thereof | |
| CN112144084A (en) | Additive and process for preparing high-tensile electrolytic copper foil by using same | |
| Nan et al. | Electrochemical mechanism of tin membrane electrodeposition under ultrasonic waves | |
| CN112133902A (en) | Sodium metal negative electrode deposition matrix and preparation method and application thereof | |
| CN111286745B (en) | Additive for high-tensile electrolytic copper foil, preparation method of electrolytic copper foil and lithium ion battery | |
| CN105002524A (en) | Addition agent and process for producing 6-micron low-warping-degree electrolytic copper foil through addition agent | |
| Zou et al. | A nuclei-rich strategy for highly reversible dendrite-free zinc metal anodes | |
| CN109208040A (en) | A kind of compound additive being used to prepare low roughness electrolytic copper foil | |
| CN117684224A (en) | Preparation method of electrolyte and production process of copper foil | |
| CN110004468B (en) | Composite additive for preparing low-brittleness electrolytic copper foil | |
| CN108998818B (en) | Method for depositing copper plating layer on surface of closed-cell foamed aluminum | |
| CN108642533B (en) | Sn-Cu electroplating solution, tin-based alloy electrode for lithium ion battery, preparation method of tin-based alloy electrode and lithium ion battery | |
| Cheng et al. | The effects of current density on microstructure and properties of electrolytic copper foils | |
| Sknar et al. | Electrodeposition of copper from a methanesulphonate electrolyte | |
| Lee et al. | Fabrication of tin-cobalt/carbon composite electrodes by electrodeposition using cationic surfactant for lithium-ion batteries | |
| WO2019004580A1 (en) | Method for manufacturing vertically-oriented porous electrode for generating hydrogen and oxygen | |
| CN116180166B (en) | Production method of 3.5-4 mu m double-sided light copper foil | |
| CN114108042B (en) | Rare earth surface treating agent for improving electrochemical corrosion resistance of copper foil surface and surface treating process | |
| TWI766752B (en) | Electrode for lithium-ion battery and lithium-ion battery comprising the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |