CN114597361A - Artificial graphite composite negative electrode material for lithium ion battery and preparation method and application thereof - Google Patents
Artificial graphite composite negative electrode material for lithium ion battery and preparation method and application thereof Download PDFInfo
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- CN114597361A CN114597361A CN202210200231.1A CN202210200231A CN114597361A CN 114597361 A CN114597361 A CN 114597361A CN 202210200231 A CN202210200231 A CN 202210200231A CN 114597361 A CN114597361 A CN 114597361A
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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
- H01M4/366—Composites as layered products
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
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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
- H01M4/58—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
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- 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 an artificial graphite composite negative electrode material and a preparation method and application thereof. The preparation method comprises the following steps: (1) calcining the green coke at a high temperature of 800-1200 ℃, and cooling to obtain a light calcined coke; (2) crushing and shaping the shallow calcined coke obtained in the step (1) to obtain coke powder; (3) mixing the coke powder obtained in the step (2) with asphalt for granulation to obtain secondary particles; (4) graphitizing the secondary particles obtained in the step (3), and then scattering and screening to obtain a screened substance; (5) and (5) carrying out carbon coating treatment on the screened material obtained in the step (4) to obtain the artificial graphite composite negative electrode material. The graphite cathode material prepared by the invention is used for the lithium ion battery, has high capacity and high multiplying power, and has simple preparation process and higher practicability.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to an artificial graphite composite negative electrode material for a lithium ion battery, and a preparation method and application thereof.
Background
The lithium ion battery has a series of advantages of high specific capacity, high working voltage, good safety, no memory effect and the like, and is widely applied to various portable electronic instruments and equipment such as notebook computers, mobile phones and instrument and meter lamps. With the popularization of new energy automobiles, the application range of the new energy automobiles is expanded to the fields of electric automobiles and the like. In recent years, with increasing demands for miniaturization, weight reduction, multifunction, and long-term driving of electronic products and vehicle-mounted and energy storage devices, demands for high energy density, high rate performance, and long cycle life of lithium ion batteries have been increasing.
The cathode material is one of the core components of the battery and plays a critical role in the comprehensive performance of the battery. In the existing negative electrode material types, the graphite material has the advantages of low charge-discharge platform, high theoretical lithium intercalation capacity, good conductivity and the like, and becomes a commercial lithium ion battery negative electrode material. The artificial graphite has good compatibility with electrolyte and better cycle and rate performance, and is a preferred negative electrode material of a power battery with long cycle life and high rate performance. The raw materials for preparing the artificial graphite mainly comprise green coke and calcined coke, the artificial graphite obtained after the green coke is graphitized has good multiplying power but low capacity, and the artificial graphite obtained after the calcined coke is graphitized has high capacity but low multiplying power. In order to solve the problems, the prior art respectively crushes, grades and sieves the raw coke and the calcined coke to obtain D50The composite artificial graphite material is prepared by bonding raw coke powder and calcined coke powder through secondary granulation technology treatment and finally graphitizing, wherein the raw coke powder and the calcined coke powder are small-particle coke powder of 5-8 mu m, but two kinds of artificial graphite are separated in the charging and discharging process, and the comprehensive performance of the artificial graphite cathode material is not obviously improved.
Disclosure of Invention
In order to overcome the problems of the conventional artificial graphite cathode material, the invention provides an artificial graphite composite cathode material with high capacity and high multiplying power, and a preparation method and application thereof.
The invention provides a preparation method of an artificial graphite composite negative electrode material, which comprises the following steps:
(1) calcining the green coke at a high temperature of 800-1200 ℃, and cooling to obtain a light calcined coke;
(2) crushing and shaping the shallow calcined coke obtained in the step (1) to obtain coke powder;
(3) mixing the coke powder obtained in the step (2) with asphalt for granulation to obtain secondary particles;
(4) graphitizing the secondary particles obtained in the step (3), and then scattering and screening to obtain a screened substance;
(5) and (5) carrying out carbon coating treatment on the screened substance obtained in the step (4) to obtain the artificial graphite composite negative electrode material.
According to the invention, in the step (1), the raw coke is at least one selected from petroleum coke raw coke, needle coke raw coke, pitch coke raw coke and intermediate-phase coke.
According to the present invention, in the step (1), the green coke has an average particle diameter D506 to 25mm, preferably 10 to 20mm, for example 10mm, 15mm, 20 mm.
According to the present invention, in the step (1), the equipment used in the high-temperature calcination is not particularly limited, and the calcination may be performed in calcination equipment known in the art, such as a pot calciner and a rotary kiln.
According to the invention, in the step (1), the high-temperature calcination is carried out for 6-10 hours, such as 6 hours, 7 hours, 8 hours, 9 hours, 10 hours.
According to the invention, in the step (1), the high-temperature calcination temperature is preferably 800-1050 ℃, such as 850 ℃, 950 ℃ and 1050 ℃.
According to the invention, in the step (2), the crushing refers to crushing and screening the shallow calcined coke to obtain coke powder.
According to the invention, in the step (2), the average particle diameter D of the coke powder505 to 12 μm, preferably 5 to 8 μm, for example, 5 μm, 6 μm, 7 μm, 8 μm.
According to the invention, in the step (2), the pulverization can be carried out by using a micro powder pulverization device known in the art, and the pulverizer can be, for example, an impact pulverizer, an air flow vortex pulverizer, an attritor mill, a pendulum mill.
According to the invention, in the step (2), the shaping is to spheroidize the surface of the powder particles of the shallow calcined coke and remove burrs on the surface of the powder particles.
According to the present invention, in the step (2), the shaping device is not particularly limited, and may be a shaping device known in the art, such as a jet vortex mill.
According to the invention, in the step (3), the mass ratio of the coke powder to the asphalt is 100 (8-30), preferably 100 (10-30), such as 100:15, 100:20 and 100: 25.
According to the invention, in step (3), the bitumen is selected from coal bitumen or petroleum bitumen.
Preferably, in the step (3), the softening point of the asphalt is 120-250 ℃, for example, 150 ℃, 180 ℃, 200 ℃, 220 ℃; the carbon residue value of the asphalt is more than or equal to 50 percent, such as 56 percent, 60 percent and 62 percent.
According to the invention, in the step (3), the mixing granulation comprises stirring under the protection of inert gas and under the heating condition (for example, 250-650 ℃). The invention aims to realize full contact and uniform heating of materials, further bond coke powder with small particle size after asphalt is melted to obtain secondary particles with large particles, and realize secondary granulation.
Preferably, the stirring speed of the mixing granulation is 30-50 rpm/min.
Preferably, the inert gas is N2Or Ar.
Preferably, in the granulation process, the temperature is gradually increased, for example, the granulation process is firstly heated to 250-350 ℃ and is kept warm for a period of time, then is heated to 350-450 ℃ and is kept warm for a period of time, and then is heated to 450-650 ℃ and is kept warm for a period of time. Specific heating steps include, for example: heating to 300 ℃ at a heating rate of 1.5-3.0 ℃/min, and keeping the temperature for 30 min; heating to 400 ℃ at a heating rate of 0.5-1.0 ℃/min, and keeping the temperature for 60 min; heating to 500-650 ℃ at a heating rate of 1.5-3.0 ℃/min, and keeping the temperature for 3-6 hours.
According to the present invention, in step (3), the mixing granulation can be performed by using equipment known in the art, such as a granulation reaction kettle.
According to the invention, in step (3), the secondary particles have an average particle diameter D5012 to 17 μm.
According to the present invention, in the step (4), the graphitization treatment conditions include: the treatment temperature is 2600-3000 ℃, and preferably 2800 ℃; the treatment time is 5 to 24 hours, preferably 6 to 12 hours.
According to the present invention, in the step (4), the equipment used for the scattering is not particularly limited, and the scattering may be performed by using equipment known in the art, such as a turbine type scattering machine or an air flow type scattering machine.
According to the present invention, in step (4), the equipment used for the screening is not particularly limited, and equipment known in the art can be selected for screening, for example, a vibrating screening machine.
According to the present invention, in the step (5), the carbon coating method is a method known in the art, for example, any one of chemical vapor deposition, carbon source solid phase mixing calcination or carbon source liquid phase mixing calcination is adopted, but not limited thereto.
According to the invention, after the carbon coating treatment, the average particle diameter D of the artificial graphite composite negative electrode material5010 to 20 μm, for example, 14 to 20 μm, 14 to 18 μm.
According to the invention, in the step (5), the carbon source solid-phase mixed calcination or carbon source liquid-phase mixed calcination is specifically: and (5) mixing the screened substance obtained in the step (4) with a solid carbon source or a liquid carbon source, coating the carbon source on the surface of the screened substance, and calcining at high temperature. The calcination temperature is, for example, 800 to 1200 ℃,and for example, 1000 to 1200 ℃. The sintering treatment time is 1-6 hours. The calcination being carried out under protection of an inert atmosphere, e.g. N2An atmosphere or an argon atmosphere.
Preferably, the mass ratio of the solid carbon source or the liquid carbon source to the sieved material is (0.8-3): 100, and exemplary is 0.8:100, 1.0:100, 1.2:100, 1.5:100, 2:100, 3: 100.
Further preferably, the solid or liquid carbon source is pitch, the softening point of which may be selected based on the temperature of mixing with the screen. For example, when the mixing temperature is 200 ℃, if the pitch having a softening point lower than 200 ℃ is selected, a liquid carbon source is formed during mixing, and if the pitch having a softening point higher than 200 ℃ is selected, a solid carbon source is formed during mixing.
According to the invention, in the step (5), the chemical vapor deposition is carried out, for example, the sieved material obtained in the step (4) reacts with a gas carbon source (such as methane) at 700-1000 ℃.
According to the invention, the step (5) further comprises the steps of cooling, scattering, screening and demagnetizing the calcined material to obtain the artificial graphite composite negative electrode material.
The invention also provides an artificial graphite composite negative electrode material which is prepared by the method.
According to the present invention, the average particle diameter D of the artificial graphite composite anode material5010 to 20 μm, for example, 14 to 20 μm, 14 to 18 μm.
The invention also provides application of the artificial graphite composite negative electrode material in a lithium ion battery.
The invention also provides a lithium ion battery, which comprises a negative electrode, wherein the negative electrode comprises the artificial graphite composite negative electrode material.
Advantageous effects
In the preparation method, the internal structure of the green coke is continuously rearranged in the high-temperature calcination process at 800-1200 ℃ to form a crystalline region and an amorphous region. The crystalline state area consists of a plurality of parallel graphite layers; the amorphous regions consist of tetrahedrally bonded carbon and highly warped graphite platelets. In the subsequent graphitization treatment process, the graphitization degree of the amorphous region is low, the crystal face spacing (d002) of a graphite layer is large, the compatibility with electrolyte is good, the multiplying power performance is good, and the graphitization degree and the capacity of the crystalline region are high. The content of two phases of crystalline and amorphous areas is controlled by controlling the calcination temperature, so that the performance parameters of the negative electrode material in the use process can be kept in the optimal state to the greatest extent.
The graphite cathode material prepared by the invention is used for lithium ion batteries, can have high capacity and high multiplying power at the same time, has simple preparation process and higher practicability, and is suitable for lithium ion batteries for mobile electronic equipment such as mobile phones, digital cameras and the like and power lithium ion batteries for electric vehicles, thereby greatly reducing the cost.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1:
(a) coking the oil-based needle coke (D)5010mm) is calcined at the high temperature of 850 ℃ for 6 hours, and the light calcined coke is obtained after cooling; then crushing in an impact crusher, shaping and sieving to obtain average particle size D505 μm coke powder.
(b) Uniformly mixing the coke powder obtained in the step (a) and asphalt (the softening point is 150 ℃, the carbon residue value is 56%) according to the weight ratio of 100:25, putting the mixture into a granulation reaction kettle, and adding the mixture into a reactor under N2Heating to 550 ℃ under protection, wherein the stirring speed in the kettle is 30r/min, and the heating temperature-rising program is as follows: heating to 300 ℃ at a heating rate of 1.5 ℃/min, and keeping the temperature for 30 min; heating to 400 ℃ at a heating rate of 0.5 ℃/min, and keeping the temperature for 60 min; the temperature is raised to 550 ℃ at the temperature rising speed of 3.0 ℃/min, and the temperature is preserved for 6 hours. Then cooled to the chamberSieving was carried out at room temperature to obtain secondary particles having an average particle diameter D50 of 17 μm.
(c) Graphitizing the secondary particles obtained in the step (b) at the high temperature of 2800 ℃ for 10 hours, cooling, scattering the graphitized material, and screening to obtain a screened material. Crushing high-softening-point asphalt with a softening point of 200 ℃ to 3 mu m in an impact crusher, mixing the crushed asphalt with the prepared screening material according to a mass ratio of 0.8:100, and then performing N mixing2Calcining at 1200 deg.C for 4 hr under protection, cooling to room temperature, scattering, sieving, and demagnetizing to obtain artificial graphite composite material with average particle diameter D50And 18 μm.
Example 2:
(a) coking the oil-based needle coke (D)5015mm) is calcined at the high temperature of 950 ℃ for 6 hours and then cooled to obtain shallow calcined coke; then, the pulverized material was pulverized by an impact pulverizer, and then, the pulverized material was ground and sieved to obtain a coke powder having an average particle size D50 of 5 μm.
(b) Uniformly mixing the coke powder obtained in the step (a) and asphalt (the softening point is 180 ℃, the carbon residue value is 60%) according to the weight ratio of 100:20, putting the mixture into a granulation reaction kettle, and adding the mixture into a reactor under N2Heating to 600 ℃ under protection, wherein the stirring speed in the kettle is 35r/min, and the heating temperature-rising program is as follows: heating to 300 ℃ at a heating rate of 1.5 ℃/min, and keeping the temperature for 30 min; heating to 400 ℃ at a heating rate of 0.8 ℃/min, and keeping the temperature for 60 min; the temperature is raised to 600 ℃ at the temperature rising speed of 3.0 ℃/min, and the temperature is kept for 4 hours. Then cooled to room temperature and sieved to obtain secondary particles having an average particle diameter D50 of 16 μm.
(c) Graphitizing the secondary particles obtained in the step (b) at the high temperature of 3000 ℃ for 6 hours, cooling, scattering and screening the graphitized materials to obtain screened materials. Putting the prepared screened material into a rotary furnace, introducing methane at the flow rate of 1L/min in the argon atmosphere with the flow rate of 100L/min and the environment of 800 ℃, continuously introducing argon for 2 hours, switching to the argon introduction, cooling to room temperature, scattering, screening and demagnetizing to obtain the artificial graphite composite material with the average particle size D50And was 17 μm.
Example 3:
(a) coking the oil-based needle coke (D)5020mm) is calcined at 1050 ℃ for 6h and cooled to obtainTo shallow calcined coke; then crushing in an impact crusher, shaping and sieving to obtain average particle size D505 μm coke powder.
(b) Uniformly mixing the coke powder obtained in the step (a) and asphalt (the softening point is 220 ℃, the carbon residue value is 62%) according to the weight ratio of 100:15, putting the mixture into a granulation reaction kettle, and adding the mixture into a reactor under N2Heating to 650 ℃ under protection, wherein the stirring speed in the kettle is 40r/min, and the heating temperature program is as follows: heating to 300 ℃ at a heating rate of 1.5 ℃/min, and keeping the temperature for 30 min; heating to 400 ℃ at the heating rate of 1.0 ℃/min, and keeping the temperature for 60 min; the temperature is raised to 650 ℃ at the temperature rising speed of 2.0 ℃/min, and the temperature is preserved for 3 hours. Then, the mixture was cooled to room temperature and sieved to obtain secondary particles having an average particle diameter D50 of 14 μm.
(c) Graphitizing the secondary particles obtained in the step (b) at the high temperature of 2800 ℃ for 6 hours, cooling, scattering and screening the graphitized materials to obtain screened materials. 2.5g of pitch with a softening point of 150 ℃ is put into a kneading pot to be heated to 200 ℃, 100g of the sieved material is added into the kneading pot to be kneaded for 2 hours and cooled to room temperature to obtain the sieved material coated with the carbon source, and then the sieved material is placed in N2Sintering at 1150 deg.C for 6 hr under protection, cooling to room temperature, scattering, sieving, and demagnetizing to obtain artificial graphite composite material with average particle diameter D50And 16 μm.
Comparative example 1:
(a) coking the oil-based needle coke (D)5010mm) was pulverized by an impact pulverizer, and then, the pulverized material was shaped and classified to obtain a coke powder having an average particle size D50 of 5 μm.
(b) Uniformly mixing the coke powder obtained in the step (a) and asphalt according to the weight ratio of 100:20, putting the mixture into a granulation reaction kettle, and adding the mixture into a reactor under the condition of N2Heating to 550 ℃ under protection, wherein the stirring speed in the kettle is 30r/min, and the heating temperature program is as follows: heating to 300 ℃ at a heating rate of 1.5 ℃/min, and keeping the temperature for 30 min; heating to 400 ℃ at a heating rate of 0.5 ℃/min, and keeping the temperature for 60 min; the temperature is raised to 550 ℃ at the temperature rising speed of 3.0 ℃/min, and the temperature is preserved for 6 hours. Then, the mixture was cooled to room temperature and sieved to obtain secondary particles having an average particle diameter D50 of 17 μm.
(c) Graphitizing the secondary particles obtained in the step (b) at the high temperature of 2800 ℃ for 10 hours, cooling the graphitized particlesThe materials are scattered and screened to obtain screened materials. Crushing high-softening-point asphalt with a softening point of 200 ℃ to 3 mu m in an impact crusher, mixing the crushed asphalt with the prepared screening material according to a mass ratio of 0.8:100 to obtain screening material coated with a carbon source, and then performing N treatment on the screening material2Sintering at 1200 deg.C for 4 hr under protection, cooling to room temperature, scattering, sieving, and demagnetizing to obtain artificial graphite composite material with average particle diameter D50And 18 μm.
Comparative example 2:
(a) coking the oil-based needle coke (D)5010mm) is calcined at 1350 ℃ for 6h, and calcined coke is obtained after cooling; then, the pulverized material was pulverized by an impact pulverizer, and then, the pulverized material was shaped and classified to obtain a coke powder having an average particle size D50 of 5 μm.
(b) Uniformly mixing the coke powder obtained in the step (a) and asphalt according to the weight ratio of 100:20, putting the mixture into a granulation reaction kettle, and adding the mixture into a reactor under the condition of N2Heating to 550 ℃ under protection, wherein the stirring speed in the kettle is 30r/min, and the heating temperature-rising program is as follows: heating to 300 ℃ at a heating rate of 1.5 ℃/min, and keeping the temperature for 30 min; heating to 400 ℃ at a heating rate of 0.5 ℃/min, and keeping the temperature for 60 min; the temperature is raised to 550 ℃ at the temperature rising speed of 3.0 ℃/min, and the temperature is preserved for 6 hours. Then cooling to room temperature, and sieving to obtain average particle diameter D50Is a secondary particle of 17 μm.
(c) Graphitizing the secondary particles obtained in the step (b) at the high temperature of 2800 ℃ for 10 hours, cooling, scattering and screening the graphitized materials to obtain screened materials. Crushing high-softening-point asphalt with a softening point of 200 ℃ to 3 mu m in an impact crusher, mixing the crushed asphalt with the prepared screening material according to a mass ratio of 0.8:100 to obtain screening material coated with a carbon source, and then performing N treatment on the screening material2Sintering at 1200 deg.C for 4 hr under protection, cooling to room temperature, scattering, sieving, and demagnetizing to obtain artificial graphite composite material with average particle diameter D50And 18 μm.
Test example
The electrochemical performance of the negative electrode materials of examples 1 to 3 and comparative examples 1 to 2 was tested, and the following details were found:
electrochemical performance test
Semi-electric testing methodThe method comprises the following steps: the negative electrode materials prepared in examples 1-3 and comparative examples 1-2 are respectively taken, uniformly mixed according to the mass ratio of the graphite negative electrode material, conductive carbon black (SP), carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR) of 95:1:1.5:2.5, coated on copper foil, and dried in a vacuum drying oven at 120 ℃ for 12 hours to obtain the negative electrode sheet. And (3) carrying out simulated battery assembly on the cathode plate in an argon-protected Braun glove box, wherein the electrolyte is as follows: 1mol/L LiPF6The solvent is EC: DEC: DMC (volume ratio is 1:1: 1); the metal lithium sheet is a counter electrode. The simulated battery is tested in a 5V and 10mA Xinwei battery test cabinet, the charge-discharge voltage is 0.01-1.5V, the charge-discharge rate is 0.2C, and the first discharge capacity and the first charge-discharge efficiency obtained by the test are listed in Table 1.
The maximum charging rate test method comprises the following steps: and (3) charging the simulated battery to 100% SOC under different multiplying powers (multiplying power is 1C, 2C, 3C, 4C and 5C), disassembling the battery, observing the lithium precipitation condition of the negative plate, and recording as the maximum charging multiplying power when the lithium precipitation occurs in the negative plate.
Table 1 test results of physical and chemical properties and electrochemical properties of graphite negative electrode material
As can be seen from table 1, the graphite negative electrode material prepared by the present invention has high capacity and high rate when used in a lithium ion battery, and the present invention has the advantages of simple preparation process and high practicability, and is suitable for lithium ion batteries for mobile electronic devices such as mobile phones and digital cameras, and power lithium ion batteries for electric vehicles, thereby greatly reducing the cost.
The above description is directed to exemplary embodiments of the present invention. However, the scope of protection of the present application is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement and the like made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the artificial graphite composite negative electrode material is characterized by comprising the following steps of:
(1) calcining the green coke at a high temperature of 800-1200 ℃, and cooling to obtain a light calcined coke;
(2) crushing and shaping the shallow calcined coke obtained in the step (1) to obtain coke powder;
(3) mixing the coke powder obtained in the step (2) with asphalt for granulation to obtain secondary particles;
(4) graphitizing the secondary particles obtained in the step (3), and then scattering and screening to obtain a screened substance;
(5) and (5) carrying out carbon coating treatment on the screened material obtained in the step (4) to obtain the artificial graphite composite negative electrode material.
2. The production method according to claim 1, wherein in the step (1), the green coke is at least one selected from the group consisting of petroleum coke green coke, needle coke green coke, pitch coke green coke, and mesophase coke.
Preferably, in the step (1), the green coke has an average particle diameter D506-25 mm.
Preferably, in the step (1), the high-temperature calcination time is 6-10 hours.
Preferably, in the step (1), the temperature of the high-temperature calcination is 800-1050 ℃.
3. The method according to claim 1 or 2, wherein in the step (2), the pulverization is performed by pulverizing the calcined coke and sieving to obtain coke powder.
Preferably, in the step (2), the average particle diameter D of the coke powder505 to 12 μm, preferably 5 to 8 μm.
4. The preparation method according to any one of claims 1 to 3, wherein in the step (3), the mass ratio of the coke powder to the asphalt is 100 (8-30).
Preferably, in step (3), the asphalt is selected from coal asphalt or petroleum asphalt.
Preferably, in the step (3), the softening point of the asphalt is 120-250 ℃; the carbon residue value of the asphalt is more than or equal to 50 percent.
5. The method according to any one of claims 1 to 4, wherein in the step (3), the mixing granulation comprises stirring under heating under an inert gas atmosphere.
Preferably, the inert gas is N2Or Ar.
Preferably, the heating condition is 250-650 ℃.
Preferably, in the granulation process, the temperature is gradually increased, the mixture is heated to 350 ℃ for a period of time, then heated to 350-450 ℃ for a period of time, and then heated to 450-650 ℃ for a period of time. Preferably, the heating step comprises: heating to 300 ℃ at a heating rate of 1.5-3.0 ℃/min, and keeping the temperature for 30 min; heating to 400 ℃ at a heating rate of 0.5-1.0 ℃/min, and keeping the temperature for 60 min; heating to 500-650 ℃ at a heating rate of 1.5-3.0 ℃/min, and preserving heat for 3-6 hours.
Preferably, in the step (3), the secondary particles have an average particle diameter D5012 to 17 μm.
6. The production method according to any one of claims 1 to 5, wherein the temperature of the graphitization treatment in step (4) is 2600 to 3000 ℃.
7. The method for preparing the carbon coating material according to any one of claims 1 to 6, wherein in the step (5), the carbon coating method adopts any one of but not limited to chemical vapor deposition, carbon source solid phase mixed calcination or carbon source liquid phase mixed calcination.
8. An artificial graphite composite negative electrode material, characterized in that the artificial graphite composite negative electrode material is prepared by the preparation method of any one of claims 1 to 7.
Preferably, the average particle diameter D of the artificial graphite composite anode material5010 to 20 μm.
9. Use of the artificial graphite composite negative electrode material according to claim 8 in a lithium ion battery.
10. A lithium ion battery comprising a negative electrode comprising the artificial graphite composite negative electrode material of claim 8.
Priority Applications (1)
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| CN115385330A (en) * | 2022-06-14 | 2022-11-25 | 岳阳耀宁新能源科技有限公司 | Preparation method of high-energy-density low-expansion quick-charging graphite cathode |
| CN115490228A (en) * | 2022-09-21 | 2022-12-20 | 湖南宸宇富基新能源科技有限公司 | Coke micropowder-based graphite material, preparation thereof and application thereof in lithium secondary battery |
| CN115536019A (en) * | 2022-09-29 | 2022-12-30 | 大理宸宇储能新材料有限公司 | Artificial graphite material, preparation thereof and application thereof in lithium secondary battery |
| CN115893402A (en) * | 2022-11-24 | 2023-04-04 | 银硅(宁波)科技有限公司 | Method for preparing low-expansion high-rate graphite negative electrode material by using crucible waste |
| CN116239382A (en) * | 2022-12-23 | 2023-06-09 | 合肥国轩新材料科技有限公司 | Preparation method of high-pressure compact composite graphite and lithium ion battery |
| CN116654922A (en) * | 2023-06-30 | 2023-08-29 | 安徽科达新材料有限公司 | Artificial graphite negative electrode material and preparation method and application thereof |
| TWI816598B (en) * | 2022-11-03 | 2023-09-21 | 台灣中油股份有限公司 | Method for producing negative electrode carbon material and its lithium ion secondary battery |
| TWI838162B (en) | 2023-03-09 | 2024-04-01 | 台灣中油股份有限公司 | Preparation method of soft carbon and lithium-ion secondary battery |
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| CN115385330A (en) * | 2022-06-14 | 2022-11-25 | 岳阳耀宁新能源科技有限公司 | Preparation method of high-energy-density low-expansion quick-charging graphite cathode |
| CN115490228A (en) * | 2022-09-21 | 2022-12-20 | 湖南宸宇富基新能源科技有限公司 | Coke micropowder-based graphite material, preparation thereof and application thereof in lithium secondary battery |
| CN115490228B (en) * | 2022-09-21 | 2024-02-09 | 湖南宸宇富基新能源科技有限公司 | Coke micro powder-based graphite material, preparation method thereof and application thereof in lithium secondary battery |
| CN115536019A (en) * | 2022-09-29 | 2022-12-30 | 大理宸宇储能新材料有限公司 | Artificial graphite material, preparation thereof and application thereof in lithium secondary battery |
| CN115536019B (en) * | 2022-09-29 | 2024-02-09 | 大理宸宇储能新材料有限公司 | Artificial graphite material, preparation thereof and application thereof in lithium secondary battery |
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| CN115893402A (en) * | 2022-11-24 | 2023-04-04 | 银硅(宁波)科技有限公司 | Method for preparing low-expansion high-rate graphite negative electrode material by using crucible waste |
| CN116239382A (en) * | 2022-12-23 | 2023-06-09 | 合肥国轩新材料科技有限公司 | Preparation method of high-pressure compact composite graphite and lithium ion battery |
| TWI838162B (en) | 2023-03-09 | 2024-04-01 | 台灣中油股份有限公司 | Preparation method of soft carbon and lithium-ion secondary battery |
| CN116654922A (en) * | 2023-06-30 | 2023-08-29 | 安徽科达新材料有限公司 | Artificial graphite negative electrode material and preparation method and application thereof |
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