CN109750329A - A kind of production method of ventilative cellular electrolytic copper foil - Google Patents
A kind of production method of ventilative cellular electrolytic copper foil Download PDFInfo
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- CN109750329A CN109750329A CN201810885621.0A CN201810885621A CN109750329A CN 109750329 A CN109750329 A CN 109750329A CN 201810885621 A CN201810885621 A CN 201810885621A CN 109750329 A CN109750329 A CN 109750329A
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- copper foil
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Abstract
The invention discloses a kind of production methods of ventilative cellular electrolytic copper foil, it is characterised in that the following steps are included: carrying out reduction to copper ion using titanium roller to obtain copper atom；Iridium is applied as electrolytic anode plate using titanium；Electrolyte uses 99.9% tough cathode, carries out aerobic reaction with analytical pure sulfuric acid and pure copper-bath is made, solution is diluted using RO film plasma water；In electrolyte copper content be 80g/L, sulfuric acid content 120g/L；Current density 34A/dm2；Electrolyte is heated to 55 degree；Sprinkling is carried out to titanium cylinder using low pressure micro-atomizing nozzle and dissolves edible gelatine liquid；Gelatin liquid is atomized on titanium roller, gelatin on baking titanium roller is carried out with quartz burner and solidifies；Solidification gelatin rotates into electrolyte with titanium roller.The ventilative cellular electrolytic copper foil electrolytic copper foil of one kind is produced by the present invention, ventilative cellular electrolytic copper foil institutional framework presentation is latticed, is evenly distributed, the thickness uniformity deviation is less than 0.11um, tensile strength 30kg/mm2, air permeability 30%.
Description
Technical field
The invention belongs to electrolytic copper foil production technical field more particularly to a kind of producers of ventilative cellular electrolytic copper foil
Method.
Background technique
Currently, China's new energy pure electric automobile passes through the research and development of more than ten years, have been achieved for a series of prominent
It is broken, also start gradually to launch into market, but still there is a problem of many.Wherein, the cruising ability and dynamic property of electric car
It can be the focus of this problem.And electrokinetic cell system is the key technical problem for restricting cruising ability and power performance.
Lithium ion battery is most active and fastest-rising battery product in current Battery Market, is come from development trend
It sees, the significant challenge that battery manufacturers face is always constant demand of the consumer to bigger energy density, either volume
Energy density or gravimetric energy density.
With the continuous promotion of energy density, also to copper foil, more stringent requirements are proposed for power battery manufacturer, extra thin copper foil
(≤6 μm), the copper foil of high-tensile, micropore copper foil, coating copper foil etc. emerge one after another.Although lithium electrolytic copper foil is well sold and in short supply, to copper
For foil enterprise, it could constantly show one's talent in continuous turn of the market immediately following the newest demand in market,.
Summary of the invention
The purpose of the present invention is to provide a kind of production methods of ventilative cellular electrolytic copper foil, to solve above-mentioned background skill
The problem of being proposed in art.
To achieve the above object, the invention provides the following technical scheme: a kind of producer of ventilative cellular electrolytic copper foil
Method, it is characterised in that the following steps are included:
Step (1): reduction is carried out to copper ion to obtain copper atom using titanium roller；
Step (2): iridium is applied as electrolytic anode plate using titanium；
Step (3): electrolyte uses 99.9% tough cathode, carries out aerobic reaction with analytical pure sulfuric acid and pure copper-bath is made,
Solution is diluted using RO film plasma water；
Step (4): in electrolyte copper content be 80g/L, sulfuric acid content 120g/L；Current density 34A/dm2；By electrolyte plus
Heat is to 55 degree；
Step (5): sprinkling is carried out to titanium cylinder using low pressure micro-atomizing nozzle and dissolves edible gelatine liquid；
Step (6): atomization gelatin liquid carries out gelatin on baking titanium roller with quartz burner and solidifies on titanium roller；
Step (7): solidification gelatin rotates into electrolyte with titanium roller；
Step (8): when titanium roller rotates, since gelatin solidification hinders copper ion to be precipitated on titanium roller；
Step (9): it since titanium roller restores copper ion in the electrolytic solution, is added in mixing such as additives polyethylene glycol, SP, chloride ions
Under agent effect, electrolytic copper foil is deposited in the case where not there is solidification gelatin, due to electrolyte constant temperature 50-60 degree, solidifies gelatin when rotated
Slowly it is dissolved in electrolyte；
Step (10): undissolved solidification gelatin is washed away by high-pressure spraying copper-bath, to guarantee that residual part is distinguished
It washes off；
Step (11): the ventilative copper foil of honeycomb fashion is carried out through chemical passivation, prevents cellular ventilative copper foil oxidation.
Preferably, described use in step (2) carries out spraying titanium painting iridium in anode plate 1mm titanium plate, applies iridium layer.
Preferably, described 300 grams of edible gelatine impregnate 24 hours in 1000ml pure water in step (5), and are stirred with machinery
It mixes uniformly, fineness D90=10um.
Preferably, the nozzle in step (5) uses low pressure micro-atomizing nozzle threads 1/4, pressure 3kg/cm3, angle
75 degree of degree.
Preferably, described to add 30 grams of sp, 15 grams of polyethylene glycol 5ml hydrochloric acid solutions in 1000ml in step (9).
Preferably, the copper content 80g/L, sulfuric acid 130g/L, current density 34A/ in electrolyte in step (9)
dm2。
Preferably, the flooding nozzle in step (10) use pvc spray head, pressure 3kg/cm3,75 degree of angle.
Preferably, the passivation in step (11) is using environmentally friendly Non-water washing passivation technology: glucose sugar 50g/L, phenylpropyl alcohol three
Nitrogen azoles 0.1g/L.
Compared with prior art, the beneficial effects of the present invention are: producing a kind of ventilative cellular electrolytic copper foil by the present invention
Electrolytic copper foil breathes freely honeycomb fashion electrolytic copper foil while mitigating lithium ion battery weight, the electricity of lithium ion battery is substantially improved
Tankage has great impetus to the promotion of power battery industry technology.Cellular electrolytic copper foil has up to 30% hole
Rate can reduce the invalid quality of battery using metal mesh foil, and then promote electricity under the premise of not changing electrochemical material system
The energy density in pond.In addition, ventilative honeycomb fashion electrolytic copper foil can effectively increase electrolyte three-dimensional space penetrating power with
And contact of the electrode material with collector, and then promote the high rate performance of battery and reduce electrode material obscission.This is ventilative
Cellular electrolytic copper foil consistent, impulse- free robustness and breathable copper foil with the thickness uniformity, the ventilative cellular electrolytic copper foil
Institutional framework presentation is latticed, is evenly distributed, and the thickness uniformity deviation is less than 0.11um, tensile strength 30kg/mm2, air permeability
30%。
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution in the embodiment of the present invention is clearly and completely retouched
It states, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the present invention
In embodiment, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
Embodiment 1
The present invention provides a kind of technical solution: a kind of production method of ventilative cellular electrolytic copper foil, it is characterised in that including with
Lower step: electrolyte preparation is exactly that pot for smelted copper is added using 99.9% tough cathode, analytical pure sulfuric acid and RO reverse osmosis deionized water
In, in the case where temperature is 55 degree of constant temperature, in electrolyte copper content be 70g/L, sulfuric acid content 110g/L；Current density
35A/dm2；Sprinkling is carried out to titanium cylinder using low pressure micro-atomizing nozzle and dissolves edible gelatine liquid, is atomized gelatin liquid in titanium roller
On, gelatin on baking titanium roller, which is carried out, with quartz burner solidifies；Solidification gelatin rotates into electrolyte with titanium roller；The rotation of titanium roller
When turning, since gelatin solidification hinders copper ion to be precipitated on titanium roller；Since titanium roller restores copper ion in the electrolytic solution, adding
Under the effect of the additive packages such as 40 grams of sp of agent, 10 grams of polyethylene glycol 7ml hydrochloric acid solutions, electrolytic copper foil is not in the case where there is solidification gelatin
Deposition solidifies gelatin and is slowly dissolved in electrolyte when rotated due to electrolyte constant temperature 50-60 degree；Undissolved solidification is bright
Glue is washed away by high-pressure spraying copper-bath, to guarantee that residual fraction washes；The ventilative copper foil of honeycomb fashion is blunt through chemistry
Change and carry out, prevents cellular ventilative copper foil oxidation.
Embodiment 2
The present invention provides a kind of technical solution: a kind of production method of ventilative cellular electrolytic copper foil, it is characterised in that including with
Lower step: electrolyte preparation is exactly that pot for smelted copper is added using 99.9% tough cathode, analytical pure sulfuric acid and RO reverse osmosis deionized water
In, in the case where temperature is 55 degree of constant temperature, in electrolyte copper content be 60g/L, sulfuric acid content 130g/L；Current density
32A/dm2；Sprinkling is carried out to titanium cylinder using low pressure micro-atomizing nozzle and dissolves edible gelatine liquid, is atomized gelatin liquid in titanium roller
On, gelatin on baking titanium roller, which is carried out, with quartz burner solidifies；Solidification gelatin rotates into electrolyte with titanium roller；The rotation of titanium roller
When turning, since gelatin solidification hinders copper ion to be precipitated on titanium roller；Since titanium roller restores copper ion in the electrolytic solution, adding
Under the effect of the additive packages such as 20 grams of sp of agent, 20 grams of polyethylene glycol 4ml hydrochloric acid solutions, electrolytic copper foil is not in the case where there is solidification gelatin
Deposition solidifies gelatin and is slowly dissolved in electrolyte when rotated due to electrolyte constant temperature 50-60 degree；Undissolved solidification is bright
Glue is washed away by high-pressure spraying copper-bath, to guarantee that residual fraction washes；The ventilative copper foil of honeycomb fashion is blunt through chemistry
Change and carry out, prevents cellular ventilative copper foil oxidation.
Embodiment 3
The present invention provides a kind of technical solution: a kind of production method of ventilative cellular electrolytic copper foil, it is characterised in that including with
Lower step: electrolyte preparation is exactly that pot for smelted copper is added using 99.9% tough cathode, analytical pure sulfuric acid and RO reverse osmosis deionized water
In, in the case where temperature is 55 degree of constant temperature, in electrolyte copper content be 70g/L, sulfuric acid content 100g/L；Current density
34A/dm2；Sprinkling is carried out to titanium cylinder using low pressure micro-atomizing nozzle and dissolves edible gelatine liquid, is atomized gelatin liquid in titanium roller
On, gelatin on baking titanium roller, which is carried out, with quartz burner solidifies；Solidification gelatin rotates into electrolyte with titanium roller；The rotation of titanium roller
When turning, since gelatin solidification hinders copper ion to be precipitated on titanium roller；Since titanium roller restores copper ion in the electrolytic solution, adding
Under the effect of the additive packages such as 25 grams of sp of agent, 20 grams of polyethylene glycol 10ml hydrochloric acid solutions, electrolytic copper foil is not in the case where there is solidification gelatin
Deposition solidifies gelatin and is slowly dissolved in electrolyte when rotated due to electrolyte constant temperature 50-60 degree；Undissolved solidification is bright
Glue is washed away by high-pressure spraying copper-bath, to guarantee that residual fraction washes；The ventilative copper foil of honeycomb fashion is blunt through chemistry
Change and carry out, prevents cellular ventilative copper foil oxidation.
Embodiment 4
The present invention provides a kind of technical solution: a kind of production method of ventilative cellular electrolytic copper foil, it is characterised in that including with
Lower step: electrolyte preparation is exactly that pot for smelted copper is added using 99.9% tough cathode, analytical pure sulfuric acid and RO reverse osmosis deionized water
In, in the case where temperature is 55 degree of constant temperature, in electrolyte copper content be 80g/L, sulfuric acid content 120g/L；Current density
34A/dm2；Sprinkling is carried out to titanium cylinder using low pressure micro-atomizing nozzle and dissolves edible gelatine liquid, is atomized gelatin liquid in titanium roller
On, gelatin on baking titanium roller, which is carried out, with quartz burner solidifies；Solidification gelatin rotates into electrolyte with titanium roller；The rotation of titanium roller
When turning, since gelatin solidification hinders copper ion to be precipitated on titanium roller.；Since titanium roller restores copper ion in the electrolytic solution, adding
Under adding the additive packages such as 30 grams of sp of agent, 15 grams of polyethylene glycol 5ml hydrochloric acid solutions to act on, electrolytic copper foil is not having solidification gelatin
Lower deposition solidifies gelatin and is slowly dissolved in electrolyte when rotated due to electrolyte constant temperature 50-60 degree；Undissolved solidification
Gelatin is washed away by high-pressure spraying copper-bath, to guarantee that residual fraction washes；The ventilative copper foil of honeycomb fashion is through chemistry
Passivation carries out, and prevents cellular ventilative copper foil oxidation.
It producing in practice, discovery carries out sprinkling dissolution to titanium cylinder using low pressure micro-atomizing nozzle and eats gelatine liquid,
Solid content, which sprays particle to atomization, certain influence, and atomization colloid, which is sticked, does not occur trickling phenomenon in titanium roller.Following data.Such as table 1.
Table 1, which is atomized colloid solid content, influences fluid
| Solid content | Colloidal state mobility | Solid content | Colloidal state mobility |
| 10 | It is thin | 60 | It is excellent |
| 20 | It is thin | 70 | Difference |
| 30 | It is dilute | 80 | Difference |
| 40 | It is good | 90 | It is poor |
| 50 | It is excellent | 100 | It is poor |
It is found by table 1, colloid solid content is to the excellent certain effect of mobility, and in product link, suitable solid content can be reduced
Colloid sticks on titanium roller, and phenomenon of trickling does not occur.
It producing in practice, discovery carries out sprinkling dissolution to titanium cylinder using low pressure micro-atomizing nozzle and eats gelatine liquid,
Colloidal particle size, which sprays particle to atomization, certain influence, and atomization colloid, which is sticked, adhesion phenomenon does not occur in titanium roller.Following data.Such as table
2。
2 colloidal particle size of table influences titanium roller
| Granularity (um) | Titanium roller fogging degree | Granularity (um) | Titanium roller fogging degree |
| 100 | Particle adhesion is serious | 40 | Particle adhesion is few |
| 90 | Particle adhesion is serious | 30 | Particle adhesion is few |
| 80 | Particle adhesion is poor | 20 | Without particle adhesion |
| 70 | Particle adhesion is poor | 10 | Without particle adhesion |
| 60 | Particle adhesion is poor | 5 | Without particle adhesion |
| 50 | Particle adhesion is poor |
It is found by table 2, colloidal particle size is to the excellent certain effect of mobility, and in product link, suitable granularity can reduce colloid
It sticks on titanium roller, do not stick together phenomenon.
It producing in practice, discovery carries out sprinkling dissolution to titanium cylinder using low pressure micro-atomizing nozzle and eats gelatine liquid,
There are certain influence in ultraviolet curing temperature, time on titanium roller, and atomization colloid, which is sticked, adhesion phenomenon does not occur in titanium roller.Following data.
Such as table 3.
Three solidification temperature of table, time influence titanium roller
| Solidification temperature | Curing time | Colloidal titanium roller surface layer situation | Remain colloid situation | Titanium roller situation after rinse spray |
| 50 | 15 | Hardness is excessively soft | Nothing | Completely |
| 60 | 15 | Hardness is suitable | Slightly | Completely |
| 70 | 15 | Hardness is really up to the mark | Largely | Residual |
| 80 | 15 | Colloid paste falls | Largely | Residual |
| 60 | 10 | Hardness is excessively soft | Nothing | Completely |
| 60 | 15 | Hardness is suitable | Slightly | Completely |
| 60 | 20 | Colloid is really up to the mark | Largely | Residual |
It is found by table 3, curing time, temperature solidify certain effect to colloid, and in product link, the suitable colloid that solidifies can be with
Effective colloid sticks on titanium roller, while colloid can be effectively prevent to solidify in the generation for not dissolving phenomenon on titanium roller.
The above implementation light transmittance measurement is measured by following technological means, the DR81 light transmittance produced using domestic producer
Instrument carries out online record data and is obtained.
The optimum state that the present invention is implemented exactly is handled titanium cylinder using gelatin gels solidification, and 30 grams of sp of use,
In 15 grams of polyethylene glycol and 5ml hydrochloric acid solution mixing addition electrolyte, wherein copper 80g/L in electrolyte, sour 120g/L, electric current are close
34A/dm2 is spent, performance can be produced and stablized, gas permeability is outstanding, and cellular ventilative electrolytic copper foil in homogeneous thickness especially solves
Tension is low in practice, air permeability is low contradiction.
Beneficial effects of the present invention: a kind of ventilative cellular electrolytic copper foil electrolytic copper foil, the ventilative bee are produced by the present invention
The presentation of socket electrolytic copper foil institutional framework is latticed, is evenly distributed, and the thickness uniformity deviation is less than 0.11um, tensile strength
30kg/mm2, air permeability 30%.
It should be noted that, in this document, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those
Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or equipment
Intrinsic element.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (8)
1. a kind of production method of ventilative cellular electrolytic copper foil, it is characterised in that the following steps are included:
Step (1): reduction is carried out to copper ion to obtain copper atom using titanium roller；
Step (2): iridium is applied as electrolytic anode plate using titanium；
Step (3): electrolyte uses 99.9% tough cathode, carries out aerobic reaction with analytical pure sulfuric acid and pure copper-bath is made,
Solution is diluted using RO film plasma water；
Step (4): in electrolyte copper content be 80g/L, sulfuric acid content 120g/L；Current density 34A/dm2；By electrolyte plus
Heat is to 55 degree；
Step (5): sprinkling is carried out to titanium cylinder using low pressure micro-atomizing nozzle and dissolves edible gelatine liquid；
Step (6): atomization gelatin liquid carries out gelatin on baking titanium roller with quartz burner and solidifies on titanium roller；
Step (7): solidification gelatin rotates into electrolyte with titanium roller；
Step (8): when titanium roller rotates, since gelatin solidification hinders copper ion to be precipitated on titanium roller；
Step (9): it since titanium roller restores copper ion in the electrolytic solution, is added in mixing such as additives polyethylene glycol, SP, chloride ions
Under agent effect, electrolytic copper foil is deposited in the case where not there is solidification gelatin, due to electrolyte constant temperature 50-60 degree, solidifies gelatin when rotated
Slowly it is dissolved in electrolyte；
Step (10): undissolved solidification gelatin is washed away by high-pressure spraying copper-bath, to guarantee that residual part is distinguished
It washes off；
Step (11): the ventilative copper foil of honeycomb fashion is carried out through chemical passivation, prevents cellular ventilative copper foil oxidation.
2. a kind of production method of ventilative cellular electrolytic copper foil according to claim 1, it is characterised in that: described in step
Suddenly iridium layer is applied using spraying titanium painting iridium is carried out in anode plate 1mm titanium plate in (2).
3. a kind of production method of ventilative cellular electrolytic copper foil according to claim 1, it is characterised in that: described in step
Suddenly 300 grams of edible gelatine impregnate 24 hours in 1000ml pure water in (5), and, fineness D90=10um uniform with mechanical stirring.
4. a kind of production method of ventilative cellular electrolytic copper foil according to claim 1, it is characterised in that: described in step
Suddenly in (5) nozzle use low pressure micro-atomizing nozzle threads 1/4, pressure 3kg/cm3,75 degree of angle.
5. a kind of production method of ventilative cellular electrolytic copper foil according to claim 1, it is characterised in that: described in step
Suddenly 30 grams of sp, 15 grams of polyethylene glycol 5ml hydrochloric acid solutions are added in (9) in 1000ml.
6. a kind of production method of ventilative cellular electrolytic copper foil according to claim 1, it is characterised in that: described in step
Suddenly copper content 80g/L, sulfuric acid 130g/L, current density 34A/dm2 in electrolyte in (9).
7. a kind of production method of ventilative cellular electrolytic copper foil according to claim 1, it is characterised in that: described in step
Suddenly in (10) flooding nozzle use pvc spray head, pressure 3kg/cm3,75 degree of angle.
8. a kind of production method of ventilative cellular electrolytic copper foil according to claim 1, it is characterised in that: described in step
Suddenly passivation uses environmentally friendly Non-water washing passivation technology: glucose sugar 50g/L, phenylpropyl triazole 0.1g/L in (11).
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| CN201810885621.0A CN109750329A (en) | 2018-08-06 | 2018-08-06 | A kind of production method of ventilative cellular electrolytic copper foil |
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| CN201810885621.0A CN109750329A (en) | 2018-08-06 | 2018-08-06 | A kind of production method of ventilative cellular electrolytic copper foil |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006152420A (en) * | 2004-12-01 | 2006-06-15 | Mitsui Mining & Smelting Co Ltd | Electrolytic copper foil and method for producing the same |
| CN103526237A (en) * | 2013-09-25 | 2014-01-22 | 山东金盛源铜业有限公司 | Production method of electrolytic copper foil applied to high-end super capacitor |
| CN104903495A (en) * | 2013-01-24 | 2015-09-09 | 古河电气工业株式会社 | Electrolytic copper foil and method for producing same |
| CN106987871A (en) * | 2017-03-12 | 2017-07-28 | 山东金盛源电子材料有限公司 | A kind of production method of three-dimensional porous electrolytic copper foil applied to gel polymer lithium ion battery |
-
2018
- 2018-08-06 CN CN201810885621.0A patent/CN109750329A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006152420A (en) * | 2004-12-01 | 2006-06-15 | Mitsui Mining & Smelting Co Ltd | Electrolytic copper foil and method for producing the same |
| CN104903495A (en) * | 2013-01-24 | 2015-09-09 | 古河电气工业株式会社 | Electrolytic copper foil and method for producing same |
| CN103526237A (en) * | 2013-09-25 | 2014-01-22 | 山东金盛源铜业有限公司 | Production method of electrolytic copper foil applied to high-end super capacitor |
| CN106987871A (en) * | 2017-03-12 | 2017-07-28 | 山东金盛源电子材料有限公司 | A kind of production method of three-dimensional porous electrolytic copper foil applied to gel polymer lithium ion battery |
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