CN116791155A - Preparation method of electrolytic copper foil based on pulse electroplating - Google Patents
Preparation method of electrolytic copper foil based on pulse electroplating Download PDFInfo
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- CN116791155A CN116791155A CN202310886573.8A CN202310886573A CN116791155A CN 116791155 A CN116791155 A CN 116791155A CN 202310886573 A CN202310886573 A CN 202310886573A CN 116791155 A CN116791155 A CN 116791155A
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- Prior art keywords
- pulse
- electrolyte
- copper foil
- electrolytic copper
- electrolytic
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000011889 copper foil Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000009713 electroplating Methods 0.000 title abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 6
- 239000011888 foil Substances 0.000 claims abstract description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910001431 copper ion Inorganic materials 0.000 claims description 8
- 238000007747 plating Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 230000003746 surface roughness Effects 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- UAYKGOMDUQLCJS-UHFFFAOYSA-N ethylsulfanyl acetate Chemical compound CCSOC(C)=O UAYKGOMDUQLCJS-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229960003151 mercaptamine Drugs 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The application discloses a preparation method of an electrolytic copper foil based on pulse electroplating, which comprises the following steps: selecting a proper electrolyte and adding the electrolyte into an electrolytic tank; setting a proper electrolyte flow rate; the pulse power supply is connected to set the average current density to be 20-50A/dm 2 The pulse width is 1-10 ms, the duty ratio is 1-30%, and the pulse waveform is rectangular wave; starting the pulse power supply to start pulse electrolysis of the raw foil. The application can obtain the copper foil with fine grains by controlling the pulse parameters; the application can weaken hydrogen evolution by controlling pulse parameters, thereby reducing the generation of holes; the method can lead the surface of the copper foil to be smooth and uniform, and is not easy to generate defects.
Description
Technical Field
The application relates to the technical field of electrolytic copper foil, in particular to a preparation method of electrolytic copper foil based on pulse electroplating.
Background
The electrolytic copper foil is a cathode current collector widely used in commercial lithium batteries at present, and the copper foil current collector has the functions of collecting and transmitting charges in the lithium ion battery and bearing cathode active materials. In the charge-discharge cycle process of the lithium ion battery, as the intercalation and deintercalation of lithium ions in the negative electrode have certain requirements on the mechanical properties of the copper foil current collector, under certain thickness and quality conditions, the development of the copper foil with higher tensile strength and elongation has important significance for improving the performance of the lithium battery, and has important value for the industries such as copper foil industry, energy storage equipment, electric automobiles and the like. At present, the production of electrolytic copper foil is mainly based on direct current plating, and a thicker diffusion layer is easy to form at the interface of electrolyte and a cathode during direct current plating, so that the concentration of metal ions near the surface of the cathode is reduced, the electrodeposition speed is hindered, the deposition speed cannot be improved when the current density is increased, the hydrogen evolution is aggravated, the current efficiency is low, the phenomena of hydrogen embrittlement, pinholes, scorching and the like appear on a coating, and the quality of the coating is reduced.
Disclosure of Invention
In view of the above technical problems in the related art, the present application provides a method for preparing an electrolytic copper foil based on pulse plating, which can solve the above problems.
In order to achieve the technical purpose, the technical scheme of the application is realized as follows:
the preparation method of the electrolytic copper foil based on pulse electroplating comprises the following steps:
s100, selecting proper electrolyte, and adding the electrolyte into an electrolytic tank;
s200, setting a proper flow rate of electrolyte;
s300, switching on a pulse power supply, and setting the average current density to be 20-50A/dm 2 The pulse width is 1-10 ms, the duty ratio is 1-30%, and the pulse waveform is rectangular wave;
s400, starting a pulse power supply to start pulse electrolysis foil generation.
Further, the electrolyte in step S100 is an electrolyte containing copper ions and necessary additives at a temperature of 40-70 ℃, and the pH of the electrolyte is more than 3.
Further, the content of copper ions in the electrolyte is 10-100 g/L, and the additive comprises mercapto-containing organic matters (R-SH), polyether organic matters, a surfactant and hydrochloric acid.
Further, in the electrolytic cell in step S100, a rotating roller is prepared by using titanium metal as a cathode, the surface roughness Ra of the cathode is less than 1 mu m, and a plurality of insoluble substrates which are fixed and semi-wound around the cathode are used as anodes.
Further, the flow rate of the electrolyte in the step S200 is 30-60 m 3 /h。
The application has the beneficial effects that: the application can obtain the copper foil with fine grains by controlling the pulse parameters; the application can weaken hydrogen evolution by controlling pulse parameters, thereby reducing the generation of holes; the method can lead the surface of the copper foil to be smooth and uniform, and is not easy to generate defects.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
The application is described in further detail below with reference to the accompanying drawings.
Fig. 1 is a schematic diagram of a pulse waveform of a pulse power supply according to an embodiment of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the application, fall within the scope of protection of the application.
The application discloses a preparation method of electrolytic copper foil based on pulse electroplating, which comprises the steps of firstly injecting electrolyte containing copper ions into an electrolytic tank, wherein the concentration of the copper ions is 10-100 g/L, the pH value is above 3, then heating the electrolyte to 40-70 ℃ and setting the flow rate to 30-60 m 3 Preferably, the other necessary additives are injected into the electrolytic tank, the dosage is set according to the requirement, and the electrolyte is preparedThe necessary additives include organic matter containing mercapto group (R-SH), polyether organic matter, surfactant and hydrochloric acid, wherein the organic matter containing mercapto group (R-SH) is one or more of mercaptoethanol, mercaptoacetic acid, ethyl mercaptoacetate, mercaptoethylamine and mercaptopropyl trimethoxy silane, polyether organic matter block polyether L35 (DOW company numbering, the same applies below), one or more of block polyether L45 and block polyether L61, and surfactant sodium dodecyl sulfonate and/or sodium dodecyl sulfate.
The pulse power supply is connected (the power supply can adopt a water-cooled pulse rectifier) and the average current density is set to be 20-50A/dm 2 The pulse width is 1-10 ms, the duty ratio is 1-30%, and the pulse waveform is rectangular wave. Specifically, each time the current is turned on and off, a period is formed, the current conduction time in one period is 1-10 ms, and the current conduction time accounts for 1-30% of the duration of the whole period. The rectangular wave diagram used is shown in fig. 1, the abscissa t is time, and the ordinate a is current. When the current is in the on state, the pulse current density is very high, and the nucleation speed is larger than the growth speed. When the current is in an off state, the growth speed of the crystal grains is reduced, and copper ions in the enrichment region diffuse to the depletion region, so that concentration polarization is weakened. The mode of controlling the periodic on-off of the current enables the nucleation speed of the crystal grains to be far greater than the growth speed, so that the crystal is fine, concentration polarization is weakened, and the crystal grains are uniformly deposited.
After the pulse power supply is switched on, electrolysis is carried out by applying pulse current to the anode, copper ions are reduced to the surface of the cathode in a periodic manner in the electrolysis process, a layer of compact copper foil is formed, and the surface is in a smooth and uniform state. The copper foil is deposited on the surface of the rotating cathode roller, and the copper foil on the roller surface is continuously stripped and wound through the stripping roller and the winding roller, so that continuous electrolysis is realized. The copper foil prepared by the method has the characteristics that about 3500 crystal grains are collected in the section of the copper foil, the average equivalent circular diameter of the crystal grains is calculated to be 0.6 mu m, the twin crystal proportion is 40%, the tensile strength is 750-800 MPa, the elongation is 5-6%, the glossiness is 110-140 GS, and the foil surface has no light penetration point and is uniform and compact.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the application.
Claims (5)
1. The preparation method of the electrolytic copper foil based on pulse plating is characterized by comprising the following steps of:
s100, selecting proper electrolyte, and adding the electrolyte into an electrolytic tank;
s200, setting a proper flow rate of electrolyte;
s300, connecting a pulse power supply, wherein the pulse waveform is rectangular, and the average current density is set to be 20-50A/dm 2 Pulse width is 1-10 ms, duty ratio is 1-30%;
s400, starting a pulse power supply to start pulse electrolysis foil generation.
2. The method for producing an electrolytic copper foil based on pulse plating according to claim 1, wherein the electrolyte in step S100 is an electrolyte containing copper ions and necessary additives at a temperature of 40 to 70 ℃, and the PH of the electrolyte is > 3.
3. The method for preparing the electrolytic copper foil based on pulse plating according to claim 2, wherein the content of copper ions in the electrolyte is 10-100 g/L, and the additives include mercapto group-containing organic matters (R-SH), polyether-type organic matters, surfactants and hydrochloric acid.
4. The method for producing an electrolytic copper foil based on pulse plating according to claim 1, wherein the electrolytic bath in step S100 is provided with a rotating roller made of titanium metal as a cathode, the surface roughness Ra of the cathode is less than 1 μm, and a plurality of insoluble substrates of a stationary semi-toroidal cathode are provided as anodes.
5. The method for producing an electrolytic copper foil based on pulse plating according to claim 1, wherein the flow rate of the electrolyte in step S200 is 30 to 60m 3 /h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310886573.8A CN116791155A (en) | 2023-07-19 | 2023-07-19 | Preparation method of electrolytic copper foil based on pulse electroplating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310886573.8A CN116791155A (en) | 2023-07-19 | 2023-07-19 | Preparation method of electrolytic copper foil based on pulse electroplating |
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| Publication Number | Publication Date |
|---|---|
| CN116791155A true CN116791155A (en) | 2023-09-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202310886573.8A Pending CN116791155A (en) | 2023-07-19 | 2023-07-19 | Preparation method of electrolytic copper foil based on pulse electroplating |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118704053A (en) * | 2024-08-27 | 2024-09-27 | 江西华创新材有限公司 | Three-dimensional porous copper foil for lithium ion battery current collector and preparation method thereof |
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2023
- 2023-07-19 CN CN202310886573.8A patent/CN116791155A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118704053A (en) * | 2024-08-27 | 2024-09-27 | 江西华创新材有限公司 | Three-dimensional porous copper foil for lithium ion battery current collector and preparation method thereof |
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