CN106299380A - A kind of ultraviolet light polymerization carbon-coated aluminum foils collector and preparation method - Google Patents
A kind of ultraviolet light polymerization carbon-coated aluminum foils collector and preparation method Download PDFInfo
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- CN106299380A CN106299380A CN201610715505.5A CN201610715505A CN106299380A CN 106299380 A CN106299380 A CN 106299380A CN 201610715505 A CN201610715505 A CN 201610715505A CN 106299380 A CN106299380 A CN 106299380A
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- carbon
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- aluminum foils
- coated aluminum
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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
- 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
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
- 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
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- 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
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Abstract
The open a kind of ultraviolet light polymerization carbon-coated aluminum foils collector of the present invention, including current collector aluminum foil, the surface of current collector aluminum foil is uniformly coated with carbonaceous conductive slurry, and carbonaceous conductive slurry consists of the following components in percentage by weight: material with carbon element 5 20%, UV-cured resin 3 10%, light trigger 0.5 10%, solvent 65 90%, auxiliary agent 0.03 1%.Ultraviolet light polymerization carbon-coated aluminum foils collector of the present invention uses acrylic resin to make dispersant and firming agent, significantly reduces the consumption of organic resin, adds the contact between material with carbon element, reduce resistance.Present invention employs the light-cured acrylic resin of modification, irradiate with ultraviolet light and lower can efficiently cross-link, it is to avoid the solidification of excessive temperature makes aluminium foil gross distortion, and obtain that adhesion is good, solvent resistance by force, the combination property such as stable chemical nature.
Description
Technical field
The invention belongs to field of lithium ion battery material, specifically a kind of ultraviolet light polymerization carbon-coated aluminum foils collector and preparation
Method.
Background technology
New-energy automobile has the advantages such as zero-emission, quiet and charging cost be low, is increasingly looked at by the parent of user.Lithium from
It is high that sub-battery has energy density, has extended cycle life and voltage platform advantages of higher becomes the first-selection of new-energy automobile.Iron phosphate
The electrokinetic cell safety of lithium system is high, low price, occupies the major part market share in the most domestic electrokinetic cell.Phosphorus
Acid ferrum lithium major defect be ionic diffusion coefficient and conductivity the most relatively low, respectively 5 × 10-15cm2·S-1, 10-9S·cm-1。
Currently mainly by reducing the method such as material particle size and carbon cladding both performances of improvement.In lithium ion battery, interface resistance is also
It it is the key factor affecting the internal resistance of cell.Positive electrode active materials and aluminum foil current collector contact point have bigger resistance, at battery
Polarization is produced during use.After aluminium foil surface one layer of carbonaceous conductive layer of coating, material with carbon element is between positive active material and aluminium foil, rises
To transitional function, add being fully contacted of aluminium foil and active material, significantly reduce the interface of positive electrode and collector
Resistance.Additionally, carbon coat can also increase the adhesion of active material and collector, and there is stronger decay resistance,
Aluminium foil is played a protective role, increases the cycle life of battery, improve high rate capability.Domestic main power lithium battery manufacturer is
Carbon-coated aluminum foils is progressively used to substitute original aluminium foil.
The preparation of electrocondution slurry is the key of carbon-coated aluminum foils technology, and carbon-coated aluminum foils of good performance must have following base
This condition: 1. adhesion is good, the resin in slurry and aluminium foil surface need stronger chemically or physically active force, it is ensured that coating
Stable；2. conductivity is high, and first material with carbon element must account for solid content more than 50, and the material with carbon element selected has preferably conduction
Property；3. stable chemical nature, the resin of selection, dispersant, auxiliary agent etc. have stronger resistance to chemical attack, oxidation resistent susceptibility.
The carbon-coated aluminum foils that processability is excellent needs, while ensureing adhesion, farthest to promote electric conductivity,
So in a certain amount of material with carbon element, adding the fewest resin.This requires that resin has stronger dispersibility and adhesion
Power.The crosslinking curing of resin is to improve to be coated with film dynamic performance intensity, solvent resistance and the important means of chemical stability.
Many thermosetting resin function admirables, can meet above-mentioned condition, when however it is necessary that the highest crosslinking temperature or crosslinking
Between, needing the temperature of 170-180 DEG C, the crosslinking time of more than 1min as epoxy-amino group is full cross-linked, its cross-linking efficiency is low, no
It is beneficial to the production of streamline.Aluminium foil in current driving force lithium electricity is between 13-20 μm, and under this high-temperature baking, aluminium foil can seriously become
Shape, changes tension of aluminum foil distribution, causes following process difficulty.Along with aluminum foil thickness is the most thinning, baking temperature will be further
Decline.
Summary of the invention
For the deficiencies in the prior art, the present invention proposes one, and solvent resistance is good, electric conductivity is high and chemical stability good
Ultraviolet light polymerization carbon-coated aluminum foils collector.The surface-coated of this aluminum foil current collector has carbonaceous conductive slurry, and carbonaceous conductive slurry uses
Acrylic resin itself is as dispersant material with carbon element, and addition is few, while ensureing superior electrical conductivity, has excellence
Mechanical strength and the coating of uniform and smooth.The process of the present invention can use water-based system, has environmental protection, low cost etc. excellent
Gesture.Baking temperature in the carbon coat employing ultraviolet technique of the carbon-coated aluminum foils of the present invention only need to be between 60-110 DEG C, it is possible to protects
Card aluminium foil processing is stable.Relatively low baking temperature also significantly reduces energy consumption.
This carbon-coated aluminum foils collector can be used for cobalt acid lithium, LiMn2O4, LiFePO4 and ternary material etc. as positive electrode
Lithium ion battery in, improve the electric conductivity of carbon coat aluminum foil current collector, chemical stability and mechanical performance.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of ultraviolet light polymerization carbon-coated aluminum foils collector, including current collector aluminum foil, it is characterised in that described current collector aluminum foil
Surface be uniformly coated with carbonaceous conductive slurry, described carbonaceous conductive slurry consists of the following components in percentage by weight: material with carbon element 5-
20%, UV-cured resin 3-10%, light trigger 0.5-10%, solvent 65-90%, auxiliary agent 0.03-1%.
Scheme further, described material with carbon element is one or more in white carbon black, Graphene, graphite flake, CNT.
Scheme further, described UV-cured resin is epoxy modified acrylic resin, polyurethane-modified acrylic acid tree
Fat, polyester modification acrylic resin, carbon-carbon double bonds acrylic resin in one or more.
Further scheme, described light trigger be benzophenone, benzoin isobutyl propanol, 2,2 '-azo group-bis-(2-amidino groups
Propane), triaryl sulfonium salts light trigger, methyl benzoylformate, acylphosphanes hydrochlorate light trigger, NITRODIAZONIUM FLUOROBORATE, water
One or more in dissolubility arone photoinitiator.
Scheme further, described solvent is one or more in dimethylbenzene, deionized water, alcohols, ketone, esters.
Scheme further, described auxiliary agent includes defoamer, substrate wetting agents.
Invention additionally discloses the preparation method of a kind of ultraviolet light polymerization carbon-coated aluminum foils collector, comprise the following steps:
(1) UV-cured resin is dissolved in solvent, adds auxiliary agent, stir, add material with carbon element, condense water-cooled
But disperse 3-5h with high speed dispersor under the conditions of, add light trigger, stir, form slurry；
(2) step (1) slurry employing nick version is coated in current collector aluminum foil, at the hot blast of 60-110 DEG C and wavelength is
The ultraviolet light of 10-400nm irradiates and keeps 10-200s in baking oven, obtains ultraviolet light polymerization carbon-coated aluminum foils collector.
Scheme further, described high speed dispersor rotating speed is at more than 4000r/min.
Scheme further, the viscosity of described slurry is 20-200mPa S, and the solid content of slurry is 5-30%.
Scheme further, described carbon-coated aluminum foils carbon coat thickness is 1-3 μm.
Beneficial effects of the present invention: the carbon-coated aluminum foils collector of the present invention uses acrylic resin to make dispersant and solidification
Agent, significantly reduces the consumption of organic resin, adds the contact between material with carbon element, reduces resistance.Present invention employs and change
Property light-cured acrylic resin, can efficiently cross-link under irradiating with ultraviolet light, it is to avoid the solidification of excessive temperature makes the aluminium foil tight
Heavily deform, and obtain the combination properties such as adhesion is good, solvent resistance strong, stable chemical nature.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the embodiment of the present invention 3.
Fig. 2 is the structural representation before the carbon-coated aluminum foils carbon coat photo-initiated crosslinking of the present invention.
In figure: the crosslinked group such as double bond in 1-acrylic resin, epoxy radicals, 2-light trigger, 3 acrylic acid resin, 4-
Material with carbon element, 5-aluminum foil substrate.
Detailed description of the invention
With specific embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings.
Embodiment 1
A kind of ultraviolet light polymerization carbon-coated aluminum foils collector, including current collector aluminum foil, the surface of current collector aluminum foil uniformly coats
Carbonaceous conductive slurry, carbonaceous conductive slurry is had to consist of the following components in percentage by weight:
The preparation method of ultraviolet light polymerization carbon-coated aluminum foils collector:
The water-soluble modified acrylic resin of carbon-carbon double bonds is mixed with deionized water, adds substrate wetting agents and froth breaking
Agent, stirs, and adds carbon black；Under condensed water cooling condition, the high speed dispersor of 4000r/min disperses 4h；Add
Light trigger acylphosphanes hydrochlorate, low speed dispersion 0.5h；Gained slurry viscosity under 10/S shear rate is 200mPa S, admittedly contain
Amount is 20%.Utilizing nick version coating equipment to coat, under the conditions of 90 DEG C of hot blasts, the ultraviolet light of 300-380nm wavelength irradiates ring
Border is dried 10 seconds.After drying, carbon coat thickness is 2 μm.
Embodiment 2
A kind of ultraviolet light polymerization carbon-coated aluminum foils collector, including current collector aluminum foil, the surface of current collector aluminum foil uniformly coats
Carbonaceous conductive slurry, carbonaceous conductive slurry is had to consist of the following components in percentage by weight:
The preparation method of ultraviolet light polymerization carbon-coated aluminum foils collector:
Epoxy modified acrylic resin is mixed with dimethylbenzene, adds substrate wetting agents and defoamer, stir, then add
Enter Graphene；Under condensed water cooling condition, the high speed dispersor of 5000r/min disperses 3h；Add triaryl sulfonium salts light
Initiator, low speed dispersion 0.5h；Gained slurry viscosity under 10/S shear rate is 70mPa S, and solid content is 15%.Utilize
Nick version coating equipment coats, and under the conditions of 110 DEG C of hot blasts, the ultraviolet light of 240-350nm wavelength irradiates in environment and is dried 60 seconds.
After drying, carbon coat thickness is 1.5 μm.
Embodiment 3
A kind of ultraviolet light polymerization carbon-coated aluminum foils collector, including current collector aluminum foil, the surface of current collector aluminum foil uniformly coats
Carbonaceous conductive slurry, carbonaceous conductive slurry is had to consist of the following components in percentage by weight:
The preparation method of ultraviolet light polymerization carbon-coated aluminum foils collector:
Unsaturated polyester modified for water solublity acrylic resin is mixed homogeneously with deionized water, adds substrate wetting agents and disappear
Infusion, stirs, and adds graphite flake；Under condensed water cooling condition, the high speed dispersor of 5000r/min disperses 5h；
Add light trigger 2,2 '-azo group-bis-(2-amidine propane), low speed dispersion 0.5h；Gained slurry is under 10/S shear rate
Viscosity is 20mPa S, and solid content is 5%.Nick version coating equipment is utilized to coat, under the conditions of 70 DEG C of hot blasts, 280-350nm
The ultraviolet light of wavelength irradiates in environment and is dried 200 seconds.After drying, carbon coat thickness is 3 μm.
Embodiment 4
A kind of ultraviolet light polymerization carbon-coated aluminum foils collector, including current collector aluminum foil, the surface of current collector aluminum foil uniformly coats
Carbonaceous conductive slurry, carbonaceous conductive slurry is had to consist of the following components in percentage by weight:
The preparation method of ultraviolet light polymerization carbon-coated aluminum foils:
Mix acrylic resin modified for soluble epoxide with deionized water, add substrate wetting agents and defoamer, stirring
Uniformly, white carbon black and graphite flake are added；Under condensed water cooling condition, the high speed dispersor of 5500r/min disperses 3h；Add
Light trigger NITRODIAZONIUM FLUOROBORATE, low speed dispersion 0.5h；Gained slurry viscosity under 10/S shear rate is 110mPa S, Gu
Content is 30%.Utilizing nick version coating equipment to coat, under the conditions of 60 DEG C of hot blasts, the ultraviolet light of 250-380nm wavelength irradiates
Environment is dried 100 seconds.After drying, carbon coat thickness is 1 μm.
Fig. 1 is the embodiment of the present invention 3 gained carbon-coated aluminum foils surface SEM figure, and wherein laminated structure is graphite flake, figure layer carbon material
Material sharp outline, is conducive to fully contacting with positive electrode.
Fig. 2 is the microstructure schematic diagram of the present invention, and acrylic resin has preferable peptizaiton, acrylic acid chain to white carbon black
Section absorption provides steric hindrance at carbon material surface, it is ensured that material with carbon element stable dispersion.Light trigger causes the unsaturated bond in resin, ring
The groups such as oxygen key crosslink, last fully solidification, make figure layer have higher adhesion and solvent resistance.
Table one is 4 embodiment gained carbon-coated aluminum foils solvent resistances of the present invention.In table, data are the most molten with speckling with
The cotton swab coating surface of agent, until exposing the number of times of aluminum foil substrate institute wiping.Painting carbon prepared by the method for the present invention is described
Aluminium foil has good solvent resistance, it is ensured that have stable performance in the battery.
The solvent resistant wiping properties of the carbon-coated aluminum foils that table one embodiment 1-4 obtains
| Water | NMP | Electrolyte | |
| Embodiment 1 | 930 times | 390 times | 610 times |
| Embodiment 2 | 1020 times | 420 times | 650 times |
| Embodiment 3 | 650 times | 350 times | 550 times |
| Embodiment 4 | 810 times | 370 times | 580 times |
Above content is only to present configuration example and explanation, affiliated those skilled in the art couple
Described specific embodiment makes various amendment or supplements or use similar mode to substitute, without departing from invention
Structure or surmount scope defined in the claims, all should belong to protection scope of the present invention.
Claims (10)
1. a ultraviolet light polymerization carbon-coated aluminum foils collector, including current collector aluminum foil, it is characterised in that described current collector aluminum foil
Surface is uniformly coated with carbonaceous conductive slurry, and described carbonaceous conductive slurry consists of the following components in percentage by weight: material with carbon element 5-
20%, UV-cured resin 3-10%, light trigger 0.5-10%, solvent 65-90%, auxiliary agent 0.03-1%.
Ultraviolet light polymerization carbon-coated aluminum foils collector the most according to claim 1, it is characterised in that described material with carbon element is charcoal
One or more in black, Graphene, graphite flake, CNT.
Ultraviolet light polymerization carbon-coated aluminum foils collector the most according to claim 1, it is characterised in that described ultraviolet light polymerization tree
Fat be epoxy modified acrylic resin, polyurethane modified acrylic resin, polyester modification acrylic resin, the third of carbon-carbon double bonds
One or more in olefin(e) acid resin.
Ultraviolet light polymerization carbon-coated aluminum foils collector the most according to claim 1, it is characterised in that described light trigger is two
Benzophenone, benzoin isobutyl propanol, 2,2 '-azo group-bis-(2-amidine propane), triaryl sulfonium salts light trigger, benzoyl first
One or more in acid methyl ester, acylphosphanes hydrochlorate light trigger, NITRODIAZONIUM FLUOROBORATE, water solublity arone photoinitiator.
Ultraviolet light polymerization carbon-coated aluminum foils collector the most according to claim 1, it is characterised in that described solvent is diformazan
One or more in benzene, deionized water, alcohols, ketone, esters.
Ultraviolet light polymerization carbon-coated aluminum foils collector the most according to claim 1, it is characterised in that described auxiliary agent includes froth breaking
Agent, substrate wetting agents.
7. the method preparing ultraviolet light polymerization carbon-coated aluminum foils collector as claimed in claim 1, it is characterised in that include
Following steps:
(1) UV-cured resin is dissolved in solvent, adds auxiliary agent, stir, add material with carbon element, condensed water cooling bar
Disperse 3-5h with high speed dispersor under part, add light trigger, stir, form slurry；
(2) step (1) slurry employing nick version is coated in current collector aluminum foil, is 10-at the hot blast of 60-110 DEG C and wavelength
The ultraviolet light of 400nm irradiates and keeps 10-200s in baking oven, obtains ultraviolet light polymerization carbon-coated aluminum foils collector.
Method the most according to claim 7, it is characterised in that described high speed dispersor rotating speed is at more than 4000r/min.
Method the most according to claim 7, it is characterised in that the viscosity of described slurry is 20-200mPa S, consolidating of slurry
Content is 5-30%.
Method the most according to claim 7, it is characterised in that described carbon-coated aluminum foils carbon coat thickness is 1-3 μm.
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| CN201610715505.5A CN106299380B (en) | 2016-08-24 | 2016-08-24 | A kind of ultraviolet light solidification carbon-coated aluminum foils collector and preparation method |
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| CN201610715505.5A CN106299380B (en) | 2016-08-24 | 2016-08-24 | A kind of ultraviolet light solidification carbon-coated aluminum foils collector and preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113359042A (en) * | 2021-06-07 | 2021-09-07 | 芜湖天弋能源科技有限公司 | Method for nondestructive testing of carbon coating missing layer of anode of lithium ion battery |
| CN114447284A (en) * | 2022-01-13 | 2022-05-06 | 东莞市无中有新能源科技有限公司 | Preparation method of graphene negative plate and lithium battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113359042A (en) * | 2021-06-07 | 2021-09-07 | 芜湖天弋能源科技有限公司 | Method for nondestructive testing of carbon coating missing layer of anode of lithium ion battery |
| CN114447284A (en) * | 2022-01-13 | 2022-05-06 | 东莞市无中有新能源科技有限公司 | Preparation method of graphene negative plate and lithium battery |
| CN114447284B (en) * | 2022-01-13 | 2024-04-05 | 东莞市无中有新能源科技有限公司 | Preparation method of graphene negative plate and lithium battery |
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