CN109243671A - A kind of preparation method of graphene composite conductive slurry - Google Patents
A kind of preparation method of graphene composite conductive slurry Download PDFInfo
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- CN109243671A CN109243671A CN201811439341.3A CN201811439341A CN109243671A CN 109243671 A CN109243671 A CN 109243671A CN 201811439341 A CN201811439341 A CN 201811439341A CN 109243671 A CN109243671 A CN 109243671A
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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Abstract
The invention proposes a kind of preparation methods of graphene composite conductive slurry; specific step is as follows: (1) preparing graphene powder: preparing graphene oxide solution by modified Hummers method; then ultrasonic ball milling is stirred; freeze-drying obtains graphene oxide powder, and graphene powder is restored to obtain under nitrogen protection；(2) it prepares graphene composite conductive slurry: graphene powder is added in solvent, stir ultrasonic ball milling dispersion, add dispersing agent, the same ultrasound ball milling that stirs further disperses, then shearing dispersion is carried out with high speed shearing emulsification homogenizer, last centrifuging and taking upper liquid is to get arriving finely dispersed graphene composite conductive slurry.This method preparation is simple, and at low cost, short preparation period, good dispersion is not susceptible to reunite, and good conductivity can be widely applied in production.
Description
Technical field
The present invention relates to electrocondution slurry preparation fields, particularly relate to a kind of preparation method of graphene composite conductive slurry.
Background technique
The energy also brings many serious problems to us while pushing human social development, such as: energy crisis, ring
Border pollution.In order to solve these problems, it is now desired to which we find reproducible clean energy resource, such as: solar energy, wind energy, biology
Energy, tide energy etc..These renewable and clean energy resources have many advantages, such as abundance, cleaning, environmental protection, pollution-free, but are using
In the process, there are many problems has dependence to environmental requirement height；Energy fluctuation is big, cannot continue to supply.Electrochemistry storage
Energy device can export these energy storages again when to be used.Lithium ion battery has energy as optimal energy storage device
The advantages that metric density is high, self-discharge rate is low, have extended cycle life, safety and environmental protection, memory-less effect, is now widely used for our and gives birth to
In producing and living.
Lithium ion battery is mainly made of anode, cathode, electrolyte, diaphragm etc., and opposite and other components, anode is entire
The ratio highest accounted in battery, and also maximum is influenced on battery performance, so mostly important to the research of anode.Positive electrode is general
All over having a problem that: poorly conductive, this just affects the insertion and abjection of lithium ion between the materials, to limit entire lithium
The performance of ion battery usually will add conductive agent in anode preparation, to improve the electric conductivity of positive electrode.
Graphene is as one kind with carbon atom sp2The bi-dimensional cellular shape nano crystal material that hydridization is formed is in the world most
Thin carbon material has one layer of carbon atom thickness.Graphene has some advantages as conductive agent: 1. graphene is lighter, does
When conductive agent, additional amount is few；2. graphene has excellent conduction, heating conduction, when doing conductive agent, can be very good to improve electricity
The electric conductivity of pole material.
Currently, apply the research on conductive agent to have much graphene, a generally existing serious problem: graphite
Alkene poor dispersion is easy to happen reunion when doing conductive agent, to influence electric conductivity.
Summary of the invention
The present invention proposes a kind of preparation method of graphene composite conductive slurry, this method is simple, it is at low cost, preparation week
Phase is short, and the good dispersion of graphene composite conductive slurry is made, is not susceptible to reunite, good conductivity can be widely used in life
In production.
The technical scheme of the present invention is realized as follows:
A kind of preparation method of graphene composite conductive slurry, the specific steps are as follows:
(1) it prepares graphene powder: graphene oxide solution being prepared by modified Hummers method, then stirring ultrasound
Ball milling, freeze-drying obtain graphene oxide powder, graphene powder are restored to obtain under nitrogen protection；
(2) it prepares graphene composite conductive slurry: graphene powder obtained by step (1) is added in solvent, stirring is super
The dispersion of sound ball milling, adds dispersing agent, same to stir ultrasonic ball milling and further disperse, then with high speed shearing emulsification homogenizer into
Row shearing dispersion, last centrifuging and taking upper liquid to get arrive finely dispersed graphene composite conductive slurry.
Preferably, in step (1), the raw material for preparing graphene oxide solution is natural flake graphite, the natural scale
The mesh number of graphite is 325~800 mesh.
Preferably, in step (1), the concentration of graphene oxide solution is 0.1~1mg/ml, speed of agitator is 1000~
2000rmp, mixing time be 1~3h, ultrasonic power be 600~1000W, ultrasonic time be 1~3h, rotational speed of ball-mill be 600~
1200rmp, Ball-milling Time are 30min~1.5h, and reduction temperature is 200~500 DEG C, and the recovery time is 1.5~3h.
Preferably, in step (2), the mass ratio of graphene powder and solvent is 1: 20~1: 10.
Preferably, in step (2), the solvent is water, methanol, ethyl alcohol, acetone, N-Methyl pyrrolidone, N-N dimethyl
One or more of acetamide, isopropanol.
Preferably, in step (2), dispersing agent is dodecyl sodium sulfate, neopelex, cetyl bromination
One or more of ammonium, polyethylene glycol, Kynoar, polyvinylpyrrolidone, sodium carboxymethylcellulose.
Preferably, in step (2), speed of agitator is 1000~2000rmp, and mixing time is 1~3h, and ultrasonic power is
600~1000W, ultrasonic time are 1~3h, and rotational speed of ball-mill is 600~1200rmp, and Ball-milling Time is 30min~1.5h, high speed
It is 3~5h that emulsification pretreatment homogenizer, which shears jitter time, and centrifugal rotational speed is 3000~5000rmp, and centrifugation time is 2~8min.
The present invention also provides a kind of graphene composite conductive slurries prepared using the above method.
The invention has the benefit that
1. the present invention prepares the graphene oxide solution of low concentration using modified Hummers method, freeze-drying, nitrogen is also
Original obtains graphene powder, obtains 3~5 layers of graphene powder, and suppleness is high；It is multiple since the concentration of graphene oxide solution is low
Conjunction is easier to disperse when preparing electrocondution slurry.
2. the ultrasonic ball milling of stirring is used for multiple times in the present invention, and shearing point is carried out using with high speed shearing emulsification homogenizer
Dissipate, the dispersibility for repeatedly improving graphene may be implemented, and use graphene as conductive material, can make up it is respective not
Foot, further increases the electric conductivity of positive electrode.
3. this method preparation is simple, at low cost, short preparation period, good dispersion is not susceptible to reunite, and good conductivity can
To be widely applied in production.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
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 creative efforts belongs to the model that the present invention protects
It encloses.
Embodiment 1
A kind of preparation method of graphene composite conductive slurry, the specific steps are as follows:
(1) using the natural flake graphite of 500 mesh as raw material, graphene oxide solution is prepared by modified Hummers method,
And its concentration is formulated as 0.1mg/ml, then stir 3h under 2000rmp revolving speed, the ultrasound 1.5h under 800W power,
Ball milling 1.5h under 1000rmp revolving speed finally under nitrogen protection restores 3h under 500 DEG C of reduction temperatures and obtains graphene powder；
(2) preparation of graphene composite conductive slurry: graphene powder is added in solvent, stirs ultrasonic ball milling point
It dissipates, adds dispersing agent, the same ultrasound ball milling that stirs further disperses, and then carries out shearing point with high speed shearing emulsification homogenizer
Dissipate, last centrifuging and taking upper liquid to get arrive finely dispersed graphene composite conductive slurry.
The mass ratio of graphene powder and solvent is 1: 8, the component of solvent are as follows: 70%N- methyl pyrrolidone, 30%
N-N dimethyl acetamide, then 3h is stirred under 2000rmp revolving speed, the ultrasound 1.5h under 800W power, under 1000rmp revolving speed
Ball milling 1.5h；Dispersing agent is added in scattered solvent mixed solution, dispersing agent are as follows: the 20% 12 of dispersing agent gross mass
Sodium alkyl sulfonate, 20% neopelex, 10% Kynoar, 30% polyvinylpyrrolidone, 20% carboxymethyl
Sodium cellulosate equally stirs 3h under 2000rmp revolving speed, ultrasound 1.5h, the ball milling under 1000rmp revolving speed under 800W power
1.5h, then shearing dispersion 5h is carried out with high speed shearing emulsification homogenizer；It finally is centrifuged 5min under 3000rmp revolving speed, is divided
The graphene composite conductive slurry dissipated.
By the graphene composite conductive slurry of preparation with iron phosphate lithium electrode active material is compound prepares electrode slice, then group
It dresses up button cell and carries out electrochemical property test.Compared with the button cell of no addition graphene, in same test condition
Under, cycle performance improves 30%.
Embodiment 2
The concentration of the graphene oxide solution of preparation is 1mg/ml, and other processes are the same as embodiment 1.
By the graphene composite conductive slurry of preparation with iron phosphate lithium electrode active material is compound prepares electrode slice, then group
It dresses up button cell and carries out electrochemical property test.Compared with the button cell of no addition graphene, in same test condition
Under, cycle performance improves 10%.
Embodiment 3
The mass ratio of graphene powder and solvent is 1: 10, and other processes are the same as embodiment 1.
By the graphene composite conductive slurry of preparation with iron phosphate lithium electrode active material is compound prepares electrode slice, then group
It dresses up button cell and carries out electrochemical property test.Compared with the button cell of no addition graphene, in same test condition
Under, cycle performance improves 15%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of graphene composite conductive slurry, which is characterized in that specific step is as follows:
(1) it prepares graphene powder: graphene oxide solution is prepared by modified Hummers method, then stir ultrasonic ball milling,
Freeze-drying obtains graphene oxide powder, and graphene powder is restored to obtain under nitrogen protection；
(2) it prepares graphene composite conductive slurry: graphene powder obtained by step (1) is added in solvent, stir ultrasonic ball
Mill dispersion, adds dispersing agent, and the same ultrasound ball milling that stirs further disperses, and is then cut with high speed shearing emulsification homogenizer
Cutting dissipate, last centrifuging and taking upper liquid to get arrive finely dispersed graphene composite conductive slurry.
2. a kind of preparation method of graphene composite conductive slurry as described in claim 1, which is characterized in that in step (1),
The raw material for preparing graphene oxide solution is natural flake graphite, and the mesh number of the natural flake graphite is 325~800 mesh.
3. a kind of preparation method of graphene composite conductive slurry as described in claim 1, which is characterized in that in step (1),
The concentration of graphene oxide solution is 0.1~1mg/ml, and speed of agitator is 1000~2000rmp, and mixing time is 1~3h, is surpassed
Acoustical power be 600~1000W, ultrasonic time be 1~3h, rotational speed of ball-mill be 600~1200rmp, Ball-milling Time be 30min~
1.5h, reduction temperature are 200~500 DEG C, and the recovery time is 1.5~3h.
4. a kind of preparation method of graphene composite conductive slurry as described in claim 1, which is characterized in that in step (2),
The mass ratio of graphene powder and solvent is 1: 20~1: 10.
5. a kind of preparation method of graphene composite conductive slurry as described in claim 1, which is characterized in that in step (2),
Solvent is one or more of water, methanol, ethyl alcohol, acetone, N-Methyl pyrrolidone, N-N dimethyl acetamide, isopropanol.
6. a kind of preparation method of graphene composite conductive slurry as described in claim 1, which is characterized in that in step (2),
Dispersing agent is dodecyl sodium sulfate, neopelex, cetyl ammonium bromide, polyethylene glycol, Kynoar, gathers
One or more of vinylpyrrolidone, sodium carboxymethylcellulose.
7. a kind of preparation method of graphene composite conductive slurry as described in claim 1, which is characterized in that in step (2),
Speed of agitator is 1000~2000rmp, and mixing time is 1~3h, and ultrasonic power is 600~1000W, and ultrasonic time is 1~3h,
Rotational speed of ball-mill is 600~1200rmp, and Ball-milling Time is 30min~1.5h, and high speed shearing emulsification homogenizer shearing jitter time is
3~5h, centrifugal rotational speed are 3000~5000rmp, and centrifugation time is 2~8min.
8. the graphene composite conductive slurry of the method according to claim 1 to 7 preparation.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109811382A (en) * | 2019-03-28 | 2019-05-28 | 烟台恒诺新材料有限公司 | A kind of application of graphene oxide conductive paste in black holesization is directly electroplated |
| CN110868768A (en) * | 2019-10-25 | 2020-03-06 | 中国航发北京航空材料研究院 | Metal fiber reinforced graphite composite membrane for preventing and removing ice, preparation method and structure |
| CN111172744A (en) * | 2019-12-30 | 2020-05-19 | 比音勒芬服饰股份有限公司 | Electromagnetic wave absorbing composite textile fabric and preparation method thereof |
| CN111697232A (en) * | 2020-06-11 | 2020-09-22 | 内蒙古中科四维热管理材料有限公司 | Preparation methods of conductive agent and electrode plate and assembly method of battery |
| CN112890300A (en) * | 2021-02-05 | 2021-06-04 | 东莞市中科智恒新材料有限公司 | Far infrared quartz tube applied to low-temperature non-combustible electronic cigarette atomizer and preparation method thereof |
| CN113135564A (en) * | 2021-05-11 | 2021-07-20 | 中钢集团南京新材料研究院有限公司 | Preparation method of stable graphene aqueous dispersion liquid |
| CN113745517A (en) * | 2021-08-25 | 2021-12-03 | 金川集团股份有限公司 | Preparation method of conductive paste |
| CN113745518A (en) * | 2021-08-25 | 2021-12-03 | 金川集团股份有限公司 | Preparation method of graphene composite conductive slurry |
| CN114023510A (en) * | 2021-10-28 | 2022-02-08 | 山东华冠智能卡有限公司 | Preparation method of aqueous graphene conductive paste |
| CN114264699A (en) * | 2021-12-10 | 2022-04-01 | 重庆石墨烯研究院有限公司 | Preparation method of graphene electrode of gas sensor |
| CN114744159A (en) * | 2022-05-07 | 2022-07-12 | 中国人民解放军陆军工程大学 | Battery cathode slurry manufacturing method and battery |
| CN115093692A (en) * | 2022-06-27 | 2022-09-23 | 中国石油大学(北京) | Graphene composite electromagnetic shielding film and preparation method thereof |
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| CN106654204A (en) * | 2016-12-15 | 2017-05-10 | 中国航空工业集团公司北京航空材料研究院 | Preparation method for graphene conductive slurry |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109811382A (en) * | 2019-03-28 | 2019-05-28 | 烟台恒诺新材料有限公司 | A kind of application of graphene oxide conductive paste in black holesization is directly electroplated |
| CN109811382B (en) * | 2019-03-28 | 2021-04-20 | 烟台恒诺新材料有限公司 | Application of graphene oxide conductive paste in black hole direct electroplating |
| CN110868768A (en) * | 2019-10-25 | 2020-03-06 | 中国航发北京航空材料研究院 | Metal fiber reinforced graphite composite membrane for preventing and removing ice, preparation method and structure |
| CN111172744A (en) * | 2019-12-30 | 2020-05-19 | 比音勒芬服饰股份有限公司 | Electromagnetic wave absorbing composite textile fabric and preparation method thereof |
| CN111697232A (en) * | 2020-06-11 | 2020-09-22 | 内蒙古中科四维热管理材料有限公司 | Preparation methods of conductive agent and electrode plate and assembly method of battery |
| CN112890300A (en) * | 2021-02-05 | 2021-06-04 | 东莞市中科智恒新材料有限公司 | Far infrared quartz tube applied to low-temperature non-combustible electronic cigarette atomizer and preparation method thereof |
| CN113135564A (en) * | 2021-05-11 | 2021-07-20 | 中钢集团南京新材料研究院有限公司 | Preparation method of stable graphene aqueous dispersion liquid |
| CN113745517A (en) * | 2021-08-25 | 2021-12-03 | 金川集团股份有限公司 | Preparation method of conductive paste |
| CN113745518A (en) * | 2021-08-25 | 2021-12-03 | 金川集团股份有限公司 | Preparation method of graphene composite conductive slurry |
| CN114023510A (en) * | 2021-10-28 | 2022-02-08 | 山东华冠智能卡有限公司 | Preparation method of aqueous graphene conductive paste |
| CN114023510B (en) * | 2021-10-28 | 2024-05-14 | 山东华冠智能卡有限公司 | Preparation method of aqueous graphene conductive paste |
| CN114264699A (en) * | 2021-12-10 | 2022-04-01 | 重庆石墨烯研究院有限公司 | Preparation method of graphene electrode of gas sensor |
| CN114744159A (en) * | 2022-05-07 | 2022-07-12 | 中国人民解放军陆军工程大学 | Battery cathode slurry manufacturing method and battery |
| CN115093692A (en) * | 2022-06-27 | 2022-09-23 | 中国石油大学(北京) | Graphene composite electromagnetic shielding film and preparation method thereof |
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Application publication date: 20190118 |