CN108330516A - A kind of production method of high performance lithium ion battery ultrathin electrolytic copper foil - Google Patents
A kind of production method of high performance lithium ion battery ultrathin electrolytic copper foil Download PDFInfo
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- CN108330516A CN108330516A CN201810072468.XA CN201810072468A CN108330516A CN 108330516 A CN108330516 A CN 108330516A CN 201810072468 A CN201810072468 A CN 201810072468A CN 108330516 A CN108330516 A CN 108330516A
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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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Abstract
The present invention relates to a kind of production methods of high performance lithium ion battery ultrathin electrolytic copper foil, include the following steps：1) plating solution is prepared：Prepare sulfuric acid copper content be 310~380g/L, the plating solution that sulfuric acid content is 120~140g/L；2) additive is used：Collagen and SPS are continuously added dropwise into plating solution, the content for controlling collagen in plating solution is 0.05~0.8g/KAh, and the content of SPS is 0.05~0.5g/KAh；3) electro-deposition：Adjust plating solution temperature be 50~55 DEG C, using high frequency pulse power supply current density be 40~70A/dm2Under copper ion in plating solution between cathode-anode plate carry out electro-deposition, the frequency for controlling high frequency pulse power supply is 50~100Hz, using 0.75~0.9 duty ratio, in ultrathin electrolytic copper foil is made on cathode.This method can obtain the ultrathin electrolytic copper foil with the dual light of high tensile strength and ductility.
Description
Technical field
The present invention relates to a kind of production method of electrolytic copper foil more particularly to a kind of lithium ion battery ultrathin electrolytic copper foils
Production method, belong to the production technical field of electrolytic copper foil.
Background technology
In the recent period, the whole world is all in propelled at high velocity and development new-energy automobile industry, and lithium ion battery is as new energy indispensability
Electrical source of power is also grown rapidly.Electrolytic copper foil had not only served as the carrier of negative electrode active material in lithium ion battery, but also filled
Collection when cathode electron stream and transmission body, so, electrolytic copper foil is to the charge and discharge of lithium ion battery, service life, secure side
Face etc. all has a great impact.
With the development of battery manufacturing technology, the thickness of electrolytic copper foil used in lithium ion battery is also gradually thinning；This is just
It is required that extra thin copper foil has higher tensile strength, higher ductility simultaneously, ensure during battery production processes use
The defects of being not in fracture, deformation；Lower surface roughness and uniformly, it is uniform in order to the active material thickness of coating,
Extend battery.It is known that electrolytic copper foil thickness is thinner, technology content is higher, and production is more difficult to；Existing skill
It is produced in art in the method for thin and dual light copper foil to pursue low roughness, needs that a large amount of additive is added, thus make
It is mingled with a large amount of organic matter in copper foil, reduces the internal performance of copper foil.
Invention content
It is insufficient existing for method of the present invention for existing production ultrathin electrolytic copper foil, a kind of high-performance lithium ion electricity is provided
The production method of pond ultrathin electrolytic copper foil.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
A kind of production method of high performance lithium ion battery ultrathin electrolytic copper foil, includes the following steps：
1) plating solution is prepared：Prepare sulfuric acid copper content be 310~380g/L, the plating solution that sulfuric acid content is 120~140g/L；
2) additive is used：Collagen and SPS are continuously added dropwise into the plating solution of step 1), controls collagen in plating solution
Content be 0.05~0.8g/KAh, the content of SPS is 0.05~0.5g/KAh；
3) electro-deposition：The temperature for adjusting plating solution is 50~55 DEG C, close in electric current using high frequency pulse power supply in electrolytic cell
Degree is 40~70A/dm2Under copper ion in plating solution between cathode-anode plate carry out electro-deposition, control high frequency pulse power supply
Frequency is 50~100Hz, using 0.75~0.9 duty ratio, in obtained ultrathin electrolytic copper foil on cathode.
Further, the frequency of control high frequency pulse power supply is 70~80Hz in step 3), using 0.8~0.9 duty ratio.
Further, the content of collagen is 0.2~0.4g/KAh in control plating solution in step 2), and the content of SPS is 0.1
~0.2g/KAh.
Further, sulfuric acid copper content is 340~360g/L in the step 1) plating solution, sulfuric acid content is 125~135g/L,
The temperature for adjusting plating solution is 50~52 DEG C.
Further, the cathode described in step 3) is titanium cathode roller.
The beneficial effects of the invention are as follows：
1) this method only uses minimal amount of additive, and by coordinating high frequency pulse power supply, it is that 6-9 is micro- that thickness, which can be obtained,
Rice, surface color is uniform, and two sides glossiness is quite and in 150-250GU, hair side roughness Ra≤0.2 μm, Rz≤2.0 μm,
The ultrathin electrolytic copper foil of dual light with high tensile strength and ductility；
2) the active material thickness that the ultrathin electrolytic copper foil obtained by the method using the present invention can be such that two sides coats is uniform, protects
Two finishing coat charge and discharge cycles balance is demonstrate,proved, the service life of battery is extended, and can prevent from occurring when pole piece coiling or overcharge disconnected
The problems such as splitting, deforming preferably ensure that the application of battery.
Specific implementation mode
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.
Preparatory condition：
Quantitative deionized water and the concentrated sulfuric acid are got to from fixed storage tank in the pot for smelted copper equipped with electrolytic copper plate, then are passed through
Compressed air carries out oxidation reaction, has just obtained copper sulfate solution, chemical reaction equation is as follows：(1)2Cu+O2=2CuO,
(2)CuO+H2SO4=CuSO4+H2O.By this electrolyte using accurate filters such as activated carbons at different levels, filter bag, filter stick, filter cores
After squeeze into head tank.
Embodiment 1：
A kind of production method of high performance lithium ion battery ultrathin electrolytic copper foil, includes the following steps：
1) the sulfuric acid copper content of electrolyte is 340~360g/L in control head tank, sulfuric acid content is 125~135g/L；
2) collagen and SPS are continuously added dropwise into head tank, the content for controlling collagen in plating solution is 0.3g/KAh,
The content of SPS is 0.15g/KAh, is flowed into electrolytic cell after being sufficiently stirred；
3) electro-deposition：Adjust plating solution temperature be 50 DEG C, using high frequency pulse power supply current density be 60A/dm2Lower pair
Copper ion in plating solution between cathode-anode plate carries out electro-deposition, and the frequency for controlling high frequency pulse power supply is 70Hz, using 0.8
The ultrathin electrolytic copper foil that thickness is 6 microns is made in the surface of titanium cathode roller in duty ratio.
Embodiment 2：
A kind of production method of high performance lithium ion battery ultrathin electrolytic copper foil, includes the following steps：
1) the sulfuric acid copper content of electrolyte is 310~330g/L in control head tank, sulfuric acid content is 120~130g/L；
2) collagen and SPS are continuously added dropwise into head tank, the content for controlling collagen in plating solution is 0.05g/
The content of KAh, SPS are 0.5g/KAh, are flowed into electrolytic cell after being sufficiently stirred；
3) electro-deposition：Adjust plating solution temperature be 52 DEG C, using high frequency pulse power supply current density be 70A/dm2Lower pair
Copper ion in plating solution between cathode-anode plate carries out electro-deposition, and the frequency for controlling high frequency pulse power supply is 50Hz, using 0.9
The ultrathin electrolytic copper foil that thickness is 6 microns is made in the surface of titanium cathode roller in duty ratio.
Embodiment 3：
A kind of production method of high performance lithium ion battery ultrathin electrolytic copper foil, includes the following steps：
1) the sulfuric acid copper content of electrolyte is 360~380g/L in control head tank, sulfuric acid content is 130~140g/L；
2) collagen and SPS are continuously added dropwise into head tank, the content for controlling collagen in plating solution is 0.8g/KAh,
The content of SPS is 0.05g/KAh, is flowed into electrolytic cell after being sufficiently stirred；
3) electro-deposition：The temperature for adjusting plating solution is 55 DEG C, right in the case where current density is 40A/dm2 using high frequency pulse power supply
Copper ion in plating solution between cathode-anode plate carries out electro-deposition, and the frequency for controlling high frequency pulse power supply is 100Hz, using 0.75
Duty ratio, it is 6 microns of ultrathin electrolytic copper foil that thickness, which is made, in the surface of titanium cathode roller.
Comparative example：
1) the sulfuric acid copper content of electrolyte is 340~360g/L in control head tank, sulfuric acid content is 125~135g/L；
2) continuous simultaneously in head tank that collagen and SPS is added dropwise, the content for controlling collagen in electrolyte is 5g/
The content of KAh, SPS are 4g/KAh, are flowed into electrolytic cell after being sufficiently stirred；
3) high-frequency direct-current power supply is used, is 60A/dm in current density2Under copper ion between cathode-anode plate carry out electricity
6 microns of ultrathin electrolytic copper foils of lithium ion battery are made in the surface of titanium cathode roller in deposition.We are by embodiment 1-3 and right
6 microns of ultrathin electrolytic copper foils that ratio obtains have carried out the detection of performance, and the results are shown in Table 1.
The performance test results of 1 embodiment 1-3 of table and comparative example gained ultrathin electrolytic copper foil
As can be seen from the above table, under same electrolyte conditions, high frequency pulse power supply is coordinated using a small amount of additive,
The coating of more excellent performance can be obtained under suitable pulse frequency and duty ratio, and there is high tensile strength, ductility and more
Low roughness fully meets the performance requirement of high-end lithium ion battery ultrathin electrolytic copper foil.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of production method of high performance lithium ion battery ultrathin electrolytic copper foil, which is characterized in that include the following steps：
1) plating solution is prepared：Prepare sulfuric acid copper content be 310~380g/L, the plating solution that sulfuric acid content is 120~140g/L；
2) additive is used：It is continuously added dropwise collagen and SPS into the plating solution of step 1), controls containing for collagen in plating solution
Amount is 0.05~0.8g/KAh, and the content of SPS is 0.05~0.5g/KAh；
3) electro-deposition：The temperature for adjusting plating solution is 50~55 DEG C, is in current density using high frequency pulse power supply in electrolytic cell
40~70A/dm2Under copper ion in plating solution between cathode-anode plate carry out electro-deposition, control the frequency of high frequency pulse power supply
For 50~100Hz, using 0.75~0.9 duty ratio, in ultrathin electrolytic copper foil is made on cathode.
2. production method according to claim 1, which is characterized in that the frequency of control high frequency pulse power supply is in step 3)
70~80Hz, using 0.8~0.9 duty ratio.
3. production method according to claim 1 or 2, which is characterized in that collagen in control plating solution in step 2)
Content is 0.2~0.4g/KAh, and the content of SPS is 0.1~0.2g/KAh.
4. production method according to claim 3, which is characterized in that sulfuric acid copper content is 340 in the step 1) plating solution
~360g/L, sulfuric acid content are 125~135g/L, and the temperature for adjusting plating solution is 50~52 DEG C.
5. production method according to claim 4, which is characterized in that the cathode described in step 3) is titanium cathode roller.
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| CN108330516B CN108330516B (en) | 2019-09-10 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276416A (en) * | 2013-06-27 | 2013-09-04 | 灵宝华鑫铜箔有限责任公司 | Additive for electrolytic copper foil, and production technique of electrolytic copper foil |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276416A (en) * | 2013-06-27 | 2013-09-04 | 灵宝华鑫铜箔有限责任公司 | Additive for electrolytic copper foil, and production technique of electrolytic copper foil |
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