CN110004468A - A kind of compound additive preparing low brittleness electrolytic copper foil - Google Patents
A kind of compound additive preparing low brittleness electrolytic copper foil Download PDFInfo
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- CN110004468A CN110004468A CN201910320604.7A CN201910320604A CN110004468A CN 110004468 A CN110004468 A CN 110004468A CN 201910320604 A CN201910320604 A CN 201910320604A CN 110004468 A CN110004468 A CN 110004468A
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- Prior art keywords
- copper foil
- compound additive
- electrolytic copper
- thiocarbamide
- preparing low
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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
Abstract
The invention discloses a kind of compound additives for preparing low brittleness electrolytic copper foil, belong to electrolytic copper foil production technical field.The compound additive includes sodium isethionate (PEG), 2-mercaptobenzimidazoles (M), modified thiocarbamide (TU), gelatin.The electrolytic copper foil produced by additive of the present invention, room temperature tensile strength >=480Mpa, room temperature elongation percentage >=17%；180 DEG C of tensile strength >=300Mpa, 180 DEG C of elongation percentage >=13%.Such electrolytic copper foil properties are especially suitable for automobile power cell and large capacity cellular li-ion battery uses.
Description
Technical field
The present invention relates to electrolytic copper foil technical fields, and in particular to a kind of to prepare low the compound of brittleness electrolytic copper foil and add
Add agent.
Background technique
Basic material of the electrolytic copper foil as electronics industry, plays very important effect in the development of electronics industry.
Electrolytic copper foil is the sedimentary obtained with electro-deposition techniques, and since it has purity is high, deposition rate is fast, and expense is low, work temperature
Low and simple operation and other advantages are spent, therefore are widely used in CCL (copper-clad plate) and PCB (printed board) industry.
Additive plays an important role in electrolytic copper foil preparation.Additive it is many kinds of, various additives are in electro-deposition
Different effects is played in the process.If chloride ion can increase cathodic polarization and inhibit metal misgrowth, to improve copper foil
Elastic strength, hardness and smooth sense；Gelatin can refine crystal grain, improve copper foil hair side peak valley shape and increase copper foil consistency；
Sodium isethionate (PEG) can increase cathodic polarization, have preferable wetting action to cathode surface, can make in electrodeposition process
The bubble of generation quickly escapes, and eliminates bubble hydrogen and is adsorbed on pin hole caused by deposition layer surface.
Thiocarbamide is also the common additive of acid copper, is not only good brightener and grain refiner.Tiny
Crystal grain often has preferable mechanical property.Thiocarbamide can decompose in copper deposition process, and it is residual that the sulfide of generation has part
It stays in copper foil, so as to cause embrittlement.When thiocarbamide reaches 12mg/L, layers of copper is bright, but is difficult to remove from cathode plate, because
It is big for layers of copper brittleness, it is easily broken off the fragment for becoming tiny, when the thiocarbamide that a small amount of (3-9mg/L) is added, the roughness of copper foil is bright
It is aobvious to reduce, and concentration continues to increase, increased trend, brittleness also significantly increase roughness again.
Electrolytic copper foil tensile property in the prior art is not high, and elongation percentage is not high, and pole piece bears not living rapidly charge and discharge, holds
Easily it is cracked；Copper foil surface is more coarse, little with negative electrode active material contact area.
Summary of the invention
The object of the present invention is to provide a kind of compound additives for preparing low brittleness electrolytic copper foil, and thus Additive Production goes out
The electrolytic copper foil brittleness come is low, and tensile strength is big, and peel strength is good, the copper foil particularly suitable as electric vehicle lithium ion battery
Material can bear charge and discharge rapidly without being easy to appear cracking.
The purpose of the present invention is what is be achieved through the following technical solutions, a kind of compound addition preparing low brittleness electrolytic copper foil
Agent, the compound additive include sodium isethionate (PEG), 2-mercaptobenzimidazoles (M), modified thiocarbamide (TU), gelatin.
Preferably, the compound additive includes following component: sodium isethionate 4-6.5 mg/L, 2-sulfydryl benzo miaows
Azoles (M) 5-9 mg/L, modified thiocarbamide (TU) 2-5 mg/L, gelatin 3-6 mg/L.
Preferably, the compound additive includes following component: 5 mg/L of sodium isethionate, 2-mercaptobenzimidazoles
(M) 6 mg/L, modified thiocarbamide (TU) 4 mg/L, 4 mg/L of gelatin.
Preferably, the compound additive includes following component: 4 mg/L of sodium isethionate, 2-mercaptobenzimidazoles
(M) 9 mg/L, modified thiocarbamide (TU) 2 mg/L, 6 mg/L of gelatin.
Preferably, the compound additive includes following component: 6.5 mg/L of sodium isethionate, 2-mercaptobenzimidazoles
(M) 5 mg/L, modified thiocarbamide (TU) 5mg/L, 3 mg/L of gelatin.
The modified thiocarbamide the preparation method comprises the following steps: thiocarbamide and diethylene triamine pentacetic acid (DTPA) are mixed in the ratio of 3:1, carry out
Heating water bath is warming up to 80-90 degree, keeps constant temperature 30-45 minutes of 80-90 degree, and be stirred continuously, then slowly drops temperature
To 40-50 degree, stops heating and stirring after continuing stirring 45 minutes, be cooled to room temperature.
The processing step and parameter of present invention deposition copper foil are as follows:
Taking copper content is 80~100g/L, and sulfuric acid content is 90~140g/L, and chloride ion is 20~30ppm, and temperature is 45~60
DEG C electrolyte, the compound additive is then added into the electrolyte, makes electrolyte in 40~70m3/h of flow, is adjusted
Economize on electricity source controls current density in 65 A/dm2 of 55-.60-80 s is reacted, 18 μm of copper foil is prepared.
Preferably, the present invention deposits the processing step and parameter of copper foil are as follows:
Taking copper content is 90~100g/L, and sulfuric acid content is 120~140g/L, chloride ion 30ppm, the electrolysis that temperature is 45 DEG C
Then liquid adds the compound additive into the electrolyte, make electrolyte in 60~70m3/h of flow, adjusting power supply will
Current density is controlled in 65 A/dm2 of 60-.70-80 s is reacted, 18 μm of copper foil is prepared.
Preferably, the present invention deposits the processing step and parameter of copper foil are as follows:
Taking copper content is 80~90g/L, and sulfuric acid content is 90~120g/L, chloride ion 20ppm, the electrolysis that temperature is 65 DEG C
Then liquid adds the compound additive into the electrolyte, make electrolyte in 70~80m3/h of flow, adjusting power supply will
Current density is controlled in 60 A/dm2 of 55-.60-70 s is reacted, 18 μm of copper foil is prepared.
Beneficial effects of the present invention: there is not been reported as electrolytic copper foil additive for modified thiocarbamide, with diethylenetriamine five
The modified thiocarbamide of acetic acid is not shown in there is technical report as additive to improve the mechanical property of electrolytic copper foil.It is used in the present invention
Thiocarbamide after modified, reduce decomposition of the thiocarbamide under electrolyte environment, preferably resolve common thiocarbamide to participate in copper heavy
It can decompose during product, the sulfide of generation remains in copper foil as impurity, so as to cause the problem of embrittlement.Therefore,
Enough modified thiocarbamides can be added in production, not only can guarantee that the copper foil produced had preferable brightness and compactness, but also
With stronger tensile strength and elongation percentage.
After measured, the electrolytic copper foil produced by additive of the present invention, room temperature tensile strength >=480Mpa, room temperature extend
Rate >=17%；180 DEG C of tensile strength >=300Mpa, 180 DEG C of elongation percentage >=13%.
Such electrolytic copper foil properties are especially suitable for automobile power cell and large capacity cellular li-ion battery uses.It is fine and smooth
Smooth grain structure, uniform surface density is big with negative electrode active material contact area, can be substantially reduced inside battery contact
Resistance prevents pole piece to be cracked, and battery is made to have excellent charge-discharge characteristic.
Specific embodiment
Embodiment one: the compound additive for preparing low brittleness electrolytic copper foil is made of the following components: sodium isethionate 5
Mg/L, 2-mercaptobenzimidazoles (M), 6 mg/L, modified thiocarbamide (TU) 4 mg/L, 4 mg/L of gelatin.According to above-mentioned compound addition
Agent, the depositing operation process for depositing copper foil are as follows: take copper content for 90g/L, sulfuric acid content 120g/L, chloride ion 25ppm,
The electrolyte that temperature is 50 DEG C, the compound additive is then added into the electrolyte, makes electrolyte in flow 60m3/
H adjusts power supply and controls current density in 60A/dm2.70 s are reacted, 18 μm of copper foil is prepared.After tested, it thus makes
Room temperature tensile strength=520Mpa of standby electrolytic copper foil, room temperature elongation percentage=18.6%, 180 DEG C tensile strength=325Mpa, 180 DEG C
Elongation percentage=12.5%.
Embodiment two: the compound additive for preparing low brittleness electrolytic copper foil is made of the following components: sodium isethionate
6.5 mg/L, 2-mercaptobenzimidazoles (M), 5 mg/L, modified thiocarbamide (TU) 5 mg/L, 6 mg/L of gelatin.According to above-mentioned compound
Additive, the depositing operation process for depositing copper foil are as follows: taking copper content is 100g/L, sulfuric acid content 100g/L, and chloride ion is
20ppm, the electrolyte that temperature is 60 DEG C, the compound additive is then added into the electrolyte, makes electrolyte in flow
For 70m3/h, adjusts power supply and control current density in 55A/dm2.60s is reacted, 18 μm of copper foil is prepared.After tested,
Thus room temperature tensile strength=510Mpa of the electrolytic copper foil prepared, room temperature elongation percentage=17.8%；180 DEG C of tensile strength=
340Mpa, 180 DEG C of elongation percentage=13.2%.
Embodiment three: the compound additive for preparing low brittleness electrolytic copper foil is made of the following components: sodium isethionate 4
Mg/L, 2-mercaptobenzimidazoles (M), 9 mg/L, modified thiocarbamide (TU) 2 mg/L, 3 mg/L of gelatin.According to above-mentioned compound addition
Agent, the depositing operation process for depositing copper foil are as follows: take copper content for 80g/L, sulfuric acid content 140g/L, chloride ion 30ppm,
The electrolyte that temperature is 45 DEG C, the compound additive is then added into the electrolyte, makes electrolyte in flow 40m3/
H adjusts power supply and controls current density in 65A/dm2.80s is reacted, 18 μm of copper foil is prepared.After tested, it thus prepares
Electrolytic copper foil room temperature tensile strength=550Mpa, room temperature elongation percentage=18.1%；180 DEG C of tensile strength=352Mpa, 180 DEG C
Elongation percentage=13.0%.
Claims (6)
1. a kind of compound additive for preparing low brittleness electrolytic copper foil, it is characterised in that the compound additive includes ethoxy sulphur
Sour sodium (PEG), 2-mercaptobenzimidazoles (M), modified thiocarbamide (TU), gelatin.
2. a kind of compound additive for preparing low brittleness electrolytic copper foil as described in claim 1, it is characterised in that described compound
Additive includes following component: sodium isethionate 4-6.5 mg/L, 2-mercaptobenzimidazoles (M) 5-9 mg/L, modified thiocarbamide
(TU) 2-5 mg/L, gelatin 3-6 mg/L.
3. a kind of compound additive for preparing low brittleness electrolytic copper foil as described in claim 1, it is characterised in that described compound
Additive includes following component: 5 mg/L of sodium isethionate, 2-mercaptobenzimidazoles (M), 6 mg/L, modified thiocarbamide (TU) 4
Mg/L, 4 mg/L of gelatin.
4. a kind of compound additive for preparing low brittleness electrolytic copper foil as described in claim 1, it is characterised in that described compound
Additive includes following component: 4 mg/L of sodium isethionate, 2-mercaptobenzimidazoles (M), 9 mg/L, modified thiocarbamide (TU) 2
Mg/L, 6 mg/L of gelatin.
5. a kind of compound additive for preparing low brittleness electrolytic copper foil as described in claim 1, it is characterised in that described compound
Additive includes following component: 6.5 mg/L of sodium isethionate, 2-mercaptobenzimidazoles (M), 5 mg/L, modified thiocarbamide (TU)
5mg/L, 3 mg/L of gelatin.
6. a kind of compound additive for preparing low brittleness electrolytic copper foil as described in claim 1, it is characterised in that the modification
Thiocarbamide the preparation method comprises the following steps: thiocarbamide and diethylene triamine pentacetic acid (DTPA) are mixed in the ratio of 3:1, carry out heating water bath, be warming up to
80-90 degree keeps constant temperature 30-45 minutes of 80-90 degree, and is stirred continuously, and temperature is then slowly dropped to 40-50 degree, continues
Stop heating and stirring after stirring 45 minutes, is cooled to room temperature.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910320604.7A CN110004468B (en) | 2019-04-20 | 2019-04-20 | Composite additive for preparing low-brittleness electrolytic copper foil |
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| CN201910320604.7A CN110004468B (en) | 2019-04-20 | 2019-04-20 | Composite additive for preparing low-brittleness electrolytic copper foil |
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| CN110004468A true CN110004468A (en) | 2019-07-12 |
| CN110004468B CN110004468B (en) | 2021-03-23 |
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| CN201910320604.7A Active CN110004468B (en) | 2019-04-20 | 2019-04-20 | Composite additive for preparing low-brittleness electrolytic copper foil |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110938848A (en) * | 2019-12-26 | 2020-03-31 | 江苏艾森半导体材料股份有限公司 | Composition for electrolytic deposition of copper and acid copper electroplating solution |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0334657A2 (en) * | 1988-03-25 | 1989-09-27 | FUKUDA METAL FOIL & POWDER INDUSTRIAL CO. LTD. | Method of surface treatment of copper foil or copper clad laminate for internal layer |
| 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 |
| CN106480479A (en) * | 2016-10-12 | 2017-03-08 | 东莞华威铜箔科技有限公司 | The preparation method of flexible additive for electrolytic copper foil, product and its application |
| CN108425122A (en) * | 2018-03-23 | 2018-08-21 | 江西铜业集团有限公司 | A kind of electrolytic copper foil titanium-based oxide coated anode surface scale minimizing technology |
| CN109537054A (en) * | 2018-11-26 | 2019-03-29 | 江西理工大学 | A kind of high-rate lithium-rich manganese-based anode material monocrystalline and preparation method thereof |
-
2019
- 2019-04-20 CN CN201910320604.7A patent/CN110004468B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0334657A2 (en) * | 1988-03-25 | 1989-09-27 | FUKUDA METAL FOIL & POWDER INDUSTRIAL CO. LTD. | Method of surface treatment of copper foil or copper clad laminate for internal layer |
| 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 |
| CN106480479A (en) * | 2016-10-12 | 2017-03-08 | 东莞华威铜箔科技有限公司 | The preparation method of flexible additive for electrolytic copper foil, product and its application |
| CN108425122A (en) * | 2018-03-23 | 2018-08-21 | 江西铜业集团有限公司 | A kind of electrolytic copper foil titanium-based oxide coated anode surface scale minimizing technology |
| CN109537054A (en) * | 2018-11-26 | 2019-03-29 | 江西理工大学 | A kind of high-rate lithium-rich manganese-based anode material monocrystalline and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| D.N. UPADHYAY ET AL.: "Effect of thiourea and substituted thioureas on copper underpotential deposition on gold", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
| 许洪胤 等: "环氧固化剂硫脲改性二乙烯三胺的制备工艺", 《热固性树脂》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110938848A (en) * | 2019-12-26 | 2020-03-31 | 江苏艾森半导体材料股份有限公司 | Composition for electrolytic deposition of copper and acid copper electroplating solution |
| CN110938848B (en) * | 2019-12-26 | 2021-05-11 | 江苏艾森半导体材料股份有限公司 | Composition for electrolytic deposition of copper and acid copper electroplating solution |
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| CN110004468B (en) | 2021-03-23 |
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Denomination of invention: A composite additive for preparing low brittleness electrolytic copper foil Effective date of registration: 20211018 Granted publication date: 20210323 Pledgee: Shandong Shengmu Tourism Development Co.,Ltd. Pledgor: SHANDONG JINSHENGYUAN ELECTRONIC MATERIAL Co.,Ltd. Registration number: Y2021980010790 |
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