CN116207269A - High-conductivity nano-coating current collector, electrode, battery and preparation method of current collector - Google Patents
High-conductivity nano-coating current collector, electrode, battery and preparation method of current collector Download PDFInfo
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- CN116207269A CN116207269A CN202310202924.9A CN202310202924A CN116207269A CN 116207269 A CN116207269 A CN 116207269A CN 202310202924 A CN202310202924 A CN 202310202924A CN 116207269 A CN116207269 A CN 116207269A
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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
- 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
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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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- 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
- H01M4/668—Composites of electroconductive material and synthetic resins
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The application relates to the field of electrode materials, in particular to a high-conductivity nano-coating current collector, an electrode, a battery and a preparation method of the current collector. A high-conductivity nano-coating current collector comprises a current collector and nano-conductive coatings coated on two sides of the current collector, wherein the nano-conductive coatings contain graphene oxide grafted binders. The preparation method of the high-conductivity nano-coating current collector comprises the following steps: step one: preparing a graphene oxide grafted binder; step two: preparing a coating slurry, wherein the coating slurry comprises the graphene oxide grafted binder; step three: coating the coating slurry on at least one surface of a current collector, and drying to prepare the coating current collector. According to the application, the graphene oxide grafted binder is added into the coating, so that the binder has certain conductivity, and the conductive material and the current collector are bonded without affecting the overall conductive effect of the electrode.
Description
Technical Field
The application relates to the field of electrode materials, in particular to a high-conductivity nano-coating current collector, an electrode, a battery and a preparation method of the current collector.
Background
The lithium ion battery is applied in the fields of consumer electronics, electric vehicles and the like on a large scale, and the market also provides higher requirements on the aspects of energy density, cycle life, use safety and the like of the lithium ion battery. The current collector conductive primer technology can effectively reduce the contact resistance of the electrode material and the current collector, increase the bonding force between the electrode material and the current collector, reduce the internal resistance of the battery and prolong the service life of the battery.
However, a certain amount of adhesive is needed in the preparation process of the nano conductive coating current collector, the adhesive does not have conductivity, too much addition can cause the reduction of the conductivity of the conductive nano conductive coating, too little addition can not well bond the conductive material, and meanwhile, too thick nano conductive coating can influence the overall conductive effect of the electrode, so that the capability of the nano conductive coating for further improving the conductivity of the electrode material with poor conductivity is inhibited.
Disclosure of Invention
In order to overcome the problems in the prior art, the application provides a high-conductivity nano-coating current collector, an electrode, a battery and a preparation method of the current collector.
The application provides a high-conductivity nano-coating current collector, an electrode, a battery and a preparation method of the current collector, wherein the preparation method adopts the following technical scheme:
a high-conductivity nano-coating current collector comprises a current collector and nano-conductive coatings coated on two sides of the current collector, wherein the nano-conductive coatings contain graphene oxide grafted binders.
By adopting the technical scheme, the graphene oxide grafted binder is added into the coating, so that the binder has certain conductivity, and the conductive material and the current collector are bonded without affecting the overall conductive effect of the electrode.
The graphene oxide binder is prepared by polymerizing a modified intermediate prepared by reacting a composition with hydroxy acrylic acid and a binder monomer after the reaction of polyisocyanate and graphene oxide. Among them, graphene oxide is an oxide of graphene, its color is brown yellow, and common products in the world are in the form of powder, flakes and solution. The oxidized graphene has more active property due to the increased oxygen-containing functional groups, and the graphene can improve the property through various reactions with the oxygen-containing functional groups.
The nano conductive coating comprises a solution, a conductive material dispersed in the solution and a graphene oxide grafted binder.
The preparation method of the high-conductivity nano-coating current collector comprises the following steps: step one: preparing a graphene oxide grafted binder; step two: preparing a coating slurry, wherein the coating slurry comprises the graphene oxide grafted binder; step three: coating the coating slurry on at least one surface of a current collector, and drying to prepare the coating current collector.
Preferably, the method for preparing the graphene oxide grafted binder in the first step comprises the following steps: uniformly mixing polyisocyanate and graphene oxide in ethyl acetate solvent, filtering after the reaction is finished, and reacting the composition with hydroxy acrylic ester to prepare a modified intermediate; and polymerizing the modified intermediate and a binder monomer, and adding a grafting initiator to synthesize the graphene oxide grafted binder.
The reaction formula of the polyisocyanate and the modified intermediate mixed with graphene oxide and reacted with ethyl hydroxy acrylate is:
by adopting the technical scheme, one isocyanate group of the polyisocyanate reacts with the hydroxyl or carboxyl of the graphene oxide, and the other isocyanate group reacts with the hydroxyl of the hydroxyacrylic acid, so that the double bond on the hydroxyacrylic acid is reserved, and the graphene oxide and the hydroxyacrylate are connected to form a modified intermediate. The graphene oxide grafted adhesive formed by polymerizing the modified intermediate and the adhesive monomer has an adhesive effect and a certain conductivity. The traditional adhesive layer has poor conductivity, the resistance of the adhesive layer is larger in the process of using the battery, the prepared modified intermediate and the adhesive of the acrylic monomer are polymerized and connected to synthesize the graphene oxide adhesive, and the graphene oxide adhesive is added on the basis of the adhesive and the conductive material in the same proportion, so that the nano conductive coating has better conductivity and lower resistance.
Preferably, the polyisocyanate is one or more of an aromatic isocyanate, a cycloaliphatic isocyanate and an aliphatic isocyanate.
Through the adoption of the technical scheme, the polyisocyanate is one of main raw materials of the polyurethane adhesive, wherein the polyurethane adhesive comprises the aromatic isocyanate, the alicyclic isocyanate and the aliphatic isocyanate, the aliphatic isocyanate is of a chain structure, the acrylic ester reacted with the aliphatic isocyanate is of a chain structure, the aromatic isocyanate and the alicyclic isocyanate are easier to react, and compared with the aromatic isocyanate and the alicyclic isocyanate which are provided with rigid ring structures, the chain structure of the aliphatic isocyanate has better flexibility, yellowing reaction is not easy to occur, and the polyurethane adhesive has better ageing resistance.
Preferably, the mass ratio of the modified intermediate to the binder monomer is 1:10-100.
Preferably, the binder monomer is an acrylic monomer including one or more of acrylic acid, methyl methacrylate, butyl acrylate, isobutyl acrylate, methacrylic acid and derivatives thereof.
The original graphene oxide and acrylic glue mixed contact can only play a role in co-operation, but cannot play a role in chemical connection, and by adopting the technical scheme, the modified intermediate formed by connecting the graphene oxide and the hydroxy acrylic acid ester has double bonds, so that the graphene oxide and acrylic monomers can be chemically connected, and the polymerization of the modified intermediate and the adhesive monomers is completed.
Preferably, the grafting initiator adopts persulphate compound, the grafting reaction temperature is 50-80 ℃, the reaction time is 5-10 hours, and the solid content of the graphene oxide grafting adhesive is 20-30%.
Preferably, the method for preparing the high-conductivity nano coating slurry in the second step comprises the following steps: and mixing the conductive material, the graphene oxide grafted binder and the solvent according to a certain proportion, and stirring and dispersing for 2-10h to prepare the high-conductivity nano coating slurry. The mass ratio of the conductive material to the graphene oxide grafted binder is 1:0.5-1.5, and the solid content of the high-conductivity nano coating material is 5-10%. The conductive material is one or more of conductive carbon black, conductive graphite, carbon nano tube and graphene, and the solvent is water.
An electrode comprises the high-conductivity nano-coating current collector.
A battery comprising one of the above electrodes.
In summary, the present application includes at least one of the following beneficial technical effects:
1. according to the invention, graphene oxide is grafted to the binder molecules through polymerization reaction, so that the binder has certain conductivity, and the nano conductive coating can bond conductive materials and current collectors without affecting the overall conductive effect of the electrode.
Drawings
Fig. 1 is a schematic diagram of a highly conductive nano-coating current collector layer structure.
Reference numerals illustrate: 1. a current collector; 2. a nano conductive coating.
Detailed Description
The present application is described in further detail below in conjunction with fig. 1.
The embodiment of the application discloses a high-conductivity nano-coating current collector, an electrode, a battery and a preparation method of the current collector.
Example 1
A high-conductivity nano-coating current collector comprises a current collector 1 and nano-conductive coatings 2 coated on two sides of the current collector, wherein the nano-conductive coatings 2 contain graphene oxide grafted binders. The graphene oxide grafted binder is added into the coating, so that the binder has certain conductivity, and the conductive material and the current collector are bonded without affecting the overall conductive effect of the electrode.
The graphene oxide binder is prepared by polymerizing a modified intermediate prepared by reacting a composition with hydroxy acrylic acid and a binder monomer after the reaction of polyisocyanate and graphene oxide.
The nano conductive coating comprises a solution, a conductive material dispersed in the solution and a graphene oxide grafted binder.
The preparation method of the high-conductivity nano-coating current collector comprises the following steps:
step one: uniformly mixing 1kg of isophorone diisocyanate and 0.5kg of graphene oxide in a solvent butyl acetate, filtering after the reaction is finished, and reacting with 0.5kg of hydroxyethyl acrylate to prepare a modified intermediate; then 1kg of modified intermediate is dissolved in 10kg of acrylic acid, slowly dripped into a reaction kettle for emulsion polymerization, the reaction temperature is 70 ℃, the reaction time is 8 hours, and a persulfate compound is added to obtain graphene oxide grafted binder emulsion, and the solid content is adjusted to 25%;
step two: 10kg of conductive carbon black, 20kg of the prepared graphene oxide grafted binder emulsion and 157.5kg of water are mixed and dispersed for 4 hours to prepare 8% solid high-conductivity nano coating slurry;
step three: and coating the high-conductivity nano coating slurry on two sides of a 13 mu m aluminum current collector with a thickness of 1 mu m by using a coating machine, and drying to obtain the high-conductivity nano coating current collector.
An electrode comprises the high-conductivity nano-coating current collector.
A battery comprising one of the above electrodes.
Example 2
A highly conductive nano-coated current collector, electrode, battery, and method as in example 1, differ only in: the preparation method of the high-conductivity nano-coating current collector comprises the following steps:
step one: 1kg of isophorone diisocyanate and 0.5kg of graphene oxide are uniformly mixed in a solvent butyl acetate, filtered after the reaction is finished, and then reacted with 0.5kg of hydroxyethyl acrylate to prepare a modified intermediate. Then 1kg of modified intermediate is dissolved in 50kg of acrylic acid, slowly dripped into a reaction kettle for emulsion polymerization, the reaction temperature is 50 ℃, the reaction time is 8 hours, and a persulfate compound is added to obtain graphene oxide grafted binder emulsion, and the solid content is adjusted to 25%.
Step two: 10kg of conductive carbon black, 40kg of the prepared graphene oxide grafted binder emulsion and 200kg of water are mixed and dispersed for 6 hours to prepare the high-conductivity nano coating slurry with 8% of solid content.
Step three: and coating the high-conductivity nano coating slurry on two sides of a 13 mu m aluminum current collector with a thickness of 1 mu m by using a coating machine, and drying to obtain the high-conductivity nano coating current collector.
Example 3
A highly conductive nano-coated current collector, electrode, battery, and method as in example 1, differ only in: the preparation method of the high-conductivity nano-coating current collector comprises the following steps:
step one: 1kg of isophorone diisocyanate and 0.5kg of graphene oxide are uniformly mixed in a solvent butyl acetate, filtered after the reaction is finished, and then reacted with 0.5kg of hydroxyethyl acrylate to prepare a modified intermediate. Then 1kg of modified intermediate is dissolved in 80kg of acrylic acid, slowly dripped into a reaction kettle for emulsion polymerization, the reaction temperature is 80 ℃, the reaction time is 5 hours, and a persulfate compound is added to obtain graphene oxide grafted binder emulsion, and the solid content is adjusted to 25%.
Step two: 10kg of conductive carbon black, 40kg of the prepared graphene oxide grafted binder emulsion and 200kg of water are mixed and dispersed for 6 hours to prepare the high-conductivity nano coating slurry with 8% of solid content.
Step three: and coating the high-conductivity nano coating slurry on two sides of a 13 mu m aluminum current collector with a thickness of 1 mu m by using a coating machine, and drying to obtain the high-conductivity nano coating current collector.
Example 4
A highly conductive nano-coated current collector, electrode, battery, and method as in example 1, differ only in: the preparation method of the high-conductivity nano-coating current collector comprises the following steps:
step one: 1kg of isophorone diisocyanate and 0.5kg of graphene oxide are uniformly mixed in a solvent butyl acetate, filtered after the reaction is finished, and then reacted with 0.5kg of hydroxyethyl acrylate to prepare a modified intermediate. Then 1kg of modified intermediate is dissolved in 80kg of acrylic acid, slowly dripped into a reaction kettle for emulsion polymerization, the reaction temperature is 70 ℃ and the reaction time is 6 hours, and a persulfate compound is added to obtain graphene oxide grafted binder emulsion, and the solid content is adjusted to 25%.
Step two: 10kg of conductive carbon black, 60kg of the prepared graphene oxide grafted binder emulsion and 242.5kg of water are mixed and dispersed for 8 hours to prepare the high-conductivity nano coating slurry with 8% of solid content.
Step three: and coating the high-conductivity nano coating slurry on two sides of a 13 mu m aluminum current collector with a thickness of 1 mu m by using a coating machine, and drying to obtain the high-conductivity nano coating current collector.
Example 5
A highly conductive nano-coated current collector, electrode, battery, and method as in example 1, differ only in: the preparation method of the high-conductivity nano-coating current collector comprises the following steps:
step one: 1kg of isophorone diisocyanate and 0.5kg of graphene oxide are uniformly mixed in a solvent butyl acetate, filtered after the reaction is finished, and then reacted with 0.5kg of hydroxyethyl acrylate to prepare a modified intermediate. Then 1kg of modified intermediate is dissolved in 100kg of acrylic acid, slowly dripped into a reaction kettle for emulsion polymerization, the reaction temperature is 60 ℃, the reaction time is 5 hours, and a grafting initiator is added to obtain graphene oxide grafting adhesive emulsion, and the solid content is adjusted to 25%.
Step two: 10kg of conductive carbon black, 40kg of the prepared graphene oxide grafted binder emulsion and 200kg of water are mixed and dispersed for 8 hours to prepare the high-conductivity nano coating slurry with 8% of solid content.
Step three: and coating the high-conductivity nano coating slurry on two sides of a 13 mu m aluminum current collector with a thickness of 1 mu m by using a coating machine, and drying to obtain the high-conductivity nano coating current collector.
The foregoing are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in any way, therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.
Comparative example 1
The highly conductive nano-coated current collector, electrode and battery are the same as in example 1, wherein the preparation method of the highly conductive nano-coated current collector is only different from example 1 in that: in the first step, no conductive polymer grafting is used, and in the second step, a polyacrylic acid (PAA) aqueous solution with the solid content of 25% is mixed with conductive carbon black to prepare the high-conductivity nano coating slurry.
Comparative example 2
The highly conductive nano-coated current collector, electrode and battery are the same as those in example 2, and the preparation method of the highly conductive nano-coated current collector is only different from that in example 2 in that: in the second step, 10kg of the conductive carbon black was replaced with a mixture of 9.5kg of the conductive carbon black and 0.5kg of carbon nanotubes.
Comparative example 3
The highly conductive nano-coated current collector, electrode and battery are the same as in example 3, wherein the preparation method of the highly conductive nano-coated current collector is only different from example 3 in that: in the second step, stirring and dispersing time is 10 hours.
Performance test of highly conductive nanocoating current collector:
the highly conductive nanocoating current collectors prepared in examples 1-5 and comparative examples 1-3 were tested for surface sheet resistance and penetration resistance according to the following methods, and the test results are shown in the following tables.
(1) Surface sheet resistance: a 4-probe resistance meter test (probe type, full pressure stroke) is adopted;
(2) Penetration resistance: the highly conductive nanocoating current collectors prepared in each example and comparative example were cut into squares of about 5cm x 5cm using a pole piece resistance tester, placed under a test head, and maintained at a test pressure of 0.3t for 5s.
| Sequence number | Surface sheet resistance/mΩ | Penetration sheet resistance/mΩ |
| Example 1 | 1.928 | 2.532 |
| Example 2 | 2.556 | 3.867 |
| Example 3 | 2.576 | 3.979 |
| Example 4 | 3.593 | 4.895 |
| Example 5 | 2.625 | 3.837 |
| Comparative example 1 | 2.435 | 5.534 |
| Comparative example 2 | 2.154 | 3.032 |
| Comparative example 3 | 2.353 | 3.761 |
As shown by test results, the embodiment 1 is the best embodiment, the surface sheet resistance and the penetrating sheet resistance of the prepared high-conductivity nano-coating current collector are minimum, and the fact that graphene oxide is grafted onto binder molecules is verified, and the high-conductivity nano-coating current collector has a good conductive effect when being applied to a nano-conductive coating.
Claims (12)
1. The utility model provides a high conductive nano-coating current collector which characterized in that: the nano conductive coating comprises a current collector (1) and nano conductive coatings (2) coated on two sides of the current collector, wherein the nano conductive coatings (2) contain graphene oxide grafted binders.
2. A highly conductive nanocoating current collector as claimed in claim 1, wherein: the graphene oxide binder is prepared by polymerizing a modified intermediate prepared by reacting a composition with hydroxy acrylic acid and a binder monomer after the reaction of polyisocyanate and graphene oxide is synthesized.
3. A highly conductive nanocoating current collector as claimed in claim 1, wherein: the nano conductive coating comprises a solution, a conductive material dispersed in the solution and a graphene oxide grafted binder.
4. A preparation method of a high-conductivity nano-coating current collector is characterized by comprising the following steps of: the method comprises the following steps:
step one: preparing a graphene oxide grafted binder;
step two: preparing a coating slurry, wherein the coating slurry comprises the graphene oxide grafted binder;
step three: coating the coating slurry on at least one surface of a current collector, and drying to prepare the coating current collector.
5. The method for preparing the high-conductivity nano-coating current collector according to claim 4, wherein the method comprises the following steps: the method for preparing the graphene oxide grafted binder in the first step comprises the following steps: uniformly mixing polyisocyanate and graphene oxide in ethyl acetate solvent, filtering after the reaction is finished, and reacting the composition with hydroxy acrylic ester to prepare a modified intermediate; and polymerizing the modified intermediate and a binder monomer, and adding a grafting initiator to synthesize the graphene oxide grafted binder.
6. The method for preparing the high-conductivity nano-coating current collector according to claim 5, wherein the method comprises the following steps: the isocyanate is one or more of aromatic isocyanate, alicyclic isocyanate and aliphatic isocyanate.
7. The method for preparing the high-conductivity nano-coating current collector according to claim 5, wherein the method comprises the following steps: the mass ratio of the modified intermediate to the binder monomer is 1:10-100.
8. The method for preparing the high-conductivity nano-coating current collector according to claim 5, wherein the method comprises the following steps: the binder monomer is an acrylic monomer and comprises one or more of acrylic acid, methyl methacrylate, butyl acrylate, isobutyl acrylate, methacrylic acid and derivatives thereof.
9. The method for preparing the high-conductivity nano-coating current collector according to claim 5, wherein the method comprises the following steps: the grafting initiator adopts persulphate compound, the grafting reaction temperature is 50-80 ℃, the reaction time is 5-10 hours, and the solid content of the graphene oxide grafting binder is 20-30%.
10. The method for preparing the high-conductivity nano-coating current collector according to claim 4, wherein the method comprises the following steps: the method for preparing the coating slurry in the second step comprises the following steps: mixing a conductive material, a graphene oxide grafted binder and a solvent according to a certain proportion, stirring and dispersing for 2-10h to prepare high-conductivity nano coating slurry; the mass ratio of the conductive material to the graphene oxide grafted binder is 1:0.5-1.5, and the solid content of the high-conductivity nano coating material is 5-10%; the conductive material is one or more of conductive carbon black, conductive graphite, carbon nano tube and graphene, and the solvent is water.
11. An electrode, characterized by: a highly conductive nanocoating current collector comprising any one of claims 1 to 3.
12. A battery, characterized in that: an electrode comprising the electrode of claim 11.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117352738A (en) * | 2023-11-08 | 2024-01-05 | 丽岛新能源(安徽)有限公司 | Carbon-coated aluminum foil and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117352738A (en) * | 2023-11-08 | 2024-01-05 | 丽岛新能源(安徽)有限公司 | Carbon-coated aluminum foil and preparation method thereof |
| CN117352738B (en) * | 2023-11-08 | 2024-03-15 | 丽岛新能源(安徽)有限公司 | Carbon-coated aluminum foil and preparation method thereof |
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