CN110034302A - A kind of ultra-thin utter misery collector and preparation method thereof - Google Patents
A kind of ultra-thin utter misery collector and preparation method thereof Download PDFInfo
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- CN110034302A CN110034302A CN201910244969.6A CN201910244969A CN110034302A CN 110034302 A CN110034302 A CN 110034302A CN 201910244969 A CN201910244969 A CN 201910244969A CN 110034302 A CN110034302 A CN 110034302A
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- collector
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- thin
- negatively charged
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of ultra-thin utter misery collectors and preparation method thereof, comprising the following steps: carries out positively charged processing after cleaning collector again, obtains the positively charged collector in surface；After binder is dissolved, anionic surfactant and conductive agent are sequentially added, stirs evenly to form negatively charged waterborne conductive slurry；By the negatively charged waterborne conductive slurry ultrasonic atomizatio at aerosol after, then electrostatic precipitation is dried on the positively charged collector, obtain ultra-thin utter misery collector.By the collector of this method preparation, its conductive coating is thin and uniform, and adhesion strength is strong, has good conductive property.
Description
Technical field
The invention belongs to field of lithium ion battery material, and in particular to a kind of ultra-thin utter misery collector and preparation method thereof.
Background technique
Petroleum resources are increasingly in short supply at present, and environmental pollution is serious, in order to solve problem above, Development of EV and mixing
Power vehicle is one of main method.However for a long time, the restriction that the development of electric car is developed by power battery technology.
Although being commercialized power lithium-ion battery with many excellent performances, as power battery is in electric powered motor system
Extensive utilization in system, gradually exposes that a series of such as charging time are long, the side such as durability, reliability and safety difference of battery
The problem of face.To solve the above-mentioned problems, R&D worker does a lot of work, including coating conductive layer on a current collector
To reduce the research of internal resistance.
In traditional electrodes of lithium-ion batteries manufacture craft, active material slurry is directly coated at collection liquid surface, does
Realize that active material is fixed on collection liquid surface by binder after dry.However the design of such structure there are metal collector with
Contact area between active material particle is limited, and interface resistance is larger, causes the rising of the internal resistance of cell, special for battery performance
It is the performance presence negative effect under the conditions of high current charge-discharge, the adhesion strength of binder is limited, in lasting charge and discharge
Cheng Zhong, it is easy to expanding to disengage between active material and collector occurs, the internal resistance of cell is caused further to increase, so that battery
Cycle life and security performance are affected.Therefore, the interface resistance between collector and active material is reduced, is improved between the two
Adhesion strength is to promote the important means of performance of lithium ion battery.The main method solved the problems, such as at present has to increase to be bonded in slurry
Agent dosage, collection liquid surface chemical attack, corona apply the methods of coating containing conductive material in collection liquid surface to increase
Add the adhesion strength of collector and active material.In the above-mentioned methods, consumption of binder increase will increase the internal resistance of cell, reduce energy
Density；Chemical treatment and sided corona treatment can generate damage to collection liquid surface, reduce foil intensity, influence further battery processability
Can, and high production cost；And in the coating of collection liquid surface coating conductive material, which has good conductive property, compared with
High specific surface area, excellent adhesive property, and there is better deformability relative to metal collector, active material can be increased
The conductive contact of material and collector reduces interface internal resistance, and improves adhesion strength between the two.
But electrocondution slurry is mainly adhered to afflux by way of being coated with and infiltrating by collector conductive coating at this stage
On body.The storage material slot of intaglio plate coating will keep the state overflowed, and the slurry that recessed roller only comes with spilling contacts, so can not be by storage material
All slurry liquids in slot cmpletely utilize, and can not recycle, therefore cause certain waste；The painting of comma roller coating
Cloth quality and the operational relationship of its each composition unit are larger, specifically for the transmission ratio ratio between driving motor and rotation pressure roller
It is relatively difficult to adjust control, often results in and be unevenly coated, when coating, slurry liquid is easy the gap between baffle and transmission pressure roller
Outflow, leakproofness is sufficiently complete, and when coating, manpower is needed constantly to stir storage material slot；The part of slit type extrusion coated head
Structure is complex, it is desirable that the machining accuracy of traction roller and crack cutter head is higher, and equipment cost is higher.Above-mentioned coating method obtains
The collector painting layer of charcoal arrived is uneven and thickness is bigger than normal.Pattern of invasion, which is divided into, to be directly put into electrocondution slurry infiltration for collector and incites somebody to action
Collector pretreatment is positively charged, electrocondution slurry pre-process it is negatively charged after the two ways that infiltrates again, no matter which kind of infiltration side
Formula when taking out collector after infiltration, can all cause curtain coating phenomenon, so that it is uneven to cause utter misery thickness, and pattern of invasion obtains
The painting carbon layer arrived is partially thick.
Summary of the invention
Based on this, the present invention provides a kind of ultra-thin utter misery collectors and preparation method thereof, by collector and electrocondution slurry
Respectively by processing, keep collector positively charged, electrocondution slurry is negatively charged, and it is molten that electrocondution slurry is atomized into negatively charged gas
Glue, negatively charged aerosol granularity is tiny and uniform, then utilizes the positive and negative charge principle that there is a natural attraction between the sexes, negatively charged gas
Colloidal sol selects the absorption of positively charged afflux surface layer to neutralize charge, and after the completion of neutralization, aerosol no longer toward adsorbing on collector, is obtained
To the presoma for applying layer of charcoal.The presoma low temperature drying getting the product of layer of charcoal will be applied.Collector obtained by this method
It is thin and uniform to apply layer of charcoal, solves many deficiencies in the prior art.
To achieve the goals above, the invention adopts the following technical scheme:
A kind of preparation method of utter misery collector, comprising the following steps:
A, positively charged processing is carried out after cleaning collector again, obtains the positively charged collector in surface；
B, after dissolving binder, anionic surfactant and conductive agent are sequentially added, stir evenly to be formed it is negatively charged
Waterborne conductive slurry；
C, after by the negatively charged waterborne conductive slurry ultrasonic atomizatio at aerosol, electrostatic precipitation is described positively charged
On collector, drying obtains utter misery collector.Negatively charged waterborne conductive slurry ultrasonic atomizatio i.e. will be negatively charged at aerosol
Solia particle and liquid particle are suspended in air and form negatively charged smog and mist in the waterborne conductive slurry of lotus, drift power
Around positively charged collector obtained in step a, during negatively charged aerosol is adsorbed on positively charged collector
And charge, after the completion of charging neutrality, aerosol obtains the ultra-thin presoma for applying layer of charcoal no longer toward adsorbing on collector.
Further, in step a, the cleaning successively includes oil removing and washing.
Further, the specific steps of the oil removing are as follows: collector is put into the degreasing fluid that temperature is 70 ~ 80 DEG C and is impregnated
It is taken out after 3 ~ 5min.
Preferably, the degreasing fluid is 10 ~ 20g/L sodium carbonate, 10 ~ 20g/L sodium phosphate, 5 ~ 10g/L sodium metasilicate and 2 ~ 3g/
The mixed aqueous solution of L OP emulsifier.
Further, in step a, the specific steps of the positively charged processing are as follows: the collector after cleaning is placed in content
To impregnate 10 ~ 15min in 2 ~ 4g/L quaternary ammonium salt surface active agent liquid.
Preferably, the quaternary ammonium salt surface active agent is alkyl quaternary ammonium salts or amine salt type.
Further, in step b, the content of each component in the negatively charged waterborne conductive slurry are as follows: the bonding
Agent 1 ~ 2g/L, the 20 ~ 40g/L of conductive agent, the anionic surfactant and the negatively charged waterborne conductive slurry
Volume ratio be (1 ~ 2): 1000.
In step b, the binder includes one of sodium carboxymethylcellulose, Kynoar or polytetrafluoroethylene (PTFE)；
The anionic surfactant includes sodium alkyl sulfonate, sodium alklyarylsulfonate, sodium alkyl sulfate or secondary alkyl sulfuric acid
The mixing of one or both of sodium；
The conductive agent is to disperse sufficient carbon material in an aqueous solvent, and the partial size of the carbon material is 10 ~ 50nm comprising
The mixing of one or more of carbon black, graphite, carbon nanotube, graphene.
Preferably, in step c, the temperature of the drying is 60 ~ 80 DEG C, and the time is 6 ~ 8h.
It is another object of the present invention to provide a kind of utter misery collector, the collector uses above-mentioned preparation method system
At.
Compared with prior art, the invention has the following advantages:
By collector and electrocondution slurry respectively by processing, keep collector positively charged, electrocondution slurry is negatively charged, then conductive
For slurry atomization at negatively charged aerosol, aerosol granularity is tiny and uniform, using the positive and negative charge principle that there is a natural attraction between the sexes, makes
Aerosol is attached to the surface layer of collector, neutralizes charge, after the completion of charging neutrality, aerosol is no longer adsorbed.It is this by conductive paste
Material is atomized into the heavy carbon technique of electrostatic of the selectivity after aerosol, carbon material is equably deposited on collector, the painting of generation
Layer of charcoal is thin and uniform, the thickness for applying layer of charcoal is made in the present invention no more than 100nm, and binding force is strong, has good electric conductivity
Energy.
Detailed description of the invention
Fig. 1 is the section SEM that the collector that the embodiment of the present invention 1 obtains applies layer of charcoal；
Fig. 2 is the surface SEM that the collector that the embodiment of the present invention 1 obtains applies layer of charcoal.
Specific embodiment
To facilitate the understanding of the present invention, below in conjunction with specific embodiments to invention is more fully described.But
It is that the invention can be realized in many different forms, however it is not limited to embodiments described herein.On the contrary, providing
The purpose of these embodiments is to make to make the present disclosure more fully understandable.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
Embodiment 1
A, by collector be 75 DEG C in temperature degreasing fluid (composition proportion is sodium carbonate 15g/L, sodium phosphate 15g/L, sodium metasilicate
The mixed aqueous solution of 7g/L and OP emulsifier 3g/L) impregnate 5min after, take out washing after, then immerse content be 4g/L hexadecane
15min is impregnated in base trimethyl ammonium chloride, obtains the positively charged collector in surface；
B, after dissolving sodium carboxymethylcellulose, nonylphenol polyoxyethylene ether and partial size are sequentially added as the carbon black of 10 ~ 50nm
With the mixture of graphite, after high-speed stirred, formation is uniformly dispersed and negatively charged waterborne conductive slurry.In electrocondution slurry,
Carboxymethylcellulosodium sodium content is 1g/L, and the content of the mixture of carbon black and graphite is 30g/L, sodium alkyl sulfonate and electrocondution slurry
Volume ratio be 1:1000；
C, by waterborne conductive slurry ultrasonic atomizatio negatively charged obtained in step b at aerosol, it is being distributed in step a band just
Around the collector of charge, since there is a natural attraction between the sexes for positive and negative charge, electrocondution slurry is uniformly deposited on the surface of collector, and formation is led
Electrocoat is finally dried again, obtains ultra-thin utter misery collector.The SEM of products obtained therefrom characterization can be seen that obtained collection
It is thin and uniform that fluid applies layer of charcoal.
Collector obtained in embodiment 1 is applied into layer of charcoal and carries out SEM characterization, Fig. 1 is the section that collector applies layer of charcoal
SEM, Fig. 2 are the surface SEM that collector applies layer of charcoal.According to Fig. 1 as can be seen that painting carbon layer obtained is very in the present invention
It is thin, within 100nm；And it can be seen that the highly uniform table for being attached to collector of the painting layer of charcoal in the present invention according to fig. 2
Face, therefore, the painting layer of charcoal in the present invention are ultra-thin and uniform, so that its electrical property is very excellent.
Embodiment 2
A, by collector be 70 DEG C in temperature degreasing fluid (composition proportion is sodium carbonate 10g/L, sodium phosphate 20g/L, sodium metasilicate
The mixed aqueous solution of 5g/L and OP emulsifier 2g/L) impregnate 5min after, take out washing after, then immerse content be 2g/L hexadecane
15min is impregnated in base trimethyl ammonium chloride, obtains the positively charged collector in surface；
B, after dissolving Kynoar, sodium alkyl sulfate and partial size are sequentially added as the graphene of 10 ~ 50nm, high-speed stirred
Afterwards, it is formed and is uniformly dispersed and negatively charged waterborne conductive slurry.In electrocondution slurry, Kynoar content is 2g/L, stone
The content of black alkene is 20g/L, and the volume ratio of sodium alkyl sulfate and electrocondution slurry is 2:1000；
C, by waterborne conductive slurry ultrasonic atomizatio negatively charged obtained in step b at aerosol, it is being distributed in step a band just
Around the collector of charge, since there is a natural attraction between the sexes for positive and negative charge, electrocondution slurry is uniformly deposited on the surface of collector, and formation is led
Electrocoat is finally dried again, obtains ultra-thin utter misery collector.
Embodiment 3
A, by collector be 80 DEG C in temperature degreasing fluid (composition proportion is sodium carbonate 20g/L, sodium phosphate 10g/L, sodium metasilicate
The mixed aqueous solution of 10g/L and OP emulsifier 2g/L) impregnate 3min after, take out washing after, then immerse content be 3g/L 16
10min is impregnated in alkyl trimethyl ammonium chloride, obtains the positively charged collector in surface；
B, after dissolving polytetrafluoroethylene (PTFE), the carbon nanotube that sodium alklyarylsulfonate and partial size are 10 ~ 50nm is sequentially added, it is high
After speed stirring, formation is uniformly dispersed and negatively charged waterborne conductive slurry.In electrocondution slurry, polytetrafluoroethylene content is
1g/L, the content of carbon nanotube are 40g/L, and the volume ratio of sodium alklyarylsulfonate and electrocondution slurry is 1:1000；
C, by waterborne conductive slurry ultrasonic atomizatio negatively charged obtained in step b at aerosol, it is being distributed in step a band just
Around the collector of charge, since there is a natural attraction between the sexes for positive and negative charge, electrocondution slurry is uniformly deposited on the surface of collector, and formation is led
Electrocoat is finally dried again, obtains ultra-thin utter misery collector.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of ultra-thin utter misery collector, which comprises the following steps:
A, positively charged processing is carried out after cleaning collector, obtains the positively charged collector in surface；
B, after dissolving binder, anionic surfactant and conductive agent are sequentially added, stir evenly to be formed it is negatively charged
Waterborne conductive slurry；
C, after by the negatively charged waterborne conductive slurry ultrasonic atomizatio at aerosol, electrostatic precipitation is described positively charged
Utter misery collector is obtained on collector, after drying.
2. preparation method as described in claim 1, which is characterized in that in step a, the cleaning successively includes oil removing and water
It washes.
3. preparation method as claimed in claim 2, which is characterized in that the specific steps of the oil removing are as follows: be put into collector
It is taken out after impregnating 3 ~ 5min in the degreasing fluid that temperature is 70 ~ 80 DEG C.
4. preparation method as claimed in claim 3, which is characterized in that the degreasing fluid is 10 ~ 20g/L sodium carbonate, 10 ~ 20g/
The mixed aqueous solution of L sodium phosphate, 5 ~ 10g/L sodium metasilicate and 2 ~ 3g/L OP emulsifier.
5. preparation method as described in claim 1, which is characterized in that in step a, the specific steps of the positively charged processing
Are as follows: it is that 10 ~ 15min is impregnated in 2 ~ 4g/L quaternary ammonium salt surface active agent liquid that the collector after cleaning, which is placed in content,.
6. preparation method as claimed in claim 5, which is characterized in that the quaternary ammonium salt surface active agent is alkyl quaternary ammonium salts
Or amine salt type.
7. preparation method as described in claim 1, which is characterized in that in step b, the negatively charged waterborne conductive slurry
The content of middle each component are as follows: the 1 ~ 2g/L of binder, the 20 ~ 40g/L of conductive agent, the anionic surfactant and institute
The volume ratio for stating negatively charged waterborne conductive slurry is (1 ~ 2): 1000.
8. preparation method as described in claim 1, which is characterized in that in step b, the binder includes carboxymethyl cellulose
One of sodium, Kynoar or polytetrafluoroethylene (PTFE)；
The anionic surfactant includes sodium alkyl sulfonate, sodium alklyarylsulfonate, sodium alkyl sulfate or secondary alkyl sulfuric acid
The mixing of one or both of sodium；
The conductive agent is to disperse sufficient carbon material in an aqueous solvent, and the partial size of the carbon material is 10 ~ 50nm comprising
The mixing of one or more of carbon black, graphite, carbon nanotube, graphene.
9. preparation method as described in claim 1, which is characterized in that in step c, the temperature of the drying is 60 ~ 80 DEG C, when
Between be 6 ~ 8h.
10. a kind of ultra-thin utter misery collector, which is characterized in that be made using the described in any item preparation methods of claim 1 ~ 9.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707328A (en) * | 2019-10-31 | 2020-01-17 | 江苏万源新材料股份有限公司 | Preparation method of graphene-coated aluminum foil |
| CN111430661A (en) * | 2020-04-09 | 2020-07-17 | 烟台鑫盛源新材料有限公司 | Conductive slurry for lithium ion battery aluminum foil electrode, aluminum foil and preparation method |
| CN112820879A (en) * | 2020-12-31 | 2021-05-18 | 佛山市中技烯米新材料有限公司 | Battery current collector and preparation method thereof |
| CN113625374A (en) * | 2021-07-12 | 2021-11-09 | 安徽菲尔慕材料有限公司 | Manufacturing process of polyimide hardened film of flexible high-hardness high-folding screen |
| CN113717595A (en) * | 2021-07-14 | 2021-11-30 | 安徽南都华拓新能源科技有限公司 | Carbon-coated current collector coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113625374A (en) * | 2021-07-12 | 2021-11-09 | 安徽菲尔慕材料有限公司 | Manufacturing process of polyimide hardened film of flexible high-hardness high-folding screen |
| CN113717595A (en) * | 2021-07-14 | 2021-11-30 | 安徽南都华拓新能源科技有限公司 | Carbon-coated current collector coating and preparation method thereof |
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