CN109065878A - A kind of preparation method of modified graphene composite graphite negative electrode material - Google Patents
A kind of preparation method of modified graphene composite graphite negative electrode material Download PDFInfo
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- CN109065878A CN109065878A CN201810927704.1A CN201810927704A CN109065878A CN 109065878 A CN109065878 A CN 109065878A CN 201810927704 A CN201810927704 A CN 201810927704A CN 109065878 A CN109065878 A CN 109065878A
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- modified graphene
- negative electrode
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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
- C01—INORGANIC CHEMISTRY
- 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 present invention relates to new energy battery material technical fields, specifically disclose a kind of preparation method of modified graphene composite graphite negative electrode material, steps are as follows: silane coupling agent being mixed with grapheme material and obtains mixture A in a solvent;Agitation and filtration obtains mixture B;By the isolated modified graphene material of mixture B;Modified graphene material and graphite cathode material are made into mixed solution;After mixed solution is centrifugated, solid is taken to dry to obtain modified graphene composite graphite negative electrode material.Utilize preparation method provided by the invention, after treatment by grapheme material, the specific surface area and surface for changing grapheme material can, to being more advantageous to the dispersion of graphene, and be not susceptible to reunite, with graphite carry out it is mixing cured after, silane coupling agent can be such that carbon nano-tube material and graphite material crosslinks, carbon-to-carbon network structure is formed, makes negative electrode material that there is better electric conductivity and mechanical strength, extends the service life of battery.
Description
Technical field
The present invention relates to new energy battery material technical field, specifically a kind of modified graphene composite graphite negative electrode material
Preparation method.
Background technique
The stable lattice structure of graphene makes carbon atom have outstanding electric conductivity, and the electronics in graphene moves in track
When dynamic, it will not be scattered due to lattice defect or introducing foreign atom, since interatomic force is very strong, at normal temperature,
Even if surrounding carbon atom telescopes, the interference that electronics is subject in graphene is also very small.
Graphene is the highest substance of mankind's known strength, also harder than diamond, and the intensity steel more best than in the world is also
Want upper 100 times high.
Since the single layer diameter general 1 of graphene is less than between nanometer, there is great specific surface area and surface energy, because
This, graphene is easy to reunite, and affects its uniformly dispersed and stability, cause with the composite material that is modified it
Between compatibility it is poor, make graphene uniform dispersion in the composite, to its surface modification it is very necessary.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of modified graphene composite graphite negative electrode material, to graphene into
Row surface modification, change surface can and surface tension, so that reducing reunion reaches better dispersion effect, then by modified graphene
Modified graphene composite graphite negative electrode material is made with after graphite mixing, carries out it using having as cell negative electrode material
Better conductive effect and mechanical strength.
In order to solve the above technical problems, the present invention provides a kind of preparation sides of modified graphene composite graphite negative electrode material
Method, comprising the following steps:
S1, silane coupling agent and grapheme material are blended in Solvents N-methyl pyrrolidines in the ratio of 0.01~0.2:1
Mixture A is obtained in ketone;
Mixture B is obtained by filtration after stirring 1~2h in the case where temperature is 20~90 DEG C in S2, mixture A;
S3, mixture B is centrifugally separating to obtain modified graphene material;
S4, modified graphene material and graphite cathode material are mixed according to the ratio of 1:4~30, solvent are added,
It is made into the solid mixed solution containing 5%-25%;
S5, after being centrifugated the solid mixed solution containing 5%-25%, solid is taken to dry to obtain modified graphene composite stone
Black negative electrode material.
Further, the particle size range of graphene described in S1 is 0.1nm-50nm, and the general formula of the silane coupling agent is
R-Si(OR1)3Or R R2-Si(OR1)2。
Specifically, the R is hydrogen atom, methyl, ethyl, propyl, butyl, phenyl, cyclohexyl, vinyl, acrylic, ammonia
Propyl, aminoethylaminopropyl, mercaptopropyi or anilinomethyl;R1For methyl or ethyl, R2For hydrogen atom, methyl or ethyl.
Further, the mode of mixing described in S1 and S4 is one of mechanical stirring, ultrasonic disperse or ball milling dispersion
Or it is several.
Further, solvent described in S4 is water, C1-5Fatty alcohol or one of ether or a variety of, the C1-5Rouge
Fat alcohol is ethyl alcohol, methanol, propyl alcohol, butanol or amylalcohol.
Specifically, drying temperature described in S5 is 50~300 DEG C, and drying time is 1~5h, is dried in nitrogen atmosphere
It is dry.
The beneficial effects of the present invention are: being modified grapheme material using preparation method provided by the invention, change
The specific surface area of grapheme material and surface can, to be more advantageous to the dispersion of graphene, and be not susceptible to reunite, then will change
Property graphene and graphite carry out it is mixing cured, the silane coupling agent in modified graphene can make carbon nano-tube material and graphite material
Material crosslinks, and forms carbon-to-carbon network structure, so that negative electrode material is had better electric conductivity and mechanical strength, extends battery
Service life.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
In an embodiment of the present invention, a kind of preparation side of modified graphene composite graphite negative electrode material is specifically disclosed
Method, comprising the following steps:
S1, silane coupling agent and grapheme material are blended in Solvents N-methyl pyrrolidines in the ratio of 0.01~0.2:1
Mixture A is obtained in ketone;
Mixture B is obtained by filtration after stirring 1~2h in the case where temperature is 20~90 DEG C in S2, mixture A;
S3, mixture B is centrifugally separating to obtain modified graphene material;
S4, modified graphene material and graphite cathode material are mixed according to the ratio of 1:4~30, solvent are added,
It is made into the solid mixed solution containing 5%-25%;
S5, will be after the solid mixed solution centrifuge separation containing 5%-25%, taking solid in temperature is 50~300 DEG C, in nitrogen
1~5h of drying obtains modified graphene composite graphite negative electrode material.
Embodiment 1:
By 2g silane coupling agent HSi (OC6H5)3It is blended in 30gN- methyl pyrrolidone and obtains with 10g grapheme material
Mixture A;Mixture A is filtered after 20 DEG C of stirring 1h, obtains mixture B;Mixture B is centrifugally separating to obtain modified carbon nano tube
Tube material;Modified graphene material and graphite cathode material are made into the alcohol mixed solution containing 25% admittedly according to the ratio of 1:4;
After mixed solution is centrifugated, modified graphene composite graphite negative electrode material is obtained after taking 50 DEG C of drying 5h of solid, as electricity
Pond negative electrode material uses.
Embodiment 2:
By 0.1g silane coupling agent CH3Si(OCH)3It is blended in 50gN- methyl pyrrolidone and obtains with 10g grapheme material
To mixture A;Mixture A is filtered after 90 DEG C of stirring 1h, obtains mixture B;Mixture B is centrifugally separating to obtain carbon modified to receive
Nanotube material;By modified graphene material and graphite cathode material according to the ratio of 1:30 be made into admittedly containing 5% propyl alcohol mix it is molten
Liquid after being centrifugated mixed solution, obtains modified graphene composite graphite negative electrode material after taking 300 DEG C of drying 1h of solid, makees
For cell negative electrode material use.
Embodiment 3:
By 1g silane coupling agent (CH3)2Si(OCH)3It is blended in 20gN- methyl pyrrolidone and obtains with 10g grapheme material
To mixture A;Mixture A is filtered after 50 DEG C of stirring 2h, obtains mixture B;Mixture B is centrifugally separating to obtain carbon modified to receive
Nanotube material;The mixing containing 10% admittedly is made into after modified graphene material and graphite cathode material are added water according to the ratio of 1:10
Solution after being centrifugated mixed solution, obtains modified graphene composite graphite negative electrode material after taking 10 DEG C of drying 3h of solid, makees
For cell negative electrode material use.
Comparative example: graphite cathode
Performance test
Negative electrode material and conductive carbon black are ground in mortar is uniformly mixed it, is added to the N- crassitude of PVDF
In ketone (NMP) solution, stir evenly, slurry is made, wherein negative electrode material: conductive carbon black: the mass ratio of PVDF is 90:5:5,
It is coated on copper foil, pole piece is made in drying, rolling.Being made with metal lithium sheet to electrode, Celgard2400 is diaphragm,
1mol/LLiPF6/EC (ethylene carbonate)+DMC (dimethyl carbonate)+EMC (methyl ethyl carbonate rouge) (volume ratio 1: 1: 1) is electrolysis
Liquid is assembled into simulated battery in the glove box of logical argon gas, carries out electrochemical property test after standing 12h.
The beneficial effects of the present invention are: being modified grapheme material using preparation method provided by the invention, change
The specific surface area of grapheme material and surface can, to be more advantageous to the dispersion of graphene, and be not susceptible to reunite, then will change
Property graphene and graphite carry out it is mixing cured, the silane coupling agent in modified graphene can make carbon nano-tube material and graphite material
Material crosslinks, and forms carbon-to-carbon network structure, so that negative electrode material is had better electric conductivity and mechanical strength, extends battery
Service life.
Above disclosed be only a kind of preferred embodiment of the invention, cannot limit the present invention's certainly with this
Interest field, therefore equivalent changes made in accordance with the claims of the present invention, are still within the scope of the present invention.
Claims (6)
1. a kind of preparation method of modified graphene composite graphite negative electrode material, which comprises the following steps:
S1, silane coupling agent and grapheme material are blended in solvent N-methyl pyrilidone in the ratio of 0.01~0.2:1
Obtain mixture A;
Mixture B is obtained by filtration after stirring 1~2h in the case where temperature is 20~90 DEG C in S2, mixture A;
S3, mixture B is centrifugally separating to obtain modified graphene material;
S4, modified graphene material and graphite cathode material are mixed according to the ratio of 1:4~30, solvent is added, is made into
Gu the mixed solution containing 5%-25%;
S5, will after the solid mixed solution centrifuge separation containing 5%-25%, take solid dry to obtain modified graphene composite graphite it is negative
Pole material.
2. a kind of preparation method of modified graphene composite graphite negative electrode material according to claim 1, which is characterized in that
The particle size range of graphene described in S1 is 0.1nm-50nm, and the general formula of the silane coupling agent is R-Si (OR1)3Or R R2-Si
(OR1)2。
3. a kind of preparation method of modified graphene composite graphite negative electrode material according to claim 2, which is characterized in that
The R is hydrogen atom, methyl, ethyl, propyl, butyl, phenyl, cyclohexyl, vinyl, acrylic, aminopropyl, aminoethyl ammonia third
Base, mercaptopropyi or anilinomethyl;R1For methyl or ethyl, R2For hydrogen atom, methyl or ethyl.
4. a kind of preparation method of modified graphene composite graphite negative electrode material according to claim 1, which is characterized in that
The mode of mixing described in S1 and S4 is one or more of mechanical stirring, ultrasonic disperse or ball milling dispersion.
5. a kind of preparation method of modified graphene composite graphite negative electrode material according to claim 1, which is characterized in that
Solvent described in S4 is water, C1-5Fatty alcohol or one of ether or a variety of.
6. a kind of preparation method of modified graphene composite graphite negative electrode material according to claim 1, which is characterized in that
Drying temperature described in S5 is 50~300 DEG C, and drying time is 1~5h, is dried in nitrogen atmosphere.
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Cited By (4)
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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 |
CN110745819A (en) * | 2019-10-25 | 2020-02-04 | 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 |
CN113161545A (en) * | 2021-05-18 | 2021-07-23 | 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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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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