CN111180741A - Carbon-coated current collector coated with three-dimensional graphene powder and preparation method thereof - Google Patents
Carbon-coated current collector coated with three-dimensional graphene powder and preparation method thereof Download PDFInfo
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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
- H01M4/663—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
Abstract
The invention discloses a carbon-coated current collector coated with three-dimensional graphene powder and a preparation method thereof. Compared with carbon black, the three-dimensional graphene powder coated current collector has higher conductivity, coating strength and bonding strength, and can be made thinner. Compared with the conventional flake graphene powder, the three-dimensional graphene powder has the advantages of higher binding strength of the current collector coated with the graphene powder, isotropic coating performance, simpler preparation process, higher surface roughness and better binding with an active material. The lithium ion battery prepared by taking the aluminum foil coated with the three-dimensional graphene powder as the positive current collector has greatly better specific capacity, rate capability and cycling stability than the current collector coated with carbon black.
Description
Technical Field
The invention relates to the technical field of energy materials, in particular to a carbon-coated current collector coated with three-dimensional graphene powder and a preparation method thereof.
Background
With the rapid development of portable electronic devices and electric vehicles, people have higher and higher requirements on the performance of lithium ion batteries, such as higher specific capacity, better rate performance and better cycle stability. The main components of the lithium ion battery include active materials, separators, electrolytes, current collectors, etc., which have a great influence on the performance of the battery, and the current collectors are less studied. Conventionally, a copper foil is used for a negative current collector and an aluminum foil is used for a positive current collector of a lithium ion battery. Since the rolled surface of a general metal foil is smooth, problems such as poor wettability, loose bonding, low bonding strength, small bonding area, and difficulty in adhesion may occur when coating an active material, thereby causing a large interfacial resistance between the active material and a current collector, easy falling, and a large coating difficulty. These problems can cause the performance degradation of the battery, for example, the interface resistance is large, which leads to serious polarization, and affects the lithium storage capacity, rate capability and cycle stability of the active material, so that it is difficult to meet the current requirements for high rate, high energy density and long cycle life. Therefore, the improvement of the surface state and the properties of the metal foil strip, the improvement of the compatibility of the active material and the current collector, the improvement of the bonding strength and the increase of the bonding area have important significance for improving the performance of the battery. A common method is to coat carbon black on a metal foil tape such as copper or aluminum to prepare a carbon-coated current collector, particularly an aluminum foil of a positive electrode current collector, wherein carbon coating of the aluminum foil is more important for the positive electrode because the conductivity of the positive electrode material is poor.
Publication No. CN101923961A discloses a method for preparing a carbon-coated aluminum foil for an aluminum electrolytic capacitor, which comprises mixing conductive carbon black, a dispersant and a binder to prepare slurry, coating the slurry on the surface of an aluminum foil, and then treating the aluminum foil in a vacuum furnace at 300-660 ℃ for a certain time to prepare the carbon-coated aluminum foil. Publication No. CN101027736A "a carbon-coated aluminum foil was produced by coating a carbon-containing substance such as carbon black, activated carbon, etc. on an aluminum foil, followed by heat treatment at 400 to 600 c in a carbon-containing atmosphere. In recent years, attempts have been made to introduce novel carbon nanomaterials such as graphene and carbon nanotubes in order to improve the use effect. Publication No. CN109301166A "obtained wrinkled graphene by cooling the graphene in liquid nitrogen, and then coated onto aluminum foil to make a carbon-coated current collector. Publication No. CN106602076A discloses a carbon-coated aluminum foil including a three-layer structure, the first layer being activated carbon particles, the second layer being graphene sheets, and the third layer being a mixture of vapor-phase carbon fibers, carbon nanotubes and carbon black, which results in better electrical conductivity. While carbon-coated current collectors have made great progress and have achieved widespread use, there are still some problems that need to be solved to meet the application needs of high performance batteries. The carbon black widely used at present has the defects of poor conductivity, difficult dispersion, weak coating strength, weak bonding strength between the coating and a substrate, thicker coating and the like. The novel carbon nano material graphene and the carbon nano tube have the defects of difficult dispersion, anisotropy, high price and the like although the conductivity is good. Therefore, the development of novel carbon-coated current collectors is of great significance.
Disclosure of Invention
In view of the above disadvantages, an object of the present invention is to provide a method for preparing a carbon-coated current collector coated with three-dimensional graphene powder and a product thereof.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a preparation method of a carbon-coated current collector coated with three-dimensional graphene powder comprises the following steps:
(1) preparing slurry: preparing three-dimensional graphene powder, and then preparing the three-dimensional graphene powder into three-dimensional graphene powder slurry;
(2) coating: and uniformly coating the three-dimensional graphene powder slurry on a proper substrate, wherein the proper substrate is a copper foil, an aluminum foil, a stainless steel band, a plastic film or a fabric and the like. Controlling the coating speed at 20-80m/min, drying at 50-100 ℃, and forming a carbon-coated layer on a proper substrate to obtain the carbon-coated current collector. The dry film thickness of the carbon-coated layer is ensured to be between 0.2 and 4 mu m by controlling the coating speed.
As a preferable embodiment of the present invention, the step (1) specifically includes the following steps:
(1.1) mixing and uniformly stirring three-dimensional graphene powder and a dispersing agent, dissolving in a proper solvent, and uniformly mixing by sanding to obtain a three-dimensional graphene dispersion liquid; the sanding rotating speed is 1000-3000r/min, the sanding time is 0.5-10h, the situation that the binder and the conductive carbon material are bonded into a cluster can be effectively avoided through pre-dispersion, meanwhile, the dispersion effect of the three-dimensional graphene pre-dispersed by sanding is better, and the slurry particles are finer;
(1.2) sieving the dissolved three-dimensional graphene dispersion liquid to remove large particles, wherein the sieve is 800 meshes;
(1.3) mixing the three-dimensional graphene dispersion liquid and the binder solution according to a proper proportion, and fully and uniformly stirring by using a stirrer, wherein the stirrer is preferably a planetary stirrer, the stirring speed is 800-4000r/min, and the stirring time is 0.5-5h, so as to obtain the three-dimensional graphene powder slurry. The optimal viscosity of the three-dimensional graphene powder slurry is controlled to be 900-1000 mPa & s by controlling the proportion of each component and the stirring time and speed.
As a preferred scheme of the invention, the three-dimensional graphene powder, the binder and the dispersant are respectively in the following mass percentages: 2-15% of three-dimensional graphene powder, 1-5% of a binder, 0.2-5% of a dispersant and the balance of a solvent.
In a preferred embodiment of the present invention, the solvent is one or more of N-methyl pyrrolidone, ethanol or water.
In a preferred embodiment of the present invention, the binder is an aqueous or oily binder, such as one or more of polyacrylic acid, polyvinyl alcohol, styrene butadiene rubber, polyacrylonitrile, sodium carboxymethyl cellulose, acrylate multipolymer, and polyvinylidene fluoride.
In a preferred embodiment of the present invention, the dispersant is one or more of sodium deoxycholate, sodium dodecylbenzene sulfonate, polyethylene glycol, sodium dodecyl sulfate, polysorbate-80, polyvinylpyrrolidone, and cetylammonium bromide.
As a preferred embodiment of the present invention, the three-dimensional graphene powder slurry is coated on the appropriate substrate by using a doctor blade coating, gravure printing, screen printing or electrostatic spinning method.
As a preferable scheme of the invention, in the step (1), the three-dimensional graphene powder is prepared by growing vertical graphene sheets on the surface of the nano-scale carbon black by chemical vapor deposition, the growth time is 4 hours, and the three-dimensional graphene powder is subjected to jet milling treatment, the particle size distribution of the three-dimensional graphene powder is 50-150nm, and the conductivity of the three-dimensional graphene powder reaches 5.0 multiplied by 105S/m。
The carbon-coated current collector is prepared by the preparation method of the carbon-coated current collector coated with the three-dimensional graphene powder.
The invention has the beneficial effects that: the preparation method is simple and easy, is beneficial to realization, reasonably utilizes the special structure and properties of the three-dimensional graphene powder, effectively overcomes the defects of the existing carbon-coated current collector, and has the advantages of good conductivity, small interface resistance, high coating strength and interface strength, high surface roughness, contribution to enhancing the contact with an active material, capability of being made thinner, better heat dissipation capability and the like. Because the three-dimensional graphene powder is not easy to agglomerate, the slurry has good fluidity, and the coating process is simpler. Specifically, compared with the carbon black which is widely used at present, the carbon black overcomes the defects of poor conductivity, difficult dispersion, weak coating strength, weak bonding strength between the coating and a substrate, thicker coating and the like; compared with the flake graphene powder, the graphene powder overcomes the defects of difficult dispersion, anisotropy, high price and the like, has good comprehensive effect, and is beneficial to wide popularization and application.
The invention is further described with reference to the following figures and examples.
Drawings
Fig. 1 is a low-magnification SEM image of the three-dimensional graphene powder of example 1.
Fig. 2 is a high power SEM image of the three-dimensional graphene powder of example 1.
Fig. 3 is an optical photograph of the three-dimensional graphene carbon-coated aluminum foil of example 1.
Fig. 4 is an SEM photograph of the three-dimensional graphene carbon-coated aluminum foil of example 1.
Fig. 5 is an SEM photograph of the three-dimensional graphene carbon-coated aluminum foil of example 2.
Fig. 6 is an SEM photograph of the three-dimensional graphene carbon-coated aluminum foil of example 3.
Fig. 7 is an SEM photograph of the three-dimensional graphene carbon-coated aluminum foil of example 4.
Fig. 8 is an SEM photograph of a cross section of the three-dimensional graphene carbon-coated aluminum foil of example 4.
FIG. 9 is an SEM image of a carbon black-coated aluminum foil of example 5.
Fig. 10 is diagrams of the three-dimensional graphene carbon-coated aluminum foil of example 1 and the carbon black carbon-coated aluminum foil EIS of example 5.
Detailed Description
The following examples are given only for the purpose of further illustrating the invention and are not to be construed as limiting the invention in any way
Example 1:
(1) preparing a three-dimensional graphene dispersion liquid: selecting sodium deoxycholate as a dispersing agent, dissolving a certain amount of sodium deoxycholate in a certain amount of water, then adding a certain amount of three-dimensional graphene powder, stirring at the rotating speed of 1200r/min for 2 hours, and fully and uniformly stirring to obtain the three-dimensional graphene dispersion liquid. In the process, the concentrations of the three-dimensional graphene powder and the sodium deoxycholate in the dispersion liquid are respectively 8% and 1%. And then, injecting the three-dimensional graphene dispersion liquid into a sand mill for sanding, wherein the rotating speed of the sand mill is 1500r/min, and the sanding time is 2 h. The dispersion was then screened to remove large particles, 800 mesh. The three-dimensional graphene powder is ensured to be uniformly dispersed and have small particle size through sanding, and the size particle size D is detected through a laser particle sizer50Around 80 nm.
(2) Preparing a binder solution: dissolving a proper amount of polyacrylic acid binder into a proper amount of water, and fully and uniformly stirring to obtain the polyacrylic acid emulsion.
(3) Preparing three-dimensional graphene powder slurry: and (3) mixing the three-dimensional graphene powder dispersion liquid prepared in the step (1) with the polyacrylic acid emulsion prepared in the step (2), and stirring for 2 hours on a high-speed dispersion machine at a rotating speed of 1500r/min to obtain the carbon-coated slurry. The standard of the amount of each component in the step (2) and the step is to keep the concentrations of the three-dimensional graphene powder, the sodium deoxycholate and the polyacrylic acid in the final three-dimensional graphene powder slurry to be 4%, 0.5% and 2% respectively.
(4) Coating slurry: and coating the prepared three-dimensional graphene powder slurry on an aluminum foil through gravure printing, wherein the aluminum foil is preferably an aluminum foil with two unpolished sides, and cleaning the aluminum foil with alcohol to remove surface oil stains. The coating speed is 30m/min, and then the three-dimensional graphene carbon-coated aluminum foil is dried at 60 ℃ to obtain the three-dimensional graphene carbon-coated aluminum foil, wherein the thickness of the three-dimensional graphene powder layer is kept at 200-500 nm.
(5) Assembling and testing the lithium ion battery: the three-dimensional graphene carbon-coated aluminum foil is used for a positive current collector of a lithium ion battery. The preparation method comprises the following steps: coating the positive electrode slurry on the surface of the carbon-coated aluminum foil, and drying at 60 ℃. The positive electrode slurry comprises the following components: 95% of lithium iron phosphate, 2% of polyvinylidene fluoride, 3% of Super P, and N-methylpyrrolidine as a solventKetone, total solids content 50%. Then according to 2.1g/cm3And (4) rolling the mixture according to the compacted density to obtain the positive pole piece. And finally, taking graphite as a negative active material to prepare a soft package battery for testing.
Fig. 1 and 2 are SEM photographs of the three-dimensional graphene powder selected in example 1 at low and high magnification, and it can be seen that the three-dimensional graphene sheets grow perpendicular to the surface of the particles and are uniformly distributed. Fig. 3 is an optical photograph of a three-dimensional graphene carbon-coated aluminum foil, as shown in the figure, the three-dimensional graphene powder is uniformly coated on the surface of the aluminum foil, and the coating has no uneven phenomena such as scratches and large particles. Fig. 4 is an SEM photograph of the three-dimensional graphene carbon-coated aluminum foil of the present example, in which the three-dimensional graphene is adhered to the surface of the aluminum foil, the powder particle size is small, the distribution is uniform, no significant aggregation phenomenon occurs, and no large-area missing coating phenomenon occurs. Small uncoated areas were locally visible, indicating a thin coating and low slurry usage. The battery performance test shows that the current collector has outstanding performance, and the three-dimensional graphene powder is used for carbon coating of the current collector and has advantages.
Example 2:
in this example, the difference is that the sanding treatment step was carried out without a sand mill, and the other treatment steps and parameters were the same as those of example 1.
The test shows that the particle size D of the slurry prepared in this example50About 500nm, coarser than example 1. Fig. 5 is an SEM photograph of the carbon-coated aluminum foil manufactured under the above conditions, and it can be seen that, in this example, since the slurry is not pre-dispersed by sanding, the particles of the slurry are relatively large, the carbon-coated layer is not uniformly distributed, and a large foil leakage phenomenon occurs, which indicates that the sanding process is helpful for dispersing the three-dimensional graphene powder, effectively reducing the particle size, increasing the dispersion uniformity, and improving the slurry fluidity and film-forming property, thereby effectively preventing the binder from being bonded with the three-dimensional graphene powder into a mass.
Example 3:
in this example, the difference is that the content of polyacrylic acid in the three-dimensional graphene powder slurry is increased to 4%, and the other conditions are the same as those in example 1.
Fig. 6 is an SEM photograph of the carbon-coated aluminum foil manufactured in this example. Observation shows that the three-dimensional graphene powder is seriously wrapped by the binder, and the exposure of the graphene powder is reduced. The areal density of the coating is increased significantly, leading to increased weight and thicker coating. Tests show that compared with example 1, the bonding strength between the active material coating and the carbon-coated current collector in the finally prepared positive plate is not obviously improved. The reason is that the unique structure of the three-dimensional graphene powder can effectively improve the bonding strength, and the improvement of the bonding strength by improving the dosage of the binder does not greatly contribute to the improvement of the bonding strength. The heat dissipation performance and electrochemical performance of the battery are reduced due to the increase of the binder, which is caused by poor electric and heat conduction performance of the binder.
Example 4:
in this example, the difference is that the coating film parameters were changed to increase the amount of the slurry applied, thereby making the coating continuous and the thickness increased, and the other conditions were the same as in example (1).
Fig. 7 is an SEM photograph of the carbon-coated aluminum foil manufactured in this example, which shows that the coating layer is continuously dense, there is no missing coating phenomenon, and the amount of the slurry is increased. Tests show that the performance of the prepared battery is not changed greatly, which indicates that the performance of the battery cannot be further improved by increasing the use amount of the slurry.
Fig. 8 is a cross-sectional SEM photograph of the three-dimensional graphene carbon-coated aluminum foil according to the present example. It can be seen that the three-dimensional graphene powder is uniformly distributed on the surface of the aluminum foil, the agglomeration phenomenon is avoided, the thickness is distributed at 2 mu m, and the structure of the three-dimensional graphene powder can be seen visually.
Example 5:
this example provides a coating scheme of an oil-based carbon-coated slurry, in which the dispersant is 1% polyvinylpyrrolidone, the binder is 2% polyvinylidene fluoride, and the balance is solvent N-methylpyrrolidone, and the other conditions are the same as in example 1.
Example 6:
in this example, the difference is that a commercially available carbon black-coated aluminum foil is used as the current collector, and the battery assembly method is the same as in example 1.
Fig. 9 is an SEM photograph of the carbon-coated aluminum foil manufactured in this example. It can be seen that most of the carbon black particles in the coating are surrounded by binder. Tests show that the bonding strength between the carbon-coated current collector prepared in the present example and the positive active material coating is greatly reduced compared to example 1. Fig. 10 is an EIS spectrum of the carbon-coated aluminum foil produced in this example and the carbon-coated aluminum foil produced in example 1, showing that the resistance of the carbon-coated aluminum foil produced in this example is greatly increased compared to example 1. The results show that the three-dimensional graphene powder as a carbon-coated filler is superior to carbon black, and higher strength and conductivity can be obtained.
Example 7:
in this example, the difference is that a battery is assembled using a bare aluminum foil as a current collector, and the battery assembly method is the same as in example 1.
The carbon-coated aluminum foil articles of examples 1-7 were subjected to performance testing, and the specific performance testing data is shown in table 1.
TABLE 1
As can be seen from the test data recorded in table 1, the bonding strength of the pole piece active material coating using the carbon-coated aluminum foil prepared from the three-dimensional graphene powder as a current collector is greatly improved compared to that of the empty aluminum foil and the carbon black-coated aluminum foil, mainly because the contact area between the three-dimensional graphene powder and the active material can be greatly increased. The charge and discharge rate performance and the cycle stability of the battery manufactured by the carbon-coated aluminum foil current collector are obviously improved compared with those of a bare aluminum foil and a carbon black-coated aluminum foil, see example 1, the specific capacity under different rates is higher, the temperature rise during high-rate discharge is lower, and the cycle performance of the battery is also very excellent, so that the carbon-coated aluminum foil current collector disclosed by the invention fully proves that the polarization of the battery is reduced, and the heat dissipation effect, the rate performance and the cycle performance of the battery are improved.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. In addition, although specific terms are used herein, they are used for convenience of description and are not to be construed as limiting the present invention in any way, and other methods similar or equivalent thereto are also within the scope of the present invention.
Claims (11)
1. A preparation method of a carbon-coated current collector coated with three-dimensional graphene powder is characterized by comprising the following steps: which comprises the following steps:
(1) preparing slurry: preparing three-dimensional graphene powder, and then preparing the three-dimensional graphene powder into three-dimensional graphene powder slurry;
(2) coating: and uniformly coating the three-dimensional graphene powder slurry on a proper substrate to obtain the carbon-coated current collector.
2. The method for preparing the carbon-coated current collector coated with the three-dimensional graphene powder according to claim 1, wherein: the step (1) specifically comprises the following steps:
(1.1) mixing and uniformly stirring three-dimensional graphene powder and a dispersing agent, dissolving in a proper solvent, and uniformly mixing by sanding to obtain a three-dimensional graphene dispersion liquid;
(1.2) screening the three-dimensional graphene dispersion liquid to remove large particles;
and (1.3) mixing the three-dimensional graphene dispersion liquid with the binder solution according to a proper proportion, and fully and uniformly stirring by using a stirrer to obtain three-dimensional graphene powder slurry.
3. The method for preparing the carbon-coated current collector coated with the three-dimensional graphene powder according to claim 2, wherein: the three-dimensional graphene powder, the binder and the dispersant are respectively prepared from the following components in percentage by mass: 2-15% of three-dimensional graphene powder, 1-5% of a binder, 0.2-5% of a dispersant and the balance of a solvent.
4. The method for preparing the carbon-coated current collector coated with the three-dimensional graphene powder according to claim 2 or 3, wherein: the solvent is one or more of N-methyl pyrrolidone, ethanol or water.
5. The method for preparing the carbon-coated current collector coated with the three-dimensional graphene powder according to claim 2 or 3, wherein: the binder is water-based or oil-based.
6. The method for preparing the carbon-coated current collector coated with the three-dimensional graphene powder according to claim 2 or 3, wherein: the binder is one or a mixture of polyacrylic acid, polyvinyl alcohol, styrene butadiene rubber, polyacrylonitrile, sodium carboxymethylcellulose, acrylate multi-polymer and polyvinylidene fluoride.
7. The method for preparing the carbon-coated current collector coated with the three-dimensional graphene powder according to claim 2 or 3, wherein: the dispersing agent is one or a mixture of sodium deoxycholate, sodium dodecyl benzene sulfonate, polyethylene glycol, sodium dodecyl sulfate, polysorbate-80, polyvinylpyrrolidone and hexadecyl ammonium bromide.
8. The method for preparing the carbon-coated current collector coated with the three-dimensional graphene powder according to claim 2 or 3, wherein: the suitable substrate is copper foil, aluminum foil, stainless steel band, plastic film or fabric.
9. The method for preparing the carbon-coated current collector coated with the three-dimensional graphene powder according to claim 1, wherein: the three-dimensional graphene powder slurry is coated on the appropriate substrate in a blade coating, gravure printing, screen printing or electrostatic spinning mode.
10. The method for preparing the carbon-coated current collector coated with the three-dimensional graphene powder according to claim 1, wherein: the three-dimensional graphene powder in the step (1) is prepared by growing vertical graphene sheets on the surface of the nano-scale carbon black through chemical vapor deposition, the diameter is 50-150nm, and the conductivity reaches 5.0 multiplied by 105S/m。
11. The carbon-coated current collector prepared by the method for preparing the carbon-coated current collector coated with the three-dimensional graphene powder according to any one of claims 1 to 10.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112126335A (en) * | 2020-10-12 | 2020-12-25 | 松山湖材料实验室 | Heat dissipation coating, preparation method thereof and electronic device |
| CN112151806A (en) * | 2020-09-15 | 2020-12-29 | 浙江长宇新材料有限公司 | Ultra-light multilayer composite current collector and preparation method thereof |
| CN112210262A (en) * | 2020-10-13 | 2021-01-12 | 松山湖材料实验室 | Heat-conducting coating and preparation method thereof |
| CN112687901A (en) * | 2020-12-21 | 2021-04-20 | 松山湖材料实验室 | Three-dimensional graphene platinum-supported catalyst and preparation method and application thereof |
| 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 |
| CN113745511A (en) * | 2020-05-29 | 2021-12-03 | 广州汽车集团股份有限公司 | Conductive slurry, preparation method of conductive slurry, negative current collector, negative plate, lithium ion battery cell, lithium ion battery pack and application of negative current collector, negative plate, lithium ion battery cell and lithium ion battery pack |
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Application publication date: 20200519 |