CN108711625A - A kind of preparation method of graphene composite conductive agent for anode material for lithium-ion batteries - Google Patents
A kind of preparation method of graphene composite conductive agent for anode material for lithium-ion batteries Download PDFInfo
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- CN108711625A CN108711625A CN201810869651.2A CN201810869651A CN108711625A CN 108711625 A CN108711625 A CN 108711625A CN 201810869651 A CN201810869651 A CN 201810869651A CN 108711625 A CN108711625 A CN 108711625A
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- graphene
- conductive agent
- lithium
- ion batteries
- anode material
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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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- 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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- 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 belongs to field of composite material preparation, are a kind of preparation methods of graphene/carbon black combined conductive agent for anode material for lithium-ion batteries, include the following steps：（1）Dispersant is dispersed with stirring in solvent；（2）Graphene, conductive black are added to stir in above-mentioned dispersion liquid with certain proportion and soaked；（3）Above-mentioned mixed liquor is added in sand mill and carries out being fully ground mixing.Conductive agent prepared by the present invention can not only increase the electric conductivity of positive electrode, and can improve the analysis liquid and sedimentation phenomenon of pure graphene slurry.
Description
Technical field
The invention belongs to field of lithium ion battery, are related to a kind of graphene composite guide for anode material for lithium-ion batteries
The preparation method of electric agent.
Background technology
As energy and environment problem becomes increasingly conspicuous, lithium ion battery is got over as the application in electric powered motor source in recent years
Come more concerned.The specific energy density and specific power density of lithium ion battery are metal oxide on 4 times of nickel-cadmium cell
Lithium ion battery is the most wide battery types of current application range, and it is most potential power battery of electric vehicle to be recognized.
And the positive plate of lithium ion battery be determine its chemical property, security performance and Costco Wholesale key factor.
The positive main material of lithium ion battery has LiFePO4, LiMn2O4, cobalt acid lithium, nickel-cobalt-manganese ternary etc. at present, this is several
Kind material is the most common positive electrode of commercial Li-ion batteries, but the electron conduction of positive electrode is bad, it is difficult to full
The normal charge and discharge of sufficient battery, cycle and high rate performance etc..Improve positive electrode electric conductivity to improve battery charge and discharge, times
Rate performance is either still all of great significance in power battery application field in energy-storage battery.
Grapheme material has extraordinary electron conduction, is conducive to the electric conductivity for improving lithium ion cell positive, full
The requirements such as the normal charge and discharge of sufficient battery, cycle and high rate performance.Each carbon atom of graphene is sp2 hydridization, and is contributed
A remaining p orbital electron forms pi bond, and pi-electron can move freely, so graphene has excellent electric conductivity.Graphene
Interatomic force it is very strong, at normal temperatures, the interference that the electronics in graphene is subject to is smaller.Transmission of the electronics in graphene
Efficiency reaches 1.5 × 105cm2/ (Vs), conductivity is up to 106S/m, resistivity about 10-6Ω cm, it is lower than copper or silver,
It is one of the material of resistivity minimum.
Conductive black is the most widely used conductive agent in current lithium ion battery, and there is good ion and electronics to lead
Electric energy power.Single carbon black pellet has very big specific surface area（700 m2/g）, the high-specific surface area of particle and accumulation are close,
The conductive network for being conducive to be formed close contact in positive electrode, reduces the interface contact resistance of electrode, plays depolarising
Effect.
Studies have shown that the carbon materials such as graphene, carbon nanotube, conductive black can effectively improve electronics in positive-active material
Expect the migration velocity between particle and collector, to reduce the resistivity of positive electrode active materials, increases the conduction between active material
Property, and improve the utilization rate of active material.
Invention content
It is an object of the invention to the electric conductivity for anode active material of lithium ion battery is poor, a kind of graphite is provided
The preparation method of alkene and conductive black composite conducting slurry, the graphene/conductive black composite mortar can effectively promote lithium ion
The conductivity of cell positive material can not only improve the electric conductivity of positive electrode, but also can also protect cathode material structure,
Improve the power density and cyclical stability of lithium ion battery entirety.
The present invention is in order to solve the above technical problems, provide a kind of technical solution：One kind containing graphene, conductive black,
The conductive composite mortar of dispersant, the conduction composite mortar are made of graphene, conductive black, dispersant, organic solvent
Colloidal mixture.
The graphene that the present invention prepares/conductive black composite mortar is improved for graphene slurry is unstable, is led to
It crosses carbon black-filled between graphene layer, prevents graphene from returning folded, keep Stability of Slurry, and form finer and close conductive mesh
Network not only increases the conductivity of anode material for lithium-ion batteries, also improves upper chromatographic solution when pure graphene slurry storage
Problem is settled with lower layer, the constituent mass ratio of the graphene composite mortar is：Graphene（Graphene）) 1-2%, conductive black
（SP）3-4%, polyvinylpyrrolidone（PVP）1-1.5%, N-Methyl pyrrolidone（NMP）92.5%-95%.The present invention is specific
Preparation process is as follows：
Step（1）：Regulating environmental humidity is 30% hereinafter, taking quantitative NMP（N-Methyl pyrrolidone）Solvent is added in stirring pipe,
Setting speed of agitator is 800-1000r/min, and dispersant is added until being completely dissolved by several times, adds graphene powder, conduction
Carbon black, mechanical agitation 15-25min；
Step（2）：By step（1）Mixed liquor obtained, which is added in clean colloid mill, carries out pre-dispersed, grinding 2-3 times；
Step（3）：By step（2）Mixed liquor obtained is transferred in sand mill, ON cycle cooling water, is adjusted sand mill and is turned
The conductive composite mortar of graphene/conductive black is prepared in speed, circular grinding 1.5-2h.
In above-mentioned preparation process, the graphene is that size is more than 5 μm, and the number of plies is 5-10 layers, and piece interlamellar spacing is 0.3 nm-
1.0 nm。
In above-mentioned preparation process, a diameter of 70-120nm of the conductive black.
In above-mentioned preparation process, step（3）The granularity of obtained conductive composite mortar should be at 10 μm hereinafter, viscosity exists
10000 mPa s hereinafter, moisture in 3000 ppm or less.
The polyvinylpyrrolidone（PVP）Specification is k-30, k-50 or k-90.
The principle of the present invention is：
Using the superior electrical conductivity energy of graphene, while using the rigid microspheres architectural characteristic of conductive black, as conductive agent,
Fine and close efficient conductive network is built between active substances in cathode materials, improves the surface electronic conductive capability of positive electrode active materials,
Positive electrode active materials are enable to meet quick charge and discharge requirement.
The present invention has the following advantages：
Graphene and conductive black are fully ground in a solvent using sand mill in the present invention, carbon black is sufficient filling in graphene
Piece interlayer so that graphene is in good dispersity, and the conductive network node between positive electrode active materials is served as by graphene,
Conductive black can play synergistic effect simultaneously, serve as network branch line, connect positive electrode particle and graphene.
Graphene in the present invention has larger specific surface area, and conductive black is molecule, and the two is in anode
It is tightly packed in material, more efficient contact can be realized with positive active material, as shown in Figure 1, greatly reducing electrode active
The contact resistance of property material, and in the structure breaking that can prevent active material to a certain degree.
Conductive black is added in the present invention to be filled in graphene sheet layer, prevents from folding for its time, keeps the stability of slurry, has
Effect improves the upper chromatographic solution and lower layer's sedimentation phenomenon of pure graphene slurry.
It can be coated on graphene and conductive black surface using dispersant in the present invention, weaken Van der Waals for,
It can preferably realize the compound of carbon nanotube and carbon black.
The carbon black conductive agent added in the present invention is cheap.
The method of the present invention is simple for process, energy consumption is small, is suitable for large-scale production.
Description of the drawings
Fig. 1 is that graphene/conductive black composite mortar forms the structural schematic diagram contacted with positive electrode active materials.
Specific implementation mode
Embodiment 1：
Step（1）：It is first turned on dehumidifier, adjusts indoor humidity to 30% hereinafter, device therefor instrument is fully dry, NMP is used in combination
It cleans up；
Step（2）：The NMP of 940 g is weighed, is added in agitator tank, the PVP-K30 of 10g is added in whipping process, is waited for fully molten
The Graphene powder of 10g and the conductive black of 40g is added in Xie Hou, continues to stir, until dry powder fully soaks in solvent；
Step（3）：The complete composite mortar of above-mentioned wetting is transferred to and is sanded in machine equipment；
Step（4）：Adjustment sand mill rotating speed is 1000r/min, and 6h is sanded in cycle, while enabling circulating cooling water management sand mill
Feed bin temperature is at 55 DEG C hereinafter, the moisture result for measuring the graphene composite mortar is 2337ppm, testing graininess result
（D50）It it is 8 μm, viscosity test is 6500 mPa s；
Step（5）：By the graphene composite mortar in lithium ion battery ternary system material, according to ternary active material,
Kynoar, graphene composite mortar conductive agent mass ratio be 95: 3 :2 are made anode sizing agent (in terms of conductive agent),
It stirs evenly and is coated on plate glass, anode pole piece is obtained after drying.It is 30.5 Ω cm to measure the pole piece resistivity.
Embodiment 2：
Step（1）：It is first turned on dehumidifier, adjusts indoor humidity to 30% hereinafter, device therefor instrument is fully dry, NMP is used in combination
It cleans up；
Step（2）：The NMP of 940 g is weighed, is added in agitator tank, the PVP-K30 of 10g is added in whipping process, is waited for fully molten
The Graphene powder of 15g and the conductive black of 35g is added in Xie Hou, continues to stir, until dry powder fully soaks in solvent；
Step（3）：The complete composite mortar of above-mentioned wetting is transferred to and is sanded in machine equipment；
Step（4）：Adjustment sand mill rotating speed is 1000r/min, and 6h is sanded in cycle, while enabling circulating cooling water management sand mill
Feed bin temperature is at 55 DEG C hereinafter, the moisture result for measuring the graphene composite mortar is 2452ppm, testing graininess result
（D50）It it is 8.2 μm, viscosity test is 8521 mPa s；
Step（5）：By the graphene composite mortar in lithium ion battery ternary system material, according to ternary active material,
Kynoar, graphene composite mortar conductive agent mass ratio be 95: 3 :2 are made anode sizing agent (in terms of conductive agent),
It stirs evenly and is coated on plate glass, anode pole piece is obtained after drying.It is 43.3 Ω cm to measure the pole piece resistivity.
The test result of comparative example 1, since there is carbon black stronger oil absorption, accounting of the carbon black in conductive agent to carry
The viscosity test results of Gao Hou, embodiment 2 rise.
The test result of comparative example 1, the pole piece resistivity measurement result of embodiment 2 rise, but the result compared to
The pole piece resistance of the pure carbon black conductive agent anode of tradition is more superior.
Claims (9)
1. a kind of preparation method of graphene composite conductive agent for anode material for lithium-ion batteries, it is characterised in that method walks
It is rapid as follows：
（1）Take quantitative NMP（N-Methyl pyrrolidone）Solvent is added in stirring pipe, and setting speed of agitator is 800-1000r/min,
Dispersant is added by several times；
（2）Suitable conductive agent graphene powder, conductive black are weighed, is added dissolved in the nmp solvent of dispersant, setting is stirred
Speed 500-600r/min is mixed, conductive agent dry powder is made fully to soak in nmp solvent；
（3）The complete mixed liquor of above-mentioned wetting is added in clean colloid mill, is ground 2-3 times；
（4）Mixed liquor after above-mentioned grinding is transferred in sand mill, sand mill rotating speed is set, the control of sand mill feed bin temperature exists
55 DEG C hereinafter, cycle sand milling 1.5-2h, obtains graphene/conductive black composite mortar.
2. a kind of preparation side of graphene composite conductive agent for anode material for lithium-ion batteries according to claim 1
Method, it is characterised in that：The mass percent of each ingredient is：Graphene is 20-40 parts, and conductive black is 60-80 parts, and dispersant is
20 parts -25 parts, NMP is 3000-5000 parts, and the mass ratio of graphene and conductive black contained therein is 1:4-2:3.
3. a kind of preparation side of graphene composite conductive agent for anode material for lithium-ion batteries according to claim 1
Method, it is characterised in that：The conductive agent is the mixture of graphene, conductive black.
4. a kind of preparation side of graphene composite conductive agent for anode material for lithium-ion batteries according to claim 1
Method, it is characterised in that：The piece interlamellar spacing of the graphene is 0.3 nm-1.0 nm；The number of plies of the graphene is less than or equal to 10
Layer.
5. a kind of preparation side of graphene composite conductive agent for anode material for lithium-ion batteries according to claim 1
Method, it is characterised in that：A diameter of 70-120nm of the conductive black.
6. a kind of preparation side of graphene composite conductive agent for anode material for lithium-ion batteries according to claim 1
Method, it is characterised in that：The dispersant is polyvinylpyrrolidone（PVP）.
7. a kind of preparation side of graphene composite conductive agent for anode material for lithium-ion batteries according to claim 1
Method, it is characterised in that：The solvent is N-Methyl pyrrolidone（NMP）.
8. a kind of preparation side of graphene composite conductive agent for anode material for lithium-ion batteries according to claim 1
Method, it is characterised in that：Sand mill filled media used in grinding distribution is zirconia ball, and zirconium bulb diameter is in 0.8mm-1.2mm.
9. a kind of preparation side of graphene composite conductive agent for anode material for lithium-ion batteries according to claim 1
Method, it is characterised in that：Sand mill need to be equipped with cooling recirculation system, with control material temperature.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109637697A (en) * | 2018-12-24 | 2019-04-16 | 广东省稀有金属研究所 | A kind of graphene conductive slurry and preparation method thereof |
| CN110120499A (en) * | 2019-05-10 | 2019-08-13 | 华瑞墨石丹阳有限公司 | A kind of graphite nano plate and its preparation method and application |
| CN111785965A (en) * | 2020-05-22 | 2020-10-16 | 浙江兴海能源科技有限公司 | Nanoscale graphene material dispersing process |
| CN113659144A (en) * | 2021-08-09 | 2021-11-16 | 东莞市鹏威能源科技有限公司 | Graphene-based composite conductive agent, and preparation method and application thereof |
| CN114447269A (en) * | 2021-12-28 | 2022-05-06 | 华为数字能源技术有限公司 | Positive electrode conductive agent, preparation method thereof, positive electrode piece and battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109637697A (en) * | 2018-12-24 | 2019-04-16 | 广东省稀有金属研究所 | A kind of graphene conductive slurry and preparation method thereof |
| CN110120499A (en) * | 2019-05-10 | 2019-08-13 | 华瑞墨石丹阳有限公司 | A kind of graphite nano plate and its preparation method and application |
| CN111785965A (en) * | 2020-05-22 | 2020-10-16 | 浙江兴海能源科技有限公司 | Nanoscale graphene material dispersing process |
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| CN113659144A (en) * | 2021-08-09 | 2021-11-16 | 东莞市鹏威能源科技有限公司 | Graphene-based composite conductive agent, and preparation method and application thereof |
| CN114447269A (en) * | 2021-12-28 | 2022-05-06 | 华为数字能源技术有限公司 | Positive electrode conductive agent, preparation method thereof, positive electrode piece and battery |
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Application publication date: 20181026 |