CN116377526A - Additive for electrolytic copper, electrolyte, copper foil and preparation method of additive - Google Patents
Additive for electrolytic copper, electrolyte, copper foil and preparation method of additive Download PDFInfo
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- CN116377526A CN116377526A CN202310016807.3A CN202310016807A CN116377526A CN 116377526 A CN116377526 A CN 116377526A CN 202310016807 A CN202310016807 A CN 202310016807A CN 116377526 A CN116377526 A CN 116377526A
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- copper foil
- crystal face
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- electrolytic copper
- electrolyte
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000011889 copper foil Substances 0.000 title claims abstract description 111
- 239000000654 additive Substances 0.000 title claims abstract description 53
- 230000000996 additive effect Effects 0.000 title claims abstract description 41
- 239000003792 electrolyte Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000010949 copper Substances 0.000 title abstract description 5
- 229910052802 copper Inorganic materials 0.000 title abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 57
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 17
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- 108010010803 Gelatin Proteins 0.000 claims abstract description 14
- 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 14
- 229920000159 gelatin Polymers 0.000 claims abstract description 14
- 239000008273 gelatin Substances 0.000 claims abstract description 14
- 235000019322 gelatine Nutrition 0.000 claims abstract description 14
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 14
- -1 polydithio-dipropyl Polymers 0.000 claims abstract description 11
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 11
- 102000008186 Collagen Human genes 0.000 claims abstract description 10
- 108010035532 Collagen Proteins 0.000 claims abstract description 10
- 229920001436 collagen Polymers 0.000 claims abstract description 10
- 239000001888 Peptone Substances 0.000 claims abstract description 5
- 108010080698 Peptones Proteins 0.000 claims abstract description 5
- 235000019319 peptone Nutrition 0.000 claims abstract description 5
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000012137 tryptone Substances 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 238000000034 method Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000013528 artificial neural network Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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)
- Laminated Bodies (AREA)
Abstract
An additive for electrolytic copper, an electrolyte, a copper foil and a preparation method thereof, wherein the additive comprises a (220) crystal face accelerator and/or a (220) crystal face inhibitor, and the (220) crystal face accelerator is any one or more of sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium phenyl polydithio-propane sulfonate and sodium N, N-dimethyl-dithiocarbonyl propane sulfonate; (220) The crystal face inhibitor is one or more of gelatin, collagen, peptone and tryptone. When the electrolytic copper foil is prepared, the additive is few in types, the electrolyte is high in stability, the tensile strength and the elongation of the copper foil can be obviously improved, after the additive is added, the prepared electrolytic copper foil has different crystal face ratios, the (220) crystal face ratio is between 20% and 90%, the tensile strength is more than or equal to 400MPa, the elongation is more than or equal to 3%, and the mechanical property requirement of the electrolytic copper foil can be met.
Description
Technical Field
The invention belongs to the technical field of electrolytic copper foil, and in particular relates to an additive for electrolytic copper, electrolyte, copper foil and a preparation method thereof.
Background
The electrolytic copper foil is widely applied to industries such as electronic information, new energy, 5G communication and the like due to the excellent electric conduction and heat conduction properties, and is used as a neural network for electronic signal and power transmission and a lithium battery negative electrode current collector, so that higher requirements are put on the performance of the copper foil, wherein the tensile strength and the elongation percentage are key factors for influencing the performance of the copper foil. In order to ensure that the copper foil current collector is not broken and wrinkled in the process of signal efficient transmission and rolling when the circuit board is bent or subjected to abrupt temperature change, the copper foil needs to have higher tensile strength and elongation.
In the preparation of the electrolytic copper foil, electrolytic process parameters and additives can influence the quality of the copper foil, wherein the additives are the most important factors for controlling the quality of the electrolytic copper foil, and the electrolytic copper foil with compact structure and smooth surface can be obtained by adding proper additives.
However, in the current electrolytic copper foil production process, the high-end additive is mostly imported, the formula is complex, the proportion is unknown, the dosage is difficult to master, the problems of edge tearing, uneven thickness of the copper foil breadth, wrinkling, high warping degree and the like of the copper foil are easily caused when the electrolytic copper foil is used, and the tensile strength of the electrolytic copper foil cannot meet the requirement of customers on higher tensile strength of the copper foil.
Disclosure of Invention
The invention aims to provide an additive for electrolytic copper, electrolyte, copper foil and a preparation method thereof, so as to solve the problem that the existing additive cannot meet the mechanical property requirement of the electrolytic copper foil.
The technical scheme adopted by the invention is as follows:
an additive for electrolytic copper foil comprising a (220) crystal face promoter and/or a (220) crystal face inhibitor:
the (220) crystal face accelerator is any one or more of sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium phenyl polydithio-propane sulfonate and sodium N, N-dimethyl-dithio carbonyl propane sulfonate;
the (220) crystal face inhibitor is any one or more of gelatin, collagen, peptone and tryptone.
Further, the (220) crystal face accelerator is sodium polydithio-dipropyl sulfonate, and the concentration is 5-120 mg/L.
Further, the (220) crystal face inhibitor is at least one of gelatin, collagen and peptone, and the concentration is 5-120 mg/L.
An electrolyte comprises the additive for regulating and controlling the electrolytic copper foil.
A method for preparing a copper foil, comprising the steps of:
step A: preparing a copper sulfate main electrolyte;
and (B) step (B): adding the additive for the electrolytic copper foil for regulating the crystal face orientation in any scheme into the copper sulfate main electrolyte, and uniformly mixing to obtain the electrolyte, wherein the mass ratio of the (220) crystal face accelerator to the (220) crystal face inhibitor is 1:1-1:6, preparing a base material;
step C: and (5) electrodepositing the electrolyte to obtain the copper foil.
Further, in the step A, the concentration of copper ions, sulfuric acid and chloride ions in the copper sulfate main electrolyte is sequentially 100g/L, 105g/L and 40mg/L.
In the step B, the temperature of the main copper sulfate electrolyte water area is raised to 50 ℃, then the additive is added, and finally the ultrasonic stirring is carried out uniformly.
Further, in the step C, the electrodeposition is carried out by adopting direct current with the current density of 30-80A/dm 2 。
Further, in the step C, the distance between the anode and the cathode is 6cm.
A copper foil is prepared by the preparation method of the copper foil.
The invention has the beneficial effects that:
the additive for the electrolytic copper foil can remarkably improve the tensile property and the elongation rate of the electrolytic copper foil by controlling the crystal face orientation regulation and the crystal face competition regulation of the electrolytic copper foil, has few additive types and high electrolyte stability, can regulate the crystal face ratio of the electrolytic copper foil by different proportions of the additive, has the crystal face ratio of (220) between 20% and 90%, has the tensile strength of more than or equal to 400MPa and the elongation rate of more than or equal to 3%, and can meet the mechanical property requirement of the electrolytic copper foil.
Drawings
FIG. 1 is a graph (magnification 2000) of the microscopic morphology of the matte surface of a copper foil without the additive of the invention added.
FIG. 2 is a plot (2000-fold magnification) of the micro-topography of the matte surface of an electrodeposited copper foil according to example 1 of the present invention, wherein FIGS. 2a,2b, and 2c are plots of the micro-topography of the matte surface of an electrodeposited copper foil according to example 1, having sodium polydithio-dipropyl sulfonate (SPS) concentrations of 5, 10, and 15 mg/L, respectively.
FIG. 3 is an XRD and crystal face ratio pattern of the electrolytic copper foil of example 1 of the present invention, wherein FIG. 3a is an XRD pattern of the electrolytic copper foil of example 1 and FIG. 3b is a crystal face ratio pattern of the electrolytic copper foil of example 1.
FIG. 4 is a stress-strain curve of the electrolytic copper foil according to example 1 of the present invention.
FIG. 5 is a graph (2000-fold magnification) showing the microscopic morphology of the matte surface of an electrolytic copper foil according to example 2 of the present invention, wherein FIGS. 5a,5b,5c are respectively graphs showing the microscopic morphology of the matte surface of an electrolytic copper foil according to example 2, in which Gelatin (Gelatin) concentration is 10, 15, and 30 mg/L.
FIG. 6 is an XRD and crystal face ratio pattern of the electrolytic copper foil of example 2 of the present invention, wherein FIG. 6a is an XRD pattern of the electrolytic copper foil of example 1 and FIG. 6b is a crystal face ratio pattern of the electrolytic copper foil of example 2.
FIG. 7 is a stress-strain curve of an electrodeposited copper foil according to example 2 of the present invention.
FIG. 8 is an XRD and crystal face ratio pattern of the electrolytic copper foil of example 3 of the present invention, wherein the XRD pattern of the electrolytic copper foil of example 1 of FIG. 8a and the crystal face ratio pattern of the electrolytic copper foil of example 3 of FIG. 8b are shown.
FIG. 9 is a stress-strain curve of an electrodeposited copper foil according to example 3 of the present invention.
FIG. 10 is an XRD and crystal face ratio plot of the electrolytic copper foil of example 4 of the present invention, wherein FIG. 10a is an XRD plot of the electrolytic copper foil of example 1 and FIG. 10b is a crystal face ratio plot of the electrolytic copper foil of example 4.
FIG. 11 is a stress-strain curve of an electrodeposited copper foil according to example 4 of the present invention.
FIG. 12 is an XRD and crystal face ratio pattern of the electrolytic copper foil of example 5 of the present invention, wherein FIG. 12a is an XRD pattern of the electrolytic copper foil of example 1 and FIG. 12b is a crystal face ratio pattern of the electrolytic copper foil of example 5.
FIG. 13 is a stress-strain curve of an electrodeposited copper foil according to example 5 of the present invention.
FIG. 14 is an XRD and crystal face ratio plot of the electrolytic copper foil of example 6 of the present invention, wherein FIG. 14a is an XRD plot of the electrolytic copper foil of example 1 and FIG. 14b is a crystal face ratio plot of the electrolytic copper foil of example 6.
FIG. 15 is a stress-strain curve of an electrodeposited copper foil according to example 6 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the present invention, sodium polydithio-dipropyl sulfonate is purchased from the microphone reagent, CAS:27206-35-5;
gelatin was purchased from das chemical company, deutsche, the company (tendril, china);
collagen was purchased from Shanghai microphone reagent, CAS:9064-67-9.
Example 1
The additive for electrolytic copper foil of this example comprises (220) a crystal plane accelerator, and (220) a sodium polydithio-dipropyl sulfonate (SPS) was used as the crystal plane accelerator, and three parts of the additive were prepared at concentrations of (a) 5mg/L, (b) 10mg/L and (c) 15 mg/L, respectively, corresponding to examples 1a, 1b and 1c.
The electrolyte of this example, including the additive of this example, specifically, copper sulfate, sulfuric acid and chloride ions were prepared with ultrapure water as the main electrolyte, and the concentrations of copper ions, sulfuric acid and chloride ions in the main electrolyte were 100g/L, 105g/L and 40mg/L in this order.
The preparation method of the copper foil comprises the following steps:
step A: preparing copper sulfate, sulfuric acid and chloride ions with ultrapure water as main electrolyte, wherein the concentrations of the copper ions, the sulfuric acid and the chloride ions in the main electrolyte are sequentially 100g/L, 105g/L and 40mg/L, and carrying out suction filtration once after complete dissolution to remove impurities.
And (B) step (B): and (3) regulating the temperature of the prepared main electrolyte, and heating the main electrolyte to 50 ℃ in a water bath.
Step C: adding main electrolyte and additive into electrolytic tank simultaneously, ultrasonic treating for one minute, heating and stirring continuously, spacing between cathode and anode plates of 6cm, and carrying out DC deposition with current density of 30A/dm 2 And (3) stripping the copper foil from the cathode, washing with water, and drying with cold air after electrodeposition for a certain time to obtain the copper foil.
Example 1a matte micro-topography of a copper foil prepared with three concentrations of additives (a) 5mg/L, (b) 10mg/L and (c) 15 mg/L is shown in fig. 2a,2b,2c, respectively.
XRD and crystal face occupancy patterns of the copper foil obtained in example 1 are shown in FIGS. 3a and 3 b.
The stress-strain curve of the copper foil obtained in example 1 is shown in fig. 4.
In contrast, an electrodeposited copper foil was prepared without the addition of additives, and the preparation procedure was the same as in example 1, with a rough surface microtopography of the electrodeposited copper foil without the addition of additives shown in fig. 1.
Example 2
The additives for electrolytic copper foil of this example include (220) crystal face inhibitor Gelatin (Gelatin), and were prepared in three parts at concentrations of (a) 10mg/L, (b) 15 mg/L and (c) 30mg/L, respectively, corresponding to examples 2a,2b and 2c.
The electrolyte of this example is different from example 1 in that only the additive is added.
The electrolytic preparation process of the copper foil of this example was the same as in example 1, except that the additives were different.
The roughened surface micro-morphology of the copper foil obtained in example 2 is shown in fig. 5a,5b, 5c.
XRD and crystal face occupancy patterns of the electrolytic copper foil obtained in example 2 are shown in FIGS. 6a and 6 b.
The stress-strain curve of the electrodeposited copper foil obtained in example 2 is shown in FIG. 7.
Example 3
The additive for electrolytic copper foil of this example comprises Collagen (Collagen) as a (220) crystal face inhibitor at concentrations of (a) 10, (b) 15 and (c) 30mg/L, respectively, corresponding to examples 3a, 3b and 3c.
The electrolyte of this example is different from example 1 in that only the additive is added.
The electrolytic copper foil production process of this example was the same as in example 1, except that the additives were different.
XRD and crystal face occupancy patterns of the copper foil obtained in example 3 are shown in FIGS. 8a and 8 b.
The stress-strain curve of the copper foil obtained in example 3 is shown in fig. 9.
Example 4
The additive for electrolytic copper foil of this example comprises (220) crystal face accelerator sodium polydithio-dipropyl sulfonate (SPS) with a concentration of 5mg/L and (220) crystal face inhibitor Gelatin (Gelatin) with a concentration of (a) 10, (b) 15 and (c) 30mg/L, which correspond to example 4a, example 4b and example 4c, respectively.
The electrolyte of this example is different from example 1 in that only the additive is added.
The electrolytic copper foil preparation process of this embodiment is the same as that of embodiment 1 except that the additives are different, and a detailed description thereof is omitted.
XRD and crystal face occupancy patterns of the copper foil obtained in example 4 are shown in FIGS. 10a and 10 b.
The stress-strain curve of the copper foil obtained in example 4 is shown in fig. 11.
Example 5
The additive for electrolytic copper foil of this example comprises (220) crystal face accelerator sodium polydithio-dipropyl sulfonate (SPS) at a concentration of 10mg/L, and (220) crystal face inhibitor Gelatin (Gelatin) at a concentration of (a) 10, (b) 15 and (c) 30mg/L, respectively, corresponding to example 5a, example 5b and example 5c.
The electrolyte of this example is different from example 1 in that only the additive is added.
The electrolytic copper foil preparation process of this embodiment is the same as that of embodiment 1 except that the additives are different, and a detailed description thereof is omitted.
XRD and crystal face occupancy patterns of the copper foil obtained in example 5 are shown in FIGS. 12a and 12 b.
The stress-strain curve of the copper foil obtained in example 5 is shown in fig. 13.
Example 6
The additive for electrolytic copper foil of this example comprises (220) crystal face accelerator sodium polydithio-dipropyl sulfonate (SPS) at a concentration of 10mg/L, and (220) crystal face inhibitor Collagen (Collagen) at a concentration of (a) 10, (b) 15 and (c) 30mg/L, respectively, corresponding to example 6a, example 6b and example 6c, respectively.
The electrolyte of this example is different from example 1 in that only the additive is added.
The electrolytic copper foil preparation process of this embodiment is the same as that of embodiment 1 except that the additives are different, and a detailed description thereof is omitted.
XRD and crystal face occupancy patterns of the copper foil obtained in example 6 are shown in FIGS. 14a and 14 b.
The stress-strain curve of the copper foil obtained in example 6 is shown in fig. 15.
Comparative example:
in comparison with example 1, the additive provided by the present invention was not added during the preparation of the copper foil, and the rest of the preparation steps were the same as those in example 1, and the rough surface micro-morphology of the electrodeposited copper foil to which the additive was not added was shown in fig. 1.
The copper foils obtained in examples 1-6 and comparative examples were tested as follows:
(1) Tensile strength and elongation: testing according to GB/T29847-2013 standard;
(2) XRD tests and calculates the (220) crystal plane ratio.
The test results are shown in table 1 below.
TABLE 1 Performance test results
It should be noted that the above embodiments are only for illustrating the present invention, but the present invention is not limited to the above embodiments, and any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention falls within the protection scope of the present invention.
Claims (10)
1. An additive for electrolytic copper foil, characterized by comprising a (220) crystal face accelerator and/or a (220) crystal face inhibitor:
the (220) crystal face accelerator is any one or more of sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium phenyl polydithio-propane sulfonate and sodium N, N-dimethyl-dithio carbonyl propane sulfonate;
the (220) crystal face inhibitor is any one or more of gelatin, collagen, peptone and tryptone.
2. The additive for electrolytic copper foil according to claim 1, wherein the (220) crystal face promoter is sodium polydithio-dipropyl sulfonate and the concentration is 5-120 mg/L.
3. The additive for electrolytic copper foil according to claim 1, wherein the (220) crystal face inhibitor is at least one of gelatin, collagen and peptone, and the concentration is 5 to 120 mg/L.
4. An electrolytic solution comprising the additive for electrolytic copper foil according to any one of claims 1 to 3.
5. The preparation method of the copper foil is characterized by comprising the following steps of:
step A: preparing a copper sulfate main electrolyte;
and (B) step (B): adding the additive for the electrolytic copper foil for regulating and controlling the crystal face orientation according to any one of claims 1-3 into a copper sulfate main electrolyte, and uniformly mixing to obtain the electrolyte, wherein the mass ratio of the (220) crystal face accelerator to the (220) crystal face inhibitor is 1:1-1:6, preparing a base material;
step C: and (5) electrodepositing the electrolyte to obtain the copper foil.
6. The method for producing a copper foil according to claim 5, wherein in the step A, the concentration of copper ions, sulfuric acid and chloride ions in the copper sulfate main electrolyte is 100g/L, 105g/L and 40mg/L in this order.
7. The method of claim 5, wherein in step B, the temperature of the main electrolyte water area of the copper sulfate is raised to 50 ℃, then the additive is added, and finally the ultrasonic stirring is carried out uniformly.
8. The method of producing a copper foil according to claim 5, wherein in the step C, the electrodeposition is performed by using a direct current having a current density of 30 to 80A/dm 2 。
9. The method of producing a copper foil according to claim 8, wherein in the step C, the pitch between the anode and the cathode is 6cm.
10. A copper foil prepared by the method of any one of claims 5 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310016807.3A CN116377526A (en) | 2023-01-06 | 2023-01-06 | Additive for electrolytic copper, electrolyte, copper foil and preparation method of additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310016807.3A CN116377526A (en) | 2023-01-06 | 2023-01-06 | Additive for electrolytic copper, electrolyte, copper foil and preparation method of additive |
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| Publication Number | Publication Date |
|---|---|
| CN116377526A true CN116377526A (en) | 2023-07-04 |
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| CN202310016807.3A Pending CN116377526A (en) | 2023-01-06 | 2023-01-06 | Additive for electrolytic copper, electrolyte, copper foil and preparation method of additive |
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