CN112301382B - Preparation method of high-ductility low-profile electrolytic copper foil - Google Patents
Preparation method of high-ductility low-profile electrolytic copper foil Download PDFInfo
- Publication number
- CN112301382B CN112301382B CN202010925800.XA CN202010925800A CN112301382B CN 112301382 B CN112301382 B CN 112301382B CN 202010925800 A CN202010925800 A CN 202010925800A CN 112301382 B CN112301382 B CN 112301382B
- Authority
- CN
- China
- Prior art keywords
- copper foil
- gelatin
- copper
- solution
- gelatin solution
- 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.)
- Active
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a preparation method of a copper foil with high ductility and low profile, which comprises the following steps: 1) dissolving gelatin powder in water, and stirring to obtain gelatin solution; 2) carrying out microwave irradiation on the gelatin solution; 3) mixing the gelatin solution after microwave irradiation with the copper sulfate solution to uniformly disperse gelatin molecules in the copper sulfate solution to form a copper foil electrolyte; 4) and sending the copper foil electrolyte into a copper foil electrolytic deposition system to prepare the electrolytic copper foil. The concentration of gelatin in the gelatin solution is 10 mg/L-500 mg/L, and the concentration of gelatin in the copper foil electrolyte is 0.1-10 mg/L. In the preparation method, the gelatin solution is subjected to microwave irradiation in a proper intensity range before being mixed with the copper sulfate solution, so that the stability of the gelatin in the copper sulfate solution and in the subsequent copper foil electrolytic deposition process is obviously improved, and the effects of refining grains, reducing the roughness of the copper foil and improving the elongation are exerted.
Description
Technical Field
The invention belongs to the technical field of electrolytic copper foil preparation, and particularly relates to a preparation method of a high-ductility low-profile copper foil.
Background
The copper foil is used as a carrier of an electronic and signal conduction channel in a circuit board and is an important raw material in PCB manufacture. With the development of high-frequency and high-speed PCBs, low-roughness copper foils are increasingly widely applied. From the influence factor of the loss theory, the surface roughness of the copper foil influences the conductor loss of the transmission line, and the larger the roughness is, the larger the Hammerstad coefficient in the skin effect is, and the larger the conduction loss and the total loss are. At 10GHz, the loss of the low-profile copper foil and the strip transmission line of the standard foil is 0.548 dB/in and 0.61 dB/in respectively. Therefore, the low-roughness copper foil is beneficial to reducing the loss of high-frequency and high-speed signals.
In addition, for the electrolytic copper foil for the printed circuit board, the processing treatment is often required under high temperature and high pressure, and the copper foil and the base material have different thermal expansion rates, if the copper foil has poor high temperature extensibility, peeling or cracking of the copper foil can occur under heating due to internal stress, and the use stability is difficult to ensure.
In the electrodeposition stage of the electrolytic copper foil, the electrolysis process parameters (such as copper ion concentration, acid concentration, current density, temperature and the like) and the addition of additives can influence the microstructure of the raw foil, thereby influencing the service performance of the copper foil. The additive is the most critical factor in production due to the advantages of outstanding effect, strong diversity and the like, and particularly, the surface roughness and the mechanical property of the copper foil are closely related to the additive. Many studies have been conducted by each research unit on additives and methods of use thereof.
The patent (application number: 201510148125.3) discloses a production process of low warpage electrolytic copper foil, which comprises the steps of dissolving copper solution and electrolyzing to generate foil, wherein the copper solution is dissolved in copper solution to obtain Cu in copper sulfate electrolyte2+The concentration is 70g/L-95g/L, H2SO4The concentration is 90g/L-120g/L, the hydroxyethyl cellulose is 3g/L-30g/L, the gelatin is 2g/L-35g/L, the additive A is 5g g/L-35g/L, and the additive B is 1g g/L-20 g/L; the process conditions of the step of electrolytic foil generation are that the temperature is 45-55 ℃, and the current density is 45-70A/dm2(ii) a The additive A is one or more of polyethylene glycol, sodium polydithio-dipropyl sulfonate and thiourea; the additive B is one or more of amide, HCl and saccharin sodium.
The patent application No. 201710370851.9 discloses a method of electroplating a slip ring with reduced contact noise. Providing a conductive substrate; electroplating a copper layer on a base material, and electroplating a nickel layer and/or a nickel-phosphorus layer on the copper layer; and electroplating a gold layer on the nickel layer and/or the nickel-phosphorus layer. In the electroplating of the copper layer on the substrate, at least one brightener from the brightener list consisting of: 3-carboxy-1- (phenylmethyl) pyridinium chloride sodium salt, cationic polymers having urea groups, 1- (3-sulfopropyl) -pyridinium betaine, 1- (2-hydroxy-3-sulfopropyl) -pyridinium betaine, propargyl (3-sulfopropyl) ether sodium salt, saccharin sodium, sodium allylsulfonate, N-dimethyl-N- (3-cocamidopropyl) -N- (2-hydroxy-3-sulfopropyl) ammonium betaine, polyamines, 1H-imidazole polymers having (chloromethyl) oxirane, 3-carboxy-1- (phenylmethyl) pyridinium chloride sodium salt, 1-benzyl-3-sodium carboxy-pyridinium chloride, salts of these compounds, and their use in the preparation of pharmaceutical compositions, Arsenic trioxide, antimony potassium tartrate, potassium tellurate, alkali metal arsenite, potassium tellurate, potassium selenocyanate, alkali metal antimony oxystartatrate, sodium selenite, thallium sulfate and carbon disulfide.
The patent (application No. 201910427884.1) discloses a method for preparing electrolytic copper foil for high-temperature high-elongation power battery and its additive, firstly, heating and dissolving high-purity copper wire to generate copper sulfate electrolyte; secondly, filtering the prepared copper sulfate electrolyte, then feeding the filtered copper sulfate electrolyte into a head tank, adding an additive into the head tank, and then electrolyzing to generate a foil; and finally, treating the prepared copper foil by using an anti-oxidation liquid. The additive comprises a grain refiner, wherein the grain refiner is an aqueous solution of polyethyleneimine derivatives, sodium thiolpropane sulfonate, polyethylene glycol and ethylene thiourea.
The patent (application number: 201610888713.5) discloses a preparation method of an additive for a flexible electrolytic copper foil, a product and application thereof, wherein the additive comprises the following raw material components in percentage by weight: sodium 3-mercaptopropane sulfonate; sodium polydithio-dipropyl sulfonate; ethylene thiourea; 2-mercaptothiazoline; sodium hydroxymethyl sulfonate; polyethylene glycol; fatty amine polyoxyethylene ethers; hydroxyethyl cellulose. The additive is used for preparing 6-12 um electrolytic copper foil, when the electrolytic copper foil is prepared, the additive for the electrolytic copper foil is added in the electrolytic process of electrolyte, the flow rate of the additive is 100-300mL/Min, and the electrolyte is as follows: the copper ion content is 80-120g/L, the sulfate radical content is 90-130g/L, and the temperature of the working solution is 45-60 ℃.
The patent application number 201410083759.0 discloses an electrolytic copper foil additive for flexible circuit board, its preparation method and application. The additive comprises the following solute components in mass per liter of additive solution: 10-20 mg of cellulose; 1-3 mg of titanium sulfate; 3-7 mg of sodium tungstate; 5-15 mg of polypropylene glycol.
From the above studies, it is known that the type and amount of the additive are important to control. The performance of the prepared copper foil can be improved in more aspects or is particularly improved in one aspect by using more additives or using more additives; on the other hand, however, this also complicates the production flow, liquid supply lines, etc., complicates the filtration flow required to obtain the purified liquid, increases the production cost, complicates the process control, and increases the variability factor because the interaction between different additives is not particularly clear. In addition, excessive levels of certain additives can even have a large negative impact on performance.
Disclosure of Invention
In view of the above-mentioned disadvantages, the present invention provides a method for producing a high-ductility low-profile electrolytic copper foil having excellent high ductility with less additives.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a high-ductility low-profile copper foil comprises the following steps:
1) dissolving gelatin powder in water, and stirring to obtain gelatin solution;
2) carrying out microwave irradiation on the gelatin solution;
3) mixing the gelatin solution after microwave irradiation with the copper sulfate solution to uniformly disperse gelatin molecules in the copper sulfate solution to form a copper foil electrolyte;
4) and sending the copper foil electrolyte into a copper foil electrolytic deposition system to prepare the electrolytic copper foil.
More specifically, the concentration of the gelatin solution in the step 1) is 10 mg/L-500 mg/L.
More specifically, step 2) sends into a spiral pipe through the flow valve with gelatin solution, be provided with microwave generator below the spiral pipe, gelatin solution flows through the spiral pipe, opens microwave generator simultaneously, controls the microwave irradiation intensity that gelatin solution stands through adjusting gelatin solution velocity of flow and microwave frequency and power.
Further, the microwave frequency of the microwave generator in the step 2) is 0.5 GHz-200 GHz, and the power is 10-1000W; the flow rate of the gelatin solution in the spiral tube is 0.5L/min-50L/min.
Further, the copper sulfate solution in the step 3) contains sulfate ions, copper ions, hydrogen protons and chloride ions, wherein the concentration of the chloride ions is 15-30 mg/L, the concentration of the copper ions is 60-110 g/L, and the concentration of the sulfuric acid is 80-120 g/L.
Further, the mixing volume ratio of the gelatin solution and the copper sulfate solution in the step 3) enables the concentration of gelatin in the copper foil electrolyte to be 0.1-10 mg/L.
Further, the current density of the electrolytic copper foil prepared in the step 4) is 45-65A/dm2The temperature is 50-60 ℃.
The inventors' above-mentioned preparation method was obtained based on the following findings in the studies by the inventors. The inventor finds that gelatin molecules can be adsorbed on the surface of a cathode to hinder electrodeposition of copper ions, promote electrochemical polarization of the copper cathode, increase deposition overpotential and promote copper nucleation, so that grains are refined, surface roughness is reduced, good uniform deformability of a copper foil is facilitated, and high elongation is achieved. However, gelatin is easy to hydrolyze in a copper sulfate acid solution, and low molecular weight polypeptide formed after hydrolysis loses the effect of refining copper foil grains; and the small gelatin molecules remaining in the electrolyte easily induce the generation of impurity defects in the copper foil, thereby damaging the quality of the copper foil. In the research, the inventor finds that the microwave irradiation with proper intensity can stabilize the gelatin molecular chain and effectively inhibit the hydrolysis kinetic process of the gelatin. Therefore, in the preparation method, the gelatin solution is subjected to microwave irradiation in a proper intensity range before being mixed with the copper sulfate solution, so that the stability of the gelatin in the copper sulfate solution and in the subsequent copper foil electrolytic deposition process is obviously improved, and the effects of refining grains, reducing the roughness of the copper foil and improving the elongation are exerted.
By adopting the technical scheme, the invention can achieve the following effects: (1) the additive is only two types of gelatin and chloride ions, and the complex formed by the copper ions and the chloride ions can provide binding sites for the gelatin, so that the gelatin can form an adsorption layer on the (220) crystal face of the copper. The prepared copper foil has good physical properties, and can remarkably simplify the production and preparation process and reduce the production cost under the condition of meeting corresponding requirements. (2) The hydrolysis kinetic process of the gelatin is inhibited, the performance stability of the electrolyte is improved, and the quality consistency of the product is ensured. (3) The room temperature elongation of the copper foil obtained by the preparation method is 8-10%, which is superior to the industry standard. (4) The copper foil obtained by the preparation method has the smooth surface roughness Ra of less than 0.3 mu m and the rough surface roughness Rz of less than 2 mu m, and the aim of the invention is achieved.
Drawings
FIG. 1 is a schematic view of a system used for preparing an electrolytic copper foil according to embodiments of the present invention.
Wherein: 1a is a deionized water flow valve; 1b is a gelatin solution flow valve; 2 is a copper sulfate solution flow valve; 3 is a copper foil electrolyte flow valve; 4 is a stirrer; 5 is a gelatin powder feeding port; 6 is a gelatin dissolving tank; 7 is a copper sulfate dissolving tank; 8 is a mixer; 9 is copper foil deposition system; 10 is a microwave generator; 11 is a glass spiral tube.
Detailed Description
FIG. 1 is a schematic view of a system for manufacturing an electrolytic copper foil according to embodiments of the present invention. As shown in the drawing, the process for preparing an electrolytic copper foil according to the embodiments of the present invention is summarized as follows:
1) putting a certain amount of gelatin powder into a gelatin dissolving tank 6 through a feeding port 5, injecting water with a set volume through a flow valve 1a, and fully stirring and dissolving through a stirrer 4 to obtain a gelatin solution with a set concentration;
2) sending the gelatin solution into a glass spiral tube 11 through a flow valve 1b, passing through the glass spiral tube at a set flow rate, simultaneously starting a microwave generator 10 above and below the spiral tube, setting microwave power, and controlling the microwave irradiation intensity of the gelatin by adjusting the flow rate, the microwave power and the frequency;
3) dissolving copper sulfate and copper chloride in a copper sulfate dissolving tank 7 to prepare a copper sulfate solution containing chloride ions;
4) the copper sulfate solution and the gelatin solution after microwave irradiation enter a mixer 8 together through a flow valve 2, gelatin molecules are uniformly dispersed in the copper sulfate solution through the self-mixing action of a helical blade to form a copper foil electrolyte, and the copper foil electrolyte is sent to a copper foil electrolytic deposition system 9 through a flow valve 3 to prepare the electrolytic copper foil.
Examples and comparative examples of the present invention in the above step 4, the copper foil electrodeposition system used was an industrial titanium cathode roll foil forming machine, and the current density of the electrolytic copper foil prepared in the step was 45 to 65A/dm2The temperature is 50-60 ℃, the concentration of copper ions in the used copper foil electrolyte is 60-110 g/L, the concentration of sulfuric acid is 80-120g/L, and the concentration of chlorine ions is concentratedThe degree is 15-30 mg/L.
The present invention will be described more specifically with reference to specific examples.
Example 1:
the preparation process comprises the following steps:
1) putting gelatin powder into a gelatin dissolving tank through a feeding hole, injecting water into the gelatin dissolving tank through a flow valve, and fully stirring and dissolving the gelatin powder by a stirrer to obtain a gelatin solution with the concentration of 30 mg/L;
2) sending the gelatin solution into a glass spiral tube through a gelatin flow valve, passing through the glass spiral tube at a set flow rate of 5L/min, simultaneously starting a microwave generator above and below the spiral tube, and setting the microwave power to be 100 and the frequency to be 10 GHz;
3) the irradiated gelatin solution and the copper sulfate solution enter a mixer together, gelatin molecules are uniformly dispersed in the copper sulfate solution through the self-mixing action of the helical blade to form a copper foil electrolyte, and the copper foil electrolyte is sent to a copper foil electrolytic deposition system to prepare the copper foil. The concentration of gelatin in the electrolyte was controlled by a copper sulfate solution flow valve and a gelatin flow valve, and the flow rate of the copper sulfate solution at which the copper sulfate solution flow valve was opened was 45L/min.
After the deposition of the copper foil is finished, carrying out a series of passivation drying treatments on the copper foil, and then measuring the physical and mechanical properties, wherein the high-temperature mechanical properties are tested by referring to a copper foil experimental method for a GB/T29847-.
The copper foil obtained in this example had the following properties: high temperature tensile strength =165 MPa; high temperature elongation = 10.7%.
Example 2:
the concentration of gelatin used in step 1) was 10 mg/L, and the rest was the same as in example 1.
The copper foil samples obtained had the following relevant properties: high temperature tensile strength =169 MPa; high temperature elongation = 13.0%.
Example 3:
the concentration of gelatin used in step 1) was 100 mg/L, and the rest was the same as in example 1.
The copper foil samples obtained had the following relevant properties: high temperature tensile strength =152 MPa; high temperature elongation = 10.4%.
Example 4:
the flow rate used in step 2) was 0.5L/min, the microwave power was 10W and the frequency was 0.5 GHz, and the flow rate of the copper sulfate solution in step 3) was 24.5L/min, the rest being the same as in example 1.
The copper foil samples obtained had the following relevant properties: high temperature tensile strength =159 MPa; high temperature elongation = 12.1%.
Example 5:
the flow rate used in step 2) was 50L/min, the microwave power was 1000W and the frequency was 200 GHz, and the flow rate of the copper sulfate solution in step 3) was 245L/min, the rest being the same as in example 1.
The copper foil samples obtained had the following relevant properties: high temperature tensile strength =148 MPa; high temperature elongation = 12.7%.
The following are comparative examples
Example 6:
the concentration of gelatin used in step 1) was 800 mg/L, and the rest was the same as in example 1.
The copper foil samples obtained had the following relevant properties: high temperature tensile strength =121 MPa; high temperature elongation = 3.1%. The copper foil contains more pinhole defects and inclusions.
Example 7:
the concentration of gelatin used in step 1) was 0.5 mg/L, and the rest was the same as in example 1.
The copper foil samples obtained had the following relevant properties: high temperature tensile strength =131 MPa; high temperature elongation = 4.8%.
Example 8:
the microwave power used in step 2) was 0W and the frequency was 0Hz, and the rest was the same as in example 1.
The copper foil samples obtained had the following relevant properties: high temperature tensile strength =137 MPa; high temperature elongation =4.4%, the copper foil contains a small amount of inclusion defects.
Example 9:
the microwave power used in step 2) was 5000W, the frequency was 300GHz, and the rest was the same as in example 1.
The copper foil samples obtained had the following relevant properties: high temperature tensile strength =112 MPa; the elongation at high temperature is =1.2%, a plurality of flocculent substances exist in the solution, the copper foil is not compact, and the defects are more.
Table 1 summarizes the conditions of the examples and comparative examples
As can be seen from the analysis of comparative examples 1, 2 and 3, when the concentration of the gelatin solution prepared in step 1) is within the range disclosed in the present invention, the obtained copper foil has excellent high temperature elongation.
It can be seen from the analysis of comparative examples 1, 4 and 5 that the copper foil obtained has excellent high temperature elongation when the gelatin flow rate, microwave power and frequency parameters used are controlled within the ranges disclosed in the present invention.
As can be seen from the analysis of comparative examples 1, 6 and 7, when the concentration of the gelatin solution prepared in step 1) is too high or too low (as in examples 6 and 7), the obtained copper foil cannot reach the high elongation level of 10% at high temperature.
Analysis of comparative examples 1 and 8 shows that without microwave curing, the resulting copper foil has poor properties and contains a small amount of inclusion defects.
Analysis of comparative examples 1 and 9 revealed that if the microwave curing strength was too high, the gelatin deteriorated to a flocculent solid, which was deposited on the cathode surface, not only failing to exert a beneficial effect but also hindering the deposition of the copper foil, seriously impairing the copper foil performance.
Claims (4)
1. A preparation method of a high-ductility low-profile copper foil is characterized by comprising the following steps:
1) dissolving gelatin powder in water, and stirring to obtain gelatin solution;
2) carrying out microwave irradiation on the gelatin solution;
3) mixing the gelatin solution after microwave irradiation with the copper sulfate solution to uniformly disperse gelatin molecules in the copper sulfate solution to form a copper foil electrolyte;
4) sending the copper foil electrolyte into a copper foil electrolytic deposition system to prepare the electrolytic copper foil;
wherein the copper sulfate solution in the step 3) contains sulfate ions, copper ions, hydrogen protons and chloride ions, the concentration of the chloride ions is 15-30 mg/L, the concentration of the copper ions is 60-110 g/L, and the concentration of the sulfuric acid is 80-120 g/L; step 3) mixing the gelatin solution and the copper sulfate solution according to the volume ratio to ensure that the concentration of gelatin in the copper foil electrolyte is 0.1-10 mg/L;
the concentration of gelatin in the gelatin solution is 10 mg/L-500 mg/L.
2. The method of claim 1, wherein the copper foil has a high ductility and a low profile, and the method comprises the steps of: and 2) sending the gelatin solution into a spiral pipe through a flow valve, wherein a microwave generator is arranged above and below the spiral pipe, the gelatin solution flows through the spiral pipe, the microwave generator is started simultaneously, and the microwave irradiation intensity of the gelatin solution is controlled by adjusting the flow rate, the microwave frequency and the power of the gelatin solution.
3. The method of claim 2, wherein the copper foil has a high ductility and a low profile, and the method comprises the steps of: step 2), the microwave frequency of the microwave generator is 0.5 GHz-200 GHz, and the power is 10-1000W; the flow rate of the gelatin solution in the spiral tube is 0.5L/min-50L/min.
4. The method of claim 1, wherein the copper foil has a high ductility and a low profile, and the method comprises the steps of: step 4) preparing the electrolytic copper foil with the current density of 45-65A/dm2The temperature is 50-60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010925800.XA CN112301382B (en) | 2020-09-07 | 2020-09-07 | Preparation method of high-ductility low-profile electrolytic copper foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010925800.XA CN112301382B (en) | 2020-09-07 | 2020-09-07 | Preparation method of high-ductility low-profile electrolytic copper foil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112301382A CN112301382A (en) | 2021-02-02 |
| CN112301382B true CN112301382B (en) | 2021-11-26 |
Family
ID=74483843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010925800.XA Active CN112301382B (en) | 2020-09-07 | 2020-09-07 | Preparation method of high-ductility low-profile electrolytic copper foil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112301382B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105398A (en) * | 1993-10-22 | 1995-07-19 | 古尔德电子有限公司 | Electrodeposited copper foil and process for making same |
| 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 |
| CN1506499A (en) * | 2002-12-11 | 2004-06-23 | 财团法人工业技术研究院 | Making process of electrolytic copper foil with great high-temperature elongation |
| CN1995469B (en) * | 2006-11-28 | 2011-06-15 | 山东金宝电子股份有限公司 | High temperature high ductibility electrolytic copper foil production process |
| CN102383148A (en) * | 2011-11-18 | 2012-03-21 | 山东金宝电子股份有限公司 | Mixed additive for electrolytic copper foil, preparation method for mixed additive, and method for preparing ultralow-profile electrolytic copper foil |
| CN103074657A (en) * | 2013-02-26 | 2013-05-01 | 灵宝华鑫铜箔有限责任公司 | Additive for electrolytic copper foil and production process of electrolytic copper foil for 7-mu. m double-light lithium ion battery |
| CN110093635A (en) * | 2019-04-24 | 2019-08-06 | 福建清景铜箔有限公司 | High-intensitive electrolytic copper foil and its various products for using the copper foil |
-
2020
- 2020-09-07 CN CN202010925800.XA patent/CN112301382B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105398A (en) * | 1993-10-22 | 1995-07-19 | 古尔德电子有限公司 | Electrodeposited copper foil and process for making same |
| 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 |
| CN1506499A (en) * | 2002-12-11 | 2004-06-23 | 财团法人工业技术研究院 | Making process of electrolytic copper foil with great high-temperature elongation |
| CN1995469B (en) * | 2006-11-28 | 2011-06-15 | 山东金宝电子股份有限公司 | High temperature high ductibility electrolytic copper foil production process |
| CN102383148A (en) * | 2011-11-18 | 2012-03-21 | 山东金宝电子股份有限公司 | Mixed additive for electrolytic copper foil, preparation method for mixed additive, and method for preparing ultralow-profile electrolytic copper foil |
| CN103074657A (en) * | 2013-02-26 | 2013-05-01 | 灵宝华鑫铜箔有限责任公司 | Additive for electrolytic copper foil and production process of electrolytic copper foil for 7-mu. m double-light lithium ion battery |
| CN110093635A (en) * | 2019-04-24 | 2019-08-06 | 福建清景铜箔有限公司 | High-intensitive electrolytic copper foil and its various products for using the copper foil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112301382A (en) | 2021-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110438531B (en) | Preparation method and system of ultrathin copper foil applied to lithium battery | |
| CN109267111B (en) | Additive for electrolytic copper foil and application thereof, electrolytic copper foil and preparation method and application thereof, and lithium ion battery | |
| EP0443009A4 (en) | Electrodeposited foil with controlled properties for printed circuit board applications and procedures and electrolyte bath solutions for preparing the same | |
| CN108396346B (en) | Preparation method and application of graphene copper/steel composite material | |
| CN112111761A (en) | Electrolyte of high-elongation electrolytic copper foil and application thereof | |
| CN112469194A (en) | Low-profile electrolytic copper foil for high-density interconnected circuit board | |
| KR101535853B1 (en) | Manufacturing method of high strength copper foil using micro-hardening and high strength copper foil manufactured by the same | |
| DE102022200586A1 (en) | HIGH STRENGTH COPPER FOIL AND PRODUCTION PROCESS THEREOF | |
| CN112144084A (en) | Additive and process for preparing high-tensile electrolytic copper foil by using same | |
| CN111455416B (en) | Preparation process of high-mechanical-property electrolytic copper foil of high-precision circuit board | |
| CN112176366B (en) | Electrolyte of high-ductility electrolytic copper foil and application | |
| KR910010147B1 (en) | Metallization of electrically insulating polymeric film substrates | |
| CN110592623B (en) | Formula and method of nickel electroplating solution for improving uniform distribution of neodymium iron boron magnet coating | |
| CN107557826A (en) | A kind of acid electrochemical copper plating solution | |
| CN105002524A (en) | Addition agent and process for producing 6-micron low-warping-degree electrolytic copper foil through addition agent | |
| CN110670093A (en) | Production method of 4.5-micron double-sided photoelectrolysis copper foil | |
| CN112301382B (en) | Preparation method of high-ductility low-profile electrolytic copper foil | |
| JP2023512132A (en) | Electrolytic copper foil for high frequency/high speed printed circuit board and its preparation method | |
| CN113445081A (en) | Additive for electrolytic copper foil, electrolyte for electrolytic copper foil, copper foil and method for producing the same | |
| CN104846407A (en) | Additive and process for producing 6mu.m high-tensile-strength electrolytic copper foil by using same | |
| CN112962128B (en) | Coarsening process method of high-peeling-resistance copper foil | |
| CN114622238B (en) | Preparation and application of transition metal-based hydrogen and oxygen evolution dual-functional electrode | |
| CN105297087A (en) | Electroplating liquid for hydroxylamine reducing agent cyanide-free univalence copper plating and electroplating method | |
| CN105274589A (en) | Alkaline cyanogen-free copper plating electroplating liquid and electroplating method thereof | |
| CN114016098A (en) | Copper-clad plate electroplating Ni-Co-Ce film plating solution for PCB and film preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20211029 Address after: 322100 Huayuan village, Nanma Town, Dongyang City, Jinhua City, Zhejiang Province Applicant after: Zhejiang Huayuan new energy Co.,Ltd. Address before: 310058 Yuhang Tang Road, Xihu District, Hangzhou, Zhejiang 866 Applicant before: ZHEJIANG University |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |