CN111232970B - Graphite negative electrode material, lithium ion battery, preparation method and application - Google Patents

Graphite negative electrode material, lithium ion battery, preparation method and application Download PDF

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CN111232970B
CN111232970B CN201811436178.5A CN201811436178A CN111232970B CN 111232970 B CN111232970 B CN 111232970B CN 201811436178 A CN201811436178 A CN 201811436178A CN 111232970 B CN111232970 B CN 111232970B
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mesocarbon microbeads
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谢秋生
董爱想
陈然
刘盼
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Yunnan Shanshan New Materials Co ltd
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Abstract

The invention discloses a graphite cathode material, a lithium ion battery, a preparation method and application. The preparation method comprises the following steps: graphitizing the mixture of the mesocarbon microbeads, the anthracite powder and the catalyst at high temperature; wherein the mass ratio of the mesocarbon microbeads to the anthracite powder is 1:9-8:1; the particle size D50 of the anthracite powder is 10-20 mu m. The graphite cathode material prepared by the preparation method provided by the invention has high compaction density, and accordingly, the energy density of the battery is improved.

Description

Graphite negative electrode material, lithium ion battery, preparation method and application
Technical Field
The invention belongs to the field of lithium electronic batteries, and particularly relates to a graphite negative electrode material, a lithium ion battery, a preparation method and an application.
Background
The mesocarbon microbeads graphitized product is an excellent lithium ion battery cathode material, and in recent years, the lithium ion battery is widely applied to mobile phones, notebook computers, digital cameras and portable electrical appliances. The lithium ion battery has excellent performances of large energy density, high working voltage, small volume, light weight, no pollution, quick charge and discharge, long cycle life and the like, and is an ideal energy source developed in the 21 st century. The mesocarbon microbeads as the negative electrode material of the lithium ion secondary battery have the characteristics of low potential, good flatness, high specific gravity, high initial charging and discharging efficiency, good processability and the like. Theoretically, the reversible lithium storage capacity of LiC6 can reach 372mAh/g, but the reversible lithium storage capacity of the mesocarbon microbeads is only about 310mAh/g, and the energy density is low. The common artificial graphite powder has irregular shape and large specific surface area (usually more than 5m < 2 >/g), which causes poor material processing performance, low first efficiency and high ash content, and is not easy to ensure stable batch.
With the rapid development of the electronic information industry, the requirements of various products on miniaturization and light weight are continuously improved, and the requirements on high performance such as high capacity and rapid charging of lithium ion secondary batteries are increasingly urgent. The improvement of the capacity of the lithium ion battery mainly depends on the development and the improvement of a carbon negative electrode material, so that the improvement of the specific capacity of the negative electrode material of the lithium ion battery, the improvement of the compaction density of the material, the reduction of the first irreversible capacity and the improvement of the cycling stability are always the key points of research and development.
Therefore, in order to overcome the respective performance deficiencies of the mesocarbon microbeads and the common artificial graphite, the prior art modifies the mesocarbon microbeads or the artificial graphite. The mesocarbon microbeads are treated by crushing, pretreatment, mixing with needle coke green coke powder, and high-temperature treatment for catalytic graphitization, so that the quality of the negative electrode material for the lithium ion secondary battery can be effectively improved, the reversible lithium storage capacity of graphite can be improved, and the compaction density of the material can be improved. The literature: (1) The material research journal Vol.21No.4P.404-408 (2007) reports that the intermediate phase carbon for the lithium ion battery is subjected to catalytic heat treatment, so that the irreversible electrochemical reaction on the surface of the carbon is effectively relieved; (2) US2006001003 reports a method of catalytic graphitization treatment of artificial graphite-based negative electrode materials, which can improve rapid charge and discharge performance and cycle performance.
However, the disadvantages of the improved methods reported in the above documents are that the preparation process is complicated, the added components are not easily obtained, and the production cost is increased; and the improved compaction density is low, so that the energy density of the battery is low, and the requirements of people on lithium ion capacity at the present stage, such as strong endurance, long standby time and the like, cannot be met.
Disclosure of Invention
The invention aims to solve the technical problems of low compacted density, high production cost, complex preparation process, difficult obtainment of added components and the like of a graphite cathode material in the prior art, and provides a graphite cathode material, a lithium ion battery, a preparation method and application. The preparation method can improve the compaction density of the graphite cathode material, thereby improving the cycle performance and the capacity exertion of the lithium ion battery.
The compacted density of the graphite cathode material in the prior art is generally low, and correspondingly, the prepared lithium ion battery active substance is low, so that the electric capacity of the battery is low, and the cycle performance of the battery is poor.
The invention solves the technical problems through the following technical scheme.
One of the technical schemes provided by the invention is as follows: a preparation method of a graphite negative electrode material comprises the following steps: graphitizing the mixture of the mesocarbon microbeads, the anthracite powder and the catalyst at high temperature to obtain the carbon microbeads; wherein the mass ratio of the mesocarbon microbeads to the anthracite powder is 1:9-8:1; the particle size D50 of the anthracite powder is 10-20 mu m.
In the present invention, in order to effectively increase the product compacted density and easily prepare a high compacted density anode material, the mesocarbon microbeads are preferably the mesocarbon microbeads after the pulverization pretreatment, and the particle diameter D50 of the powder obtained after the pulverization pretreatment is preferably 20 to 30 μm, more preferably 20.7 to 29.7 μm, such as 25.6 μm; the mesocarbon microbeads are preferably mesocarbon microbeads prepared by liquid phase polymerization of pitch, such as those prepared from coal tar pitch or petroleum pitch.
In the invention, the amount of the catalyst can be conventional in the field, and is preferably 4-10%, more preferably 4.9-8.9%, and even more preferably 5.5% or 6.4% of the mass sum of the mesocarbon microbeads and the anthracite powder; the catalyst can be catalyst used for preparing graphite cathode material, which is conventional in the field, preferably one or more of carbide or oxide of silicon, iron, tin or boron, more preferably SiO 2 、Fe 2 O 3 、SnO 2 、B 2 O 3 Or SiC.
In the present invention, the pulverized anthracite has a particle size D50 of preferably 10.4 to 19.9 μm, and more preferably 15.2 μm.
In the invention, the mass ratio of the mesocarbon microbeads to the anthracite powder is preferably 1:2-5:1, more preferably 1:1 or 2:1.
According to the invention, the mixture is obtained by mixing the mesocarbon microbeads, the anthracite powder and the catalyst by adopting a cantilever double-helix conical mixer, and the mesocarbon microbeads or the anthracite powder is alternately added in the feeding process so as to ensure that the mixture is uniform and consistent with the catalyst mixture; the mixing time is preferably 1 to 5 hours, more preferably 2 to 2.5 hours.
The graphitization high-temperature treatment process can utilize the prior art, preferably adopts a conventional graphitization processing furnace, and the graphitization high-temperature treatment temperature can be conventional in the field, and is preferably controlled within the range of 2800-3200 ℃, such as 2800 ℃, 3000 ℃ or 3200 ℃; the graphitization high temperature treatment time may be conventional in the art, preferably from 12 to 60 hours, more preferably from 24 to 48 hours, for example 36 hours.
The second technical scheme of the invention is as follows: the graphite negative electrode material prepared by the preparation method.
Preferably, the particle size D50 of the composite graphite negative electrode material of the lithium ion battery is 10-30 μm; the true density is 2.20g/cm 3 The above; the ash content is below 0.10 percent, and the percentage is the mass percentage of the residue after drying to the substance before drying; the compacted density is 1.75g/cm 3 The above; the specific surface area is 2.5m 2 The ratio of the carbon atoms to the carbon atoms is less than g.
Specific performance parameters and detection methods thereof are shown in table 1 below.
TABLE 1 Performance parameters of lithium ion battery composite graphite cathode materials
Figure BDA0001883842530000031
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Figure BDA0001883842530000041
Wherein:
the particle diameter D50 of the composite graphite negative electrode material of the lithium ion battery is preferably 10.8, 20.3, 20.8, 22.1, 23.1, 22.6, 23.1 or 29.6 μm.
The true density of the lithium ion battery composite graphite negative electrode material is preferably 2.22-2.26g/cm 3 。
The lithium ion battery composite graphite negative electrode material is preferably 0.01% or 0.02%, and the percentage is the mass percentage of the dried remainder in the material before drying.
The compacted density of the lithium ion battery composite graphite negative electrode material is preferably 1.76, 1.78 or 1.79g/cm 3 。
The specific surface area of the composite graphite negative electrode material of the lithium ion battery is preferably 1.6, 2.1, 2.3 or 2.4m 2 /g。
The third technical scheme of the invention is as follows: the application of the graphite negative electrode material in a lithium ion battery.
The fourth technical scheme of the invention is as follows: a lithium ion battery containing the graphite cathode material.
The first discharge capacity of the lithium ion battery is above 355mAh/g, such as 356.3mAh/g, 357.1mAh/, 355.9mAh/g, 359.5mAh/g, 357.5mAh/g, 358.3mAh/g, 360.7mAh/g or 359.1mAh/g (measured by a multichannel battery test Bt2000 type).
Wherein the lithium ion battery has a first discharge efficiency of 91% or more, such as 91.6%, 93.1%, 91.5%, 92.9%, 91.9%, 92.7%, or 93.4% (as measured by multichannel Battery test Bt 2000).
In the present invention, the D50 refers to the particle size corresponding to the cumulative percentage of particle size distribution of the sample reaching 50%, and generally means that the particles with the particle size larger than the D50 account for 50% and the particles with the particle size smaller than the D50 account for 50% of the sample. D50 may also be referred to as median diameter or median particle diameter.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the compacted density of the graphite negative electrode material prepared by the invention is 1.75g/cm 3 The electrochemical performance (such as discharge capacity) and the specific surface are ensured at the same timeThe indexes such as product and the like are equivalent to those of the prior art, so that the cycle performance and the capacity exertion of the lithium ion battery are greatly improved; the increase in compaction density increases the energy density of the battery and other performance metrics associated therewith, such as endurance and standby time. In addition, the use of the anthracite powder in the preparation method of the graphite cathode material reduces the production and processing cost of the composite graphite cathode material of the lithium ion battery, and the processing cost is only 20 percent of the cost of the conventional raw materials; and the raw material has wide source and is easy to process.
Drawings
Fig. 1 is a first charge and discharge curve of the composite graphite anode material of example 2 of the present invention.
Fig. 2 is a cycle curve of the composite graphite anode material of example 2 of the present invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
Example 1
Pulverizing and grading the mesocarbon microbeads to obtain F1 material (D50 is 25.6 μm), mixing the F1 material 20kg with anthracite powder (D50 is 15.2 μm) 10kg, and catalyst (SiO) 2 ) 1.6kg of the graphite composite negative electrode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours, and then catalytic graphitization (3000 ℃) treatment is carried out for 48 hours, so that the composite graphite negative electrode material is prepared, the half-cell capacity is 356.3mAh/g, and the primary efficiency is 91.6%.
Example 2
Pulverizing and grading the mesocarbon microbeads to obtain F1 material (D50 is 25.6 μm), mixing the F1 material 15kg with anthracite powder (D50 is 19.9 μm) 15kg, and catalyst (Fe) 2 O 3 ) 2.5kg of the graphite composite negative electrode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours, and then catalytic graphitization (3200 ℃) treatment is carried out for 48 hours, so that the composite graphite negative electrode material is prepared, the half-cell capacity is 357.1mAh/g, and the primary efficiency is 93.4%.
Example 3
Pulverizing and grading the mesocarbon microbeads to obtain F1 (D50 is 20.7 μm), mixing the F1 with anthracite powder (D50 is 15.2 μm) 20kg and catalyst (SnO) 2 ) 3.2kg of the graphite composite negative electrode material is alternately added into a cantilever double-helix conical mixer to be mixed for 1 hour and then is subjected to catalytic graphitization (2800 ℃) for 36 hours to prepare the composite graphite negative electrode material with the half-cell capacity of 355.9mAh/g and the primary efficiency of 92.7 percent.
Example 4
Pulverizing and grading the mesocarbon microbeads to obtain F1 material (D50 is 29.7 μm), mixing the F1 material 25kg with anthracite powder (D50 is 19.9 μm) 5kg, and catalyst (B) 2 O 3 ) 3.2kg of the graphite composite negative electrode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then is subjected to catalytic graphitization (3000 ℃) for 48 hours to prepare the composite graphite negative electrode material with the half-cell capacity of 359.5mAh/g and the primary efficiency of 91.9 percent.
Example 5
Pulverizing and grading the mesocarbon microbeads to obtain F1 material (D50 of 20.7 μm), mixing 3.3kg of F1 material with 28kg of anthracite powder (D50 of 10.4 μm), and adding catalyst (SiO) 2 ) 3.2kg of the graphite composite negative electrode material is alternately added into a cantilever double-helix conical mixer to be mixed for 5 hours, and then catalytic graphitization (3000 ℃) treatment is carried out for 60 hours, so that the composite graphite negative electrode material is prepared, the half-cell capacity is 357.5mAh/g, and the primary efficiency is 92.9%.
Example 6
Pulverizing and grading the mesocarbon microbeads to obtain F1 material (D50 is 25.6 μm), mixing the F1 material 20kg with anthracite powder (D50 is 15.2 μm) 10kg, and catalyst (SiO) 2 ) 2kg of the graphite powder is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then is subjected to catalytic graphitization (3000 ℃) treatment for 48 hours to prepare the composite graphite cathode material, the half-cell capacity is 358.3mAh/g, and the primary efficiency is 91.5%.
Example 7
The mesocarbon microbeads are crushed and graded in a crushing and grading machine to obtain an F1 material (D50 is 25.6 mu m), 20kg of the F1 material, 10kg of anthracite (D50 is 10.4 mu m) and 2kg of catalyst (SiC) are alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours, and then catalytic graphitization (3000 ℃) treatment is carried out for 12 hours to obtain the composite graphite cathode material, wherein the half-cell capacity is 360.7mAh/g, and the primary efficiency is 93.1%.
Example 8
Pulverizing and grading the mesocarbon microbeads to obtain F1 material (D50 of 20.7 μm), mixing the F1 material 28kg with anthracite powder (D50 of 19.9 μm) 3.5kg, and catalyst (SiO) 2 ) 2kg of the graphite composite negative electrode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2.5 hours and then is subjected to catalytic graphitization (3000 ℃) for 48 hours to prepare the composite graphite negative electrode material, the half-cell capacity is 359.1mAh/g, and the primary efficiency is 91.6%.
Comparative example 1
Pulverizing and grading the mesocarbon microbeads in a pulverizing and grading machine to obtain F1 material (D50 is 20.7 μm), mixing the F1 material 30kg with catalyst (SiO) 2 ) 2kg of the anode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then is subjected to catalytic graphitization (3000 ℃) treatment for 48 hours to prepare the anode material, the half-cell capacity is 335.0mAh/g, and the primary efficiency is 93.2%.
Comparative example 2
30kg of anthracite powder (D50 is 19.9 mu m) and 2kg of catalyst (SiC) are alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours, and then catalytic graphitization (3000 ℃) treatment is carried out for 48 hours to prepare the cathode material of the invention, the half-cell capacity is 356.3mAh/g, and the primary efficiency is 90.5%.
Comparative example 3
The mesocarbon microbeads are crushed and graded in a crushing and grading machine to obtain an F1 material (D50 is 25.6 mu m), 20kg of the F1 material and 10kg of anthracite (D50 is 10.4 mu m) are alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then are treated by conventional graphitization (2800 ℃) for 48 hours to prepare the composite graphite cathode material, the capacity of a half cell is 343.2mAh/g, and the primary efficiency is 90.6%.
Comparative example 4
Pulverizing and grading the mesocarbon microbeads to obtain F1 material (D50 is 23.2 μm), mixing the F1 material 15kg with anthracite powder (D50 is 28.5 μm) 15kg, and catalyst (Fe) 2 O 3 ) 2.5kg of the graphite composite negative electrode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then is subjected to catalytic graphitization (3200 ℃) for 48 hours to prepare the composite graphite negative electrode material with the half-cell capacity of 352.3mAh/g and the primary efficiency of 85.6 percent.
Comparative example 5
Pulverizing and grading the mesocarbon microbeads to obtain F1 (D50 of 20.1 μm), mixing the F1 with anthracite (D50 of 8.7 μm) 5kg and catalyst (Fe) 2 O 3 ) 2.5kg of the graphite composite negative electrode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then is subjected to catalytic graphitization (3200 ℃) for 48 hours to prepare the composite graphite negative electrode material with half-cell capacity of 346.8mAh/g and primary efficiency of 88.7 percent.
Comparative example 6
Pulverizing and grading the mesocarbon microbeads to obtain F1 (D50 of 23.1 μm), mixing the F1 with anthracite powder (D50 of 20.3 μm) 28.5kg and catalyst (Fe) 2 O 3 ) 2.5kg of the graphite composite negative electrode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then is subjected to catalytic graphitization (3200 ℃) for 48 hours to prepare the composite graphite negative electrode material with the half-cell capacity of 343.6mAh/g and the primary efficiency of 89.5 percent.
Comparative example 7
Pulverizing and grading the mesocarbon microbeads to obtain F1 (D50 of 23.1 μm), mixing the F1 with anthracite (D50 of 20.9 μm) 2.5kg and catalyst (Fe) 2 O 3 ) 2.5kg of the graphite composite negative electrode material is alternately added into a cantilever double-helix conical mixer to be mixed for 2 hours and then is subjected to catalytic graphitization (3200 ℃) for 48 hours to prepare the composite graphite negative electrode material with half-cell capacity of 341.6mAh/g and primary efficiency of 88.5 percent.
The raw materials in the above examples are all conventional commercial products.
Effect example 1
(1) The graphite negative electrode materials of examples 1 to 8 and comparative examples 1 to 7 were subjected to particle size, true density, compacted density, specific surface area, ash content, and the like, respectively, and the results are shown in table 2. The name and model of the instrument used for the test are as follows: particle size, laser particle size distribution instrument MS2000; a real-density super constant-temperature water tank SC-15; ash content, high temperature electric furnace SX2-2.5-12; compacting density, pole piece rolling mill JZL235X35-B111; specific surface area, specific surface area determinator NOVA2000.
(2) The physical properties and electrochemical properties of the graphite negative electrode materials of examples 1 to 8 and comparative examples 1 to 7 were measured by a conventional measurement method, and the results are shown in table 2.
The half cell testing method comprises the following steps: uniformly mixing a graphite sample, an N-methyl pyrrolidone solution containing 6-7% of polyvinylidene fluoride (PVDF) and 2% of conductive carbon black, coating the mixture on a copper foil, and putting the coated pole piece into a vacuum drying oven at the temperature of 110 ℃ for vacuum drying for 4 hours for later use. The simulated cells were assembled in an argon filled German Braun glove box with electrolyte of 1M LiPF6+ EC: DEC =1:1 (volume ratio), the metal lithium sheet is a counter electrode, the electrochemical performance test is carried out on a battery tester of ArbinBT2000 type U.S. the charging and discharging voltage range is 0.005-1.0V, and the charging and discharging rate is 0.1C.
(3) The graphite negative electrode material for a lithium ion battery of example 2 was tested by a full battery test method. The full battery test method comprises the following steps: the graphite negative electrode material in example 2 is used as a negative electrode, lithium cobaltate is used as a positive electrode, a solution with the volume ratio of 1M-LiPF6EC to DMC to EMC =1:1 is used as an electrolyte to assemble a full cell, and the capacity retention rate can reach over 90% after the full cell is tested for 1C charging and discharging for 300 weeks, which shows that the cycle performance is good, and the result is shown in FIG. 2.
TABLE 2
Figure BDA0001883842530000091
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Figure BDA0001883842530000101
From the above data it can be seen that:
(1) The specific surface area of the graphite cathode material prepared by the method can be controlled to be 2.5m 2 Less than g, discharge capacity up to 355mAh/g, compact density not less than 1.75g/cm 3 (ii) a The gram volume and the compaction density are higher, the loss of irreversible volume is reduced, the energy density is improved, and the using amount of the anode is reduced; the specific surface area is controlled in a proper range, so that the phenomenon of ballooning generated by a lithium ion battery system is favorably inhibited, and the safety performance of the battery is good; the overcharge performance is better; the pole piece has good processability; an ideal voltage platform, the discharge voltage can reach a steady state soon, as shown in fig. 1; the high-current performance is better; the cycle performance is good, and the capacity retention rate can reach more than 90% after 300 cycles, as shown in figure 2.
(2) It can be seen from comparative examples 1 to 3 that the graphite negative electrode material finally obtained only by using any two of the mesocarbon microbeads, the catalyst and the anthracite powder has the problems of low discharge capacity, low compacted density or large specific surface area. Wherein, the discharge capacity of the graphite anode material in the comparative example 1 is only 335.0mAh/g; the specific surface area of the graphite negative electrode material in comparative example 2 was too large, as high as 3.8m 2 (ii)/g; the discharge capacity in comparative example 3 was only 343.2mAh/g.
(3) From comparative examples 4 and 5, it is known that when the particle size D50 of the pulverized anthracite is greater than 20 μm, or less than 10 μm, the discharge capacity of the battery prepared (as low as 346.8mAh/g in comparative example 5) and/or the primary efficiency is low (as low as 85.6% in comparative example 4, as low as 88.7% in comparative example 5) is low.
(4) It can be seen from comparative examples 6 and 7 that when the mass ratio of the mesocarbon microbeads to the anthracite powder is not in the range of 1:9-8:1, the obtained graphite anode material has low battery discharge capacity and low first efficiency.

Claims (20)

1. The preparation method of the graphite negative electrode material is characterized by comprising the following steps of:
graphitizing the mixture of the mesocarbon microbeads, the anthracite powder and the catalyst at high temperature; wherein the mass ratio of the mesocarbon microbeads to the anthracite powder is 1:9-8:1; the grain diameter D50 of the anthracite powder is 10-20 mu m; the catalyst is one or more of carbide or oxide of silicon, iron, tin or boron.
2. The method according to claim 1, wherein the mesocarbon microbeads have a particle size D50 of 20 to 30 μm;
and/or the mesocarbon microbeads are prepared by liquid phase polymerization of asphalt.
3. The method according to claim 2, wherein the mesocarbon microbeads have a diameter D50 of 20.7 to 29.7. Mu.m.
4. The method of claim 3, wherein the mesocarbon microbeads have a D50 of 25.6 μm.
5. The method of claim 2, wherein the pitch is coal tar pitch or petroleum pitch.
6. The method according to claim 1, wherein the amount of the catalyst is 4 to 10% of the sum of the mass of the mesocarbon microbeads and the pulverized anthracite.
7. The method of claim 6, wherein the catalyst is SiO 2 、Fe 2 O 3 、SnO 2 、B 2 O 3 Or SiC;
and/or the dosage of the catalyst is 4.9-8.9% of the sum of the mass of the mesocarbon microbeads and the anthracite powder.
8. The method according to claim 7, wherein the catalyst is used in an amount of 5.5% or 6.4% by mass of the sum of the mesocarbon microbeads and the pulverized anthracite.
9. The method according to claim 1, wherein the pulverized anthracite has a particle size D50 of 10.4 to 19.9 μm;
and/or the mass ratio of the mesocarbon microbeads to the anthracite powder is 1:2-5:1.
10. The method according to claim 9, wherein the pulverized anthracite has a particle size D50 of 15.2 μm;
and/or the mass ratio of the mesocarbon microbeads to the anthracite powder is 1:1 or 2:1.
11. The method according to claim 1, wherein the mixture is obtained by mixing the mesocarbon microbeads with the anthracite powder and the catalyst using a cantilever twin-screw conical mixer.
12. The method of claim 11, wherein the mixing is for a time of 1 to 5 hours.
13. The method of claim 12, wherein the mixing is for a time of 2 to 2.5 hours.
14. The method according to claim 1, wherein the temperature of the graphitization high-temperature treatment is 2800 to 3200 ℃;
and/or the time of the graphitization high-temperature treatment is 12-60 hours.
15. The method according to claim 14, wherein the graphitization high temperature treatment is at 2800 ℃, 3000 ℃ or 3200 ℃;
and/or the time of the graphitization high-temperature treatment is 24-48 hours.
16. The method according to claim 15, wherein the graphitization high-temperature treatment is performed for a period of 36 hours.
17. The production method according to any one of claims 1 to 16, characterized in that the graphitization high-temperature treatment is performed in a graphitization processing furnace.
18. A graphite negative electrode material produced by the production method according to any one of claims 1 to 17.
19. Use of the graphitic negative electrode material according to claim 18 in a lithium ion battery.
20. A lithium ion battery comprising the graphitic negative electrode material according to claim 18.
CN201811436178.5A 2018-11-28 2018-11-28 Graphite negative electrode material, lithium ion battery, preparation method and application Active CN111232970B (en)

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