CN109755569A - The granulation processing procedure of lithium cell cathode material - Google Patents
The granulation processing procedure of lithium cell cathode material Download PDFInfo
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- CN109755569A CN109755569A CN201711077277.4A CN201711077277A CN109755569A CN 109755569 A CN109755569 A CN 109755569A CN 201711077277 A CN201711077277 A CN 201711077277A CN 109755569 A CN109755569 A CN 109755569A
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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
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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
- H01M4/04—Processes of manufacture in general
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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 discloses a kind of granulation processing procedure of lithium cell cathode material.The granulation processing procedure of above-mentioned lithium cell cathode material binds carbon substrate and grafting material without using the mode of high-temperature fusion, and then can reach the processing procedure effect of energy conservation, low pollution and high production capacity.
Description
Technical field
The present invention is granulated processing procedure about a kind of carbon substrate, especially with regard to a kind of granulation system for lithium cell cathode material
Journey.
Background technique
The development of lithium ion battery largely depends on the exploitation and application of high-performance positive and negative electrode material.With
For negative electrode material, prior art person is had been found that using the battery cathode formed by being granulated processing procedure, in addition to can substantially mention
It rises except battery life, more can effectively promote capacitance.
Common cathode is granulated processing procedure in prior art, is first to mix coke and pitch in a manner of high-temperature fusion, then
It is sequentially completed again by programs such as carbonization, graphitizations.Fig. 1 is that cell negative electrode material used in prior art is granulated system
Journey.Firstly, then mixing coke and pitch use high-temperature fusion, coke can uniformly be mixed with pitch as shown at step 110,
As shown at step 120.Above-mentioned high-temperature fusion step 120 need to usually be completed in the environment of about 600-700 DEG C.
Coke and asphalt mixture after high-temperature fusion first carry out destruction step 130, then carry out the step of sieve classification
Rapid 140.The mixture particle for filtering out appropriate partial size, followed by sequentially carry out carburising step 150, with graphitization step 160,
The material that can be used for battery cathode can be obtained.
In the above-mentioned methods, need to come uniformly to mix coke and pitch using high temperature melting.The process of high-temperature fusion, not only needs
Mass energy is consumed, time-consuming could complete for about 17-20 hours is generally also needed.Therefore, the above-mentioned granulation processing procedure using high-temperature fusion
Often production capacity is extremely low, it is difficult to a large amount of batch productions.Furthermore pitch is during high-temperature fusion, when being heated to about 300 DEG C or more
When, a large amount of air pollution can be generated.Therefore, production efficiency and environment are being stressed friendly (environmental friendly)
The general orientation laid equal stress on of green industry (green industry) development on, there are still many improved spaces for the above method.
In view of this, exploitation can in the granulation processing procedure that cell negative electrode material is effectively performed, combine reduction energy consumption,
With the granulation processing procedure for the lithium cell cathode material for reducing environmental pollution, being one is quite worth industry to be paid attention to and can effectively promote production
The project of industry competitiveness.
Summary of the invention
In view of in above-mentioned background of invention, in order to meet the requirement in industry, the present invention provides a kind of lithium ion battery anode material
The granulation processing procedure of material, the granulation processing procedure of above-mentioned lithium cell cathode material, not only processing procedure is simple, cost is cheap, and having more can be substantially
It reduces in the energy consumption and environmental pollution being granulated in processing procedure, it is preferred that the granulation processing procedure of above-mentioned lithium cell cathode material is being taken into account
While environmentally friendly, still can the dynamical carbon substrate granulation product of output, and then can have both simultaneously environmental protection with effective promotion industry
The effect of competitiveness.
A purpose of the present invention is that a kind of granulation processing procedure of lithium cell cathode material is provided, by without using high-temperature fusion
Mode, to reduce the energy consumption in processing procedure, and reduce environmental pollution.
Another object of the present invention is to provide a kind of granulation processing procedure of lithium cell cathode material, by using couplant come
Carbon substrate and grafting material are binded, so that sticking in the granulation processing procedure of above-mentioned lithium cell cathode material without using high-temperature fusion
Carbon substrate and grafting material are closed, and then achievees the effect that energy conservation and reduces pollution.
Another object of the present invention is to provide a kind of granulation processing procedure of lithium cell cathode material, by using couplant come
Carbon substrate and grafting material are binded, so that sticking in the granulation processing procedure of above-mentioned lithium cell cathode material without using high-temperature fusion
Carbon substrate and grafting material are closed, so that the granulation processing procedure of lithium cell cathode material need to wait high-temperature fusion without every batch of production
17-20 hours heating times, and then achieve the effect that save processing procedure required time and promote production capacity.
According to above-described purpose, present invention discloses a kind of granulation processing procedures of lithium cell cathode material.Above-mentioned lithium electricity
The granulation processing procedure of pond negative electrode material include mixing carbon substrate and grafting material, addition couplant, pressurization, carbonization, broken, sieving,
And graphitization and etc..Wherein, above-mentioned couplant have adhesion, will not react with carbon substrate or grafting material,
And it the characteristics such as can be removed in subsequent carburising step or graphitization step.In a preferable example according to the present invention, on
Stating couplant can be a solution form, and solvent used in above-mentioned solution can be in subsequent carburising step or graphitization step
Volatilization.Above-mentioned pressurization steps, which can be, uses cold pressing, hot pressing, molding, extruding, screw extrusion or other prior art persons institute ripe
The mode known is formed by presoma and pressurizes to mix for carbon substrate, grafting material, with couplant, carbon-based to be promoted
The bonding density of material, and the solvent of part couplant is removed simultaneously.According to the technique and scheme of the present invention, adding by couplant
Add, can not only avoid the various disadvantages for binding carbon substrate and grafting material using energy consumption and the high-temperature fusion mode of high pollution,
Carbon substrate and grafting material can be more allowed to achieve the effect that perfect bonding.
Detailed description of the invention
Fig. 1 is that the carbon substrate of prior art is granulated the schematic diagram of processing procedure.
Fig. 2 is the schematic diagram of the granulation processing procedure of lithium cell cathode material according to the present invention.
Figure number explanation:
The carbon substrate of 100 prior arts is granulated processing procedure
110 mixing steps
120 high-temperature fusion steps
130 destruction steps
140 sifting steps
150 carburising steps
160 graphitization steps
The granulation processing procedure of 200 lithium cell cathode materials
210 mixing steps
220 addition couplant steps
230 pressurization steps
240 carburising steps
250 destruction steps
260 sifting steps
270 graphitization steps.
Specific embodiment
One embodiment of the invention discloses a kind of granulation processing procedure of lithium cell cathode material.Fig. 2 is one according to the present embodiment
Lithium cell cathode material granulation processing procedure schematic diagram.As shown in Fig. 2, the granulation processing procedure of above-mentioned lithium cell cathode material includes
Mix carbon substrate and grafting material, addition couplant, pressurization, carbonization, broken, sieving and graphitization.
According to the granulation processing procedure 200 of the lithium cell cathode material of the present embodiment, first carbon substrate and grafting material are mixed
It closes, as indicated in step 210.In the preferable example according to the present embodiment, above-mentioned carbon substrate can be selected from one of following or
A combination thereof: coke, needle coke, petroleum coke, little particle natural graphite, graphene, carbon nanotube (Carbon Nanotube；
CNT), vapor deposition carbon fiber (Vapor grown carbon fiber；VGCF) or other known this those skilled in the art are familiar with
Carbon material.In the preferable example according to the present embodiment, above-mentioned grafting material be can be selected from one of following or its group
It closes: pitch, resin.In the preferable example according to the present embodiment, the weight ratio of above-mentioned carbon substrate and grafting material is about 3:1
~20:1.In the preferable example according to the present embodiment, step 210 has no other other than carbon substrate and grafting material
Addition.In the preferable example according to the present embodiment, above-mentioned steps 210 can be to be carried out at room temperature.
Next, adding couplant in the mixing of carbon substrate and grafting material to form a presoma, such as step 220 institute
Show.Above-mentioned couplant has adhesion, chemical reaction will not occur with carbon substrate or grafting material and can be in subsequent carbon
Change the characteristics such as removed in step or graphitization step.In the preferable example according to the present embodiment, above-mentioned carbon substrate, engagement
The weight ratio of material and couplant is about 50:10:1~30:1:5.In the preferable example according to the present embodiment, above-mentioned coupling
Agent can be selected from following one or combinations thereof: carboxymethyl cellulose (Carboxymethyl Cellulose, abbreviation CMC), wheat
Bud dextrin, butadiene-styrene rubber (Styrene-Butadiene Rubber, abbreviation SBR), paraffin (paraffin).According to this implementation
In one preferable example of example, above-mentioned couplant can be solution form, wherein the solvent in above-mentioned solution can be in subsequent carbonization
It volatilizees in step or graphitization step.In the preferable example according to the present embodiment, above-mentioned solvent be can be selected from following one
Person or combinations thereof: water, alcohol, isopropanol (IPA), ethyl acetate (ethyl acetate), petroleum ether (Petroleum
ether)。
After adding couplant, add to above-mentioned carbon substrate, grafting material, with the presoma that couplant mixes
Pressure, as shown in step 230.In the preferable example according to the present embodiment, above-mentioned pressurization steps 230 can be using cold pressing,
Mode known to 60~200 DEG C of hot pressing, molding, extruding, screw extrusion or other prior art persons.By pressurization, Ke Yiti
Rise the adaptation of carbon substrate and grafting material.In the preferable example according to the present embodiment, by pressurization also removable portion
Solvent in couplant.
Then, it is carbonized to being formed by bulky grain after above-mentioned pressurization steps, as illustrated in step 240, to form carbonization
Carbon substrate afterwards.In the preferable example according to the present embodiment, above-mentioned carburising step can be the item at about 600~1500 DEG C
It is carried out under part, is more preferably that above-mentioned carburising step can be and carry out under conditions of about 900~1300 DEG C.According to the present embodiment
In one preferable example, above-mentioned couplant can be removed during carburising step.
After carburising step, destruction step 250 is first carried out, the bulky grain of the carbon substrate after above-mentioned carbonization is crushed and is pluralized
A little particle.In the preferable example according to the present embodiment, above-mentioned destruction step 250 can be the carbon substrate after carbonization is big
Particle Breakage pluralizes the little particle of about 10~25 μm of a partial size.Sifting step 260 is carried out after destruction step, from those small
In grain, the little particle with expected partial size is filtered out to carry out down-stream.
It is then graphitized by the little particle after sifting step to obtain graphited carbon material, such as step 270 institute
Show.In the preferable example according to the present embodiment, above-mentioned graphitization step can be to carry out under conditions of about 3000 DEG C.Such as
This, that is, complete the granulation processing procedure of lithium cell cathode material.
The preferable example of the granulation processing procedure of bright lithium cell cathode material of the invention will be chatted below.
Example 1:(coke；Pitch；Maltodextrin；Distilled water).
400 grams of maltodextrin is added first in 3000 grams of distilled water, quickly stirring again after being first slowly stirred, with shape
At coupling agent solution.
Next, 1000 grams of coke of mixing, 300 grams of 100 grams of pitch and above-mentioned coupling agent solution, and at room temperature into
Row is puddled, to form presoma.
Above-mentioned presoma is squeezed using machine for producing coal bars, make coke, pitch, with the mixing of couplant more evenly, and allow
Compress closer between coke and pitch.The pressure of above-mentioned extruding is about 0.5kgf/cm2。
By presoma after extruding, about 1100 DEG C of high temperature cabonization is first passed through, and is crushed in the carbonized.
It is sieved for broken little particle, to obtain the little particle that partial size D50 is fallen in 14~20 μ ms.With
Afterwards, the little particle after sieving is carried out to about 2950 DEG C of graphitization.
Example 2:(natural graphite；Phenolic resin；CMC；Distilled water).
300 grams of CMC is added first in 3000 grams of distilled water, and quickly stirred, to form coupling agent solution.
Next, 400 grams of agent solution of 1000 grams of natural graphite of mixing, 200 grams of phenolic resin and coupling, and in room temperature
Under puddled, to form presoma.
Above-mentioned presoma is pressed using cold press, makes to compress between natural graphite, phenolic resin and couplant
It is closer.The pressure about 0.5kgf/cm of above-mentioned cold press pressurization2。
Presoma after cold pressing, first passes through 1300 DEG C of high temperature cabonization, and be crushed in the carbonized.
It is sieved for broken little particle, to obtain the little particle that partial size D50 is fallen in 14~20 μ ms.With
Afterwards, the little particle after sieving is carried out to 2950 DEG C of graphitization.
Example 3:(natural graphite；Pitch；Graphene；SBR；Distilled water).
It takes the SBR of 100 grams of commercially available solid contents 50% to be added in 3000 grams of distilled water first, and quickly stirs, to be formed
Couple agent solution.
Next, 500 grams of agent solution of 1000 grams of natural graphite of mixing, 5 grams of graphene, 150 grams of pitch and coupling, and
It is puddled at room temperature, to form presoma.
Above-mentioned presoma is squeezed using machine for producing coal bars, makes the mixing of natural graphite, graphene, pitch and couplant more
Uniformly, it and allows between natural graphite, graphene and pitch and compresses closer.The pressure about 0.5kgf/ that above-mentioned machine for producing coal bars squeezes
cm2。
By presoma after extruding, 1100 DEG C of high temperature cabonization is first passed through, and is crushed in the carbonized.
It is sieved for broken little particle, to obtain the little particle that partial size D50 is fallen in 14~20 μ ms.With
Afterwards, the little particle after sieving is carried out to 2950 DEG C of graphitization.
Example 4:(natural graphite；Pitch；Paraffin).
Uniformly 1000 grams of natural graphite of mixing, 120 grams of pitch and 50 grams of paraffin powder, and puddled at room temperature, with
Form presoma.
Above-mentioned presoma is subjected to 80 DEG C of hot pressing using hot press, makes to compress more between natural graphite, pitch and paraffin
Closely.The operating pressure of above-mentioned hot press about 0.5kgf/cm2。
Presoma after hot pressing first passes through 1100 DEG C of high temperature cabonization, and is crushed in the carbonized.
It is sieved for broken little particle, to obtain the little particle that partial size D50 is fallen in 14~20 μ ms.With
Afterwards, the little particle after sieving is carried out to 2950 DEG C of graphitization.
In conclusion the invention discloses a kind of granulation processing procedures of lithium cell cathode material.Above-mentioned lithium cell cathode material
Being granulated processing procedure includes mixing carbon substrate and grafting material, addition couplant, pressurization, carbonization, broken, sieving and graphitization etc.
Step.According to the present invention, the granulation processing procedure of above-mentioned lithium cell cathode material need not be binded carbon-based using the mode of high-temperature fusion
Material and grafting material, so can reach the processing procedure effect of energy conservation, low pollution and high production capacity.
Claims (10)
1. a kind of granulation processing procedure of lithium cell cathode material, characterized by comprising:
Mix carbon substrate and grafting material；
Couplant is added in carbon substrate and grafting material, to form a presoma；
It pressurizes to above-mentioned presoma；
It is carbonized to the presoma after above-mentioned pressurization, to form the carbon substrate after carbonization；And
Carbon substrate after carbonization is graphitized.
2. the granulation processing procedure of lithium cell cathode material according to claim 1, which is characterized in that above-mentioned carbon substrate is selected from down
One or a combination set of column: coke, needle coke, petroleum coke, little particle natural graphite, graphene, carbon nanotube and vapor deposition
Carbon fiber.
3. the granulation processing procedure of lithium cell cathode material according to claim 1, which is characterized in that above-mentioned grafting material is selected from
It is one or a combination set of following: pitch, resin.
4. the granulation processing procedure of lithium cell cathode material according to claim 1, which is characterized in that above-mentioned couplant is selected from down
One or a combination set of column: carboxymethyl cellulose, maltodextrin, butadiene-styrene rubber, paraffin.
5. the granulation processing procedure of lithium cell cathode material according to claim 1, which is characterized in that above-mentioned couplant includes one
Solvent, above-mentioned solvent are selected from following one or combinations thereof: water, alcohol, isopropanol, ethyl acetate, petroleum ether.
6. the granulation processing procedure of lithium cell cathode material according to claim 1, which is characterized in that carried out to above-mentioned presoma
The step of pressurization, is selected from one or a combination set of following manner: cold pressing, 60~200 DEG C of hot pressing, molding, extruding and screw extrusion.
7. the granulation processing procedure of lithium cell cathode material according to claim 1, which is characterized in that above-mentioned carbon substrate, engagement
The weight ratio of material and couplant is 50:10:1~30:1:5.
8. the granulation processing procedure of lithium cell cathode material according to claim 1, which is characterized in that it include a destruction step,
Above-mentioned destruction step is that the carbon substrate after above-mentioned carbonization is broken into a plurality of little particles.
9. the granulation processing procedure of lithium cell cathode material according to claim 8, which is characterized in that above-mentioned short grained partial size
10~25 μm.
10. the granulation processing procedure of lithium cell cathode material according to claim 1, which is characterized in that above-mentioned carburising step is
It is carried out under conditions of 600~1500 DEG C, wherein above-mentioned graphitization step is carried out under conditions of 3000 DEG C.
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| CN202111097199.0A CN113903916A (en) | 2017-11-06 | 2017-11-06 | Application of coupling agent in granulation process of lithium battery negative electrode material and granulation process of lithium battery negative electrode material |
| CN201711077277.4A CN109755569A (en) | 2017-11-06 | 2017-11-06 | The granulation processing procedure of lithium cell cathode material |
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| CN113716544A (en) * | 2021-08-20 | 2021-11-30 | 中钢集团鞍山热能研究院有限公司 | Preparation method of low-cost high-rate negative electrode material coke |
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| CN114226054B (en) * | 2022-01-14 | 2023-03-10 | 江西华赛新材料有限公司 | Production system for preparing battery and lithium carbonate by using waste lithium iron phosphate positive plates |
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Application publication date: 20190514 |
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