CN115838948A - Collagen-free additive for copper foil processing and copper foil processing technology - Google Patents
Collagen-free additive for copper foil processing and copper foil processing technology Download PDFInfo
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- CN115838948A CN115838948A CN202211586909.0A CN202211586909A CN115838948A CN 115838948 A CN115838948 A CN 115838948A CN 202211586909 A CN202211586909 A CN 202211586909A CN 115838948 A CN115838948 A CN 115838948A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000011889 copper foil Substances 0.000 title claims abstract description 119
- 239000000654 additive Substances 0.000 title claims abstract description 50
- 230000000996 additive effect Effects 0.000 title claims abstract description 43
- 238000012545 processing Methods 0.000 title claims abstract description 36
- 238000005516 engineering process Methods 0.000 title abstract description 12
- 238000000137 annealing Methods 0.000 claims abstract description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 24
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 17
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 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 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 150000002170 ethers Chemical class 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- 230000035484 reaction time Effects 0.000 claims abstract description 11
- 150000003585 thioureas Chemical class 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000007664 blowing Methods 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- -1 sodium sulfonate salts Chemical class 0.000 claims description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910001431 copper ion Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 6
- PTYCIYHGEPJZCK-UHFFFAOYSA-N 1-methyl-3-[(2-phenylacetyl)amino]thiourea Chemical compound CNC(=S)NNC(=O)CC1=CC=CC=C1 PTYCIYHGEPJZCK-UHFFFAOYSA-N 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 claims description 3
- DBOBDMZHSHKLSJ-UHFFFAOYSA-N n-(phenylcarbamothioyl)acetamide Chemical compound CC(=O)NC(=S)NC1=CC=CC=C1 DBOBDMZHSHKLSJ-UHFFFAOYSA-N 0.000 claims description 3
- XOGTZOOQQBDUSI-UHFFFAOYSA-M Mesna Chemical compound [Na+].[O-]S(=O)(=O)CCS XOGTZOOQQBDUSI-UHFFFAOYSA-M 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 150000003384 small molecules Chemical class 0.000 claims 1
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011888 foil Substances 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 102000008186 Collagen Human genes 0.000 description 16
- 108010035532 Collagen Proteins 0.000 description 16
- 229920001436 collagen Polymers 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005520 cutting process Methods 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 230000002411 adverse Effects 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 description 2
- 230000008485 antagonism Effects 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- ZNEWHQLOPFWXOF-UHFFFAOYSA-N coenzyme M Chemical compound OS(=O)(=O)CCS ZNEWHQLOPFWXOF-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- RGBLSOOLFKMJGA-UHFFFAOYSA-N [Na].C(=O)=CCC Chemical compound [Na].C(=O)=CCC RGBLSOOLFKMJGA-UHFFFAOYSA-N 0.000 description 1
- KHAZIIVSIJPRGF-UHFFFAOYSA-N [Na].CCCS Chemical compound [Na].CCCS KHAZIIVSIJPRGF-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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- 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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Abstract
The invention relates to a collagen-free additive for processing copper foil and a copper foil processing technology, belonging to the technical field of lithium-ion battery copper foil additives, wherein the collagen-free additive for processing the copper foil consists of micromolecules of sodium sulfonate, thiourea derivatives containing amido bonds and ether derivatives containing hydrophilic functional groups; the copper foil processing technology comprises the following steps: s1, preparing electrolyte for Harlin groove flaking, adding a collagen-free additive for copper foil processing into the electrolyte, and performing air blowing circulation stirring; s2, setting reaction time and reaction current, controlling groove pressure and preparing a sample copper foil; s3, carrying out a low-temperature annealing process; and S4, testing. The additive system only has three components, and the content of each additive component is easy to regulate and control; the prepared lithium-ion electro-deposited copper foil has uniform crystal grain shape and small size, and the tensile strength of the mechanical property of the bright and uniform foil surface can reach 37kgf/mm 2 The elongation can reach 8%.
Description
Technical Field
The invention belongs to the technical field of lithium battery copper foil additives, and particularly relates to a collagen-free additive for copper foil processing and a copper foil processing technology.
Background
With the rapid development of the electric automobile industry, the copper foil is one of important basic materials of a new energy power lithium battery, the demand of the copper foil is increasing day by day, the requirement on the quality performance of the copper foil is continuously improved, the excellent comprehensive mechanical property can ensure that the battery is not easy to break in the working process, the capacity and the safety of the battery are improved, and the tensile strength of the conventional 6 mu m copper foil is 32-35kgf/mm at present 2 The elongation is 5% -8%. According to the current literature report, when the performance of the copper foil is regulated and controlled through an additive process, the tensile strength and the elongation rate tend to show opposite change trends. Therefore, the improvement of the tensile strength and the elongation of the copper foil simultaneously becomes a problem to be solved in the field of research on the mechanical properties of the copper foil.
Collagen is the most commonly used inhibiting additive in the production of the lithium electrolytic copper foil at present, the molecular weight of the collagen can influence the surface appearance and the grain morphology of the copper foil, when the adsorption area on the surface of a cathode is large, the rough surface of the copper foil is in a gully shape, and the grains are uniform and fine; when the molecular weight is small, the adsorption area is small, the rough surface of the copper foil is in a pointed cone shape, the crystal grain shape is not uniform, and the adverse effect is generated on the performance of the copper foil due to the difficulty in controlling the molecular weight of the collagen.
At present, additive components in the research of a plurality of additive systems of lithium electric copper foil are various, besides common accelerators and inhibitors, the systems also comprise a grain agent, a surface wetting agent, a dispersing agent and the like, according to the report of documents, the influence of various additives on the copper ion deposition process is synergistic, but antagonism exists among certain additives, so that the copper foil performance is adversely affected when the types of the additives in the additive systems are too various, and in addition, the content of a single additive is difficult to regulate and control.
Disclosure of Invention
The invention aims to provide a collagen-free additive for processing a copper foil and a copper foil processing technology, which solve the problems in the prior art.
The purpose of the invention can be realized by the following technical scheme:
a collagen-free additive for processing copper foil comprises micromolecules of sodium sulfonate, thiourea derivatives containing amido bonds and ether derivatives containing hydrophilic functional groups; the mass concentration ratio of micromolecules of sodium sulfonate, thiourea derivatives containing amido bonds and ether derivatives containing hydrophilic functional groups is 1:1-2:0.1-0.2.
Furthermore, the micromolecules of the sodium sulfonate salts are one of sodium polydithio-dipropyl sulfonate, 3-mercapto-propane sulfonate and 2-mercapto-ethyl sulfonate.
Furthermore, the thiourea derivative containing the amido bond is one of malonyl thiosemicarbazone, 3-methyl-1- (2-phenylacetyl amino) thiourea and 1-acetyl-3-phenylthiourea.
Further, the ether derivative containing a hydrophilic functional group is one of diethylene glycol dimethyl ether, ethylene glycol butyl ether and triethylene glycol divinyl ether.
A copper foil processing technology comprises the following steps:
s1, preparing 1.5L of electrolyte for Harlin groove flaking, adding a collagen-free additive for copper foil processing into the electrolyte, wherein the 1.5L of electrolyte contains 10ppm of micromolecules of sodium sulfonate salts, and performing air blowing circulation stirring;
and S2, setting reaction time and reaction current, controlling groove pressure and starting to prepare the sample copper foil. After the completion, the power supply is turned off, the titanium cathode is taken out, the titanium cathode is put into deionized water to be cleaned for 5s, and the copper foil is manually stripped by using an art designer knife;
s3, placing the prepared copper foil into an annealing furnace for low-temperature annealing process treatment;
and S4, cutting the prepared sample into samples of 100mm multiplied by 50mm by using a sampling plate, cutting the samples into 3 sample strips of 100mm multiplied by 15mm by using a cutting knife, and finally testing the tensile strength and the elongation by using a universal testing machine. The mechanical property and tensile strength of the copper foil can reach 37kgf/mm 2 The elongation can reach 8%.
Further, in the step S1, the sulfuric acid concentration of the electrolyte is 90-120g/L, the copper ion concentration is 80-100g/L, the chloride ion concentration is 10-50mg/L, and the temperature of the electrolyte is 50-60 ℃.
Furthermore, in the step S2, the reaction time is 50S, the reaction current is 26.5A, and the tank pressure is 4.5-5.5V.
Further, the low-temperature annealing process in step S3 includes the following steps: putting the copper foil into an annealing furnace, and heating to 60-90 ℃ within 3-5 h; and (3) heat preservation: insulating the copper foil in an annealing furnace for 1-2h; and (3) cooling: and (3) slowly cooling the copper foil along with the furnace for 3-5h, and then taking out.
The invention has the beneficial effects that:
in the invention, an additive system which does not contain collagen macromolecules is tried, and the adverse effect on the performance of the copper foil caused by difficult control and nonuniformity of the molecular weight of the collagen is avoided; the number of the components in the additive system is reduced, the antagonism among a plurality of additive components is avoided, the content of each additive component is easy to regulate, the prepared lithium electrolytic copper foil has uniform crystal grain shape and small size, and the lithium electrolytic copper foil with high tensile strength and high elongation is obtained.
In the non-collagen additive process, the additive components comprise sodium sulfonate micromolecules, thiourea derivatives containing amido bonds and ether derivatives containing hydrophilic functional groups, so that the problem that the adverse effect on the performance of a copper foil is caused due to the fact that the molecular weight of collagen is difficult to control is avoided; the additive system only has three components, and the content of each additive component is easy to regulate and control; the prepared lithium-ion electro-deposited copper foil has uniform crystal grain shape and small size, and the tensile strength of the mechanical property of the bright and uniform foil surface can reach 37kgf/mm 2 The elongation can reach 8%. The method provides a solution for avoiding the problem that the molecular weight of the collagen is difficult to control, further causing adverse effects on the performance of the copper foil, easily regulating and controlling the content of each additive component and simultaneously improving the tensile strength and the elongation percentage of the copper foil.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic view showing the appearance of the matte side of a copper foil sample prepared in example 1 of the present invention.
FIG. 2 is a 3D microscopic image of the matte side of copper foil prepared in example 1 of the present invention.
Fig. 3 is a SEM image of the matte side of the copper foil prepared in example 1 of the present invention.
Fig. 4 is an SEM image of a tensile section of the copper foil prepared in example 1 of the present invention.
FIG. 5 is a view showing the appearance of the matte side of a copper foil sample prepared in comparative example 1 of the present invention.
FIG. 6 is a 3D microscopic view of the matte side of the copper foil prepared in comparative example 1 of the present invention.
Fig. 7 is an SEM image of a matte side of the copper foil prepared in comparative example 1 of the present invention.
Fig. 8 is an SEM image of a tensile section of the copper foil prepared in comparative example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A collagen-free additive for processing copper foil comprises micromolecules of sodium sulfonate, thiourea derivatives containing amido bonds and ether derivatives containing hydrophilic functional groups; the mass concentration ratio of sodium sulfonate small molecules, thiourea derivatives containing amido bonds and ether derivatives containing hydrophilic functional groups is 1: (1-2): (0.1-0.2).
Furthermore, the micromolecules of the sodium sulfonate salts are one of sodium polydithio-dipropyl sulfonate, 3-mercapto-propane sulfonate and 2-mercapto-ethyl sulfonate.
Furthermore, the thiourea derivative containing the amido bond is one of malonyl thiosemicarbazone, 3-methyl-1- (2-phenylacetyl amino) thiourea and 1-acetyl-3-phenylthiourea.
Further, the ether derivative containing a hydrophilic functional group is one of diethylene glycol dimethyl ether, ethylene glycol butyl ether and triethylene glycol divinyl ether.
A copper foil processing technology comprises the following steps:
s1, preparing electrolyte for Harlin groove flaking, adding a collagen-free additive for copper foil processing into the electrolyte, and performing air-blowing circulation stirring at a temperature of 50-60 ℃;
and S2, setting reaction time and reaction current, controlling groove pressure and starting to prepare the sample copper foil. After the completion, the power supply is turned off, the titanium cathode is taken out, the titanium cathode is put into deionized water to be cleaned for 5s, and the copper foil is manually stripped by using an art designer knife;
s3, putting the prepared copper foil into an annealing furnace for a low-temperature annealing process;
and S4, cutting the prepared sample into samples of 100mm multiplied by 50mm by using a sampling plate, cutting the samples into 3 sample strips of 100mm multiplied by 15mm by using a cutting knife, and finally testing the tensile strength and the elongation by using a universal testing machine.
Further, in the step S1, the concentration of sulfuric acid in the electrolyte is 90-120g/L, the concentration of copper ions is 80-100g/L, the concentration of chloride ions is 10-50mg/L, and the temperature of the electrolyte is 50-60 ℃.
Furthermore, in the step S2, the reaction time is 50S, the reaction current is 26.5A, and the tank pressure is 4.5-5.5V.
Further, the low-temperature annealing process in step S3 includes the following steps: putting the copper foil into an annealing furnace, and heating to 60-90 ℃ within 3-5 h; and (3) heat preservation: insulating the copper foil in an annealing furnace for 1-2h; and (3) cooling: and (3) slowly cooling the copper foil along with the furnace for 3-5h, and then taking out.
Example 1
A copper foil processing technology comprises the following steps:
preparing 1.5L of electrolyte for harlin groove flaking, wherein the concentration of sulfuric acid in the electrolyte is 100g/L, the concentration of copper ions is 80g/L, the concentration of chloride ions is 40mg/L, and corresponding additives of sodium polydithio-dipropyl sulfonate, malonyl thiosemicarbazone and diethylene glycol dimethyl ether are proportionally mixed according to a certain mass concentration ratio of 1:2:0.2, adding the electrolyte, and performing air blowing circulation stirring, wherein the temperature is controlled to be 55 ℃; setting the reaction time to be 50s, the reaction current to be 26.5A and the groove pressure to be 4.5-5.5v, and starting to prepare the sample copper foil. After completion, the power was turned off, the titanium cathode was taken out, washed in deionized water for 5s, and the copper foil was peeled off manually using an art knife. Putting the prepared copper foil into an annealing furnace for low-temperature annealing process, wherein the low-temperature annealing process comprises the following steps of: putting the copper foil into an annealing furnace, and heating to 70 ℃ within 3 h; preserving heat: insulating the copper foil in an annealing furnace for 2 hours; and (3) cooling: and (4) slowly cooling the copper foil along with the furnace for 4 hours and then taking out. The prepared sample is cut into samples of 100mm multiplied by 50mm by a sampling plate, then cut into 3 sample strips of 100mm multiplied by 15mm by a cutting knife, and finally tested for tensile strength and elongation by a universal testing machine.
Example 2
A copper foil processing technology comprises the following steps:
preparing 1.5L of electrolyte for harlin groove flaking, wherein the concentration of sulfuric acid in the electrolyte is 100g/L, the concentration of copper ions is 80g/L, the concentration of chloride ions is 40mg/L, and adding corresponding additives of 3-mercaptopropane sodium sulfonate, 3-methyl-1- (2-phenylacetamido) thiourea and ethylene glycol butyl ether according to a certain mass concentration ratio of 1:2:0.2 is added into the electrolyte, and the air is blown for circular stirring, and the temperature is controlled to be 55 ℃; setting the reaction time to be 50s, the reaction current to be 26.5A and the groove pressure to be 4.5-5.5v, and starting to prepare the sample copper foil. After completion, the power was turned off, the titanium cathode was taken out, washed in deionized water for 5s, and the copper foil was peeled off manually using an art knife. Putting the prepared copper foil into an annealing furnace for low-temperature annealing process, wherein the low-temperature annealing process comprises the following steps of: putting the copper foil into an annealing furnace, and heating to 70 ℃ within 3 h; and (3) heat preservation: insulating the copper foil in an annealing furnace for 2 hours; and (3) cooling: and (4) slowly cooling the copper foil along with the furnace for 4 hours and then taking out. The prepared sample is cut into samples of 100mm multiplied by 50mm by a sampling plate, then cut into 3 sample strips of 100mm multiplied by 15mm by a cutting knife, and finally tested for tensile strength and elongation by a universal testing machine.
Please refer to fig. 1-4:
FIG. 1 shows the results of example 1 with no collagenThe appearance of the matte surface of the copper foil sample prepared by the additive is bright and uniform. Its tensile strength is 37kgf/mm 2 The elongation is 7 percent, and the glossiness reaches 250.
Fig. 2 is a 3D microscopic image (a) 500 times (b) 1000 times of the rough surface of the copper foil sample prepared by the collagen-free additive processing in example 1, wherein the rough surface is in a uniform ravine shape without abnormal and large copper nodules, which reflects that the process method of the collagen-free additive processing in example 1 makes the copper ion deposition behavior uniform.
Figure 3 is a matte SEM image of a copper foil sample prepared with no collagen additive processing of example 1. The rough surface crystal grains are uniform and fine in appearance and have no agglomeration phenomenon. Reflecting that the process method without the collagen additive in the embodiment 1 avoids the influence of different molecular weights of the collagen on the performance of the copper foil.
Figure 4 is an SEM image of the tensile cross-section of a copper foil sample prepared in example 1 without collagen additive processing. The middle of the stretching section of the fracture is provided with a sharp cleft point, the slippage patterns on two sides are clear and visible, the fracture belongs to slippage separation fractures, and the whole fracture form is mainly ductile fracture.
Comparative example 1
A copper foil processing technology comprises the following steps:
preparing 1.5L of electrolyte for harlin groove flaking, wherein the concentration of sulfuric acid in the electrolyte is 100g/L, the concentration of copper ions is 80g/L, the concentration of chloride ions is 40mg/L, and corresponding additive components of sodium polydithio-dipropyl sulfonate, collagen and polyethylene glycol are mixed according to a certain mass concentration ratio of 1:2:0.2, adding the electrolyte, and performing air blowing circulation stirring, wherein the temperature is controlled to be 55 ℃; setting the reaction time to be 50s, the reaction current to be 26.5A and the groove pressure to be 4.5-5.5v, and starting to prepare the sample copper foil. After completion, the power was turned off, the titanium cathode was taken out, washed in deionized water for 5s, and the copper foil was peeled off manually using an art knife. Putting the prepared copper foil into an annealing furnace for low-temperature annealing process, wherein the low-temperature annealing process comprises the following steps of: putting the copper foil into an annealing furnace, and heating to 70 ℃ within 3 h; and (3) heat preservation: insulating the copper foil in an annealing furnace for 2 hours; and (3) cooling: and (4) slowly cooling the copper foil along with the furnace for 4 hours and then taking out. The prepared sample is cut into samples of 100mm multiplied by 50mm by a sampling plate, then cut into 3 sample strips of 100mm multiplied by 15mm by a cutting knife, and finally tested for tensile strength and elongation by a universal testing machine.
Comparative example 2
A copper foil processing technology comprises the following steps:
preparing 1.5L of electrolyte for harlin groove flaking, wherein the concentration of sulfuric acid in the electrolyte is 100g/L, the concentration of copper ions is 80g/L, the concentration of chloride ions is 40mg/L, and corresponding additive components of N, N-dimethyl-dithio carbonyl propane sodium sulfonate, collagen and polyoxyethylene alkyl ether are mixed according to a certain mass concentration ratio of 1:2:0.2 is added into the electrolyte, and the air is blown for circular stirring, and the temperature is controlled to be 55 ℃; setting the reaction time to be 50s, the reaction current to be 26.5A and the groove pressure to be 4.5-5.5v, and starting to prepare the sample copper foil. After completion, the power was turned off, the titanium cathode was taken out, washed in deionized water for 5s, and the copper foil was peeled off manually using an art knife. Putting the prepared copper foil into an annealing furnace for low-temperature annealing process, wherein the low-temperature annealing process comprises the following steps of: putting the copper foil into an annealing furnace, and heating to 70 ℃ within 3 hours; and (3) heat preservation: insulating the copper foil in an annealing furnace for 2 hours; and (3) cooling: and (4) slowly cooling the copper foil along with the furnace for 4 hours and then taking out. The prepared sample is cut into samples of 100mm multiplied by 50mm by a sampling plate, then cut into 3 sample strips of 100mm multiplied by 15mm by a cutting knife, and finally tested for tensile strength and elongation by a universal testing machine.
Please refer to fig. 5-8:
FIG. 5 is an appearance of a matte side of a copper foil sample in comparative example 1, which has a bright but uneven surface.
FIG. 6 is a 3D micrograph of the matte side of the copper foil sample of comparative example 1 (a) at 500 times (b) at 1000 times; the rough surface of the copper alloy plate is in an uneven-stage-shaped gully shape and has abnormally-long copper nodules.
FIG. 7 is an SEM image of the matte side of the copper foil sample in comparative example 1, which has fine grain but is not uniform in foil side compared to the copper foil sample of example 1. Reflecting that the additive system containing collagen is influenced by the molecular weight of collagen, resulting in uneven deposition behavior of copper ions.
Fig. 8 is an SEM image of tensile fracture of the copper foil sample in comparative example 1, the copper foil mainly undergoes slip deformation, and the amount of deformation produced is small as in example 1, and therefore, the elongation is also low.
In the description of the specification, reference to the description of "one embodiment," "an example," "a specific example" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (8)
1. A collagen-free additive for processing copper foil is characterized by consisting of micromolecules of sodium sulfonate salts, thiourea derivatives containing amido bonds and ether derivatives containing hydrophilic functional groups; the mass concentration ratio of micromolecules of sodium sulfonate, thiourea derivatives containing amido bonds and ether derivatives containing hydrophilic functional groups is 1:1-2:0.1-0.2.
2. The collagen-free additive for copper foil processing according to claim 1, wherein the small molecule of sodium sulfonate is one of sodium polydithio-dipropyl sulfonate, sodium 3-mercapto-propane sulfonate, and sodium 2-mercapto-ethyl sulfonate.
3. The collagen-free additive for copper foil processing according to claim 1, wherein said thiourea derivative having an amide bond is one of malonylthiourea, 3-methyl-1- (2-phenylacetamido) thiourea, and 1-acetyl-3-phenylthiourea.
4. The collagen-free additive for copper foil processing according to claim 1, wherein said ether derivative having hydrophilic functional groups is one of diethylene glycol dimethyl ether, ethylene glycol butyl ether and triethylene glycol divinyl ether.
5. A copper foil processing process using the additive of any one of claims 1-4, comprising the steps of:
s1, preparing electrolyte for Harlin groove flaking, adding a collagen-free additive for copper foil processing into the electrolyte, and performing air blowing circulation stirring;
s2, setting reaction time and reaction current, controlling groove pressure and preparing a sample copper foil; after finishing, turning off the power supply, taking out the titanium cathode, putting the titanium cathode into deionized water for cleaning for 5s, and manually stripping the copper foil by using an art designer;
and S3, placing the prepared copper foil into an annealing furnace for low-temperature annealing process treatment.
6. The copper foil processing process according to claim 5, wherein in the step S1, the sulfuric acid concentration in the electrolyte is 90-120g/L, the copper ion concentration is 80-100g/L, the chloride ion concentration is 10-50mg/L, and the temperature of the electrolyte is 50-60 ℃.
7. The copper foil processing process according to claim 5, wherein the reaction time in step S2 is 50S, the reaction current is 26.5A, and the bath pressure is 4.5-5.5V.
8. The copper foil processing process according to claim 5, wherein the low temperature annealing process in step S3 comprises the steps of: putting the copper foil into an annealing furnace, and heating to 60-90 ℃ within 3-5 h; and (3) heat preservation: keeping the copper foil in the annealing furnace for 1-2h; and (3) cooling: and (3) slowly cooling the copper foil along with the furnace for 3-5h, and then taking out.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211586909.0A CN115838948B (en) | 2022-12-09 | Collagen-free additive for copper foil processing and copper foil processing technology |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211586909.0A CN115838948B (en) | 2022-12-09 | Collagen-free additive for copper foil processing and copper foil processing technology |
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| CN103397354A (en) * | 2013-08-08 | 2013-11-20 | 上海新阳半导体材料股份有限公司 | Additive used for reducing voids generated after annealing of through-silicon-via copper plating |
| KR20150062230A (en) * | 2013-11-28 | 2015-06-08 | 일진머티리얼즈 주식회사 | Electrolytic copper foil, electric component and battery comprising the foil and preparation method thereof |
| EP3067442A1 (en) * | 2015-03-09 | 2016-09-14 | Iljin Materials Co., Ltd. | Electrolytic copper foil, electric component and battery including the same |
| KR20190009048A (en) * | 2017-07-18 | 2019-01-28 | 케이씨에프테크놀로지스 주식회사 | Copper foil free from wrinkle and having improved charge discharge property, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same |
| CN110997983A (en) * | 2017-07-31 | 2020-04-10 | Kcf技术有限公司 | Crease-resistant copper foil, electrode comprising same, secondary battery comprising same, and method for manufacturing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103397354A (en) * | 2013-08-08 | 2013-11-20 | 上海新阳半导体材料股份有限公司 | Additive used for reducing voids generated after annealing of through-silicon-via copper plating |
| KR20150062230A (en) * | 2013-11-28 | 2015-06-08 | 일진머티리얼즈 주식회사 | Electrolytic copper foil, electric component and battery comprising the foil and preparation method thereof |
| EP3067442A1 (en) * | 2015-03-09 | 2016-09-14 | Iljin Materials Co., Ltd. | Electrolytic copper foil, electric component and battery including the same |
| KR20190009048A (en) * | 2017-07-18 | 2019-01-28 | 케이씨에프테크놀로지스 주식회사 | Copper foil free from wrinkle and having improved charge discharge property, electrode comprisng the same, secondary battery comprising the same and method for manufacturing the same |
| CN110997983A (en) * | 2017-07-31 | 2020-04-10 | Kcf技术有限公司 | Crease-resistant copper foil, electrode comprising same, secondary battery comprising same, and method for manufacturing same |
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