CN110391418A - A kind of High-performance graphene composite conducting slurry and preparation method thereof - Google Patents
A kind of High-performance graphene composite conducting slurry and preparation method thereof Download PDFInfo
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- CN110391418A CN110391418A CN201810397911.0A CN201810397911A CN110391418A CN 110391418 A CN110391418 A CN 110391418A CN 201810397911 A CN201810397911 A CN 201810397911A CN 110391418 A CN110391418 A CN 110391418A
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- graphene
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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
- C01B32/158—Carbon nanotubes
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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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- 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
- H01M4/362—Composites
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
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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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- 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
A kind of High-performance graphene composite conducting slurry and preparation method thereof.The present invention is to use the grapheme material of classification and functional modification as the raw material of slurry, combined conductive agent is formed by the way that carbon nanotube is added again, realize the combination of " line " and graphene " face " of carbon nanotube, play the advantage and its positive synergistic effect of respective material, it solves the problems, such as that graphene easily stacks and the winding easy to reunite of carbon pipe is difficult to disperse, has obtained slurry evenly dispersed, that stability is good；In addition, preparation method is simple, process costs are low, it is suitble to large-scale industrial production and application, may be used as the conductive agent of anode, negative electrode material, there is excellent chemical property.
Description
Technical field:
The present invention relates to a kind of electrocondution slurries and preparation method thereof, and in particular to a kind of graphene composite conductive slurry and its
Preparation method.
Background technique:
From the point of view of current development trend, lithium ion battery is due to energy density height, having extended cycle life and memoryless effect
Outstanding advantages of answering a, it has also become Main way of automobile power cell development.However, due to anode material for lithium-ion batteries
Lower electronic conductivity and lithium ion diffusion rate, seriously constrain giving full play to for its theoretical capacity, therefore, it has become resistances
The big bottleneck problem for hindering performance of lithium ion battery to be promoted.Faced with this situation, people are often through the method for adding conductive agent
To form effective conductive network.Specifically, when a certain amount of conductive agent is added, small conductive agent particle can fill up active material
Expect void among particles, is effectively contacted so that realizing between conductive agent and active material and between conductive agent particle, thus
Form good conductive network；
Although addition conductive agent will increase the electric conductivity of lithium ion battery electrode material, excessive addition can then reduce electricity
The energy density of pole.And traditional conductive agent needs more additional amount, could form good conductive network, and therefore, exploitation
New and effective conductive agent has become an important topic of Study on Li-ion batteries and exploitation.
Graphene as a kind of Novel Carbon Nanomaterials, is made of single layer of carbon atom layer, is two dimension truly
Crystal structure, it have unique two dimensional crystal structure and high charge migration rate, while it also have large specific surface area,
The advantages that chemical property stabilization, high-termal conductivity and high mechanical strength, it is considered to be most have one of the material of application prospect.However have
Report points out that graphene individually does lithium electricity conductive agent in use, the graphene of sheet can hinder the transmission of lithium ion, therefore meeting shadow
The performances such as the multiplying power of battery are rung, and the present invention uses supercritical CO2The method that flow process and functional modification combine is prepared into
Raw material of the grapheme material arrived as slurry, then combined conductive agent is formed by the way that carbon nanotube is added, realize carbon nanotube
" line " and graphene " face " combination, play the advantage and its positive synergistic effect of respective material, solve the easy heap of graphene
The problem of folding, lithium ion transport and carbon pipe winding hardly possible easy to reunite hindered to disperse, to obtain slurry evenly dispersed, that stability is good
Material.
Summary of the invention:
Present invention aims to the technique combined with a variety of dispersion means come serialization preparation can scale, it is low at
Originally, high performance graphene composite conductive slurry.
High-performance graphene composite conducting slurry prepared by the present invention includes the graphene/carbon nanometer that content is 3-8wt%
Pipe mixture, 0.5-2wt% dispersing agent and 90-96.5wt% solvent.
The preparation method of the graphene is to utilize supercritical CO creatively using supercritical fluid method2Fluid matasomatism
In graphite composite powder raw material, and make to make supercritical CO with supplementary means2Into graphite layers, by optimizing preparation technology parameter, from
And produce the graphene powder of high quality.The graphene powder being prepared will not destroy the structure of graphene sheet layer, also not have
There are oxidation-reduction method graphene bring fault of construction and group residual, there is high conductivity, high-termal conductivity and outstanding machinery
Etc. performances, electrode material of lithium battery can be preferably applied for.
The carbon nanotube, can be single-walled carbon nanotube, be also possible to multi-walled carbon nanotube, it is preferable that can choose
Caliber is less than the carbon nanotube of 6nm, because the carbon nanotube of this diameter can be seen as One-dimensional Quantum conducting wire, has and well leads
Electrical property.
The dispersing agent is divided into aqueous medium, Qiang Youji phase medium and weak organic phase medium, it may be preferable that for aqueous Jie
Matter can select carbon nanotube water dispersant (TNMDIS)；Alcohols can be selected for highly polar organic phase medium, DMF, NMF,
TNADIS；Phase medium organic for middle polarity can select esters, liquid-state epoxy resin, fluid silicone rubber, TNEDIS.
The High-performance graphene composite conducting slurry is so that each material is uniformly mixed using pre-dispersed equipment and technique
It closes, then is dispersed in a solvent with making carbon nanotube and graphene uniform by preferred dispersing apparatus and dispersing technology condition afterwards, shape
At stablizing available electrocondution slurry.Graphene conductive blank preparation technics route map is as shown in Fig. 1.
The dispersing technology of the High-performance graphene composite conducting slurry can be using " first grinding distribution, rear ultrasonic wavelength-division
Dissipate " combined method, can make graphene, carbon nanotube mixture in different viscosities medium in this way, especially middle and high viscosity is situated between
Efficient in matter, stable dispersion.
One of preferably, the dispersing method of the High-performance graphene composite conducting slurry specifically includes:
(1) graphene/carbon nano-tube dispersion liquid is prepared first, and decentralized medium can be water or N-Methyl pyrrolidone；
(2) sand mill is ground, and can select laboratory dispersion sand mill or small-sized basket type sand mill, sanding media can select
It is 1.0-1.2mm or smaller bead, steel ball, zirconium silicate pearl or zirconium oxide bead with diameter, can adds and disappear in sand grinding process
Infusion reduces influence of the foam to dispersion effect；
(3) ultrasonic disperse.Ultrasonic grinder or supersonic wave cleaning machine can be selected, is issued due to ultrasonic grinder
Ultrasound energy density height (energy concentrates in amplitude transformer rather than in a plane), frequency are low, are more suitable for graphene, carbon is received
The dispersion of mitron.
(4) centrifugal treating after ultrasonic, by dispersion liquid centrifugal sedimentation, removes not scattered agglomerated particles.Centrifugation knot
Supernatant liquid is crossed 300 mesh filter clothes, obtains final graphene/carbon nano-tube dispersion liquid by Shu Hou.The stone prepared using this step
Black alkene/carbon nano tube dispersion liquid stability is good, can at least place half a year or more, but the disadvantage is that needs to recalculate stone in dispersion liquid
Black alkene, the content of carbon nanotube.
Compared with traditional simple carbon black and carbon nano-tube material, " first grinding distribution, rear ultrasonic wavelength-division that the present invention uses
Dissipate " the obtained High-performance graphene composite conducting slurry of dispersing technology dispersion effect is more preferable in a solvent, such as attached drawing 2.
High-performance graphene composite conducting slurry provided by the invention is the carbon nanotube and two-dimentional planar one-dimensional linear
Graphene connect combination, with electrode active material extraordinary conductive network easy to form, pass through the conductive paste of compounding preparation
Expecting the conductive agent than any single component has better performance, such as attached drawing 3.
The preparation method of High-performance graphene composite conducting slurry of the invention is simple, process costs are low, is suitble to extensive
Industrialized production and application, may be used as the conductive agent of anode, negative electrode material, have excellent chemical property.
Detailed description of the invention:
Attached drawing 1: graphene conductive blank preparation technics route map；
Attached drawing 2: the dispersion feelings of pure nano-carbon tube dispersion liquid (figure A) and graphene/carbon nano-tube compound dispersion liquid (figure B)
Condition compares；
Attached drawing 3: graphene/carbon nano-tube composite mortar is compared with carbon nanotube, the performance of carbon black conductive agent
Specific embodiment:
Below by specific example, the present invention is described further, and preferred embodiment described herein is only used for
The description and interpretation present invention, is not intended to limit the present invention.
Embodiment 1
Present embodiments provide a kind of preparation method of High-performance graphene composite conducting slurry based on water phase comprising
Following steps:
1, carbon nanotube is dissolved in dispersing agent (TNWMIS) according to 1: 1 ratio, after mixing evenly, in sand mill
It is fully ground, sanding media is the alumina bead (specific gravity 7.8) that diameter is 1.0mm.It is added again into carbon nano tube dispersion liquid super
The graphene of critical fluids method preparation, obtained graphene/carbon nano-tube dispersion liquid each component weight ratio are as follows: carbon nanotube: stone
Black alkene: dispersing agent=1: 0.5: 1, it is fully ground again.
2, the graphene/carbon nano-tube dispersion liquid 50g in above-mentioned steps 1 is taken to be dissolved in 950g deionized water water, due to
TNWDIS solubility is small at room temperature, its dissolution can be assisted with heating water bath, but may not exceed its cloud point temperature using temperature.
3, start ultrasound, it, can be by dispersion liquid since in ultrasonic procedure, dispersion liquid can generate heat, blister, therefore after ultrasound 5min
Taking-up is statically placed in ice water cooling, defoaming, is further continued for ultrasound.Accumulative total sonication time is 30min, i.e. 5min × 6 time.
4, degree of scatter is observed, a small amount of dispersant liquid drop is picked with glass bar and adds in clear water, observes diluted state.It is scattered
Graphene/carbon nano-tube mixed liquor uniformly spread apart rapidly in water like a melted ink falls into the water, and it is not scattered
Have in water black particle appearance.
Graphene/carbon nano-tube weight ratio 3% in High-performance graphene composite conducting slurry produced above, dispersing agent are
2%.
Embodiment 2
A kind of preparation method of High-performance graphene composite conducting slurry based on organic phase is present embodiments provided, is wrapped
Include following steps:
1, it takes 30g graphene to be dissolved in 950gN- methyl pyrrolidone, after stirring, is ground with sand mill
Mill, revolving speed 2000r/min, milling time are 60 minutes；
2, it takes 20g multi-walled carbon nanotube to be added into 1 slurry of above-mentioned steps further to be ground.
3, ultrasonic disintegrator disperses, point 6 ultrasounds, and each ultrasound 5min stands 5min.
4, degree of scatter is observed.
Graphene/carbon nano-tube weight ratio 5% in the High-performance graphene composite conducting slurry of step preparation as above, dispersion
Agent, solvent content 95%.
Claims (5)
1. a kind of High-performance graphene composite conducting slurry and preparation method thereof, which is characterized in that graphene composite conductive slurry
Material includes 3-8wt% graphene/carbon nano-tube mixture, 0.5-2wt% dispersing agent and 90-96.5wt% solvent.
2. graphene composite conductive slurry according to claim 1, which is characterized in that the preparation of graphene is faced using super
Boundary CO2What the mode that flow process is combined with functional modification was prepared.
3. graphene composite conductive slurry according to claim 1, which is characterized in that carbon nanotube caliber is less than 6nm.
4. graphene composite conductive slurry according to claim 1, which is characterized in that dispersing agent is divided into aqueous medium, by force
Organic phase medium and weak organic phase medium；Carbon nanotube water dispersant (TNMDIS) can be selected for aqueous medium；For strong
Polar organic phase medium can select alcohols, DMF, NMF, TNADIS；Phase medium organic for middle polarity can select esters,
Liquid-state epoxy resin, fluid silicone rubber, TNEDIS.
5. the preparation method of graphene composite conductive slurry according to claim 1, which is characterized in that graphene composite guide
The dispersing technology of plasma-based material uses the combined method of " first grinding distribution, the dispersion of rear ultrasonic wave ".
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| CN201810397911.0A CN110391418A (en) | 2018-04-18 | 2018-04-18 | A kind of High-performance graphene composite conducting slurry and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111048780A (en) * | 2019-12-18 | 2020-04-21 | 武汉低维材料研究院有限公司 | Graphene conductive agent for lithium ion battery and preparation method thereof |
| CN114212781A (en) * | 2021-12-23 | 2022-03-22 | 江苏杉元科技有限公司 | Low-foam high-conductivity graphene aqueous slurry and preparation method thereof |
| CN115241457A (en) * | 2022-06-22 | 2022-10-25 | 中国石油大学(华东) | Three-dimensional strip-shaped graphene compound conductive paste for metal ion battery |
-
2018
- 2018-04-18 CN CN201810397911.0A patent/CN110391418A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111048780A (en) * | 2019-12-18 | 2020-04-21 | 武汉低维材料研究院有限公司 | Graphene conductive agent for lithium ion battery and preparation method thereof |
| CN114212781A (en) * | 2021-12-23 | 2022-03-22 | 江苏杉元科技有限公司 | Low-foam high-conductivity graphene aqueous slurry and preparation method thereof |
| CN115241457A (en) * | 2022-06-22 | 2022-10-25 | 中国石油大学(华东) | Three-dimensional strip-shaped graphene compound conductive paste for metal ion battery |
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Application publication date: 20191029 |