CN116065203A - Preparation method of impact-resistant electrolytic copper foil - Google Patents

Preparation method of impact-resistant electrolytic copper foil Download PDF

Info

Publication number
CN116065203A
CN116065203A CN202310092787.8A CN202310092787A CN116065203A CN 116065203 A CN116065203 A CN 116065203A CN 202310092787 A CN202310092787 A CN 202310092787A CN 116065203 A CN116065203 A CN 116065203A
Authority
CN
China
Prior art keywords
current density
concentration
copper foil
treatment
resistant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310092787.8A
Other languages
Chinese (zh)
Inventor
岳双霞
毛俊杰
朱习录
谭国培
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Longzhi New Material Technology Co ltd
Original Assignee
Hunan Longzhi New Material Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Longzhi New Material Technology Co ltd filed Critical Hunan Longzhi New Material Technology Co ltd
Priority to CN202310092787.8A priority Critical patent/CN116065203A/en
Publication of CN116065203A publication Critical patent/CN116065203A/en
Pending legal-status Critical Current

Links

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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • 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

Abstract

The invention discloses a preparation method of an impact-resistant electrolytic copper foil, which uses a copper foil raw foil prepared by a direct current deposition process as a raw material, sequentially unreels and acid-washes the raw foil, then carries out tertiary cycle roughening treatment, wherein the tertiary cycle roughening treatment operation steps comprise roughening operation and solidification operation which are sequentially carried out, sequentially carries out heat-resistant treatment and oxidation-resistant treatment with fixed electrolyte parameters after the tertiary cycle roughening treatment is completed, and then coats silane, and then dries and winds to obtain a finished copper foil after the oxidation-resistant treatment is completed. The electrolytic copper foil prepared by the method has high normal-temperature peeling strength, and low peeling strength loss rate after repeated thermal shock, and can effectively avoid delamination risk of the circuit board.

Description

Preparation method of impact-resistant electrolytic copper foil
Technical Field
The invention belongs to the technical field of electrolytic copper foil preparation, and particularly relates to a preparation method of an impact-resistant electrolytic copper foil.
Background
In the prior art, electrolytic copper foil is used as an important basic material for manufacturing copper-clad plates and printed circuit boards, is often used for manufacturing various products such as cathodes for secondary batteries, printed circuit boards, flexible printed circuit boards and the like, and the terminal application of the electrolytic copper foil relates to the technical fields of various tips such as consumer electronics, 5G communication, automotive electronics, internet of things, national defense science and technology, aerospace and the like.
Before the printed circuit board is manufactured, the electrolytic copper foil and the prepreg (base material) are subjected to hot pressing to manufacture a copper-clad plate, and then the copper-clad plate is further processed into the circuit board. In the manufacturing process of the circuit board, because the production processes of hot air leveling, lead-free soldering tin, high-speed drilling and the like need to perform thermal shock on the copper-clad plate for many times, the binding force between the electrolytic copper foil and the base material is easily reduced, the fatal defect of delamination can be caused, and the circuit board is scrapped; therefore, the prior art has higher requirements on the heat shock resistance of the electrolytic copper foil, and the electrolytic copper foil product with better heat shock resistance has advantages in the market.
Disclosure of Invention
The invention aims to overcome the defects of poor stability and low normal-temperature peeling strength of an electrolytic copper foil prepared by the existing electrolytic copper foil technology, and overcomes the defects of the existing product and technology.
The technical problems solved by the invention are realized by adopting the following technical scheme:
the preparation method of the impact-resistant electrolytic copper foil comprises the steps of taking a copper foil rough foil prepared by a direct current deposition process as a raw material, sequentially unreeling and pickling the rough foil, performing tertiary cycle roughening treatment, sequentially performing heat-resistant treatment, anti-oxidation treatment, silane coating, drying and winding to obtain a finished product copper foil;
the single cyclic roughening treatment comprises the following operation steps of sequentially performing roughening operation and curing operation: when the roughening operation is performed, the temperature of the electrolyte is 24-32 ℃ and Cu is 2+ The concentration is 7.5-11.0 g/L, H 2 SO 4 The concentration is 180-215 g/L, the flow is 6-10 m 3 And/h, the current density of the liquid inlet end is 20-26A/d 2 The current density of the liquid outlet end is 2-8A/d 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the electrolyte is 38-52℃ when the curing operation is carried out、Cu 2+ The concentration is 40-55 g/L, H 2 SO 4 The concentration is 90-120 g/L, the flow is 5-12 m 3 And/h, the current density of the liquid inlet end is 20-26A/d 2 The current density of the liquid outlet end is 20-26A/d 2 ；
When the heat-resistant treatment is carried out, the temperature of the electrolyte is 35-39 ℃ and the temperature of Zn 2+ The concentration is 2.0-3.8 g/L, ni 2+ The concentration is 0.6 to 2.0g/L, K 4 P 2 O 7 The concentration is 35-55 g/L, the pH is 9.5-10.8, the flow is 13-16 m3/h, and the current density of the liquid inlet end of the rough surface is 0.5-0.7A/d 2 The current density of the light surface is 1.3 to 1.7A/d 2 The current density of the liquid outlet end is 0.5-0.8A/d 2 ；
When the heat-resistant treatment is carried out, the temperature of the electrolyte is 25-35 ℃ and Cr is 2+ The concentration is 0.4-2.0 g/L, the pH is 10.5-12.0, the flow is 6-11 m 3 And/h, the current density of the liquid inlet end of the rough surface is 1.8-2.6A/d 2 The current density of the light surface is 1.5-2.3A/d 2 The current density of the liquid outlet end is 0.6-1.4A/d 2 。
As a further limitation, the temperature of the pickling solution is 24-32deg.C and Cu during the pickling operation 2+ The concentration is 7.5-11.0 g/L, H 2 SO 4 The concentration is 180-215 g/L, the flow is 4-5 m 3 And/h, pickling for 2-5S.
Further, by way of limitation, when the roughening operation is performed, the electrolyte temperature is 26 to 28 ℃ and Cu 2+ The concentration is 8.5-9.5 g/L, H 2 SO 4 The concentration is 190-200 g/L, the flow is 7-8 m 3 And/h, the current density of the liquid inlet end is 22-23A/d 2 The current density of the liquid outlet end is 4-5A/d 2 。
Further, by way of limitation, the electrolyte temperature is 45 to 47 ℃ and Cu is used for the curing operation 2+ The concentration is 48-50 g/L, H 2 SO 4 The concentration is 105-110 g/L, the flow is 7-8.5 m 3 And/h, the current density of the liquid inlet end is 21-22A/d 2 The current density of the liquid outlet end is 19-20A/d 2 。
As a further limitation, when the heat-resistant treatment is performed, the temperature of the electrolyte is 36-38 ℃ and the concentration of Zn < 2+ > is 2.6-3.6 g/L, ni 2+ The concentration is 0.8-1.8 g/L, K 4 P 2 O 7 The concentration is 40-50 g/L, the pH is 10.3-10.5, the flow is 14-15 m 3 And/h, the current density of the liquid inlet end of the rough surface is 0.6 to 0.65A/d 2 The current density of the light surface is 1.4 to 1.6A/d 2 The current density of the liquid outlet end is 0.6-0.65A/d 2 。
As a further limitation, the temperature of the electrolyte is 27-29 ℃ and Cr is used when the oxidation preventing treatment is performed 2+ The concentration is 0.6-1.5 g/L, the pH is 11.0-12.0, and the flow is 9-10 m 3 And/h, the current density of the liquid inlet end of the rough surface is 2.0-2.1A/d 2 The current density of the light surface is 1.7-1.8A/d 2 The current density of the liquid outlet end is 0.85-1.15A/d 2 。
By way of further limitation, the foil is subjected to a heat-resistant treatment, an oxidation-resistant treatment, and a silane coating, respectively, and then subjected to a water-washing treatment with pure water.
The invention has the advantages that:
according to the preparation method, three roughening treatment procedures are adopted when the roughened foil is treated, the number of dendritic copper nodules on the roughened surface of the copper foil is increased, the specific surface area of the roughened surface of the copper foil is increased, the roughened copper nodules which are thinner and looser after roughening is finished are solidified, the roughened dendritic copper nodules are filled and wrapped, so that the roughened dendritic copper nodules are firmly combined with each other, gaps between the roughened dendritic copper nodules and the copper foil are fully filled with fine crystals, the roughened dendritic copper nodules and the copper foil are firmly fixed on the copper foil, and the copper foil and a substrate are firmly inseparable after the copper clad laminate is pressed.
Only Zn is added into the electrolyte for heat treatment 2+ And Ni 2+ Avoiding other heavy metal ions and organic additives, reducing cost, reducing harm to environment and human body, and reducing Zn 2+ And Ni 2+ The concentration ratio of the two is 1.5-3.0, so that the roughened and solidified copper foil is electroplated with a zinc-nickel alloy layer with proper proportion and high heat resistance, thereby avoiding the defect of heat resistance caused by improper zinc-nickel proportion in the zinc-nickel alloy layer.
The copper foil product prepared by the process has high normal-temperature peeling strength, and can ensure that the peeling strength loss rate is lower than 10% after repeated thermal shock in the manufacturing process of the copper-clad plate and the circuit board, and the delamination risk of the circuit board is avoided.
Drawings
FIG. 1 is a 35 μm copper foil electron micrograph produced under the process conditions of an example of the present invention.
FIG. 2 is a 35 μm copper foil electron micrograph produced under the process conditions of example two of the present invention.
FIG. 3 is a 35 μm copper foil electron micrograph produced under the process conditions of example three of the present invention.
FIG. 4 is a comparative commercially available 35 μm copper foil electron micrograph.
Detailed Description
In order to better understand the technical solution of the present invention and make the technical means, creation characteristics, achievement purposes and effects achieved by the present invention easy to understand, the technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the specific drawings.
This embodiment is only a part of the embodiments of the present invention and represents all the embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention. It should be noted that the terms in the specification and claims of the present invention and the above-described drawings are used to distinguish between similar objects, and furthermore, the terms "comprise" and "have" and any variations thereof are intended to cover a non-exclusive inclusion, such as a process, method, system, article, or apparatus that comprises a sequence of steps or elements that is not necessarily limited to those steps or elements explicitly listed.
Embodiment one:
in example one, the impact resistant electrolytic copper foil was produced by the following method:
in the embodiment, 35 mu m of wool foil is prepared by adopting a direct current deposition process as a raw material, and the wool foil is unreeled and then subjected to Cu at the temperature of 28-30 DEG C 2+ H with concentration of 7.5-9.0 g/L 2 SO 4 Acid washing is carried out in sulfuric acid solution with the concentration of 180-215 g/L, and the flow of the sulfuric acid solution is controlled to be 4-4.5 m 3 And/h, pickling for 3S.
And taking out after the pickling is finished, and sequentially performing first roughening, first curing, second roughening, second curing, third roughening, third curing, washing, heat-resistant treatment, washing, oxidation-resistant treatment, washing, silane coating, drying and winding to obtain the finished copper foil.
In the above operation step of the first embodiment, the electrolyte corresponding to the first roughening, the second roughening and the third roughening is set to a temperature of 28 to 30 ℃ and Cu 2+ The concentration is set to be 10.2-10.8 g/L, H 2 SO 4 The concentration is set to be 205-215 g/L, and the flow rate of the electrolyte is set to be 8-10 m 3 And/h, the current density of the liquid inlet end is 23.6A/d 2 The current density of the liquid outlet end is 6A/d 2 。
Setting the electrolyte temperature corresponding to the first curing, the second curing and the third curing to 42-46 ℃ and Cu 2+ The concentration is set to be 46-49 g/L, H 2 SO 4 The concentration is set to be 95-105 g/L, and the flow rate of the electrolyte is set to be 6-9 m 3 And/h, the current density of the liquid inlet end is 23A/d 2 The current density of the liquid outlet end is 24A/d 2 。
When heat-resisting treatment is carried out, the temperature of electrolyte adopted in the corresponding process is controlled to be 37-39 ℃ and Zn is controlled 2+ The concentration is set to 3.2-3.8 g/L, ni 2+ The concentration is set to be 0.7-1.3 g/L, K 4 P 2 O 7 The concentration is set to be 35-45 g/L, the pH is controlled to be 9.8-10.2, and the flow of the electrolyte is set to be 14.5-15.5 m 3 And/h, the current density of the liquid inlet end of the rough surface is 0.7A/d 2 A light surface current density of 1.6A/d 2 The current density of the liquid outlet end is 0.7A/d 2 ；
When the antioxidation treatment is carried out, the temperature of the electrolyte adopted in the corresponding flow is controlled to be 26-28 ℃, cr 2+ The concentration is set to be 1.0-1.3 g/L, the pH is controlled to be 11.0-11.5, and the flow of the electrolyte is set to be 8-9 m 3 And/h, the current density of the liquid inlet end of the rough surface is 2.2A/d 2 A light surface current density of 1.9A/d 2 The current density of the liquid outlet end is 0.7A/d 2 。
The corresponding water washing processes in the process are the same, pure water is used for washing, water washing tanks are arranged behind each plating tank, the total number of the water washing tanks is 4, and the total number of the water washing tanks is two, namely a smooth surface and a rough surface, so that residual electrolyte on the surface of the copper foil is washed, and the next treatment process is prevented from being polluted.
Embodiment two:
in example two, an impact-resistant electrolytic copper foil was produced by the following method:
example two a 35 μm wool foil was produced as a raw material wool foil using the same batch dc deposition process as in example two. Unreeling the wool foil, and then cooling to 28-30deg.C and Cu 2+ H with concentration of 7.5-9.0 g/L 2 SO 4 Acid washing is carried out in sulfuric acid solution with the concentration of 180-215 g/L, and the flow of the sulfuric acid solution is controlled to be 4-4.5 m 3 And/h, pickling for 3S.
And taking out after the pickling is finished, and sequentially performing first roughening, first curing, second roughening, second curing, third roughening, third curing, washing, heat-resistant treatment, washing, oxidation-resistant treatment, washing, silane coating, drying and winding to obtain the finished copper foil.
In the above operation step of the second embodiment, the electrolyte corresponding to the first roughening, the second roughening and the third roughening is set to 26 to 28 ℃ and Cu 2+ The concentration is set to 8.5-9.5 g/L, H 2 SO 4 The concentration is set to 190-200 g/L, and the flow rate of the electrolyte is set to 7-8 m 3 And/h, the current density of the liquid inlet end is 22.5A/d 2 The current density of the liquid outlet end is 4A/d 2 。
Setting the temperature of electrolyte corresponding to the first curing, the second curing and the third curing to 45-46 ℃ and Cu 2+ The concentration is set to be 48-50 g/L, H 2 SO 4 The concentration is set to be 105-110 g/L, and the flow rate of the electrolyte is set to be 7-8.5 m 3 And/h, the current density of the liquid inlet end is 22A/d 2 The current density of the liquid outlet end is 19A/d 2 。
When heat-resisting treatment is carried out, the temperature of electrolyte adopted in the corresponding process is controlled to be 36-38 ℃ and Zn is controlled 2+ The concentration is set to be 2.0-2.4 g/L, ni 2+ The concentration is set to be 0.8-1.2 g/L, K 4 P 2 O 7 The concentration is set to 40-50 g/L, the pH is controlled to 10.3-10.5, and the flow of the electrolyte is set to 14-15 m 3 And/h, the current density of the liquid inlet end of the rough surface is 0.6A/d 2 A light surface current density of 1.5A/d 2 The current density of the liquid outlet end is 0.6A/d 2 ；
When the antioxidation treatment is carried out, the temperature of the electrolyte adopted in the corresponding flow is controlled to be 27-29 ℃, cr 2+ The concentration is set to be 0.8-1.0 g/L, the pH is controlled to be 11.0-11.5, and the flow rate of the electrolyte is set to be 9-10 m 3 And/h, the current density of the liquid inlet end of the rough surface is 2.0A/d 2 A light surface current density of 1.8A/d 2 The current density of the liquid outlet end is 0.85A/d 2 。
The corresponding water washing processes in the processes are the same, pure water is used for washing, water washing tanks are arranged behind the plating tanks, the total number of the water washing tanks is 4, and the number of the water washing spray pipes is two for each of the smooth surface and the rough surface, so that the residual electrolyte on the surface of the copper foil is washed, and the next treatment process is not polluted.
Embodiment III:
in example three, an impact-resistant electrolytic copper foil was produced by the following method:
example three a 35 μm wool foil was produced as a raw material wool foil using the same batch dc deposition process as in example. Unreeling the wool foil, and then cooling to 28-30deg.C and Cu 2+ H with concentration of 7.5-9.0 g/L 2 SO 4 Acid washing is carried out in sulfuric acid solution with the concentration of 180-215 g/L, and the flow of the sulfuric acid solution is controlled to be 4-4.5 m 3 And/h, pickling for 3S.
And taking out after the pickling is finished, and sequentially performing first roughening, first curing, second roughening, second curing, third roughening, third curing, washing, heat-resistant treatment, washing, oxidation-resistant treatment, washing, silane coating, drying and winding to obtain the finished copper foil.
In the above-mentioned operation step of the third embodiment, the electrolyte corresponding to the first roughening, the second roughening and the third roughening is set to 26 to 28 ℃ and Cu 2+ The concentration is set to 8.5-9.5 g/L, H 2 SO 4 The concentration is set to 190-200 g/L, and the electrolyte flow is setThe amount is 7-8 m 3 And/h, the current density of the liquid inlet end is 22.5A/d 2 The current density of the liquid outlet end is 4A/d 2 。
Setting the temperature of electrolyte corresponding to the first curing, the second curing and the third curing to 45-46 ℃ and Cu 2+ The concentration is set to be 48-50 g/L, H 2 SO 4 The concentration is set to be 105-110 g/L, and the flow rate of the electrolyte is set to be 7-8.5 m 3 And/h, the current density of the liquid inlet end is 22A/d 2 The current density of the liquid outlet end is 19A/d 2 。
When heat-resisting treatment is carried out, the temperature of electrolyte adopted in the corresponding process is controlled to be 36-38 ℃ and Zn is controlled 2+ The concentration is set to be 4.8-5.2 g/L, ni 2+ The concentration is set to be 0.8-1.2 g/L, K 4 P 2 O 7 The concentration is set to be 45-48 g/L, the pH is controlled to be 10.3-10.5, and the flow of the electrolyte is set to be 14-15 m 3 And/h, the current density of the liquid inlet end of the rough surface is 0.7A/d 2 A light surface current density of 1.5A/d 2 The current density of the liquid outlet end is 0.7A/d 2 ；
When the antioxidation treatment is carried out, the temperature of the electrolyte adopted in the corresponding flow is controlled to be 27-29 ℃, cr 2+ The concentration is set to be 0.8-1.0 g/L, the pH is controlled to be 11.0-11.5, and the flow rate of the electrolyte is set to be 9-10 m 3 And/h, the current density of the liquid inlet end of the rough surface is 2.0A/d 2 A light surface current density of 1.8A/d 2 The current density of the liquid outlet end is 0.85A/d 2 。
The corresponding water washing processes in the process are the same, pure water is used for washing, water washing tanks are arranged behind each plating tank, the total number of the water washing tanks is 4, and the total number of the water washing tanks is two, namely a smooth surface and a rough surface, so that residual electrolyte on the surface of the copper foil is washed, and the next treatment process is prevented from being polluted.
And optionally performing electron microscope treatment on the copper foil products prepared in the first embodiment, the second embodiment and the third embodiment to obtain the copper foil product corresponding to the first embodiment, the copper foil product corresponding to the second embodiment, and the copper foil product corresponding to the third embodiment, wherein the copper foil product corresponds to the first embodiment, the copper foil product corresponding to the second embodiment, the copper foil product corresponding to the third embodiment, and the copper foil product corresponding to the third embodiment. As can be seen from the electron microscope photographs of 35 μm copper foil products shown in fig. 1, 2 and 3, the copper foil product prepared by the process of the embodiment of the invention has a large number of copper nodules of the copper foil rough cured layer, is uniformly distributed and has low roughness, and the copper foil with the surface morphology has good peeling strength and no peeling residual copper.
Fig. 4 shows an electron microscope photograph of a 35 μm copper foil product from other manufacturers, and it can be seen from the photograph that the roughened layer has a smaller number of copper nodules plated, and the copper foil has uneven size, and the peel strength of the copper foil with the surface morphology is unstable.
The test results of the peel strength of the electrolytic copper foil obtained in the first, second and third examples and the test sample of the comparative example and the loss rate of the peel strength after thermal shock are shown in Table 1 (conventional test is carried out according to the standard of GBT5230-1995, and the peel strength after thermal shock is measured according to the standard of GBT5230-1995 after the test sample is baked at 180℃for 24 hours).
Table 1 test results of example 1, example 2 and comparative example samples
Figure BDA0004070799150000071
As can be seen from table 1, the comparative examples have significantly reduced peel strength after thermal shock, and the copper foil prepared in the examples has excellent high-temperature heat loss rate and less than 10% peel strength loss rate after thermal shock, and the delamination risk exists in the downstream process of manufacturing the printed wiring board.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (7)

1. A preparation method of an impact-resistant electrolytic copper foil is characterized in that a copper foil raw foil prepared by a direct current deposition process is used as a raw material, the raw foil is sequentially unreeled and pickled, then subjected to tertiary cycle roughening treatment, and after the tertiary cycle roughening treatment is completed, the copper foil is sequentially subjected to heat-resistant treatment, oxidation-resistant treatment, silane coating, then dried and wound to obtain a finished copper foil;
the single cyclic roughening treatment comprises the following operation steps of sequentially performing roughening operation and curing operation: when the roughening operation is performed, the temperature of the electrolyte is 24-32 ℃ and Cu is 2+ The concentration is 7.5-11.0 g/L, H 2 SO 4 The concentration is 180-215 g/L, the flow is 6-10 m 3 And/h, the current density of the liquid inlet end is 20-26A/d 2 The current density of the liquid outlet end is 2-8A/d 2 The method comprises the steps of carrying out a first treatment on the surface of the When the solidification operation is carried out, the temperature of electrolyte is 38-52 ℃ and Cu is 2+ The concentration is 40-55 g/L, H 2 SO 4 The concentration is 90-120 g/L, the flow is 5-12 m 3 And/h, the current density of the liquid inlet end is 20-26A/d 2 The current density of the liquid outlet end is 20-26A/d 2 ；
When the heat-resistant treatment is carried out, the temperature of the electrolyte is 35-39 ℃ and the temperature of Zn 2+ The concentration is 2.0-3.8 g/L, ni 2+ The concentration is 0.6 to 2.0g/L, K 4 P 2 O 7 The concentration is 35-55 g/L, the pH is 9.5-10.8, the flow is 13-16 m3/h, and the current density of the liquid inlet end of the rough surface is 0.5-0.7A/d 2 The current density of the light surface is 1.3 to 1.7A/d 2 The current density of the liquid outlet end is 0.5-0.8A/d 2 ；
When the heat-resistant treatment is carried out, the temperature of the electrolyte is 25-35 ℃ and Cr is 2+ The concentration is 0.4-2.0 g/L, the pH is 10.5-12.0, the flow is 6-11 m 3 And/h, the current density of the liquid inlet end of the rough surface is 1.8-2.6A/d 2 The current density of the light surface is 1.5-2.3A/d 2 The current density of the liquid outlet end is 0.6-1.4A/d 2 。
2. The method for producing an impact-resistant electrolytic copper foil according to claim 1, wherein the temperature of the pickling solution is 24 to 32 ℃ and the temperature of the Cu is at the pickling operation 2+ The concentration is 7.5-11.0 g/L, H 2 SO 4 The concentration is 180-215 g/L, the flow is 4-5 m 3 And/h, pickling for 2-5S.
3. The method for producing an impact-resistant electrolytic copper foil according to claim 1, wherein the roughening operation is performed at an electrolyte temperature of 26 to 28 ℃ and Cu 2+ The concentration is 8.5-9.5 g/L, H 2 SO 4 The concentration is 190-200 g/L, the flow is 7-8 m 3 And/h, the current density of the liquid inlet end is 22-23A/d 2 The current density of the liquid outlet end is 4-5A/d 2 。
4. The method for producing an impact-resistant electrolytic copper foil according to claim 1, wherein the curing operation is performed at a temperature of 45 to 47 ℃ in electrolyte, cu 2+ The concentration is 48-50 g/L, H 2 SO 4 The concentration is 105-110 g/L, the flow is 7-8.5 m 3 And/h, the current density of the liquid inlet end is 21-22A/d 2 The current density of the liquid outlet end is 19-20A/d 2 。
5. The method for producing an impact-resistant electrolytic copper foil according to claim 1, wherein the heat-resistant treatment is performed at a temperature of 36 to 38 ℃ and a Zn2+ concentration of 2.6 to 3.6g/L, ni 2+ The concentration is 0.8-1.8 g/L, K 4 P 2 O 7 The concentration is 40-50 g/L, the pH is 10.3-10.5, the flow is 14-15 m 3 And/h, the current density of the liquid inlet end of the rough surface is 0.6 to 0.65A/d 2 The current density of the light surface is 1.4 to 1.6A/d 2 The current density of the liquid outlet end is 0.6-0.65A/d 2 。
6. The method for producing an impact-resistant electrolytic copper foil according to claim 1, wherein the oxidation-resistant treatment is performed at an electrolyte temperature of 27 to 29 ℃ and Cr 2+ The concentration is 0.6-1.5 g/L, the pH is 11.0-12.0, and the flow is 9-10 m 3 And/h, the current density of the liquid inlet end of the rough surface is 2.0-2.1A/d 2 The current density of the light surface is 1.7-1.8A/d 2 The current density of the liquid outlet end is 0.85-1.15A/d 2 。
7. The method for producing an impact-resistant electrolytic copper foil according to claim 1, wherein the raw foil is subjected to heat-resistant treatment, oxidation-resistant treatment, silane coating, and then subjected to water-washing treatment with pure water.
CN202310092787.8A 2023-02-10 2023-02-10 Preparation method of impact-resistant electrolytic copper foil Pending CN116065203A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310092787.8A CN116065203A (en) 2023-02-10 2023-02-10 Preparation method of impact-resistant electrolytic copper foil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310092787.8A CN116065203A (en) 2023-02-10 2023-02-10 Preparation method of impact-resistant electrolytic copper foil

Publications (1)

Publication Number Publication Date
CN116065203A true CN116065203A (en) 2023-05-05

Family

ID=86178276

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310092787.8A Pending CN116065203A (en) 2023-02-10 2023-02-10 Preparation method of impact-resistant electrolytic copper foil

Country Status (1)

Country Link
CN (1) CN116065203A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116791160A (en) * 2023-07-19 2023-09-22 湖南龙智新材料科技有限公司 Preparation method of high heat-resistant electrolytic copper foil

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116791160A (en) * 2023-07-19 2023-09-22 湖南龙智新材料科技有限公司 Preparation method of high heat-resistant electrolytic copper foil
CN116791160B (en) * 2023-07-19 2024-03-19 湖南龙智新材料科技有限公司 Preparation method of high heat-resistant electrolytic copper foil

Similar Documents

Publication Publication Date Title
CN102586831B (en) Surface treatment process for reducing roughness of electrolytic copper foil
US7691487B2 (en) Electrodeposited copper foil with carrier foil
CN104962965B (en) The environment-friendly type ashing handling process of rolled copper foil
RU2287618C2 (en) Laminate foil and its production method
JPH05235542A (en) Copper foil for printed circuit board and manufacture thereof
WO2022041533A1 (en) Production method for high heat-resistant electrodeposited copper foil
KR20010089713A (en) Surface-treated copper foil and method for manufacturing the surface-treated copper foil
CN116065203A (en) Preparation method of impact-resistant electrolytic copper foil
JP7302046B2 (en) Ultra-thin copper foil and its fabrication method
CN113584537B (en) Ultra-thin copper foil with resin layer and extremely low roughness and manufacturing method thereof
WO2014042412A1 (en) Method for surface-treating copper foil and copper foil surface-treated thereby
JP2000297387A (en) Surface treating agent for copper and copper alloy
TWI585245B (en) Method for producing single sided thin metal clad laminate
CN113981494B (en) Surface treatment process for reducing heat loss rate of electrolytic copper foil in peel strength
JP6054523B2 (en) Copper foil with carrier, method for producing copper foil with carrier, copper-clad laminate obtained using copper foil with carrier, and method for producing printed wiring board
CN108330517B (en) Plating solution for stripping layer of carrier copper foil and preparation method of stripping layer
CN107645852B (en) Double-sided copper foil surface treatment process for high-frequency printed circuit board
JPS587077B2 (en) Copper foil for printed circuits and its manufacturing method
CN107018622A (en) Microcircuit substrate surface treated copper foil and its manufacture method
CN110820021B (en) Anti-stripping copper foil for circuit board and preparation method thereof
JP2001177205A (en) Copper foil bonding treatment with improved bond strength and resistance to undercutting
KR100857311B1 (en) Copper foil and surface treatment thereof
CN116791160B (en) Preparation method of high heat-resistant electrolytic copper foil
CN109930179A (en) A kind of production method and its product of extra thin copper foil
KR102504286B1 (en) Surface treated copper foil and Method for producing the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication