CN112531168A - Method for preparing lithium ion battery cathode material by liquid phase coating modification - Google Patents
Method for preparing lithium ion battery cathode material by liquid phase coating modification Download PDFInfo
- Publication number
- CN112531168A CN112531168A CN202011395757.7A CN202011395757A CN112531168A CN 112531168 A CN112531168 A CN 112531168A CN 202011395757 A CN202011395757 A CN 202011395757A CN 112531168 A CN112531168 A CN 112531168A
- Authority
- CN
- China
- Prior art keywords
- asphalt
- lithium ion
- ion battery
- graphite powder
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
-
- 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 relates to a method for preparing a lithium ion battery cathode material by liquid phase coating modification, which belongs to the technical field of lithium ion battery cathode materials, wherein asphalt is used as a coating agent, the asphalt is fully dissolved by a high-solubility organic solvent, the graphite powder is coated and modified by using a vacuum liquid phase coating technology, and the lithium ion battery cathode material with uniform granularity and excellent performance is prepared by using centrifugal separation, fluidized bed drying and carbonization technologies, wherein the specific capacity of the lithium ion battery cathode material reaches more than 365mAh/g, the charging specific capacity reaches more than 350mAh/g after 200 cycles, the prepared cathode material particles are uniform and have no adhesion, the primary cycle efficiency is high, and the primary cycle efficiency reaches more than 95%.
Description
Technical Field
The invention belongs to the technical field of negative electrode materials for lithium ion batteries, and particularly relates to a method for preparing a negative electrode material for a lithium ion battery by liquid phase coating modification.
Background
The lithium ion battery as a new generation green environmental protection battery has the advantages of high specific energy, less self-discharge, wide application temperature range, no pollution, no memory effect and the like, has wide application in the fields of mobile phones, notebook computers, electric tools and the like, is also applied in the fields of aerospace, military, electric automobiles, energy storage and the like, and becomes a research hotspot in the field of new energy at present. The cathode material of the current commercial lithium ion battery is mainly a carbon material, and the graphite material has the advantages of high specific capacity, good cycle performance, low lithium intercalation and deintercalation platform, low cost and the like, thereby becoming the cathode material of the ion lithium ion battery with the highest commercial value. However, the compatibility of graphite and organic solvent electrolyte is poor, so that excessive SEI films are formed on the surface of the negative electrode material, and the excessive SEI films not only consume a large amount of lithium and generate large irreversible capacity loss, but also increase the interface impedance, cause electrochemical dynamics barrier, and enable the graphite layer to be dissociated or even peeled off, thereby causing capacity attenuation and cycle performance reduction.
In order to obtain a negative electrode material with high electrochemical performance, the surface of the negative electrode material must be modified and modified. The invention discloses a negative electrode material for a lithium ion battery, which is prepared by adopting asphalt as a coating agent and utilizing a vacuum liquid phase coating technology to coat and modify graphite powder, and has uniform granularity and excellent performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, modify and modify the surface of a graphite cathode material for a lithium ion battery and improve the electrochemical performance of the graphite cathode material, and provides a method for preparing the lithium ion battery cathode material by liquid phase coating modification. The invention adopts asphalt as a coating agent, and utilizes a vacuum liquid phase coating technology to carry out coating modification on graphite powder so as to prepare the cathode material for the lithium ion battery with uniform particle size and excellent performance.
The invention is realized by the following technical scheme.
A method for preparing a lithium ion battery anode material by liquid phase coating modification comprises the following steps:
s1, mechanically crushing the graphite material A, and then grading the crushed fine powder according to particle size to obtain graphite powder B with the particle size of 5-50 microns and the purity of more than 99.5%;
s2, weighing asphalt, adding the asphalt into an organic solvent, and stirring at a high speed for 20-90 min to fully dissolve the asphalt to obtain an asphalt solution with the mass fraction of 3-30%; then pouring the prepared asphalt solution into a standing settling tank for standing for 6-72 h, fully settling insoluble substances in the solution, and taking supernatant to obtain coating liquid;
s3, adding the graphite powder B prepared in the step S1 into an impregnation kettle, vacuumizing for 10-120 min after the impregnation kettle is closed, then opening a suction valve of an asphalt solution, sucking the coating liquid prepared in the step S2 into the impregnation kettle and fully covering the graphite powder B, wherein the volume ratio of the graphite powder B to the coating liquid is 1: 1.2-1: 20, closing the suction valve after the liquid is fed, continuously vacuumizing the impregnation kettle for 10-120 min, simultaneously stirring the mixed liquid at a high speed for 10-120 min, opening an emptying valve after the stirring and vacuumizing operation is finished, pouring the mixed liquid into a storage tank after the internal and external pressures of the impregnation kettle are the same;
s4, firstly, carrying out centrifugal separation on the mixed solution in the storage tank to separate out upper-layer asphalt solution and asphalt-coated graphite powder, pouring the upper-layer asphalt solution into the asphalt solution storage tank, and pouring the asphalt-coated graphite powder into a container; then, adding distilled water or absolute ethyl alcohol into the container, fully stirring, washing for multiple times, then carrying out centrifugal separation again, pouring the upper-layer waste liquid after centrifugal separation into a waste liquid tank, and repeatedly washing and centrifuging the lower-layer asphalt-coated graphite powder for 3-8 times; finally, taking out the purified coated graphite powder separated by centrifugation for later use;
s5, putting the purified coated graphite powder prepared in the step S4 into a fluidized bed, drying the powder for 2-48 hours at 40-80 ℃, taking out the purified coated graphite powder, crushing the powder, and sieving the crushed powder with a 100-325-mesh sieve to prepare coated graphite fine powder for later use;
and S6, heating the coated graphite fine powder prepared in the step S5 in a fluidized bed in an inert gas environment to 650-1300 ℃, and keeping the temperature for 0.5-6 hours to prepare the asphalt liquid phase coated negative electrode material for the lithium ion battery.
Further, in the step S1, the graphite material a is one or more of natural crystalline flake graphite, natural cryptocrystalline graphite, natural crystalline vein graphite, artificial graphite, or conductive graphite.
Further, in the step S2, the asphalt is one or more of coal asphalt, petroleum asphalt, modified asphalt, or mesophase asphalt.
Further, in step S2, the organic solvent is one or more of ketones, aromatic hydrocarbons or heterocyclic compounds.
Further, in the step S4, the volume ratio of the graphite powder coated with the asphalt to the distilled water or the absolute ethyl alcohol used for each cleaning is 1:2 to 1: 10.
Compared with the prior art, the invention has the beneficial effects that:
1. the specific capacity of the lithium ion battery cathode material prepared by adopting the asphalt vacuum liquid phase coating technology is higher than that of the graphite cathode material prepared by the traditional process and reaches more than 365 mAh/g;
2. asphalt is used as a coating agent, a high-solubility organic reagent is used as a solvent, graphite powder can be effectively coated, a graphite layer is prevented from being dissociated and even peeled, the cycle performance of the negative electrode material is effectively improved, and the charging specific capacity reaches more than 350mAh/g after 200 cycles;
3. by adopting the centrifugal separation, multiple cleaning, fluidized bed drying and carbonization technologies, the prepared negative electrode material particles are uniform and have no adhesion, the first circulation efficiency is high, and the first circulation efficiency reaches more than 95%.
Drawings
FIG. 1 is an SEM photograph of the product obtained in example 3.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. Unless otherwise specified, the examples follow conventional experimental conditions. In addition, it will be apparent to those skilled in the art that various modifications or improvements can be made to the material components and amounts in these embodiments without departing from the spirit and scope of the invention as defined in the appended claims.
The invention is described in further detail below with reference to the figures and examples.
Example 1
A method for preparing a lithium ion battery anode material by liquid phase coating modification comprises the following steps:
s1, mechanically crushing the natural flake graphite, and then grading the crushed fine powder according to the particle size to obtain natural flake graphite powder with the particle size of 5-20 microns and the purity of 99.5%;
s2, weighing 3g of medium temperature coal pitch, adding the medium temperature coal pitch into 97g of toluene, stirring at a high speed (2000 rad/min) for 20min to dissolve the pitch more fully, and preparing a medium temperature coal pitch solution with the mass fraction of 3%; then, pouring the prepared asphalt solution into a standing settling tank for standing for 6 hours, fully settling insoluble substances in the solution, and taking supernatant to obtain coating liquid;
s3, adding 10g of natural crystalline flake graphite powder prepared in the step S1 into an impregnation kettle, vacuumizing for 10min after the impregnation kettle is closed, then opening a suction valve of an asphalt solution, sucking 20g of coating liquid prepared in the step S2 into the impregnation kettle, fully covering the natural crystalline flake graphite powder, closing the suction valve after the liquid inlet is finished, continuously vacuumizing the impregnation kettle for 10min, stirring the mixed liquid at a high speed (2000 rad/min) for 20min, opening an emptying valve after the stirring and vacuumizing operations are finished, and pouring the mixed liquid into a storage tank after the internal and external pressures of the impregnation kettle are the same;
s4, firstly, carrying out centrifugal separation on the mixed solution in the storage tank to separate out upper-layer asphalt solution and asphalt-coated graphite powder, pouring the upper-layer asphalt solution into the asphalt solution storage tank, and pouring the asphalt-coated graphite powder into a container; then, 30g of absolute ethyl alcohol is added into the container, the container is fully stirred and washed for multiple times, centrifugal separation is carried out again, the upper layer waste liquid after centrifugal separation is poured into a waste liquid tank, and the lower layer asphalt coated graphite powder is repeatedly washed and centrifuged for 3 times; finally, taking out the purified coated graphite powder separated by centrifugation for later use;
s5, putting the purified coated graphite powder prepared in the step S4 into a fluidized bed, drying for 48 hours at 40 ℃, taking out the purified coated graphite powder, crushing to prevent the powder from caking, and sieving by a 100-mesh sieve to prepare coated graphite fine powder for later use;
and S6, heating the coated graphite fine powder prepared in the step S5 in a fluidized bed in nitrogen atmosphere at a heating rate of 50 ℃/h to 650 ℃, and keeping the temperature for 6h at a constant temperature to prepare the asphalt liquid phase coated negative electrode material for the lithium ion battery.
Example 2
A method for preparing a lithium ion battery anode material by liquid phase coating modification comprises the following steps:
s1, mechanically crushing the natural flake graphite, and then grading the crushed fine powder according to the particle size to obtain natural flake graphite powder with the particle size of 10-25 mu m and the purity of 99.6%;
s2, weighing 6g of high-temperature coal tar pitch, adding the high-temperature coal tar pitch into 94g of pyridine, stirring at a high speed (1000 rad/min) for 30min to enable the pitch to be dissolved more fully, and preparing a high-temperature coal tar pitch solution with the mass fraction of 6%; then, pouring the prepared asphalt solution into a standing settling tank for standing for 12 hours, fully settling insoluble substances in the solution, and taking supernatant to obtain coating liquid;
s3, adding 10g of natural crystalline flake graphite powder prepared in the step S1 into an impregnation kettle, vacuumizing for 30min after the impregnation kettle is closed, then opening a suction valve of an asphalt solution, sucking 30g of coating liquid prepared in the step S2 into the impregnation kettle, fully covering the natural crystalline flake graphite powder, closing the suction valve after the liquid inlet is finished, continuously vacuumizing the impregnation kettle for 20min, stirring the mixed liquid at a high speed (1000 rad/min) for 20min, opening an emptying valve after the stirring and vacuumizing operations are finished, and pouring the mixed liquid into a storage tank after the internal and external pressures of the impregnation kettle are the same;
s4, firstly, carrying out centrifugal separation on the mixed solution in the storage tank to separate out upper-layer asphalt solution and asphalt-coated graphite powder, pouring the upper-layer asphalt solution into the asphalt solution storage tank, and pouring the asphalt-coated graphite powder into a container; then, 40g of absolute ethyl alcohol is added into the container, the container is fully stirred and washed for multiple times, centrifugal separation is carried out again, the upper layer waste liquid after centrifugal separation is poured into a waste liquid tank, and the lower layer asphalt coated graphite powder is repeatedly washed and centrifuged for 4 times; finally, taking out the purified coated graphite powder separated by centrifugation for later use;
s5, putting the purified coated graphite powder prepared in the step S4 into a fluidized bed, drying at 50 ℃ for 36 hours, taking out the purified coated graphite powder, crushing to prevent the powder from caking, and sieving by a 150-mesh sieve to prepare coated graphite fine powder for later use;
and S6, heating the coated graphite fine powder prepared in the step S5 in a fluidized bed in nitrogen atmosphere at a heating rate of 50 ℃/h to 800 ℃, and keeping the temperature for 5h at a constant temperature to prepare the asphalt liquid phase coated negative electrode material for the lithium ion battery.
Example 3
A method for preparing a lithium ion battery anode material by liquid phase coating modification comprises the following steps:
s1, mechanically crushing the natural aphanitic graphite, and then grading the crushed fine powder according to particle size to prepare natural aphanitic graphite powder with particle size of 8-30 microns and purity of 99.7%;
s2, weighing 10g of high-temperature coal tar pitch, adding the 10g of high-temperature coal tar pitch into 90g of quinoline, and stirring at a high speed (1500 rad/min) for 50min to dissolve the pitch more fully to prepare a high-temperature coal tar pitch solution with the mass fraction of 10%; then, pouring the prepared asphalt solution into a standing settling tank for standing for 24 hours, fully settling insoluble substances in the solution, and taking supernatant to obtain coating liquid;
s3, adding 10g of the natural cryptocrystalline graphite powder prepared in the step S1 into an impregnation kettle, vacuumizing for 50min after the impregnation kettle is closed, then opening a suction valve of an asphalt solution, sucking 50g of the coating solution prepared in the step S2 into the impregnation kettle, fully covering the natural cryptocrystalline graphite powder, closing the suction valve after the liquid is completely fed, continuously vacuumizing the impregnation kettle for 30min, simultaneously stirring the mixed liquid at a high speed (1000 rad/min) for 30min, opening an emptying valve after the stirring and vacuumizing operations are finished, and pouring the mixed liquid into a storage tank after the internal and external pressures of the impregnation kettle are the same;
s4, firstly, carrying out centrifugal separation on the mixed solution in the storage tank to separate out upper-layer asphalt solution and asphalt-coated graphite powder, pouring the upper-layer asphalt solution into the asphalt solution storage tank, and pouring the asphalt-coated graphite powder into a container; then, 60g of absolute ethyl alcohol is added into the container, the container is fully stirred and washed for multiple times, centrifugal separation is carried out again, the upper layer waste liquid after centrifugal separation is poured into a waste liquid tank, and the lower layer asphalt coated graphite powder is repeatedly washed and centrifuged for 5 times; finally, taking out the purified coated graphite powder separated by centrifugation for later use;
s5, putting the purified coated graphite powder prepared in the step S4 into a fluidized bed, drying at 60 ℃ for 36 hours, taking out the purified coated graphite powder, crushing to prevent the powder from caking, and sieving by a 200-mesh sieve to prepare coated graphite fine powder for later use;
and S6, heating the coated graphite fine powder prepared in the step S5 in a fluidized bed in nitrogen atmosphere at a heating rate of 50 ℃/h to 900 ℃, and keeping the temperature for 4h at a constant temperature to prepare the asphalt liquid phase coated negative electrode material for the lithium ion battery.
Example 4
A method for preparing a lithium ion battery anode material by liquid phase coating modification comprises the following steps:
s1, mechanically crushing the artificial graphite, and then grading the crushed fine powder according to particle size to obtain artificial graphite powder with the particle size of 8-40 microns and the purity of 99.8%;
s2, weighing 20g of petroleum asphalt, adding the petroleum asphalt into 80g of octyl pyrrolidone, and stirring at a high speed (2500 rad/min) for 70min to dissolve the asphalt more fully to prepare a petroleum asphalt solution with the mass fraction of 20%; then, pouring the prepared asphalt solution into a standing settling tank for standing for 48 hours, fully settling insoluble substances in the solution, and taking supernatant to obtain coating liquid;
s3, adding 10g of artificial graphite powder prepared in the step S1 into an impregnation kettle, vacuumizing for 100min after the impregnation kettle is closed, then opening a suction valve of an asphalt solution, sucking 80g of coating liquid prepared in the step S2 into the impregnation kettle, fully covering the artificial graphite powder, closing the suction valve after liquid inlet is finished, continuously vacuumizing the impregnation kettle for 10min, simultaneously stirring the mixed liquid at a high speed (1500 rad/min) for 100min, opening an emptying valve after stirring and vacuumizing are finished, and pouring the mixed liquid into a storage tank after the internal pressure and the external pressure of the impregnation kettle are the same;
s4, firstly, carrying out centrifugal separation on the mixed solution in the storage tank to separate out upper-layer asphalt solution and asphalt-coated graphite powder, pouring the upper-layer asphalt solution into the asphalt solution storage tank, and pouring the asphalt-coated graphite powder into a container; then, adding 80g of distilled water into the container, fully stirring, washing for multiple times, then carrying out centrifugal separation again, pouring the upper-layer waste liquid after centrifugal separation into a waste liquid tank, and repeatedly washing and centrifuging the lower-layer asphalt-coated graphite powder for 6 times; finally, taking out the purified coated graphite powder separated by centrifugation for later use;
s5, putting the purified coated graphite powder prepared in the step S4 into a fluidized bed, drying at 70 ℃ for 40 hours, taking out the purified coated graphite powder, crushing to prevent the powder from caking, and sieving by a 260-mesh sieve to prepare coated graphite fine powder for later use;
and S6, heating the coated graphite fine powder prepared in the step S5 in a fluidized bed in nitrogen atmosphere at a heating rate of 50 ℃/h to 1100 ℃, and keeping the temperature for 2h at a constant temperature to prepare the asphalt liquid phase coated negative electrode material for the lithium ion battery.
Example 5
A method for preparing a lithium ion battery anode material by liquid phase coating modification comprises the following steps:
s1, mechanically crushing the artificial graphite, and then grading the crushed fine powder according to particle size to obtain artificial graphite powder with the particle size of 10-50 microns and the purity of 99.9%;
s2, weighing 30g of petroleum asphalt, respectively adding the weighed petroleum asphalt into a mixed solution consisting of 30g of toluene and 40g of pyridine, and stirring at a high speed (1200 rad/min) for 90min to fully dissolve the asphalt to obtain a petroleum asphalt solution with the mass fraction of 30%; then, pouring the prepared asphalt solution into a standing settling tank for standing for 72 hours, fully settling insoluble substances in the solution, and taking supernatant to obtain coating liquid;
s3, adding 10g of artificial graphite powder prepared in the step S1 into an impregnation kettle, vacuumizing for 120min after the impregnation kettle is closed, then opening a suction valve of an asphalt solution, sucking 100g of coating liquid prepared in the step S2 into the impregnation kettle, fully covering the artificial graphite powder, closing the suction valve after liquid inlet is finished, continuously vacuumizing the impregnation kettle for 120min, simultaneously stirring the mixed liquid at a high speed (1500 rad/min) for 120min, opening an emptying valve after stirring and vacuumizing are finished, and pouring the mixed liquid into a storage tank after the internal pressure and the external pressure of the impregnation kettle are the same;
s4, firstly, carrying out centrifugal separation on the mixed solution in the storage tank to separate out upper-layer asphalt solution and asphalt-coated graphite powder, pouring the upper-layer asphalt solution into the asphalt solution storage tank, and pouring the asphalt-coated graphite powder into a container; then, adding 80g of absolute ethyl alcohol into the container, fully stirring, washing for multiple times, then carrying out centrifugal separation again, pouring the upper-layer waste liquid after centrifugal separation into a waste liquid tank, and repeatedly washing and centrifuging the lower-layer asphalt-coated graphite powder for 8 times; finally, taking out the purified coated graphite powder separated by centrifugation for later use;
s5, putting the purified coated graphite powder prepared in the step S4 into a fluidized bed, drying at 80 ℃ for 48 hours, taking out the purified coated graphite powder, crushing to prevent the powder from caking, and sieving by a 325-mesh sieve to prepare coated graphite fine powder for later use;
and S6, heating the coated graphite fine powder prepared in the step S5 in a fluidized bed in nitrogen atmosphere at a heating rate of 50 ℃/h to 1300 ℃, and keeping the temperature at a constant temperature for 0.5h to prepare the asphalt liquid phase coated negative electrode material for the lithium ion battery.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (5)
1. A method for preparing a lithium ion battery cathode material by liquid phase coating modification is characterized by comprising the following steps:
s1, mechanically crushing the graphite material A, and then grading the crushed fine powder according to particle size to obtain graphite powder B with the particle size of 5-50 microns and the purity of more than 99.5%;
s2, weighing asphalt, adding the asphalt into an organic solvent, and stirring at a high speed for 20-90 min to fully dissolve the asphalt to obtain an asphalt solution with the mass fraction of 3-30%; then pouring the prepared asphalt solution into a standing settling tank for standing for 6-72 h, fully settling insoluble substances in the solution, and taking supernatant to obtain coating liquid;
s3, adding the graphite powder B prepared in the step S1 into an impregnation kettle, vacuumizing for 10-120 min after the impregnation kettle is closed, then opening a suction valve of an asphalt solution, sucking the coating liquid prepared in the step S2 into the impregnation kettle and fully covering the graphite powder B, wherein the volume ratio of the graphite powder B to the coating liquid is 1: 1.2-1: 20, closing the suction valve after the liquid is fed, continuously vacuumizing the impregnation kettle for 10-120 min, simultaneously stirring the mixed liquid at a high speed for 10-120 min, opening an emptying valve after the stirring and vacuumizing operation is finished, pouring the mixed liquid into a storage tank after the internal and external pressures of the impregnation kettle are the same;
s4, firstly, carrying out centrifugal separation on the mixed solution in the storage tank to separate out upper-layer asphalt solution and asphalt-coated graphite powder, pouring the upper-layer asphalt solution into the asphalt solution storage tank, and pouring the asphalt-coated graphite powder into a container; then, adding distilled water or absolute ethyl alcohol into the container, fully stirring, washing for multiple times, then carrying out centrifugal separation again, pouring the upper-layer waste liquid after centrifugal separation into a waste liquid tank, and repeatedly washing and centrifuging the lower-layer asphalt-coated graphite powder for 3-8 times; finally, taking out the purified coated graphite powder separated by centrifugation for later use;
s5, putting the purified coated graphite powder prepared in the step S4 into a fluidized bed, drying the powder for 2-48 hours at 40-80 ℃, taking out the purified coated graphite powder, crushing the powder, and sieving the crushed powder with a 100-325-mesh sieve to prepare coated graphite fine powder for later use;
and S6, heating the coated graphite fine powder prepared in the step S5 in a fluidized bed in an inert gas environment to 650-1300 ℃, and keeping the temperature for 0.5-6 hours to prepare the asphalt liquid phase coated negative electrode material for the lithium ion battery.
2. The method for preparing the negative electrode material of the lithium ion battery by liquid phase coating modification according to claim 1, wherein the method comprises the following steps: in the step S1, the graphite material a is one or more of natural crystalline flake graphite, natural aphanitic graphite, natural crystalline vein graphite, artificial graphite, or conductive graphite.
3. The method for preparing the negative electrode material of the lithium ion battery by liquid phase coating modification according to claim 1, wherein the method comprises the following steps: in the step S2, the asphalt is one or more of coal asphalt, petroleum asphalt, modified asphalt or mesophase asphalt.
4. The method for preparing the negative electrode material of the lithium ion battery by liquid phase coating modification according to claim 1, wherein the method comprises the following steps: in step S2, the organic solvent is one or more of ketones, aromatic hydrocarbons or heterocyclic compounds.
5. The method for preparing the negative electrode material of the lithium ion battery by liquid phase coating modification according to claim 1, wherein the method comprises the following steps: in the step S4, the volume ratio of the graphite powder coated with pitch to the distilled water or the absolute ethyl alcohol used for each cleaning is 1:2 to 1: 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011395757.7A CN112531168B (en) | 2020-12-03 | 2020-12-03 | Method for preparing lithium ion battery cathode material by liquid phase coating modification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011395757.7A CN112531168B (en) | 2020-12-03 | 2020-12-03 | Method for preparing lithium ion battery cathode material by liquid phase coating modification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112531168A true CN112531168A (en) | 2021-03-19 |
| CN112531168B CN112531168B (en) | 2021-09-03 |
Family
ID=74996657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011395757.7A Active CN112531168B (en) | 2020-12-03 | 2020-12-03 | Method for preparing lithium ion battery cathode material by liquid phase coating modification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112531168B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113488649A (en) * | 2021-06-02 | 2021-10-08 | 东莞塔菲尔新能源科技有限公司 | Coated negative electrode material, preparation method thereof, negative plate and lithium ion battery |
| CN114873591A (en) * | 2022-04-29 | 2022-08-09 | 广东东岛新能源股份有限公司 | Low-temperature long-life natural graphite negative electrode material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101162775A (en) * | 2006-10-10 | 2008-04-16 | 中国电子科技集团公司第十八研究所 | High performance lithium ionic cell cathode material and method for producing the same |
| CN101582503A (en) * | 2008-05-14 | 2009-11-18 | 天津市铁诚电池材料有限公司 | Negative electrode material of lithium ion battery with graphite covered by asphalt and preparation method thereof |
| CN102502595A (en) * | 2011-10-14 | 2012-06-20 | 上海理工大学 | Preparation method of isotropic graphite |
| CN102910618A (en) * | 2012-10-10 | 2013-02-06 | 彩虹集团公司 | Method for improving electrical property of natural graphite |
| CN103682350A (en) * | 2013-12-25 | 2014-03-26 | 东莞市凯金新能源科技有限公司 | Preparation method of asphalt liquid phase coated modified artificial graphite lithium battery cathode material |
| CN107403917A (en) * | 2017-07-25 | 2017-11-28 | 中南钻石有限公司 | A kind of preparation of asphalt grout and the method that graphite cathode is prepared using the slurry |
| CN111211315A (en) * | 2020-02-26 | 2020-05-29 | 中国科学院山西煤炭化学研究所 | Asphalt substrate layer carbon material and preparation method and application thereof |
-
2020
- 2020-12-03 CN CN202011395757.7A patent/CN112531168B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101162775A (en) * | 2006-10-10 | 2008-04-16 | 中国电子科技集团公司第十八研究所 | High performance lithium ionic cell cathode material and method for producing the same |
| CN101582503A (en) * | 2008-05-14 | 2009-11-18 | 天津市铁诚电池材料有限公司 | Negative electrode material of lithium ion battery with graphite covered by asphalt and preparation method thereof |
| CN102502595A (en) * | 2011-10-14 | 2012-06-20 | 上海理工大学 | Preparation method of isotropic graphite |
| CN102910618A (en) * | 2012-10-10 | 2013-02-06 | 彩虹集团公司 | Method for improving electrical property of natural graphite |
| CN103682350A (en) * | 2013-12-25 | 2014-03-26 | 东莞市凯金新能源科技有限公司 | Preparation method of asphalt liquid phase coated modified artificial graphite lithium battery cathode material |
| CN107403917A (en) * | 2017-07-25 | 2017-11-28 | 中南钻石有限公司 | A kind of preparation of asphalt grout and the method that graphite cathode is prepared using the slurry |
| CN111211315A (en) * | 2020-02-26 | 2020-05-29 | 中国科学院山西煤炭化学研究所 | Asphalt substrate layer carbon material and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113488649A (en) * | 2021-06-02 | 2021-10-08 | 东莞塔菲尔新能源科技有限公司 | Coated negative electrode material, preparation method thereof, negative plate and lithium ion battery |
| CN114873591A (en) * | 2022-04-29 | 2022-08-09 | 广东东岛新能源股份有限公司 | Low-temperature long-life natural graphite negative electrode material and preparation method and application thereof |
| CN114873591B (en) * | 2022-04-29 | 2023-12-19 | 广东东岛新能源股份有限公司 | Low-temperature long-life natural graphite anode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112531168B (en) | 2021-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103682350B (en) | Preparation method of asphalt liquid phase coated modified artificial graphite lithium battery cathode material | |
| CN108390033B (en) | Preparation method and application of carbon-coated antimony nanotube material as negative electrode material of sodium-ion battery | |
| CN112531168B (en) | Method for preparing lithium ion battery cathode material by liquid phase coating modification | |
| CN102231434A (en) | Modified natural graphite material used in lithium ion battery negative electrodes, and preparation method thereof | |
| CN106887593B (en) | Preparation method of high-capacity lithium ion battery cathode material | |
| CN111785949B (en) | Modified conductive polymer coated silicon-based negative electrode material, and preparation method and application thereof | |
| CN103840161A (en) | Method for preparing lithium battery negative electrode material, and lithium battery negative electrode sheet | |
| CN105489854A (en) | Preparation method of high-capacity anode material | |
| CN113889593B (en) | Preparation method of hard carbon-coated soft carbon composite material | |
| CN113363436B (en) | Lithium ion battery with high energy density and high cycle performance | |
| CN108598437A (en) | Lithium ion battery negative material and preparation method thereof suitable for low temperature | |
| WO2016192542A1 (en) | Method for manufacturing modified graphite negative electrode material | |
| CN103280601A (en) | Method for manufacturing lithium-sulfur battery | |
| EP3483958B1 (en) | Sulfur composite cathode material and preparation method and application thereof | |
| CN102569752A (en) | Carbon modified material for lithium ion secondary battery cathode and preparation method for carbon modified material | |
| Luo et al. | In situ construction of efficient interface layer with lithiophilic nanoseeds toward dendrite‐free and low N/P ratio Li metal batteries | |
| CN108832107B (en) | Graphene quantum dot-bio-based activated carbon composite material and preparation method thereof | |
| CN108365172A (en) | A kind of lithium an- ode material and its preparation method and application of natural polymers protection | |
| CN115188949B (en) | Preparation method of mesocarbon microbead-silicon carbon composite negative electrode material | |
| CN104300148B (en) | A kind of graphite negative material of lithium ion battery and preparation method thereof | |
| CN103094536A (en) | High-capacity lithium ion secondary battery cathode carbon material | |
| US20220158178A1 (en) | Silicon-based negative electrode material, preparation method and use thereof | |
| CN103078088B (en) | Lithium ion battery cathode material | |
| CN114920242B (en) | Preparation method of high-capacity graphite composite material | |
| CN104124430A (en) | Ruthenium dioxide quantum dot modified vanadium pentoxide nano material as well as preparation method and application of material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |