CN109065878B - Preparation method of modified graphene composite graphite negative electrode material - Google Patents
Preparation method of modified graphene composite graphite negative electrode material Download PDFInfo
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- CN109065878B CN109065878B CN201810927704.1A CN201810927704A CN109065878B CN 109065878 B CN109065878 B CN 109065878B CN 201810927704 A CN201810927704 A CN 201810927704A CN 109065878 B CN109065878 B CN 109065878B
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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 relates to the technical field of new energy battery materials, and particularly discloses a preparation method of a modified graphene composite graphite negative electrode material, which comprises the following steps: mixing a silane coupling agent and a graphene material in a solvent to obtain a mixture A; stirring and filtering to obtain a mixture B; separating the mixture B to obtain a modified graphene material; preparing a modified graphene material and a graphite cathode material into a mixed solution; and after the mixed solution is subjected to centrifugal separation, drying the solid to obtain the modified graphene composite graphite cathode material. By utilizing the preparation method provided by the invention, the specific surface area and the surface energy of the graphene material are changed after the graphene material is treated, so that the dispersion of the graphene is more facilitated, the graphene is not easy to agglomerate, and after the graphene material and graphite are mixed and cured, the silane coupling agent can enable the modified graphene material and the graphite material to be crosslinked to form a carbon-carbon network structure, so that the cathode material has better conductivity and mechanical strength, and the service life of the battery is prolonged.
Description
Technical Field
The invention relates to the technical field of new energy battery materials, in particular to a preparation method of a modified graphene composite graphite negative electrode material.
Background
The stable lattice structure of the graphene enables carbon atoms to have excellent conductivity, electrons in the graphene do not scatter due to lattice defects or introduction of foreign atoms when moving in a track, and due to strong interatomic force, even if the surrounding carbon atoms collide with each other, the interference on the electrons in the graphene is very small at normal temperature.
Graphene is the highest known strength material in humans, is harder than diamond, and has a strength 100 times higher than the best steel in the world.
Because the single-layer diameter of the graphene is generally less than 1 nanometer, and the graphene has extremely large specific surface area and surface energy, the graphene is easy to agglomerate, the uniform dispersibility and stability of the graphene are influenced, the compatibility between the graphene and the modified composite material is poor, and the graphene is uniformly dispersed in the composite material and is necessary for surface modification of the graphene.
Disclosure of Invention
The invention aims to provide a preparation method of a modified graphene composite graphite cathode material, which is characterized in that graphene is subjected to surface modification to change surface energy and surface tension, so that agglomeration is reduced to achieve a better dispersion effect, and the modified graphene and graphite are mixed to prepare the modified graphene composite graphite cathode material which is used as a battery cathode material and has a better conductive effect and mechanical strength.
In order to solve the technical problem, the invention provides a preparation method of a modified graphene composite graphite negative electrode material, which comprises the following steps:
s1, mixing a silane coupling agent and a graphene material in a mass ratio of 0.01-0.2: 1 in a solvent N-methylpyrrolidone to obtain a mixture A;
s2, stirring the mixture A for 1-2 hours at the temperature of 20-90 ℃, and filtering to obtain a mixture B;
s3, centrifugally separating the mixture B to obtain a modified graphene material;
s4, mixing the modified graphene material and the graphite negative electrode material according to the mass ratio of 1: 4-30, adding a solvent to prepare a mixed solution with the solid content of 5-25%;
s5, centrifugally separating the mixed solution with the solid content of 5% -25%, and drying the solid to obtain the modified graphene composite graphite cathode material.
Further, the graphene in S1 has a particle size ranging from 0.1nm to 50nm, and the silane coupling agent has a general formula of R-Si (OR)1)3Or R R2-Si(OR1)2。
Specifically, the R is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a cyclohexyl group, a vinyl group, a propenyl group, an aminopropyl group, an aminoethylaminopropyl group, a mercaptopropyl group or an anilinomethyl group; r1Is methyl or ethyl, R2Is a hydrogen atom, a methyl group or an ethyl group.
Further, the mixing manner in S1 and S4 is one or more of mechanical stirring, ultrasonic dispersion or ball milling dispersion.
Further, the solvent described in S4 is water, C1-5One or more of the fatty alcohols or ethers of (A), C1-5The aliphatic alcohol of (a) is ethanol, methanol, propanol, butanol or pentanol.
Specifically, in S5, the drying temperature is 50-300 ℃, the drying time is 1-5 h, and drying is carried out in a nitrogen atmosphere.
The invention has the beneficial effects that: according to the preparation method provided by the invention, the graphene material is modified, the specific surface area and the surface energy of the graphene material are changed, so that the dispersion of the graphene is facilitated, the graphene is not easy to agglomerate, the modified graphene and the graphite are mixed and cured, and the silane coupling agent in the modified graphene can enable the modified graphene material and the graphite material to be crosslinked to form a carbon-carbon network structure, so that the cathode material has better conductivity and mechanical strength, and the service life of the battery is prolonged.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In an embodiment of the invention, a preparation method of a modified graphene composite graphite negative electrode material is specifically disclosed, and the preparation method comprises the following steps:
s1, mixing a silane coupling agent and a graphene material in a mass ratio of 0.01-0.2: 1 in a solvent N-methylpyrrolidone to obtain a mixture A;
s2, stirring the mixture A for 1-2 hours at the temperature of 20-90 ℃, and filtering to obtain a mixture B;
s3, centrifugally separating the mixture B to obtain a modified graphene material;
s4, mixing the modified graphene material and the graphite negative electrode material according to the mass ratio of 1: 4-30, adding a solvent to prepare a mixed solution with the solid content of 5-25%;
s5, centrifugally separating the mixed solution with the solid content of 5% -25%, and drying the solid in nitrogen for 1-5 hours at the temperature of 50-300 ℃ to obtain the modified graphene composite graphite negative electrode material.
Example 1:
2g of silane coupling agent HSi (OC)6H5)3Mixing the graphene powder with 10g of graphene material in 30g of N-methyl pyrrolidone to obtain a mixture A; stirring the mixture A for 1h at 20 ℃, and filtering to obtain a mixture B; carrying out centrifugal separation on the mixture B to obtain a modified graphene material; mixing the modified graphene material and the graphite negative electrode material according to the ratio of 1: 4 to prepare an ethanol mixed solution with the solid content of 25 percent; and (3) after the mixed solution is subjected to centrifugal separation, drying the solid at 50 ℃ for 5h to obtain the modified graphene composite graphite cathode material, and using the modified graphene composite graphite cathode material as a battery cathode material.
Example 2:
0.1g of silane coupling agent CH3Si(OCH)3Mixing the graphene powder with 10g of graphene material in 50g of N-methyl pyrrolidone to obtain a mixture A; stirring the mixture A at 90 ℃ for 1h, and filtering to obtain a mixture B; carrying out centrifugal separation on the mixture B to obtain a modified graphene material; mixing the modified graphene material and the graphite negative electrode material according to the ratio of 1: 30 ofPreparing a propanol mixed solution with the solid content of 5% in proportion, centrifugally separating the mixed solution, and drying the solid at 300 ℃ for 1h to obtain the modified graphene composite graphite cathode material which is used as a battery cathode material.
Example 3:
1g of silane coupling agent (CH)3)2Si(OCH)3Mixing the graphene powder with 10g of graphene material in 20g of N-methyl pyrrolidone to obtain a mixture A; stirring the mixture A at 50 ℃ for 2h, and filtering to obtain a mixture B; carrying out centrifugal separation on the mixture B to obtain a modified graphene material; mixing the modified graphene material and the graphite negative electrode material according to the ratio of 1: 10, adding water to prepare a mixed solution with the solid content of 10%, centrifugally separating the mixed solution, and drying the solid at 10 ℃ for 3h to obtain the modified graphene composite graphite cathode material which is used as a battery cathode material.
Performance testing
Grinding a negative electrode material and conductive carbon black in a mortar to uniformly mix the negative electrode material and the conductive carbon black, adding the ground negative electrode material and the conductive carbon black into an N-methylpyrrolidone (NMP) solution of PVDF, and uniformly stirring to prepare slurry, wherein the negative electrode material: conductive carbon black: and (3) coating PVDF on copper foil according to the mass ratio of 90:5:5, and drying and rolling to prepare the pole piece. A metal lithium sheet is used as a counter electrode, Celgard2400 is used as a diaphragm, 1mol/LLiPF6/EC (ethylene carbonate) + DMC (dimethyl carbonate) + EMC (ethyl methyl carbonate) (the volume ratio is 1: 1) is used as an electrolyte, a simulated battery is assembled in a glove box filled with argon, and the simulated battery is placed for 12 hours and then subjected to electrochemical performance test.
The invention has the beneficial effects that: according to the preparation method provided by the invention, the graphene material is modified, the specific surface area and the surface energy of the graphene material are changed, so that the dispersion of the graphene is facilitated, the graphene is not easy to agglomerate, the modified graphene and the graphite are mixed and cured, and the silane coupling agent in the modified graphene can enable the modified graphene material and the graphite material to be crosslinked to form a carbon-carbon network structure, so that the cathode material has better conductivity and mechanical strength, and the service life of the battery is prolonged.
The above disclosure is only one preferred embodiment of the present invention, and certainly should not be construed as limiting the scope of the invention, which is defined by the claims and their equivalents.
Claims (5)
1. The preparation method of the modified graphene composite graphite negative electrode material is characterized by comprising the following steps:
s1, mixing a silane coupling agent and a graphene material in a mass ratio of 0.01-0.2: 1 in a solvent N-methylpyrrolidone to obtain a mixture A;
s2, stirring the mixture A for 1-2 hours at the temperature of 20-90 ℃, and filtering to obtain a mixture B;
s3, centrifugally separating the mixture B to obtain a modified graphene material;
s4, mixing the modified graphene material and the graphite negative electrode material according to the mass ratio of 1: 4-30, adding water and C1-5One or more solvents in the fatty alcohol or the ether are prepared into mixed solution with the solid content of 5 to 25 percent;
s5, centrifugally separating the mixed solution with the solid content of 5% -25%, and drying the solid to obtain the modified graphene composite graphite cathode material.
2. The preparation method of the modified graphene composite graphite anode material as claimed in claim 1, wherein the particle size of the graphene in S1 is in the range of 0.1nm to 50nm, and the silane coupling agent has a general formula of R-Si (OR)1)3Or R R2-Si(OR1)2。
3. The preparation method of the modified graphene composite graphite anode material according to claim 2, wherein R is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a cyclohexyl group, a vinyl group, a propenyl group, an aminopropyl group, an aminoethylaminopropyl group, a mercaptopropyl group, or an anilinomethyl group; r1Is a methyl group or an ethyl group,R2is a hydrogen atom, a methyl group or an ethyl group.
4. The preparation method of the modified graphene composite graphite negative electrode material of claim 1, wherein the mixing manner in S1 and S4 is one or more of mechanical stirring, ultrasonic dispersion and ball milling dispersion.
5. The preparation method of the modified graphene composite graphite negative electrode material of claim 1, wherein the drying temperature in S5 is 50-300 ℃, the drying time is 1-5 h, and the drying is performed in a nitrogen atmosphere.
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| CN110459743A (en) * | 2019-07-23 | 2019-11-15 | 东莞市创明电池技术有限公司 | Lithium ion battery negative material and preparation method thereof applied to fast charging and discharging |
| CN110745819B (en) * | 2019-10-25 | 2022-02-18 | 哈尔滨工业大学 | Method for modifying surface of graphite material by using silane coupling agent, lithium ion battery cathode and preparation method thereof |
| CN113161545B (en) * | 2021-05-18 | 2022-06-24 | 芜湖天弋能源科技有限公司 | Graphene and graphite composite material, preparation method and application of graphene and graphite composite material as lithium ion battery negative electrode material |
| CN113809299A (en) * | 2021-09-14 | 2021-12-17 | 远景动力技术(江苏)有限公司 | Negative electrode active material, negative electrode sheet, preparation method and application of negative electrode sheet |
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