CN108649183B - Preparation method of microporous copper foil for lithium ion battery negative current collector - Google Patents

Preparation method of microporous copper foil for lithium ion battery negative current collector Download PDF

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CN108649183B
CN108649183B CN201810457178.7A CN201810457178A CN108649183B CN 108649183 B CN108649183 B CN 108649183B CN 201810457178 A CN201810457178 A CN 201810457178A CN 108649183 B CN108649183 B CN 108649183B
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titanium alloy
copper foil
working
mass
parts
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CN108649183A (en
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李丽
杨祥魁
徐树民
牛宗伟
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SHANDONG JINBAO ELECTRONICS CO Ltd
Shandong University of Technology
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SHANDONG JINBAO ELECTRONICS CO Ltd
Shandong University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/044—Activating, forming or electrochemical attack of the supporting material
    • H01M4/0442—Anodisation, Oxidation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention discloses a preparation method of microporous copper foil for a lithium ion battery negative current collector, belonging to the technical field of devices for directly converting chemical energy into electric energy, comprising the following steps of (1) treating a titanium alloy roller; (2) preparing a second working solution: the copper sulfate-sodium bromide-sodium hydrogen chloride is prepared from 40-70 parts by mass of copper sulfate, 90-100 parts by mass of sulfuric acid, 80-100 parts by mass of polyethylene glycol, 20-30 parts by mass of sodium bromide and 1000 parts by mass of water; (3) and (5) manufacturing the microporous copper foil. The method adopts the processed titanium alloy roller, so that the corrosion resistance is improved, the purity of the prepared copper foil is improved, and the good conductivity of the copper is maintained; the surface flatness of the titanium alloy roller is also improved, and the uniformity of distribution and the uniformity of size of hydrogen bubbles on the roller wall are facilitated, so that micropores with uniform pore diameters are prepared; the synergistic effect of the bromide ions and the polyethylene glycol additive in the second working solution can ensure that the aperture is more uniform, the pore wall quality is better, the porosity is reduced, and the conductivity and the mechanical property of the microporous copper foil are enhanced.

Description

Preparation method of microporous copper foil for lithium ion battery negative current collector
Technical Field
The invention belongs to the technical field of devices for directly converting chemical energy into electric energy, and particularly relates to a preparation method of a microporous copper foil for a lithium ion battery cathode current collector.
Background
The lithium ion battery has the advantages of long cycle life, high working voltage, less pollution and the like, and is widely applied to the fields of electric tools, electric vehicles, aerospace, large-scale energy storage power systems and the like. The research on lithium batteries is going into, and new electrode materials are developed to have higher capacity and more excellent electrochemical cycling performance. In research, it is found that the excellent negative electrode current collector not only has good conductivity and mechanical properties, but also can uniformly bear negative electrode active substances, which puts higher requirements on the negative electrode material.
The research and development of a novel negative current collector are paid more attention, wherein the porous copper foil current collector has a larger surface area, so that on one hand, a better volume change buffer space can be provided for a negative active material, the binding force between the negative active material and the porous copper foil current collector is enhanced, the cycle performance of the battery is further enhanced, and the capacity of the battery is increased; on the other hand, when the alloy cathode is adopted, the active material can be attached to the current collector by an electrodeposition method, so that the preparation process is simplified, and the production cost is reduced.
The Chinese patent application 201510407136.9 provides a method for manufacturing a microporous copper foil, a microporous copper foil and a manufacturing device thereof, wherein a copper foil is electroplated on a cathode roller with salient points, and the specific salient point structure of the cathode roller is utilized to form micropores on the copper foil.
And coating a polymer casting solution on the copper foil, and humidifying the polymer casting solution on the copper foil by using a humidifier, or performing phase inversion of a polymer in a non-solvent until the polymer casting solution undergoes phase inversion to form micropores. The porous copper prepared by the solid-gas eutectic condensation method has the problems of large pore diameter and even columnar pores.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a microporous copper foil for a lithium ion battery cathode current collector, wherein the formed micropores have good compactness, provide a good volume change buffer space for an active material, and simultaneously maintain excellent conductivity and mechanical properties.
In order to solve the technical problems, the technical scheme of the invention is as follows: a preparation method of a microporous copper foil of a negative current collector of a lithium ion battery is designed, and is characterized by comprising the following steps: the method comprises the following steps:
(1) treating the titanium alloy roller: adding carbon powder with the particle size of 6-10 microns into water-based working solution to prepare first working solution, and carrying out electric spark machining on a titanium alloy roller in the stirred first working solution by using a Cu-based SiC composite electrode, wherein the discharge current of electric spark is 0.8-2.1A, the pulse width is 30-40 us, and the pulse interval is 5-7 us;
(2) preparing a second working solution: the copper sulfate-sodium bromide-sodium hydrogen chloride is prepared from 40-70 parts by mass of copper sulfate, 90-100 parts by mass of sulfuric acid, 80-100 parts by mass of polyethylene glycol, 20-30 parts by mass of sodium bromide and 1000 parts by mass of water;
(3) preparing a microporous copper foil: under the environment with the temperature of 30-40 ℃, the titanium alloy roller processed in the step (1) is installed in the second working solution prepared in the step (2), the lower half part of the titanium alloy roller is immersed in the second working solution, the titanium alloy roller is connected with the negative pole of a direct current power supply, the positive pole of the direct current power supply is connected with a working electrode, the working electrode and the titanium alloy roller are arranged in a relative mode, the working surface of the working electrode is in an inwards concave arc surface shape, copper ions in the second working solution are electrodeposited on the titanium alloy roller to form a microporous copper foil, the microporous copper foil is pulled out from the roller wall of the titanium alloy roller exposed out of the second working solution, and the current density in the second working solution is 0.33-0.55A/cm2The electroplating time is 15-25 seconds.
Preferably, the titanium alloy roller is also coupled with a vibration device.
Preferably, the vibration device is an ultrasonic vibration device, the vibration frequency of the ultrasonic vibration device is 20-25 Hz, and the power is 300W.
Preferably, in the step (1), the concentration of the carbon powder in the first working solution is 20 g/L.
Preferably, in the step (1), the stirring is magnetic stirring, an insulating working liquid tank with a circular cross section is placed on a base of the magnetic stirring device, the insulating working liquid tank is filled with the first working liquid, and a stirrer of the magnetic stirring device extends into the working liquid tank; set up first magnet outside the diapire in work cistern, set up in the work cistern with first magnet matched with metal briquetting, metal briquetting passes through the thick copper wire of diameter 2 ~ 3mm and connects spark-erosion machine tool's pulse power supply, sets up second magnet on the metal briquetting, will treat the titanium alloy roller centre gripping of processing between metal briquetting and second magnet.
Compared with the prior art, the invention has the beneficial effects that:
1. the treated titanium alloy roller not only improves the corrosion resistance, but also is beneficial to improving the purity of the prepared copper foil, thereby maintaining the good conductivity of the copper; the surface flatness of the titanium alloy roller is also improved, and the uniformity of distribution and the uniformity of size of hydrogen bubbles on the roller wall are facilitated, so that micropores with uniform pore diameters are prepared; the synergistic effect of the bromide ions and the polyethylene glycol additive in the second working solution can ensure that the aperture is more uniform, the pore wall quality is better, the porosity is reduced, and the conductivity and the mechanical property of the microporous copper foil are enhanced.
2. Because the titanium alloy roller is also connected with the ultrasonic vibration device, the titanium alloy roller is in a vibration state, and in the electrolysis process, on one hand, hydrogen reduced and separated from the surface of the titanium alloy roller cannot be retained and grown on the surface of the titanium alloy roller, so that the overflow of the hydrogen is accelerated, the size of hydrogen bubbles is reduced, and the aperture of micropores in the copper foil is reduced; on the other hand, the ultrasonic cavitation inhibits the growth of crystal grains, improves the formation rate of crystal nucleus points, refines the crystal grains of the copper foil, improves the dendritic crystal structure of the copper, ensures that the copper foil has good hydrophilicity and is more tightly combined with active substances of a cathode material of a battery.
3. The stirring is added in the surface treatment of the titanium alloy roller, so that carbon powder in the first working solution is uniformly distributed, the uniformity of the corrosion-resistant layer is enhanced, the titanium alloy roller is more compact, and the corrosion resistance of the titanium alloy roller is improved.
Drawings
FIG. 1 is a schematic view of a surface treatment apparatus for a titanium alloy roll;
fig. 2 is a schematic view of an apparatus for manufacturing a microporous copper foil.
The labels in the figure are: 1. an insulating working liquid tank; 2. a first working fluid; 3. a copper wire; 4. a first magnet; 5. a base; 6. a stirrer; 7. metal briquetting; 8. a second magnet; 9. a Cu-based SiC composite electrode; 10. a titanium alloy roll; 11. a second working fluid; 12. an amplitude transformer; 13. a transducer; 14. a working electrode; 15. an ultrasonic generator; 16. a microporous copper foil.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example one
The microporous copper foil for the lithium ion battery negative current collector is prepared by the following steps:
(1) treating the titanium alloy roller 10: adding carbon powder with the particle size of 6um into the water-based working solution to prepare a first working solution 2, wherein the concentration of the carbon powder in the first working solution 2 is 20 g/L. As shown in fig. 1, an insulating working fluid tank 1 with a circular cross section is arranged on a base 5 of a magnetic stirring device, a first working fluid 2 is contained in the insulating working fluid tank 1, and a stirrer 6 of the magnetic stirring device extends into the working fluid tank; set up first magnet 4 outside the diapire in work cistern, set up in the insulating work cistern 1 with first magnet 4 matched with metal briquetting 7, metal briquetting 7 passes through the thick copper wire 3 connection electric spark machining machine tool's of diameter 2mm pulse power supply, sets up second magnet 8 on the metal briquetting 7, will treat the titanium alloy roller 10 centre gripping of processing between metal briquetting 7 and second magnet 8. Turning on a pulse power supply and a magnetic stirring device, and carrying out electric spark machining on the titanium alloy roller 10 by using a Cu-based SiC composite electrode 9, wherein the discharge current of electric sparks is 0.8A, the pulse width is 30us, and the pulse interval is 5 us. In the electric spark machining process, instantaneous high temperature generated by pulse discharge enables the surface material of the titanium alloy roller 10 to be melted and gasified to form a molten pool, Ti in the molten pool reacts with carbon powder to generate TiC, the corrosion resistance of the titanium alloy roller 10 is enhanced, meanwhile, technological parameters reduce the intensity of electric spark machining, and a smooth and flat surface is convenient to form. The Cu-based SiC composite electrode 9 reduces the loss of a tool electrode and improves the surface smoothness of the titanium alloy roller 10.
(2) Preparing a second working solution 11: is prepared by dissolving 40 parts by mass of copper sulfate, 90 parts by mass of sulfuric acid, 80 parts by mass of polyethylene glycol and 20 parts by mass of sodium bromide in 1000 parts by mass of water.
(3) Preparing a microporous copper foil: in an environment with the temperature of 30 ℃, as shown in fig. 2, the titanium alloy roller 10 processed in the step (1) is installed in the second working solution 11 prepared in the step (2), and an ultrasonic vibration device is arranged, wherein the vibration frequency of the ultrasonic vibration device is 20Hz, and the power is 300W. The ultrasonic vibration device comprises an ultrasonic generator 15, a transducer 13 and a horn 12, wherein the ultrasonic generator 15 transmits a generated ultrasonic signal to the transducer 13, the transducer 13 converts electric energy into mechanical energy for vibration to drive the horn 12, and the horn 12 is positioned in the second working fluid 11. The lower half part of the titanium alloy roller 10 is immersed in the second working solution 11, the upper half part of the titanium alloy roller is exposed out of the second working solution 11, the titanium alloy roller 10 is connected with the negative electrode of the direct current power supply, the positive electrode of the direct current power supply is connected with the working electrode 14, the working electrode 14 and the titanium alloy roller 10 are arranged in an opposite mode, and the working surface of the working electrode 14 is in an inwards concave arc surface shape. And (3) turning on a direct-current power supply, moving copper ions and hydrogen ions to the titanium alloy roller 10 serving as a negative electrode under the electrolytic action of the second working solution 11, competing and reducing the copper ions and the hydrogen ions on the titanium alloy roller 10 for precipitation, depositing the copper downwards, moving the hydrogen bubbles upwards as a dynamic template, determining the randomness of hole orientation by the dynamic template, finally generating a porous copper three-dimensional through hole structure on the wall of the titanium alloy roller 10 to form a microporous copper foil 16, and drawing the microporous copper foil 16 out of the roller wall of the titanium alloy roller 10 exposed out of the second working solution 11. The current density in the second working liquid 11 during electrodeposition was 0.33A/cm2The plating time was 15 seconds. Due to the disturbance effect of the amplitude transformer 12 on the second working solution 11, on one hand, hydrogen reduced and separated from the surface of the amplitude transformer cannot be retained and grown on the surface of the titanium alloy roller 10, so that the overflow of the hydrogen is accelerated, the size of hydrogen bubbles is reduced, and the aperture of micropores in the copper foil is reduced; on the other hand, the ultrasonic cavitation inhibits the growth of crystal grains, improves the formation rate of crystal nucleus points, refines the crystal grains of the copper foil, improves the dendritic crystal structure of the copper, ensures that the copper foil has good hydrophilicity and is more tightly combined with active substances of a cathode material of a battery.
The thickness of the microporous copper foil 16 prepared by the embodiment is 8um, the pore diameter of the micropores is 60 +/-2 um, the porosity is 36%, the tensile strength is 290MPa, and the elongation is 2.2%.
In the embodiment, the amplitude transformer 12 is arranged in the second working solution 11, and the second working solution 11 and the titanium alloy roller 10 generate an indirect connection relationship, so that the amplitude transformer 12 can drive the titanium alloy roller 10 to vibrate, and the second working solution 11 and the titanium alloy roller 10 can also generate relative motion to generate a disturbance effect on hydrogen bubbles on the titanium alloy roller 10.
Example two
The difference between the present embodiment and the first embodiment is: in the step (1), carbon powder with the particle size of 8um is added into water-based working solution to prepare first working solution 2; the metal pressing block 7 is connected with a pulse power supply of an electric spark machining tool through a copper wire 3 with the diameter of 3 mm; the discharge current of the electric spark was 1.5A, the pulse width was 35us, and the pulse interval was 6 us.
In the step (2), the second working solution 11 is prepared by dissolving 55 parts by mass of copper sulfate, 95 parts by mass of sulfuric acid, 90 parts by mass of polyethylene glycol, and 25 parts by mass of sodium bromide in 1000 parts by mass of water.
In the step (3), the process is carried out in an environment with the temperature of 35 ℃, the vibration frequency of the ultrasonic vibration device is 22Hz, and the current density in the second working solution 11 is 0.45A/cm2The plating time of the titanium alloy roll 10 in the second working liquid 11 was 20 seconds.
The thickness of the microporous copper foil 16 prepared by the embodiment is 9um, the pore diameter of the micropores is 70 +/-3 um, and the porosity is 40%. The tensile strength is 302MPa, and the elongation is 2.3%.
EXAMPLE III
The difference between the present embodiment and the first embodiment is: in the step (1), carbon powder with the particle size of 10um is added into water-based working solution to prepare first working solution 2; the metal pressing block 7 is connected with a pulse power supply of an electric spark machine tool through a copper wire 3 with the diameter of 2.5 mm; the discharge current of the electric spark was 2.1A, the pulse width was 40us, and the pulse interval was 7 us.
In the step (2), the second working solution 11 is prepared by dissolving 70 parts by mass of copper sulfate, 100 parts by mass of sulfuric acid, 100 parts by mass of polyethylene glycol, and 30 parts by mass of sodium bromide in 1000 parts by mass of water.
In the step (3), the operation is carried out in the environment with the temperature of 40 ℃, and the vibration frequency of the ultrasonic vibration device is25Hz, and a current density of 0.55A/cm in the second working liquid 112The plating time of the titanium alloy roll 10 in the second working liquid 11 was 25 seconds.
The thickness of the microporous copper foil 16 prepared by the embodiment is 11 um, the pore diameter of the micropores is 80 +/-5 um, and the porosity is 30%. The tensile strength is 295MPa, and the elongation is 2.2%.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.

Claims (5)

1. A preparation method of microporous copper foil for a lithium ion battery negative current collector is characterized by comprising the following steps: the method comprises the following steps:
(1) treating the titanium alloy roller: adding carbon powder with the particle size of 6-10 microns into water-based working solution to prepare first working solution, and carrying out electric spark machining on a titanium alloy roller in the stirred first working solution by using a Cu-based SiC composite electrode, wherein the discharge current of electric spark is 0.8-2.1A, the pulse width is 30-40 us, and the pulse interval is 5-7 us;
(2) preparing a second working solution: the copper sulfate-sodium bromide-sodium hydrogen chloride is prepared from 40-70 parts by mass of copper sulfate, 90-100 parts by mass of sulfuric acid, 80-100 parts by mass of polyethylene glycol, 20-30 parts by mass of sodium bromide and 1000 parts by mass of water;
(3) preparing a microporous copper foil: under the environment with the temperature of 30-40 ℃, the titanium alloy roller processed in the step (1) is installed in the second working solution prepared in the step (2), the lower half part of the titanium alloy roller is immersed in the second working solution, the titanium alloy roller is connected with the negative pole of a direct current power supply, the positive pole of the direct current power supply is connected with a working electrode, the working electrode and the titanium alloy roller are oppositely arranged, the working surface of the working electrode is in an inwards concave arc surface shape, copper ions in the second working solution are electrodeposited on the titanium alloy roller to form a microporous copper foil, and the microporous copper foil is exposed out of the second working solution from the titanium alloy rollerThe working fluid is drawn out from the roller wall, and the current density in the second working fluid is 0.33-0.55A/cm2The electroplating time is 15-25 seconds.
2. The method for preparing a microporous copper foil for a negative electrode current collector of a lithium ion battery according to claim 1, wherein: the titanium alloy roller is also connected with a vibration device.
3. The method for preparing a microporous copper foil for a negative electrode current collector of a lithium ion battery according to claim 2, wherein: the vibration device is an ultrasonic vibration device, the vibration frequency of the ultrasonic vibration device is 20-25 Hz, and the power is 300W.
4. The method for preparing a microporous copper foil for a negative electrode current collector of a lithium ion battery according to any one of claims 1 to 3, wherein: in the step (1), the concentration of the carbon powder in the first working solution is 20 g/L.
5. The method for preparing a microporous copper foil for a negative electrode current collector of a lithium ion battery according to claim 4, wherein: in the step (1), the stirring is magnetic stirring, an insulating working liquid tank with a circular cross section is placed on a base of a magnetic stirring device, a first working liquid is contained in the insulating working liquid tank, and a stirrer of the magnetic stirring device extends into the working liquid tank; set up first magnet outside the diapire in work cistern, set up in the work cistern with first magnet matched with metal briquetting, metal briquetting passes through the thick copper wire of diameter 2 ~ 3mm and connects spark-erosion machine tool's pulse power supply, sets up second magnet on the metal briquetting, will treat the titanium alloy roller centre gripping of processing between metal briquetting and second magnet.
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CN109728254B (en) * 2018-12-03 2020-08-11 浙江大学 Preparation technology of porous copper foil for lithium ion battery cathode
CN110190285A (en) * 2019-05-15 2019-08-30 江汉大学 A kind of battery, battery cathode, multilayer macropore copper current collector and preparation method thereof
CN112695350A (en) * 2020-11-30 2021-04-23 江苏箔华电子科技有限公司 Electrolytic copper foil and preparation process thereof
CN116657209B (en) * 2023-07-27 2023-11-14 常州欣盛半导体技术股份有限公司 Polymer fiber substrate composite metal film, preparation method and application

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WO2015008564A1 (en) * 2013-07-18 2015-01-22 ペルメレック電極株式会社 Continuous manufacturing method for electrolytic metal foil and continuous manufacturing device for electrolytic metal foil
CN104972188A (en) * 2015-07-18 2015-10-14 山东理工大学 Method for modifying surface of titanium alloy by means of electric sparks
CN204793033U (en) * 2015-07-13 2015-11-18 深圳市信宇人科技有限公司 Preparation equipment of micropore copper foil
CN106544703A (en) * 2016-08-10 2017-03-29 姚晓宁 Perforation Copper Foil foil machine and its production technology

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Publication number Priority date Publication date Assignee Title
CN1156190A (en) * 1995-12-06 1997-08-06 三井金属矿业株式会社 Copper foil for printed wiring board, its producing method and electrolytic device
WO2015008564A1 (en) * 2013-07-18 2015-01-22 ペルメレック電極株式会社 Continuous manufacturing method for electrolytic metal foil and continuous manufacturing device for electrolytic metal foil
CN204793033U (en) * 2015-07-13 2015-11-18 深圳市信宇人科技有限公司 Preparation equipment of micropore copper foil
CN104972188A (en) * 2015-07-18 2015-10-14 山东理工大学 Method for modifying surface of titanium alloy by means of electric sparks
CN106544703A (en) * 2016-08-10 2017-03-29 姚晓宁 Perforation Copper Foil foil machine and its production technology

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