CN111628169A - Low-temperature granulation method for lithium ion battery negative electrode material - Google Patents
Low-temperature granulation method for lithium ion battery negative electrode material Download PDFInfo
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- CN111628169A CN111628169A CN202010326261.8A CN202010326261A CN111628169A CN 111628169 A CN111628169 A CN 111628169A CN 202010326261 A CN202010326261 A CN 202010326261A CN 111628169 A CN111628169 A CN 111628169A
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- lithium ion
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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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
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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
- C01B32/20—Graphite
- C01B32/205—Preparation
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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 provides a low-temperature granulation method of a lithium ion battery cathode material, which comprises the steps of processing low-temperature plastic asphalt into low-temperature asphalt powder, mixing the low-temperature asphalt powder with graphite single-particle VC at the mixing speed of 200-300 rpm for 30-60 min to form a mixture; and (3) placing the mixed material into a reaction kettle, controlling the temperature of the reaction kettle to be 200-300 ℃ under an inert atmosphere, preserving heat for 1-3 hours, changing the inert atmosphere in the reaction kettle into an air atmosphere, and continuously preserving heat for 30-60 minutes to obtain the lithium ion battery cathode material subjected to low-temperature secondary granulation. The method has the characteristics of low pollution and low energy consumption, and the obtained secondary particles have better toughness and higher mechanical strength.
Description
Technical Field
The invention relates to a powder compound granulation process of a lithium ion battery cathode material, in particular to a low-temperature compound granulation process for the lithium ion battery cathode material.
Background
The composite pelletizing process is one of the commonly used preparation processes for the cathode material of the lithium ion battery at present, and is a technology for preparing various coke powder single particles or graphite powder single particles into secondary particles with a specific composite degree through the action of an adhesive. By applying the composite granulation technology, the electrochemical performance of the cathode material can be comprehensively improved.
In order to ensure that the materials obtained by composite granulation keep good mechanical properties in the graphitization process (at 3000 ℃) or the mechanical processing process (grading, screening and the like), at present, enterprises generally use high-carbon-residue asphalt as a binder, however, the asphalt can be solidified only when being subjected to heat treatment at 500 ℃ or above, so that the traditional negative electrode material granulation technology must be carried out at a higher temperature, on one hand, a large amount of heat energy is consumed, on the other hand, in the composite granulation process, a large amount of asphalt volatile matters overflow, not only the pressure on the environmental protection of the enterprises is brought, but also more seriously, a part of volatile matters can be adhered to the inner wall of a reaction kettle, and the granulation effect of the next batch of materials is influenced.
Based on the method, the invention develops a low-temperature composite granulation technology.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a low-temperature granulation method of a lithium ion battery negative electrode material.
The invention is realized by the following technical scheme:
a low-temperature granulation method of a lithium ion battery cathode material is characterized by comprising the following steps:
s1, coarse mixing: processing low-temperature plastic asphalt with the softening point lower than 150 ℃ and the ash content lower than 0.1% into low-temperature asphalt powder, and then mixing the low-temperature asphalt powder with graphite single-particle VC at the mixing speed of 200-300 rpm for 30-60 min to form a mixture; wherein the mass of the low-temperature asphalt powder accounts for 10-30% of the total mass of the mixture;
s2, granulating and solidifying: placing the mixed material into a reaction kettle, controlling the temperature of the reaction kettle to be 200-300 ℃ under an inert atmosphere, preserving the temperature for 1-3 hours, and performing low-temperature granulation; and then changing the inert atmosphere in the reaction kettle into an air atmosphere, continuously preserving the heat for 30-60 min, and curing to obtain the lithium ion battery cathode material subjected to low-temperature secondary granulation.
Preferably, in step S1, the low-temperature plastic asphalt having a softening point of less than 150 ℃ and an ash content of less than 0.1% is processed into low-temperature asphalt powder of 3 to 5 μm.
Preferably, in step S1, the low temperature plastic asphalt having a softening point of less than 150 ℃ and an ash content of less than 0.1% is processed into low temperature asphalt powder of 5 μm.
Preferably, in step S1, the carbon residue rate of the low-temperature plastic asphalt is not less than 75%.
Preferably, in step S1, the graphite single particles are natural graphite particles or microcrystalline graphite particles.
Preferably, in step S1, the graphite single particles are spherical natural graphite particles having a particle size of 8 μm.
Preferably, in step S2, the inert atmosphere includes, but is not limited to, nitrogen, argon, and other gases and mixtures thereof that do not chemically react with the reactants and equipment.
Preferably, in step S2, the stirring speed of the reaction kettle is 30 to 80rpm during the granulation and solidification process.
The invention has the following technical effects:
the method adopts low-temperature plastic asphalt with the softening point lower than 150 ℃ and the ash content lower than 0.1 percent as the adhesive to carry out compound granulation at low temperature, thereby greatly reducing the temperature required by granulation, on one hand reducing a large amount of heat energy consumption, on the other hand, in the process of compound granulation, the volatile components of the asphalt can not be volatilized and overflowed in a large amount, greatly reducing the pollution to environmental protection, and solving the problem that the volatile components can be adhered to the inner wall of the reaction kettle in the prior art. The method adopts a low-temperature oxidation non-melting granulation process, the obtained secondary particles have better toughness and higher mechanical strength, and the particles are not bonded and disintegrated in the high-temperature graphitization process, thereby having good solidification effect and mechanical stability.
Detailed Description
The present invention will be further described with reference to the following specific examples.
For the convenience of comparison with comparative examples, in all the following examples and comparative examples, the modified asphalt is low-temperature plastic asphalt powder with a softening point of 116 ℃, a char yield of 76% and a D50 of 3.4 μm; the graphite single particle is 8 mu m spherical natural graphite which is a single particle.
Example 1
Processing low-temperature plastic asphalt with the softening point lower than 150 ℃ and the ash content lower than 0.1% into low-temperature asphalt powder with the particle size of 3-5 microns, and then mixing the low-temperature asphalt powder with graphite single particles according to the proportion of 1:9, wherein the stirring speed is 200rpm, and the mixing time is 30 min. And then putting the mixture into a reaction kettle, keeping the temperature of the reaction kettle at 200 ℃ and the rotating speed at 30rpm under the nitrogen atmosphere, keeping the temperature for 1h, introducing air for replacement, keeping the temperature for 30min, transferring the material into a cooling kettle, discharging the material after the temperature is reduced to room temperature, and marking the obtained material as No. 1.
Example 2
Mixing the modified asphalt and graphite according to the proportion of 15:85, stirring at 200rpm for 30 min. And then putting the mixture into a reaction kettle, keeping the temperature of the reaction kettle at 200 ℃ and the rotating speed of 30rpm under the argon atmosphere, keeping the temperature for 1h, introducing air for replacement, keeping the temperature for 30min, transferring the material into a cooling kettle, discharging the material after the temperature is reduced to room temperature, and marking the obtained material as No. 2.
Example 3
Mixing the modified asphalt and graphite according to the proportion of 1:4, stirring at 200rpm for 30 min. And then putting the mixture into a reaction kettle, keeping the temperature of the reaction kettle at 200 ℃ and the rotating speed at 30rpm under the nitrogen atmosphere, keeping the temperature for 1h, introducing air for replacement, keeping the temperature for 30min, transferring the material into a cooling kettle, discharging the material after the temperature is reduced to room temperature, and marking the obtained material as 3 #.
Example 4
Mixing the modified asphalt and graphite according to the ratio of 3:7, stirring at 200rpm for 30 min. And then putting the mixture into a reaction kettle, keeping the temperature of the reaction kettle at 200 ℃ and the rotating speed at 30rpm under the nitrogen atmosphere, keeping the temperature for 1h, introducing air for replacement, keeping the temperature for 30min, transferring the material into a cooling kettle, discharging the material after the temperature is reduced to room temperature, and marking the obtained material as 3 #.
Example 5
Mixing the modified asphalt and graphite according to the proportion of 1:4, stirring at 300rpm for 60 min. And then putting the mixture into a reaction kettle, keeping the temperature of the reaction kettle at 200 ℃ and the rotating speed of 30rpm under the argon atmosphere, keeping the temperature for 1h, introducing air for replacement, keeping the temperature for 30min, transferring the material into a cooling kettle, discharging the material after the temperature is reduced to room temperature, and marking the obtained material as No. 5.
Example 6
Mixing the modified asphalt and graphite according to the proportion of 1:4, stirring at 250rpm, and mixing for 40 min. And then putting the mixture into a reaction kettle, keeping the temperature of the reaction kettle at 200 ℃ and the rotating speed of 30rpm under the argon atmosphere, keeping the temperature for 1h, introducing air for replacement, keeping the temperature for 30min, transferring the material into a cooling kettle, discharging the material after the temperature is reduced to room temperature, and marking the obtained material as No. 6.
Example 7
Mixing the modified asphalt and graphite according to the proportion of 1:4, stirring at 250rpm, and mixing for 40 min. And then putting the mixture into a reaction kettle, keeping the temperature of the reaction kettle at 250 ℃ under the nitrogen atmosphere and at the rotating speed of 50rpm for 2h, introducing air for replacement, keeping the temperature for 45min, transferring the material into a cooling kettle, discharging the material after the temperature is reduced to room temperature, and marking the obtained material as No. 7.
Example 8
Mixing the modified asphalt and graphite according to the proportion of 1:4, stirring at 250rpm, and mixing for 40 min. And putting the mixture into a reaction kettle, keeping the temperature of the reaction kettle at 300 ℃ and the rotating speed at 80rpm under the nitrogen atmosphere, keeping the temperature for 3 hours, introducing air for replacement, keeping the temperature for 60 minutes, transferring the material into a cooling kettle, discharging the material after the temperature is reduced to room temperature, and marking the obtained material as No. 8.
Comparative example 1
Mixing the modified asphalt and graphite according to the proportion of 1:4, stirring at 250rpm, and mixing for 40 min. And then putting the mixture into a reaction kettle, keeping the temperature of the reaction kettle at 550 ℃ and the rotating speed at 50rpm under the nitrogen atmosphere, keeping the temperature for 2 hours, transferring the material into a cooling kettle, discharging the material after the temperature is reduced to room temperature, and marking the obtained material as comparative example 1.
Comparative example 2
Mixing the modified asphalt and graphite according to the proportion of 1:4, stirring at 250rpm, and mixing for 40 min. And then putting the mixture into a reaction kettle, keeping the temperature of the reaction kettle at 250 ℃ and the rotating speed at 50rpm under the nitrogen atmosphere, keeping the temperature for 2 hours, transferring the material into a cooling kettle, discharging the material after the temperature is reduced to room temperature, and marking the obtained material as comparative example 2.
All examples and comparative examples were run in 8 serial replicates each, followed by batch, grading, and graphitization treatments. And using a VC mixing device in batches, selecting 2# as a target product in a grading device, respectively using 1# and 3# as large particles and tailings, graphitizing by using an Acheson furnace at the maximum temperature of 3000 ℃. The process data obtained are as follows:
from the particle size analysis after granulation, it can be seen that the particle size of the secondary particles obtained by the low-temperature granulation technique of the present invention is generally higher than that of comparative example 1 (conventional granulation technique), which shows that the technique of the present invention has a good compounding effect.
Analysis data show that the particle size change of the secondary particles before and after grading is lower than 0.5 mu m and obviously lower than that of the comparative example 1 through the low-temperature granulation technology, and the yield data are relatively close, which shows that the secondary particles obtained through the composite technology have strong toughness and high mechanical strength.
High-temperature graphitization: from the above data, it is understood that the solidification effect of the secondary particles can be completely achieved by the oxidation non-melting treatment, and the particles are not bonded and not disintegrated during the graphitization.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that various improvements and modifications within the structure and principle of the present invention can be realized by those skilled in the art, and the protection scope of the present invention should be considered.
Claims (8)
1. A low-temperature granulation method of a lithium ion battery cathode material is characterized by comprising the following steps:
s1, coarse mixing: processing low-temperature plastic asphalt with the softening point lower than 150 ℃ and the ash content lower than 0.1% into low-temperature asphalt powder, and then mixing the low-temperature asphalt powder with graphite single-particle VC at the mixing speed of 200-300 rpm for 30-60 min to form a mixture; wherein the mass of the low-temperature asphalt powder accounts for 10-30% of the total mass of the mixture;
s2, granulating and solidifying: placing the mixed material into a reaction kettle, controlling the temperature of the reaction kettle to be 200-300 ℃ under an inert atmosphere, preserving the temperature for 1-3 hours, and performing low-temperature granulation; and then changing the inert atmosphere in the reaction kettle into an air atmosphere, continuously preserving the heat for 30-60 min, and curing to obtain the lithium ion battery cathode material subjected to low-temperature secondary granulation.
2. The method for granulating the lithium ion battery negative electrode material at a low temperature according to claim 1, wherein the method comprises the following steps: in step S1, the low-temperature plastic asphalt with the softening point lower than 150 ℃ and the ash content lower than 0.1% is processed into low-temperature asphalt powder with the particle size of 3-5 mu m.
3. The method for granulating the lithium ion battery negative electrode material at a low temperature according to claim 1, wherein the method comprises the following steps: in step S1, low temperature plastic asphalt with a softening point of less than 150 ℃ and an ash content of less than 0.1% is processed into low temperature asphalt powder of 5 μm.
4. A low-temperature granulation method of the lithium ion battery negative electrode material according to claim 2 or 3, characterized in that: in step S1, the carbon residue rate of the low-temperature plastic asphalt is more than or equal to 75%.
5. The method for granulating the lithium ion battery negative electrode material at a low temperature according to claim 1, wherein the method comprises the following steps: in step S1, the graphite single particles are natural graphite particles or microcrystalline graphite particles.
6. The method for granulating the lithium ion battery negative electrode material at a low temperature according to claim 5, wherein the method comprises the following steps: in step S1, spherical natural graphite particles having a particle size of 8 μm are used as the graphite single particles.
7. The method for granulating the lithium ion battery negative electrode material at a low temperature according to claim 1, wherein the method comprises the following steps: in step S2, the inert atmosphere is one or more of nitrogen and argon.
8. The method for granulating the lithium ion battery negative electrode material at a low temperature according to claim 1, wherein the method comprises the following steps: in step S2, the stirring speed of the reaction kettle is 30-80 rpm during the granulation and solidification process.
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| CN202010326261.8A CN111628169A (en) | 2020-04-23 | 2020-04-23 | Low-temperature granulation method for lithium ion battery negative electrode material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811758A (en) * | 2014-02-19 | 2014-05-21 | 新乡市赛日新能源科技有限公司 | Preparation method for synthesizing graphite particle negative electrode material |
| WO2018095094A1 (en) * | 2016-11-25 | 2018-05-31 | 上海恩捷新材料科技股份有限公司 | Method for fabricating battery separator film |
| CN108821275A (en) * | 2018-07-03 | 2018-11-16 | 贵州格瑞特新材料有限公司 | A kind of lithium ion battery high capacity, high magnification graphite cathode material and preparation method thereof |
| CN110395725A (en) * | 2019-06-06 | 2019-11-01 | 湖南中科星城石墨有限公司 | A kind of fast charging type micro crystal graphite negative electrode material and preparation method thereof |
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2020
- 2020-04-23 CN CN202010326261.8A patent/CN111628169A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811758A (en) * | 2014-02-19 | 2014-05-21 | 新乡市赛日新能源科技有限公司 | Preparation method for synthesizing graphite particle negative electrode material |
| WO2018095094A1 (en) * | 2016-11-25 | 2018-05-31 | 上海恩捷新材料科技股份有限公司 | Method for fabricating battery separator film |
| CN108821275A (en) * | 2018-07-03 | 2018-11-16 | 贵州格瑞特新材料有限公司 | A kind of lithium ion battery high capacity, high magnification graphite cathode material and preparation method thereof |
| CN110395725A (en) * | 2019-06-06 | 2019-11-01 | 湖南中科星城石墨有限公司 | A kind of fast charging type micro crystal graphite negative electrode material and preparation method thereof |
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