CN106602067B - Graphite-based composite material, preparation method thereof and lithium ion battery containing composite material - Google Patents

Graphite-based composite material, preparation method thereof and lithium ion battery containing composite material Download PDF

Info

Publication number
CN106602067B
CN106602067B CN201710069655.8A CN201710069655A CN106602067B CN 106602067 B CN106602067 B CN 106602067B CN 201710069655 A CN201710069655 A CN 201710069655A CN 106602067 B CN106602067 B CN 106602067B
Authority
CN
China
Prior art keywords
natural graphite
graphite
aminated
composite material
atmosphere
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.)
Active
Application number
CN201710069655.8A
Other languages
Chinese (zh)
Other versions
CN106602067A (en
Inventor
周成坤
苗恒
潘修军
周海辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beiteri (Jiangsu) new energy materials Co., Ltd
Original Assignee
Shenzhen BTR New Energy Materials Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shenzhen BTR New Energy Materials Co Ltd filed Critical Shenzhen BTR New Energy Materials Co Ltd
Priority to CN201710069655.8A priority Critical patent/CN106602067B/en
Publication of CN106602067A publication Critical patent/CN106602067A/en
Application granted granted Critical
Publication of CN106602067B publication Critical patent/CN106602067B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a graphite-based composite material, a preparation method thereof and a lithium ion battery containing the composite graphite material, wherein the method comprises the following steps: 1) mixing activated natural graphite and asphalt uniformly according to a certain proportion, adding the mixture into a fusion machine, introducing inert gas, and performing fusion granulation at a certain temperature; 2) and carrying out carbonization treatment or graphitization treatment on the fused and granulated product to obtain the graphite-based composite material. The battery prepared by adopting the graphite-based composite material to prepare the cathode and assembled by the cathode has high capacity, good rate capability and cycle performance, the first lithium removal specific capacity is more than 360.1mAh/g, the first efficiency is more than 91.5 percent, and the capacity retention rate of the finished battery is more than 90 percent after the battery is charged and discharged at normal temperature and is cycled for 300 weeks.

Description

Graphite-based composite material, preparation method thereof and lithium ion battery containing composite material
Technical Field
The invention belongs to the technical field of negative electrode materials, and particularly relates to a graphite-based composite material, a preparation method thereof and a lithium ion battery containing the composite material.
Background
Compared with lead-acid and nickel-hydrogen batteries, the lithium ion battery has the advantages of high energy density, high working voltage, small volume, light weight, no pollution, good safety, long service life and the like, and is an ideal energy storage device. In recent years, lithium ion batteries have been developed vigorously in the aspects of mobile portable devices (mobile phones, notebook computers, digital cameras, tablet computers and the like), energy storage devices, power grid peak shaving and vehicle power batteries, but with the social progress and scientific and technological development, people have more and more urgent needs for miniaturized, lightweight and multifunctional devices, and higher requirements for the performance of the lithium ion batteries are provided, and the improvement of the performance of the lithium ion batteries greatly depends on the development and improvement of a negative electrode material.
At present, the carbon material is the most successful negative electrode material of commercial lithium ion batteries, and comprises natural graphite, artificial graphite, mesocarbon microbeads (MCMB) and the like, wherein the natural graphite has the advantages of high specific capacity, high compacted density, wide sources, simple process and the like, and always occupies the main position of the negative electrode material market, but the deficiency of the natural graphite is also obvious: the first charge-discharge efficiency is low, the irreversible capacity loss is large, the dependence on electrolyte is strong, the electrode expansion rate is large, the cycle life is limited, and the like.
Among the methods for improving the electrochemical performance of carbon negative electrode materials, the secondary granulation process is a very effective approach. The secondary granulation is a process of bonding carbon precursors with surface activity into secondary particles through high-temperature heat treatment under the assistance of adhesive pitch or other organic matters, and can shorten the transmission path of lithium ions, improve the multiplying power performance, increase the isotropy, promote the reduction of the isotropic expansion of the pole piece and the like.
CN 103311520B discloses a composite graphite negative electrode material for lithium ion batteries and a preparation method thereof, which comprises the following steps: (1) uniformly mixing spherical natural graphite, mesophase graphite and a graphitization catalyst to obtain a mixture; (2) kneading the mixture and the binder to obtain a kneaded mass; (3) carbonizing the kneaded mass, cooling, and then carrying out catalytic graphitization high-temperature treatment; (4) crushing and grading the product obtained in the step (3); wherein, the binder in the step (2) is petroleum asphalt and/or coal asphalt. The obtained composite graphite cathode has good electrochemical performance, the discharge capacity is more than 360mAh/g, the composite graphite cathode has high charge-discharge efficiency, high-current charge-discharge performance, good cycle performance and good safety. However, a large number of crushing and grinding processes adopted for preparing the material can destroy the cohesiveness among secondary particles, and simultaneously can generate a large number of active surfaces, thereby increasing the side reaction of the electrode plate in the charging and discharging processes.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a graphite-based composite material, a preparation method thereof and a lithium ion battery containing the composite material, aiming at solving the defects of low first charge-discharge efficiency, large irreversible capacity loss, strong dependence on electrolyte, large electrode expansion rate and short cycle life of natural graphite and keeping the advantage of high capacity. The battery prepared by adopting the graphite-based composite material to prepare the cathode and assembled by the cathode has high capacity, good rate capability and cycle performance, the first lithium removal specific capacity is more than 360.1mAh/g, the first efficiency is more than 91.5 percent, and the capacity retention rate of the finished battery is more than 90 percent after the battery is charged and discharged at normal temperature and is cycled for 300 weeks.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a graphite-based composite material, the method comprising the steps of:
(1) uniformly mixing activated natural graphite and asphalt to obtain a mixture;
(2) placing the mixture in a fusion machine, and performing fusion granulation in an inert atmosphere to obtain a fusion granulation product;
(3) and carrying out carbonization treatment or graphitization treatment on the fused and granulated product to obtain the graphite-based composite material.
According to the method, activated natural graphite and asphalt are mixed, and then are subjected to fusion granulation and carbonization treatment or graphitization treatment, so that the obtained graphite-based composite material has high first effect and specific capacity and very good cycle performance, and the liquid absorption performance is improved.
As a preferable technical scheme of the method, the activated natural graphite is natural graphite subjected to surface functionalization treatment.
The surface-functionalized natural graphite of the present invention has functional groups on the surface thereof, which are atoms or atomic groups that can determine the chemical properties of the organic compound.
Preferably, the surface-functionalization treated natural graphite is any one of aminated natural graphite, oxidized natural graphite, aminated complex oxidized natural graphite, a mixture of aminated natural graphite and oxidized natural graphite, and preferably a mixture of aminated natural graphite and oxidized natural graphite.
In the invention, ammoniation treatment, oxidation treatment or ammoniation composite oxidation treatment is carried out under the atmosphere of oxygen or ammonia gas, the inert property of the graphite surface is mainly changed, and some functional groups containing O or N are grafted, so that the method is more favorable for more firm bonding of secondary particles and is also favorable for improving the liquid absorption performance.
The "aminated composite oxidation treated natural graphite" in the invention refers to: the modified natural graphite is obtained by firstly carrying out ammoniation treatment and then carrying out oxidation treatment on natural graphite, or the modified natural graphite is obtained by firstly carrying out oxidation treatment and then carrying out ammoniation treatment on natural graphite.
In a further preferred embodiment of the method of the present invention, the surface-functionalized natural graphite is a mixture of aminated natural graphite and oxidized natural graphite, and under such conditions, the aminated functional group and the oxidized functional group cooperate synergistically to ensure that firm secondary particles are formed with a small amount of asphalt binder, and the coating properties can be synergistically improved through subsequent secondary granulation.
More preferably, in the mixture of aminated natural graphite and oxidized natural graphite, the mass ratio of aminated natural graphite to oxidized natural graphite is 1:9 to 9:1, for example 1:9, 1.5:8.5, 2:8, 3:7, 3.5:6.5, 4:6, 5:5, 6:4, 6.5:3.5, 7:3, 8:2 or 9:1, preferably 7:3 to 5: 5;
preferably, the aminated natural graphite is prepared by the following method: and carrying out heat treatment on the natural graphite in an ammonia atmosphere to obtain the aminated natural graphite.
Preferably, the aminated composite oxidation treated natural graphite is prepared by the first scheme or the second scheme:
the first scheme is as follows: carrying out heat treatment on the aminated natural graphite in an oxygen atmosphere and/or an air atmosphere;
scheme II: and carrying out heat treatment on the oxidized natural graphite in an ammonia atmosphere.
Preferably, the natural graphite has a median particle diameter of D50 ═ 2 to 15 μm, for example, 2, 3, 5, 6, 7, 8, 10, 12, 13, 14 or 15 μm, and preferably D50 ═ 3 to 8 μm.
Preferably, the sphericity of the natural graphite is 0.8 to 0.95, for example, 0.80, 0.82, 0.84, 0.85, 0.88, 0.90, 0.91, 0.93, 0.94, or 0.95.
Preferably, the natural graphite has a carbon content of greater than 99.95 wt.%, e.g., 99.96 wt.%, 99.97 wt.%, 99.98 wt.%, or 99.99 wt.%, etc.
Preferably, in the process of preparing the aminated natural graphite, the oxidized natural graphite and the aminated complex-oxidation treated natural graphite, the heat treatment temperature is independently 300 to 1000 ℃, for example 300 ℃, 400 ℃, 450 ℃, 500 ℃, 600 ℃, 660 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃, independently preferably 600 to 800 ℃.
In the present invention, the "temperature of the heat treatment is independently 300 to 1000 ℃" means: the heat treatment temperature in the process of preparing the ammoniated natural graphite is 300-1000 ℃; the temperature of heat treatment in the process of preparing the natural graphite subjected to oxidation treatment is 300-1000 ℃; in the first scheme for preparing the natural graphite subjected to ammoniation composite oxidation treatment, the temperature of heat treatment is 300-1000 ℃; the temperature of the heat treatment in the second scheme for preparing the natural graphite subjected to the ammoniation composite oxidation treatment is 300-1000 ℃.
Preferably, in the process of preparing the aminated natural graphite, the oxidized natural graphite and the aminated composite oxidized natural graphite, the heat treatment time is independently 2h to 6h, such as 2h, 2.5h, 3h, 3.2h, 3.5h, 4h, 4.25h, 5h, 5.2h, 5.4h, 5.7h or 6h, etc.
In the present invention, the "air atmosphere and/or oxygen atmosphere" means: the atmosphere may be an air atmosphere, an oxygen atmosphere, or a mixed atmosphere of an air atmosphere and an oxygen atmosphere.
Preferably, the flow rate of ammonia gas in the process of preparing the aminated natural graphite is 5L/h.kg-20L/h.kg, such as 5L/h.kg, 8L/h.kg, 10L/h.kg, 11L/h.kg, 12L/h.kg, 14L/h.kg, 15L/h.kg, 17L/h.kg, 18L/h.kg, 19L/h.kg or 20L/h.kg, etc.
Preferably, the flow rate of oxygen and/or air in the process of preparing the oxidation-treated natural graphite is 5L/h.kg to 20L/h.kg, such as 5L/h.kg, 6L/h.kg, 8L/h.kg, 10L/h.kg, 12L/h.kg, 14L/h.kg, 15L/h.kg, 17L/h.kg, 18L/h.kg, 18.5L/h.kg, 20L/h.kg, etc.
Preferably, in the first embodiment, the flow rate of oxygen and/or air is 5L/h.kg to 20L/h.kg, such as 5L/h.kg, 7L/h.kg, 10L/h.kg, 12L/h.kg, 13L/h.kg, 15L/h.kg, 17L/h.kg, 18L/h.kg, 19L/h.kg or 20L/h.kg.
Preferably, in the second embodiment, the flow rate of ammonia gas is 5L/h.kg-20L/h.kg, such as 5L/h.kg, 7L/h.kg, 10L/h.kg, 12.5L/h.kg, 15L/h.kg, 16L/h.kg, 17L/h.kg, 18.5L/h.kg or 20L/h.kg.
Preferably, the apparatus used for preparing the surface-functionalization treated natural graphite is a rotary kiln, a box-type heating furnace or a tube furnace.
Preferably, the asphalt in step (1) is any one or a combination of at least two of petroleum asphalt, coal asphalt or modified asphalt.
Preferably, the mass ratio of the activated natural graphite to the asphalt in the step (1) is (98-80): 2-20, such as 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 90:10, 88:12, 87:13, 85:15, 83:17, 82:18 or 80: 20.
Preferably, the inert atmosphere in step (2) is any one of a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, an argon atmosphere, a krypton atmosphere, or a xenon atmosphere, or a combination of at least two of them.
Preferably, the apparatus used for the fusion granulation in step (2) is a fusion machine, such as a commercially available mechanical fusion machine.
Preferably, the temperature of the fusion granulation in the step (2) is 500 to 800 ℃, for example, 500 ℃, 520 ℃, 525 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 600 ℃, 625 ℃, 650 ℃, 680 ℃, 700 ℃, 720 ℃, 740 ℃, 760 ℃, 780 ℃, or 800 ℃.
Preferably, the fusion granulation time in step (2) is 2h to 24h, for example, 2h, 4h, 5h, 7.5h, 10h, 12h, 14h, 15h, 18h, 20h, 21h, 22.5h or 24 h.
Preferably, the temperature of the carbonization treatment in the step (3) is 800 to 1300 ℃, for example, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1300 ℃ or the like.
Preferably, the graphitization treatment in step (3) is carried out at a temperature of 2800 to 3200 ℃, for example 2800 ℃, 2850 ℃, 2900 ℃, 2950 ℃, 3000 ℃, 3020 ℃, 3060 ℃, 3100 ℃, 3150 ℃, 3200 ℃, or the like.
Preferably, the method further comprises the step of classifying or screening after the carbonization treatment is completed, or after the graphitization treatment is completed.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) taking natural graphite with the median particle size of D50-3-8 μm as a raw material, introducing ammonia gas at the flow rate of 5-20L/h.kg, and carrying out heat treatment at 600-800 ℃ for 2-6 h to obtain aminated natural graphite;
(2) taking natural graphite with the median particle size of D50-3-8 μm as a raw material, introducing oxygen at the flow rate of 5-20L/h.kg, and carrying out heat treatment at 600-800 ℃ for 2-6 h to obtain natural graphite subjected to oxidation treatment;
(3) taking a mixture of aminated natural graphite and oxidized natural graphite as activated natural graphite, uniformly mixing the activated natural graphite and asphalt according to the ratio of (98-80) to (2-20), adding the mixture into a mechanical fusion machine, introducing nitrogen, performing fusion granulation for 2-24 h at 500-800 ℃, and cooling to obtain a fusion granulation product;
(3) and carbonizing the fused and granulated product at 800-1300 ℃, or graphitizing the fused and granulated product at 2800-3200 ℃, so as to obtain the graphite-based composite material.
According to the preferred technical scheme, a mixture of small-particle aminated natural graphite and oxidized natural graphite is used as a raw material, the raw material and asphalt in a specific proportion are mixed for fusion granulation, carbonization or graphitization is carried out, the graphite-based composite material is obtained, the capacity is kept at above 363mAh/g, the first effect is above 92%, the cycle of the finished battery is 300 weeks, and the capacity retention rate can reach above 93%.
In a second aspect, the present invention provides a graphite-based composite material prepared by the method of the first aspect.
In a third aspect, the present invention provides a negative electrode comprising the graphite-based composite material according to the second aspect. The cathode containing the graphite-based composite material is suitable for lithium ion batteries such as electric tools of mobile phones, electric automobiles, electric vehicles and the like, digital electric appliances, energy storage and the like.
In a fourth aspect, the present invention provides a lithium ion battery comprising the graphite-based composite material according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method, activated natural graphite and asphalt are mixed, and then are subjected to fusion granulation and carbonization treatment or graphitization treatment, so that the obtained graphite-based composite material has high first effect and specific capacity and very good cycle performance, and the liquid absorption performance is improved.
(2) The method comprises the steps of carrying out surface functionalization treatment on natural graphite to obtain oxidized natural graphite and aminated natural graphite, mixing the oxidized natural graphite and the aminated natural graphite to enable the aminated functional group and the oxidized functional group to have a synergistic cooperation effect, forming firm secondary particles under the condition of using a small amount of asphalt binder, and solving the disadvantage that the secondary particles are difficult to form among particles due to surface inertia of the natural graphite; through subsequent secondary granulation, granulation can be realized, dynamic surface coating can be simultaneously carried out, the coating layer is more uniform, the obtained graphite-based composite material is used for preparing a negative electrode and assembling a battery, the first effect of natural graphite can be improved, the irreversible capacity loss is reduced, the expansion rate is reduced, the cycle performance of the material is improved, the first lithium removal specific capacity is 360.1mAh/g, the first efficiency is more than 91.5%, and the capacity retention rate of the finished battery is more than 90% after 300 cycles of normal-temperature charge and discharge.
(3) The preparation method is simple, easy to operate and suitable for industrial production.
(4) The cathode containing the graphite-based composite material is suitable for lithium ion batteries such as mobile phones, electric tools such as electric automobiles and electric vehicles, digital electric appliances and energy storage batteries.
Drawings
Fig. 1 is an SEM picture of the graphite-based composite material prepared in example 2.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
Placing natural spherical graphite (D50 is 6-8 μm, S50 is 0.80-0.95) in a rotary kiln, introducing oxygen, and oxidizing at 600 ℃ for 2h with the oxygen flow rate of 10L/h.kg to obtain oxidized natural graphite (oxidized graphite). Mixing the oxidized graphite and the petroleum asphalt according to the mass ratio of 90:10, and then adding N2And (3) placing the graphite-based composite material in a 600 ℃ fusion machine for mechanical granulation in the atmosphere, cooling a reaction product to room temperature after 5 hours of mechanical granulation, and then carbonizing at 1200 ℃ to obtain the graphite-based composite material.
And (3) electrochemical performance testing:
the graphite-based composite material obtained in example 1 was used as a negative electrode active material, and the negative electrode active material CMC: SBR in a mass ratio of 96.5:1.5:2 was uniformly mixed, and then the mixture was applied to a copper foil current collector, dried, and punched for use.
Assembling the button cell:
the button cell is assembled in a glove box filled with argon, a metal lithium sheet is used as a counter electrode, and the electrolyte is 1mol/LLIPF6+EC + EMC, the diaphragm is a polyethylene/propylene composite microporous membrane, and the button cell is assembled.
Particle size test of the composite graphite material:
the particle size test was carried out with a laser particle sizer according to ISO13320 laser particle sizer standard GB/T19077.1-2003.
And (3) testing capacity and efficiency:
the electrochemical performance test is carried out on a battery tester, the charge-discharge voltage range is 0.001-1.5V, and the charge-discharge rate is 0.1C.
The first lithium-removal specific capacity, the first discharge efficiency and the granularity index obtained by the test are listed in table 1.
And (3) testing the cycle performance of the finished battery:
taking the graphite-based composite materials prepared in examples 1 to 14 and the composite graphite materials prepared in comparative examples 1 to 5 as negative electrode active substances, respectively mixing the negative electrode active substances with a conductive agent (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) as binders according to the mass ratio of SP to CMC to SBR of 96 to 1.4 to 1.2 for pulping to obtain slurry with the solid content of 40%, coating the slurry on a copper foil current collector with the thickness of 10 mu m, and preparing a negative electrode sheet by vacuum drying and rolling, wherein the compaction density of the sheet is 1.65g/cm3(ii) a The positive electrode active material lithium cobaltate (LiCoO)2) Uniformly mixing a conductive agent (SP) and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 97:2:1, and coating the mixture on an aluminum foil current collector to prepare a positive pole piece. Using 1.0 to 1.2mol/L LiPF6The positive EC/EMC/DEC is 1/1/1(V: V: V), a proper amount of additive is added, a PE/PP/PE composite film is used as a diaphragm, normal-temperature charge-discharge circulation is carried out at a multiplying power of 1C, and the charge-discharge voltage range is 3.0-4.35V. The cycle capacity retention of the finished battery is shown in table 1.
Example 2
Placing natural spherical graphite (D50 is 6-8 μm, S50 is 0.80-0.95) in a rotary kiln, introducing oxygen, and oxidizing at 500 ℃ for 2h with the oxygen flow rate of 15L/h.kg to obtain oxidized natural graphite (oxidized graphite). Mixing the oxidized graphite and the petroleum asphalt according to the mass ratio of 88:12, and then adding N2Placing the mixture in a fusion machine at 650 ℃ for mechanical granulation under the atmosphere, and after mechanical granulation for 5 hours, carrying out reactionThe graphite-based composite material is obtained by cooling the graphite-based composite material to room temperature and then carbonizing the graphite-based composite material at 1200 ℃, and the SEM picture of the obtained composite graphite material is shown in figure 1.
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Example 3
Placing natural spherical graphite (D50 is 6-8 μm, S50 is 0.80-0.95) in a rotary kiln, introducing oxygen, and oxidizing at 500 ℃ for 4h with the oxygen flow rate of 15L/h.kg to obtain oxidized natural graphite (oxidized graphite). Mixing the oxidized graphite and the petroleum asphalt according to the mass ratio of 85:15, and then adding N2And (3) placing the graphite-based composite material in a fusion machine at 650 ℃ for mechanical granulation for 5 hours under the atmosphere, cooling the reaction product to room temperature, and then carbonizing the reaction product at 1200 ℃ to obtain the graphite-based composite material.
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Example 4
Placing natural spherical graphite (D50 is 4-5 μm, S50 is 0.80-0.95) in a rotary kiln, introducing oxygen, and oxidizing at 600 ℃ for 6h with the oxygen flow rate of 5L/h.kg to obtain oxidized natural graphite (oxidized graphite). Mixing the oxidized graphite and the petroleum asphalt according to the mass ratio of 85:15, and then adding N2And (3) placing the graphite-based composite material in a fusion machine at 650 ℃ for mechanical granulation under the atmosphere, cooling a reaction product to room temperature after mechanical granulation is carried out for 10 hours, and then carrying out carbonization treatment at 1000 ℃ to obtain the graphite-based composite material.
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Example 5
Putting natural spherical graphite (D50 is 4-5 μm, S50 is 0.80-0.95) into a box furnace, introducing oxygen, and oxidizing at 600 deg.CAnd (4) taking the graphite for 6 hours, wherein the oxygen flow is 5L/h.kg, and obtaining the natural graphite (oxidized graphite) after oxidation treatment. Mixing the oxidized graphite and the coal pitch according to the mass ratio of 85:15, and then adding N2And (2) mechanically granulating in a fusion machine at 650 ℃ in the atmosphere, cooling the reaction product to room temperature after mechanical granulation for 10 hours, and graphitizing at 2800 ℃ to obtain the graphite-based composite material.
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Example 6
Putting natural spherical graphite (D50 is 4-5 μm, S50 is 0.80-0.95) into a box furnace, introducing ammonia gas, and carrying out ammoniation at 600 ℃ for 6h with the ammonia gas flow rate of 5L/h.kg to obtain ammoniated natural graphite (ammoniated graphite). Mixing ammoniated graphite and petroleum asphalt according to the mass ratio of 85:15, and then adding N2And (3) mechanically granulating in a fusion machine at 650 ℃ in the atmosphere, cooling the reaction product to room temperature after mechanical granulation for 10 hours, and carbonizing at 1200 ℃ to obtain the graphite-based composite material.
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Example 7
Putting natural spherical graphite (D50 is 6-8 μm, S50 is 0.80-0.95) into a rotary furnace, introducing ammonia gas, and ammoniating at 600 ℃ for 6h at the ammonia gas flow rate of 15L/h.kg to obtain ammoniated natural graphite (ammoniated graphite). Mixing the ammoniated graphite and the coal tar pitch according to the mass ratio of 85:15, and then adding the mixture into the mixture in the proportion of N2And (3) placing the graphite-based composite material in a fusion machine at 650 ℃ for mechanical granulation under the atmosphere, cooling a reaction product to room temperature after mechanical granulation is carried out for 10 hours, and then carrying out carbonization treatment at 1000 ℃ to obtain the graphite-based composite material.
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Example 8
Putting natural spherical graphite (D50 is 6-8 μm, S50 is 0.80-0.95) into a rotary furnace, introducing ammonia gas, and ammoniating at 600 ℃ for 6h at the ammonia gas flow rate of 15L/h.kg to obtain ammoniated natural graphite (ammoniated graphite). Mixing ammoniated graphite and petroleum asphalt according to the mass ratio of 80:20, and then adding N2And (3) placing the graphite-based composite material in a fusion machine at 500 ℃ for mechanical granulation under the atmosphere, cooling a reaction product to room temperature after mechanical granulation is carried out for 8 hours, and then carrying out carbonization treatment at 1000 ℃ to obtain the graphite-based composite material.
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Example 9
Putting natural spherical graphite (D50 is 6-8 μm, S50 is 0.80-0.95) into a rotary furnace, introducing ammonia gas, and ammoniating at 600 ℃ for 6h at the ammonia gas flow rate of 10L/h.kg to obtain ammoniated natural graphite (ammoniated graphite). Mixing ammoniated graphite and petroleum asphalt according to the mass ratio of 85:15, and then adding N2And (3) placing the graphite-based composite material in a 600 ℃ fusion machine for mechanical granulation under the atmosphere, cooling a reaction product to room temperature after mechanical granulation is carried out for 8 hours, and then carrying out graphitization treatment at 3000 ℃ to obtain the graphite-based composite material.
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Example 10
Putting natural spherical graphite (D50 is 6-8 μm, S50 is 0.80-0.95) into a rotary furnace, introducing ammonia gas, and ammoniating at 600 ℃ for 6h at the ammonia gas flow rate of 8L/h.kg to obtain ammoniated natural graphite (ammoniated graphite). Mixing the ammoniated graphite and the modified asphalt according to the mass ratio of 90:10, and then adding the mixture into the mixture in the proportion of N2Mechanically granulating in 600 deg.C fusion machine for 8 hr, cooling to room temperature, and cooling to 1200 deg.CAnd carbonizing to obtain the graphite-based composite material.
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Example 11
Putting natural spherical graphite (D50 is 6-8 μm, S50 is 0.80-0.95) into a tube furnace, introducing oxygen, and carrying out ammoniation at 600 ℃ for 3h with the ammonia flow rate of 12L/h.kg to obtain ammoniated natural graphite (ammoniated graphite). Mixing the ammoniated graphite and the modified asphalt according to the mass ratio of 90:10, and then adding the mixture into the mixture in the proportion of N2And (3) placing the graphite-based composite material in a 600 ℃ fusion machine for mechanical granulation under the atmosphere, cooling a reaction product to room temperature after mechanical granulation is carried out for 8 hours, and then carrying out graphitization treatment at 3000 ℃ to obtain the graphite-based composite material.
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Example 12
Natural spherical graphite (D50 ═ 3 to 4 μm, S50 ═ 0.80 to 0.95) was put in a rotary kiln, and was aminated at 600 ℃ for 3 hours with oxygen gas flow of 15L/h.kg to give aminated natural graphite (aminated graphite). Mixing the ammoniated graphite and the modified asphalt according to the mass ratio of 90:10, and then adding the mixture into the mixture in the proportion of N2And (2) placing the graphite-based composite material in a 600 ℃ fusion machine for mechanical granulation in the atmosphere, cooling a reaction product to room temperature after mechanical granulation is carried out for 12 hours, and then carrying out graphitization treatment at 3200 ℃ to obtain the graphite-based composite material.
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Example 13
Placing natural spherical graphite (D50 is 4-6 μm, S50 is 0.80-0.95) in a rotary kiln, introducing oxygen, oxidizing at 600 ℃ for 3.5h, wherein the oxygen flow is 13L/h.kg, and obtaining oxidized natural graphite (oxidized graphite).
Putting natural spherical graphite (D50 is 6-8 μm, S50 is 0.80-0.95) into a box furnace, introducing ammonia gas, and carrying out ammoniation at 700 ℃ for 4h at the ammonia gas flow rate of 8L/h.kg to obtain ammoniated natural graphite (ammoniated graphite).
Mixing the mixture of ammoniated graphite and oxidizing graphite (the mass ratio of the ammoniated graphite to the oxidizing graphite is 5:5) with petroleum asphalt according to the mass ratio of 86:14, and then adding the mixture into the mixture in the reactor2And (2) mechanically granulating in a fusion machine at 700 ℃ in the atmosphere, cooling a reaction product to room temperature after mechanical granulation is carried out for 10 hours, and then carbonizing at 1000 ℃ to obtain the graphite-based composite material.
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Example 14
Placing natural spherical graphite (D50 is 4-5 μm, S50 is 0.80-0.95) in a box furnace, introducing oxygen, oxidizing at 800 ℃ for 2.5h, wherein the oxygen flow rate is 15L/h.kg, and obtaining oxidized natural graphite (oxidized graphite).
Putting natural spherical graphite (D50 is 4-5 μm, S50 is 0.80-0.95) into a rotary furnace, introducing ammonia gas, and ammoniating at 650 ℃ for 4.5h, wherein the ammonia gas flow is 12.5L/h.kg, so as to obtain ammoniated natural graphite (ammoniated graphite).
Mixing the mixture of ammoniated graphite and oxidizing graphite (the mass ratio of the ammoniated graphite to the oxidizing graphite is 6:4) with petroleum asphalt according to the mass ratio of 82:18, and then adding the mixture into the mixture2And (3) placing the graphite-based composite material in a 600 ℃ fusion machine for mechanical granulation in the atmosphere, cooling a reaction product to room temperature after mechanical granulation for 14h, and graphitizing the reaction product at 3200 ℃ to obtain the graphite-based composite material.
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Comparative example 1
Except that the oxidized graphite in example 1 was replaced with natural spherical graphite (D50 ═ 6 to 8 μm, S50 ═ 0.80 to 0.95), the preparation methods and conditions were the same as in example 1, and the composite graphite material prepared was used to prepare a negative electrode, assemble a button cell, and perform performance tests in the same manner as in example 1, and the specific capacity for first delithiation, the first discharge efficiency, and the particle size index were as shown in table 1.
Comparative example 2
A composite graphite material was produced in the same manner and under the same conditions as in example 6, except that the oxidized graphite in example 7 was replaced with natural spherical graphite (D50 ═ 6 μm to 8 μm, S50 ═ 0.80 to 0.95).
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Comparative example 3
A composite graphite material was produced in the same manner and under the same conditions as in example 5, except that the aminated graphite in example 5 was replaced with natural spheroidal graphite (D50 ═ 4 μm to 5 μm, S50 ═ 0.80 to 0.95).
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Comparative example 4
A composite graphite material was produced in the same manner and under the same conditions as in example 11, except that the aminated graphite in example 11 was replaced with natural spheroidal graphite (D50 ═ 6 μm to 8 μm, S50 ═ 0.80 to 0.95).
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
Comparative example 5
A composite graphite material was produced in the same manner and under the same conditions as in example 9, except that the aminated graphite in example 9 was replaced with natural spheroidal graphite (D50 ═ 6 μm to 8 μm, S50 ═ 0.80 to 0.95) and the mechanical granulation time was changed to 10 hours.
The negative electrode was prepared, assembled into a button cell, and subjected to performance testing in the same manner as in example 1, and the first-time lithium-removal specific capacity, the first-time discharge efficiency, and the particle size index are shown in table 1.
TABLE 1
Figure BDA0001222329890000161
Figure BDA0001222329890000171
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (27)

1. A method for preparing a graphite-based composite material, comprising the steps of:
(1) uniformly mixing activated natural graphite and asphalt to obtain a mixture;
(2) placing the mixture in a fusion machine, and performing fusion granulation in an inert atmosphere to obtain a fusion granulation product;
(3) carrying out carbonization treatment or graphitization treatment on the fused and granulated product to obtain a graphite-based composite material;
wherein the activated natural graphite is natural graphite with surface functionalization treatment;
the natural graphite subjected to surface functionalization treatment is aminated and compositely oxidized, or a mixture of aminated natural graphite and oxidized natural graphite;
in the mixture of the aminated natural graphite and the oxidized natural graphite, the mass ratio of the aminated natural graphite to the oxidized natural graphite is 7: 3-5: 5;
the median particle diameter D50 of the natural graphite is 3-8 μm, and the sphericity of the natural graphite is S50 is 0.8-0.95.
2. The method according to claim 1, wherein the surface-functionalization treated natural graphite is a mixture of aminated natural graphite and oxidized natural graphite.
3. The method according to claim 1, wherein the aminated natural graphite is prepared by the following method: and carrying out heat treatment on the natural graphite in an ammonia atmosphere to obtain the aminated natural graphite.
4. The method according to claim 1, wherein the oxidation-treated natural graphite is prepared by: and (3) carrying out heat treatment on the natural graphite in an oxygen atmosphere and/or an air atmosphere to obtain the natural graphite subjected to oxidation treatment.
5. The method according to claim 1, wherein the aminated complex oxidation treated natural graphite is prepared by scheme one or scheme two:
the first scheme is as follows: carrying out heat treatment on the aminated natural graphite in an oxygen atmosphere and/or an air atmosphere;
scheme II: and carrying out heat treatment on the oxidized natural graphite in an ammonia atmosphere.
6. The method of claim 1, wherein the natural graphite has a carbon content of greater than 99.95 wt.%.
7. The method according to any one of claims 3 to 5, wherein the heat treatment temperature during the preparation of the aminated natural graphite, the oxidized natural graphite and the aminated complex oxidized natural graphite is independently 300 ℃ to 1000 ℃.
8. The method according to claim 7, wherein the heat treatment temperature is independently 600 ℃ to 800 ℃ in the process of preparing the aminated natural graphite, the oxidized natural graphite and the aminated complex oxidized natural graphite.
9. The method according to any one of claims 3 to 5, wherein the heat treatment time in the preparation of the aminated natural graphite, the oxidized natural graphite and the aminated complex oxidized natural graphite is independently 2 to 6 hours.
10. The method as claimed in claim 3, wherein the flow rate of the ammonia gas is 5L/h.kg-20L/h.kg during the preparation of the aminated natural graphite.
11. The method according to claim 4, wherein the flow rate of oxygen and/or air in the process of preparing the oxidation-treated natural graphite is 5L/h.kg to 20L/h.kg.
12. The method of claim 5, wherein in the first embodiment, the flow rate of oxygen and/or air is 5L/h.kg-20L/h.kg.
13. The method according to claim 5, wherein the flow rate of the ammonia gas in the second scheme is 5L/h.kg-20L/h.kg.
14. The method according to claim 1, wherein the surface-functionalization-treated natural graphite is prepared by using a rotary kiln, a box-type heating furnace or a tube furnace.
15. The method according to claim 1, wherein the asphalt in step (1) is any one of petroleum asphalt, coal asphalt or modified asphalt or a combination of at least two of the above.
16. The method of claim 1, wherein the mass ratio of the activated natural graphite to the pitch in step (1) is (98-80) to (2-20).
17. The method according to claim 1, wherein the inert atmosphere in the step (2) is any one of a nitrogen atmosphere, a helium atmosphere, a neon atmosphere, an argon atmosphere, a krypton atmosphere, or a xenon atmosphere, or a combination of at least two thereof.
18. The method according to claim 1, wherein the fusing granulation in the step (2) is carried out by using a fusing machine.
19. The method according to claim 1, wherein the temperature of the fusion granulation in the step (2) is 500 to 800 ℃.
20. The method according to claim 1, wherein the time for the fusion granulation in the step (2) is 2 to 24 hours.
21. The method according to claim 1, wherein the temperature of the carbonization treatment in the step (3) is 800 to 1300 ℃.
22. The method according to claim 1, wherein the temperature of the graphitization treatment in the step (3) is 2800-3200 ℃.
23. The method according to claim 1, further comprising the step of classifying or screening after the carbonization treatment is completed or after the graphitization treatment is completed.
24. Method according to claim 1, characterized in that it comprises the following steps:
(1) taking natural graphite with the median particle size of D50-3-8 μm as a raw material, introducing ammonia gas at the flow rate of 5-20L/h.kg, and carrying out heat treatment at 600-800 ℃ for 2-6 h to obtain aminated natural graphite;
(2) taking natural graphite with the median particle size of D50-3-8 μm as a raw material, introducing oxygen at the flow rate of 5-20L/h.kg, and carrying out heat treatment at 600-800 ℃ for 2-6 h to obtain natural graphite subjected to oxidation treatment;
(3) taking a mixture of aminated natural graphite and oxidized natural graphite as activated natural graphite, uniformly mixing the activated natural graphite and asphalt according to the ratio of (98-80) to (2-20), adding the mixture into a mechanical fusion machine, introducing nitrogen, performing fusion granulation for 2-24 h at 500-800 ℃, and cooling to obtain a fusion granulation product;
(4) and carbonizing the fused and granulated product at 800-1300 ℃, or graphitizing the fused and granulated product at 2800-3200 ℃, so as to obtain the graphite-based composite material.
25. A graphite-based composite material prepared by the method of claim 1.
26. A negative electrode comprising the graphite-based composite material according to claim 25.
27. A lithium ion battery comprising the graphite-based composite material according to claim 25.
CN201710069655.8A 2017-02-08 2017-02-08 Graphite-based composite material, preparation method thereof and lithium ion battery containing composite material Active CN106602067B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710069655.8A CN106602067B (en) 2017-02-08 2017-02-08 Graphite-based composite material, preparation method thereof and lithium ion battery containing composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710069655.8A CN106602067B (en) 2017-02-08 2017-02-08 Graphite-based composite material, preparation method thereof and lithium ion battery containing composite material

Publications (2)

Publication Number Publication Date
CN106602067A CN106602067A (en) 2017-04-26
CN106602067B true CN106602067B (en) 2020-01-24

Family

ID=58586937

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710069655.8A Active CN106602067B (en) 2017-02-08 2017-02-08 Graphite-based composite material, preparation method thereof and lithium ion battery containing composite material

Country Status (1)

Country Link
CN (1) CN106602067B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110870114B (en) * 2017-07-07 2023-02-17 日立化成株式会社 Method for producing negative electrode material for lithium ion secondary battery, and negative electrode material for lithium ion secondary battery
CN108422089A (en) * 2018-01-30 2018-08-21 张亮 A kind of button cell processing method of casing improving afflux performance
CN109686955A (en) * 2018-12-27 2019-04-26 洛阳月星新能源科技有限公司 A kind of porous block graphite material and preparation method thereof for coated Si
CN110078067A (en) * 2019-06-13 2019-08-02 广东凯金新能源科技股份有限公司 A kind of preparation method for the graphite cathode material that end face structure is controllable
CN112028068A (en) * 2020-09-03 2020-12-04 青海凯金新能源材料有限公司 Artificial composite graphite and processing method thereof
CN112713271B (en) * 2020-12-29 2022-07-05 上海杉杉科技有限公司 Modified graphite material, preparation method thereof, lithium ion battery and application
CN113666368B (en) * 2021-07-19 2023-05-30 广东海洋大学 Artificial graphite negative electrode material and preparation method thereof
CN114477162B (en) * 2021-12-31 2023-09-05 惠州锂威新能源科技有限公司 Preparation method of graphite anode material, product and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102034975A (en) * 2010-11-15 2011-04-27 中国科学院青岛生物能源与过程研究所 Nitrogen-doped graphite carbon serving as anode material of lithium ion battery, and preparation method and application thereof
CN103000910A (en) * 2012-11-19 2013-03-27 国网电力科学研究院武汉南瑞有限责任公司 Processing method of graphite felt electrode for all-vanadium redox flow battery
CN103303907A (en) * 2013-04-28 2013-09-18 南昌大学 Surface modification method for spherical graphite negative material
CN105024043A (en) * 2014-12-18 2015-11-04 上海杉杉科技有限公司 Rapidly-charged graphite lithium ion battery anode material and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101224882B (en) * 2007-01-16 2011-12-07 深圳市比克电池有限公司 Artificial graphite surface modifying method and lithium battery anode material produced thereby
CN102659091A (en) * 2012-05-03 2012-09-12 天津市贝特瑞新能源科技有限公司 High-capacity graphite material and preparation method as well as application thereof
KR101486760B1 (en) * 2013-11-14 2015-01-29 한국에너지기술연구원 Method for manufacturing graphene and cathode mixture comprising graphene manufactured thereby for lithium secondary battery
CN105271189A (en) * 2015-09-23 2016-01-27 东莞市迈科科技有限公司 Nitrogen doped graphene particle and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102034975A (en) * 2010-11-15 2011-04-27 中国科学院青岛生物能源与过程研究所 Nitrogen-doped graphite carbon serving as anode material of lithium ion battery, and preparation method and application thereof
CN103000910A (en) * 2012-11-19 2013-03-27 国网电力科学研究院武汉南瑞有限责任公司 Processing method of graphite felt electrode for all-vanadium redox flow battery
CN103303907A (en) * 2013-04-28 2013-09-18 南昌大学 Surface modification method for spherical graphite negative material
CN105024043A (en) * 2014-12-18 2015-11-04 上海杉杉科技有限公司 Rapidly-charged graphite lithium ion battery anode material and preparation method thereof

Also Published As

Publication number Publication date
CN106602067A (en) 2017-04-26

Similar Documents

Publication Publication Date Title
CN106654235B (en) Composite graphite material, preparation method thereof and lithium ion battery containing composite graphite material
CN106602067B (en) Graphite-based composite material, preparation method thereof and lithium ion battery containing composite material
CN110642247A (en) Artificial graphite negative electrode material, preparation method thereof and lithium ion battery
CN112573923A (en) High-rate lithium ion battery artificial graphite negative electrode material and preparation method thereof
CN103700820B (en) A kind of lithium ion selenium battery with long service life
CN109119592B (en) Lithium titanate negative electrode piece, preparation method and lithium titanate battery
CN103346293A (en) Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery
CN103094535A (en) Sulfur/carbon porous nano composite material and preparation method and application thereof
CN101197442A (en) Lithium iron phosphate lithium ion battery
CN1960040A (en) High-powered lithium ferric phosphate dynamic battery, and preparation technique
CN103647043A (en) Method for preparing negative electrode material of lithium ion secondary battery
CN112133909B (en) Antimony sulfide-based negative electrode material for lithium ion battery and preparation method thereof
WO2016169150A1 (en) Method for graphite fine powder to be doped and used as negative electrode material
CN112133896A (en) High-capacity graphite-silicon oxide composite material and preparation method and application thereof
CN114613974B (en) Long-life quick-charging type lithium ion battery cathode material and preparation method thereof
CN106532010B (en) Silicon-silicon nitride-carbon composite material and preparation method and application method thereof
CN114709415A (en) Graphite material, secondary battery, and electronic device
CN111370694B (en) High-tap-density graphite negative electrode material and preparation method thereof
CN110970599B (en) Graphene-based composite negative electrode material, preparation method thereof and lithium ion battery
CN103367728A (en) Activated natural graphite modified Li2FeSiO4 cathode material and its preparation method
CN114937758B (en) Negative electrode active material, negative electrode plate containing same and battery
CN102983333A (en) Novel preparation method of lithium vanadium phosphate/carbon composite material for positive pole of lithium ion battery
CN110993916B (en) Composite graphite negative electrode material and preparation method thereof
CN103633326A (en) Production method of lithium iron phosphate
CN114497508A (en) Power type artificial graphite composite material and preparation method thereof

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
CP01 Change in the name or title of a patent holder

Address after: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth,

Patentee after: Beitrei New Materials Group Co., Ltd

Address before: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth,

Patentee before: Shenzhen BTR New Energy Materials Inc.

CP01 Change in the name or title of a patent holder
TR01 Transfer of patent right

Effective date of registration: 20200507

Address after: No. 519, Fuxing South Road, Jintan District, Changzhou City, Jiangsu Province

Patentee after: Beiteri (Jiangsu) new energy materials Co., Ltd

Address before: 518106 Gongming City, Guangdong province Guangming New District Office of the West community high and New Technology Industrial Park, building eighth,

Patentee before: Beitrei New Materials Group Co., Ltd

TR01 Transfer of patent right