CN106544704A - A kind of preparation method of low warpage Copper Foil - Google Patents
A kind of preparation method of low warpage Copper Foil Download PDFInfo
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- CN106544704A CN106544704A CN201610956120.8A CN201610956120A CN106544704A CN 106544704 A CN106544704 A CN 106544704A CN 201610956120 A CN201610956120 A CN 201610956120A CN 106544704 A CN106544704 A CN 106544704A
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- copper foil
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Electroplating And Plating Baths Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention relates to a kind of preparation method of low warpage Copper Foil, belong to the manufacturing technology field of high-precision electrolytic copper foil, the present invention applies ultrasonic assistant electro-deposition during electrolytic preparation Copper Foil, in electrolyte of the ul-trasonic irradiation between cathode roll and positive plate, the invention has the beneficial effects as follows：1) maximum acceptable concentration of electrolyte sulfuric acid concentration can be greatly improved on the premise of the low warp value of Copper Foil is ensured, the electrical conductivity for improving electrolyte reduces tank voltage, so as to reduce the electric energy loss of Copper Foil production.2) copper foil deposition layer crystal grain is refined, on the one hand reduce Copper Foil hair side Rz values, loss of signal and distortion that Copper Foil carries out producing in signals transmission as conductor can effectively be reduced, on the other hand make copper coating finer and close so that the elongation percentage and tensile strength properties of Copper Foil has been lifted.
Description
Technical field
The present invention relates to a kind of preparation method of Copper Foil, belongs to the manufacturing technology field of high-precision electrolytic copper foil.
Background technology
Electrolytic copper foil is the basic material of electronics industry, and the direct downstream in electronic material processing industry is copper coated foil plate
(CCL) processing factory.In recent years, the manufacturing level of China CCL producers is improved constantly, and the automatization level of its equipment is also more next
It is higher.The larger Copper Foil of warpage cannot be processed in automation equipment, be the need for adapting to CCL producers automatic production line
Will, it is necessary to control the warp value of electrolytic copper foil.
Research shows, electrolytic copper foil warpage mainly due to generating internal stress in electrodeposition process, and internal stress be by
What the lattice defect in copper electrodeposition process was caused.The electrolyte adopted by current electrolysis Copper Foil producer is all copper sulphate and sulphur
The mixed solution of acid, solution negative electrode in plating can also be accompanied by liberation of hydrogen side reaction while copper is deposited.The hydrogen of high-load
And hydride is mixed into coating and can cause the highdensity dislocation of coating and twin, in turn results in the heavily stressed of coating.
For the electrolyte of production Copper Foil, sulfuric acid concentration is higher, and the liberation of hydrogen side reaction of negative electrode is stronger.In order to reduce analysis
Hydrogen reacts the impact to Copper Foil warpage, and the electrolyte for producing low warpage Copper Foil needs the maximum concentration of strict control sulfuric acid, typically
It is lower even to control in 100g/L in below 120g/L.
Relevant research shows, for sulfuric acid-copper sulphate mixed solution, in the concentration, temperature range in cupric electrolysis, solution
Relational expression between electrical conductivity and copper concentration, sulfuric acid concentration and temperature is：
+ 0.00249 [H of χ=0.134-0.00356 [Cu]2SO4]+0.00426t
The electrical conductivity of χ --- electrolyte；
[Cu] --- copper ion concentration in electrolyte；
[H2SO4] --- sulfuric acid concentration in electrolyte；
The temperature of t --- electrolyte.
According to above formula, electrolyte copper ion concentration and it is temperature-resistant in the case of, the reduction of sulfuric acid concentration can make
Electrolyte conductance declines, and tank voltage is raised, so as to the production power consumption for causing Copper Foil increases.
The cavitation of ultrasonic wave can make hydrogen enter cavitation bubble or as cavitation nucleus, so as to accelerate negative electrode hydrogen nearby
Effusion, reduce the co-deposition of hydrogen and hydride in coating, reduce copper coating internal stress.Removal of the ultrasonic wave to hydrogen is made
With come from electrolysis be initially at the resonant interaction that electrode is formed about minute bubbles, minute bubbles similar to resonator, in the effect of sound wave
Under, its resonant frequency is shown below：
fr--- gas resonance frequency；
Rr--- the resonance radius of resonance bubble；
Ph--- the pressure of effect bubble；
The ratio of the specific heat at constant pressure of γ --- gas and specific heat at constant volume；
ρ --- fluid density.
As can be seen from the above equation, the frequency of ultrasonic wave is directly related with bubble size, and the ultrasonic wave of appropriate frequency can be
The initial stage that bubble hydrogen is formed is removed, and impact of the evolving hydrogen reaction to internal stress is minimized.
The content of the invention
The present invention is for warpage easily occur and needing to rationalize control Copper Foil production in existing electrolytic copper foil process
A kind of present situation of power consumption, there is provided preparation method of low warpage Copper Foil.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：
A kind of preparation method of low warpage Copper Foil, it is characterised in that apply ultrasonic wave during electrolytic preparation Copper Foil auxiliary
Help electro-deposition.
Further, the site of action of the ultrasonic wave is the electrolyte between cathode roll and positive plate.
Further, comprise the steps：
1) tough cathode, sulfuric acid, water are mixed in proportion and dissolves to obtain copper-bath, and adjusted to processing range；
2) using step 1) obtained by copper-bath as electrolyte into electrolytic cell carry out plating production Copper Foil；
3) ultrasonic wave is opened, and the frequency and the sound intensity of ultrasonic wave is adjusted according to technological parameter.
Further, the frequency of the ultrasonic wave is 20～200KHz, and intensity is 0.05～5w/cm2。
Further, step 3) described in technological parameter be Cu2+Concentration is 70-100g/L, H2SO4Concentration is 80-160g/
L, temperature are 45-55 DEG C, current density 45-70A/dm2。
Further, step 1) in also include in copper-bath add additive the step of.
Further, the additive is the mixture of gelatin or the one or both in HEC (hydroxyethyl cellulose), is added
Measure as 0.2-20ppm.
The invention has the beneficial effects as follows：
1) maximum acceptable concentration of electrolyte sulfuric acid concentration can be greatly improved on the premise of the low warp value of Copper Foil is ensured,
The electrical conductivity for improving electrolyte reduces tank voltage, so as to reduce the electric energy loss of Copper Foil production.
2) copper foil deposition layer crystal grain is refined, and on the one hand reduces Copper Foil hair side Rz values, can effectively reduce Copper Foil work
The loss of signal and the distortion that produce in signals transmission are carried out for conductor, on the other hand makes copper coating finer and close so that copper
The elongation percentage and tensile strength properties of paper tinsel has been lifted.
3) simple to operate, process control is stable, without the need for extra additive, will not cause secondary pollution to electrolyte.
Description of the drawings
The SEM of the 18 μm low warpage Copper Foils that Fig. 1 is prepared for the inventive method；
Fig. 2 is the SEM pictures of 18 μm of Copper Foils that industry commonsense method is prepared；
Fig. 3 is ul-trasonic irradiation portion structure schematic diagram；
Specific embodiment
The principle and feature of the present invention are described below in conjunction with example, example is served only for explaining the present invention, and
It is non-for limiting the scope of the present invention.
Embodiment 1：
A kind of preparation method of low warpage Copper Foil, comprises the steps：
1) tough cathode, sulfuric acid, water are mixed in proportion and dissolves to obtain copper-bath, and adjusted to processing range；
2) using step 1) obtained by copper-bath as electrolyte into electrolytic cell carry out plating production Copper Foil；
3) ultrasonic wave is opened, in electrolyte of the ul-trasonic irradiation between cathode roll and positive plate, and according to technological parameter
Adjust the frequency and the sound intensity of ultrasonic wave.
Its technological requirement is：Cu2+Concentration is 70g/L, H2SO4Concentration is 80g/L, and electrolyte temperature is 45 DEG C, and electric current is close
Degree 45A/dm2, additive is gelatin, and addition concentration is 2ppm, and the frequency for applying ultrasonic wave is 20KHz, and the sound intensity is 0.05w/cm2。
Embodiment 2：
The present embodiment with the difference of embodiment 1 is：
Its technological parameter is required：Cu2+Concentration is 80g/L, H2SO4Concentration is 80g/L, and electrolyte temperature is 50 DEG C, electricity
Current density 70A/dm2, additive is gelatin, and addition concentration is 8ppm, and the frequency for applying ultrasonic wave is 28KHz, and the sound intensity is
0.09w/cm2。
Embodiment 3：
The present embodiment with the difference of embodiment 1 is：
Its technological parameter is required：Cu2+Concentration is 80g/L, H2SO4Concentration is 120g/L, and electrolyte temperature is 45 DEG C, electricity
Current density 50A/dm2, additive is gelatin and HEC, adds concentration and is respectively 3ppm and 3ppm, and the frequency for applying ultrasonic wave is
26KHz, the sound intensity are 0.11w/cm2。
Embodiment 4：
The present embodiment with the difference of embodiment 1 is：
Its technological parameter is required：Cu2+Concentration is 80g/L, H2SO4Concentration is 120g/L, and electrolyte temperature is 50 DEG C, electricity
Current density 70A/dm2, additive is gelatin and HEC, adds concentration and is respectively 5ppm and 4ppm, and the frequency for applying ultrasonic wave is
35KHz, the sound intensity are 0.10w/cm2。
Embodiment 5：
The present embodiment with the difference of embodiment 1 is：
Its technological parameter is required：Cu2+Concentration is 80g/L, H2SO4Concentration is 160g/L, and electrolyte temperature is 45 DEG C, electricity
Current density 50A/dm2, additive is HEC, and addition concentration is 4ppm, and the frequency for applying ultrasonic wave is 28KHz, and the sound intensity is 0.15w/
cm2。
Embodiment 6：
The present embodiment with the difference of embodiment 1 is：
Its technological parameter is required：Cu2+Concentration is 100g/L, H2SO4Concentration is 160g/L, and electrolyte temperature is 50 DEG C,
Current density 70A/dm2, additive is HEC, and addition concentration is 8ppm, and the frequency for applying ultrasonic wave is 200KHz, and the sound intensity is 5w/
cm2。
Comparative example 1：
The present embodiment with the difference of embodiment 1 is：
Its technological parameter is required：Cu2+Concentration is 80g/L, H2SO4Concentration is 80g/L, and electrolyte temperature is 50 DEG C, electricity
Current density 70A/dm2, additive is gelatin, and addition concentration is 8ppm, does not apply ultrasonic wave.
Comparative example 2：
The present embodiment with the difference of embodiment 1 is：
Its technological parameter is required：Cu2+Concentration is 80g/L, H2SO4Concentration is 120g/L, and electrolyte temperature is 50 DEG C, electricity
Current density 70A/dm2, additive is gelatin and HEC, adds concentration and is respectively 5ppm and 4ppm, does not apply ultrasonic wave.
Comparative example 3：
Its technological parameter is required：Cu2+Concentration is 100g/L, H2SO4Concentration is 160g/L, and electrolyte temperature is 50 DEG C,
Current density 70A/dm2, additive is HEC, and addition concentration is 8ppm, does not apply ultrasonic wave.
The technological parameter and tank voltage of embodiment 1～6 and comparative example 1～3, warp value measurement result are as shown in table 1.
Table 1
| Ultrasonic frequency | Ultrasonic intensity | Sulfuric acid concentration | Current density | Tank voltage | Warp value | |
| Unit | KHz | W/cm2 | g/L | A/dm2 | V | mm |
| Embodiment 1 | 20 | 0.05 | 80 | 45 | 4.9 | 2.0 |
| Embodiment 2 | 28 | 0.09 | 80 | 70 | 5.9 | 2.0 |
| Embodiment 3 | 26 | 0.11 | 120 | 50 | 4.5 | 2.5 |
| Embodiment 4 | 35 | 0.10 | 120 | 70 | 5.5 | 2.3 |
| Embodiment 5 | 28 | 0.15 | 160 | 50 | 4.2 | 2.6 |
| Embodiment 6 | 30 | 0.20 | 160 | 70 | 5.0 | 2.5 |
| Comparative example 1 | - | - | 80 | 70 | 5.9 | 8.3 |
| Comparative example 2 | - | - | 120 | 70 | 5.5 | 10.5 |
| Comparative example 3 | - | - | 160 | 70 | 5.0 | 15.0 |
For the performance of the Copper Foil that the preparation method production for verifying the present invention is obtained, we are to embodiment 1～6 and comparative example
1～3 gained Copper Foil has carried out performance test, and concrete outcome is as shown in table 2：
Table 2
Note：In table 2, peel strength is the Copper Foil to embodiment and comparative example using identical process of surface treatment, pressing
Test result after FR-4 prepregs.
Preferably to implement the present invention, the technical key point of the present invention is illustrated briefly below.
The ultrasonic frequency and the sound intensity adopted by this method is related to specific process conditions.In general, supersonic frequency
Selection be adjusted according to parameters such as the sulfuric acid concentration of electrolyte, temperature and current densities；And ultrasonic intensity by sulfuric acid concentration,
The flow effect of cathode roll rotating speed and electrolyte is larger.
In the given process condition range of the present invention, it is relatively low that the suitable ultrasonic parameters of matching can produce warpage
Copper Foil, but in production process, must assure that the technological parameters such as temperature, flow, sulfuric acid concentration and the current density of electrolyte
Stability.
The foregoing is only presently preferred embodiments of the present invention, not to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (7)
1. a kind of preparation method of low warpage Copper Foil, it is characterised in that apply ultrasonic assistant during electrolytic preparation Copper Foil
Electro-deposition.
2. the preparation method of low warpage Copper Foil according to claim 1, it is characterised in that the site of action of the ultrasonic wave
For the electrolyte between cathode roll and positive plate.
3. the preparation method of low warpage Copper Foil according to claim 1 and 2, it is characterised in that comprise the steps：
1) tough cathode, sulfuric acid, water are mixed in proportion and dissolves to obtain copper-bath, and adjusted to processing range；
2) using step 1) obtained by copper-bath as electrolyte into electrolytic cell carry out plating production Copper Foil；
3) ultrasonic wave is opened, and the frequency and the sound intensity of ultrasonic wave is adjusted according to technological parameter.
4. the preparation method of low warpage Copper Foil according to claim 3, it is characterised in that the frequency of the ultrasonic wave is 20
～200KHz, intensity are 0.05～5w/cm2。
5. the preparation method of low warpage Copper Foil according to claim 4, it is characterised in that step 3) described in technique ginseng
Number is Cu2+Concentration is 70-100g/L, H2SO4Concentration is 80-160g/L, and temperature is 45-55 DEG C, current density 45-70A/dm2。
6. the preparation method of low warpage Copper Foil according to claim 3, it is characterised in that step 1) in also include to sulfuric acid
The step of adding additive in copper solution.
7. the preparation method of low warpage Copper Foil according to claim 6, it is characterised in that the additive is gelatin or hydroxyl
The mixture of the one or both in ethyl cellulose, addition are 0.2-20ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610956120.8A CN106544704A (en) | 2016-11-03 | 2016-11-03 | A kind of preparation method of low warpage Copper Foil |
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|---|---|---|---|
| CN201610956120.8A CN106544704A (en) | 2016-11-03 | 2016-11-03 | A kind of preparation method of low warpage Copper Foil |
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| CN201610956120.8A Pending CN106544704A (en) | 2016-11-03 | 2016-11-03 | A kind of preparation method of low warpage Copper Foil |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113481550A (en) * | 2021-08-02 | 2021-10-08 | 青海电子材料产业发展有限公司 | Method for preparing low-warpage ultrathin electrolytic copper foil by subtractive method |
| CN114855228A (en) * | 2022-06-10 | 2022-08-05 | 江西省科学院能源研究所 | Online monitoring method and device for electrolytic copper foil electrodeposition process |
| CN115786997A (en) * | 2021-09-10 | 2023-03-14 | 宁德时代新能源科技股份有限公司 | Electrolytic copper foil and preparation method thereof, negative pole piece and secondary battery |
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| CN1974870A (en) * | 2006-11-23 | 2007-06-06 | 上海交通大学 | Supersonic method of lowering internal stress of electroplated copper film |
| CN103173812A (en) * | 2013-03-21 | 2013-06-26 | 山东金宝电子股份有限公司 | Mixed additive for removing internal stress of electrolytic copper foil and method for producing low-stress copper foil |
| CN104762642A (en) * | 2015-03-31 | 2015-07-08 | 灵宝华鑫铜箔有限责任公司 | Production process of electrolytic copper foil with low warping degree |
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| CN1974870A (en) * | 2006-11-23 | 2007-06-06 | 上海交通大学 | Supersonic method of lowering internal stress of electroplated copper film |
| CN103173812A (en) * | 2013-03-21 | 2013-06-26 | 山东金宝电子股份有限公司 | Mixed additive for removing internal stress of electrolytic copper foil and method for producing low-stress copper foil |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113481550A (en) * | 2021-08-02 | 2021-10-08 | 青海电子材料产业发展有限公司 | Method for preparing low-warpage ultrathin electrolytic copper foil by subtractive method |
| CN113481550B (en) * | 2021-08-02 | 2022-04-29 | 青海电子材料产业发展有限公司 | Method for preparing low-warpage ultrathin electrolytic copper foil by subtractive method |
| CN115786997A (en) * | 2021-09-10 | 2023-03-14 | 宁德时代新能源科技股份有限公司 | Electrolytic copper foil and preparation method thereof, negative pole piece and secondary battery |
| CN115786997B (en) * | 2021-09-10 | 2023-08-25 | 宁德时代新能源科技股份有限公司 | Electrolytic copper foil, preparation method thereof, negative electrode plate and secondary battery |
| EP4234768A4 (en) * | 2021-09-10 | 2024-05-08 | Contemporary Amperex Technology Co., Limited | Electrolytic copper foil and preparation method therefor, negative electrode plate, secondary battery, battery module, battery pack, and electric device |
| CN114855228A (en) * | 2022-06-10 | 2022-08-05 | 江西省科学院能源研究所 | Online monitoring method and device for electrolytic copper foil electrodeposition process |
| CN114855228B (en) * | 2022-06-10 | 2023-06-06 | 江西省科学院能源研究所 | On-line monitoring method and device for electrolytic copper foil electrodeposition process |
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