CN115784221A - Artificial graphite negative electrode material with better cycle performance and preparation method thereof - Google Patents
Artificial graphite negative electrode material with better cycle performance and preparation method thereof Download PDFInfo
- Publication number
- CN115784221A CN115784221A CN202211588865.5A CN202211588865A CN115784221A CN 115784221 A CN115784221 A CN 115784221A CN 202211588865 A CN202211588865 A CN 202211588865A CN 115784221 A CN115784221 A CN 115784221A
- Authority
- CN
- China
- Prior art keywords
- artificial graphite
- cycle performance
- precursor
- cathode material
- preparation
- 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.)
- Pending
Links
Images
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an artificial graphite cathode material with better cycle performance and a preparation method thereof, belonging to the technical field of lithium ion batteries. The artificial graphite cathode material comprises the following raw materials in parts by weight: 85-97 parts of precursor and 3-15 parts of binding material. The artificial graphite cathode material prepared by the invention has higher tap density, and the lithium ion battery prepared by the artificial graphite cathode material has the following electrochemical properties: (1) the first discharge capacity is more than 345 mAh/g; (2) The cycle performance is good, 1100 cycles are performed, and the capacity retention rate is more than 90%.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an artificial graphite cathode material with better cycle performance and a preparation method thereof.
Background
Compared with the original battery, the lithium ion battery has the characteristics of high energy density, long cycle life, no memory effect and the like, and is rapidly popularized in the aspects of mobile phones, notebook computers and the like. With the popularization of electric vehicles, especially on power batteries, the requirements of long cycle, high compaction, high capacity and high multiplying power are high, and the requirements for the cathode material are high.
In recent years, with the progress of research, researchers have found that the surface modification and structure adjustment of artificial graphite materials, or the disordering of graphite parts, are beneficial to the insertion and extraction of lithium therein, and can effectively improve the cycle and rate performance of batteries.
Chinese patent CN201510793882.6 discloses a high discharge rate lithium ion battery graphite cathode material and a preparation method thereof, which is prepared from asphalt and one or more of natural graphite, asphalt coke or petroleum coke, and the product has poor cycle performance.
Disclosure of Invention
The invention aims to solve the problems of the prior art of the cathode material of the lithium ion battery, and provides the cathode material with excellent cycle performance and excellent rate capability for the lithium ion battery and the preparation method thereof.
The invention discloses an artificial graphite cathode material with better cycle performance, which is characterized in that the preparation raw material comprises the following components in parts by weight:
85-97 parts of precursor and 3-15 parts of binding material.
In some embodiments of the invention, the precursor is selected from at least one of petroleum coke, needle coke, pitch coke, and anthracite.
In some embodiments of the invention, the binding material is selected from at least one of a resin, an upgraded asphalt, a high temperature asphalt, and a medium temperature asphalt.
In some embodiments of the invention, the particles D50 of the precursor and the binding material are both 5-12 μm.
The second aspect of the present invention is to disclose the method for preparing the artificial graphite negative electrode material having the better cycle performance according to the first aspect, wherein the method comprises the following steps:
s01, mixing the precursor with a bonding material to obtain a mixed material;
s02, introducing inert gas into the mixed material for protection, and granulating to obtain a granulated secondary granular material;
and S03, under the protection of inert gas, cooling the granulated secondary particle material, scattering and depolymerizing, and then carrying out graphitization heat treatment to obtain the long-cycle secondary particle artificial graphite cathode material, namely the artificial graphite cathode material with better cycle performance.
In some embodiments of the invention, the mixing in S01 is performed at 60 ℃ or lower.
In some embodiments of the invention, in S02, the granulation is at 0-650 ℃ for 5-8 hours.
In some embodiments of the invention, in S02, the particles D50 of the secondary particulate material are between 15 and 30 μm.
In some embodiments of the invention, S03, the deagglomerated particles have a D50 of 13 to 25 μm.
In some embodiments of the present invention, in S03, the cooling is cooling to room temperature, the temperature of the graphitization heat treatment is 2500 to 3000 ℃, and the treatment time is 30 to 50 hours.
In some embodiments of the present invention, in S02 and/or S03, the inert gas is selected from one or more of nitrogen, argon, helium and neon.
In some embodiments of the invention, (1) the predetermined size and resolution of the clear pictures are different
Collecting particle pictures with different definition degrees, wherein the content of the particle pictures is the same, the resolution is the same, and calculating the NSRR of the image;
wherein n is the number of images;
wherein u is x 、u y Representing the mean, σ, of the different images x and y x 2 、σ y 2 Representing the variance, σ, of different images x and y, respectively xy Representing the covariance of the different images x and y. c1= (k) 1 L) 2 ，c2＝(k 2 L) 2 Are all constants to maintain a steady state. Where L refers to the dynamic range of pixel values, typically k1=0.010-0.015, and k2=0.030-0.035. The larger the value, the better the quality of the graph.
(2) Acquiring images in real time, and calculating NSRR:
(3) Analyzing and judging, and if the definition reaches a threshold value, carrying out the next automatic identification step; if the threshold value is not reached, the image is acquired again;
in research, the results of k1 and k2 are more accurate when the values of k1 and k2 meet the following formula in the processes of granulation, depolymerization and scattering:
wherein, b is a constant and takes a value of 0.8-0.9; when D50 is below 15 μm, a is 0.09-0.10; when the D50 is more than 15 μm, the value of a is 0.11-0.12.
The invention has the beneficial effects that:
the artificial graphite cathode material prepared by the invention has higher tap density, and the lithium ion battery prepared by the artificial graphite cathode material has the following electrochemical properties: (1) the first discharge capacity is more than 345 mAh/g; (2) The cycle performance is good, 1100 cycles are performed, and the capacity retention rate is more than 90%.
The preparation method of the invention adds a shaping procedure to modify the surface of the product in order to obtain better circulation, thereby effectively improving the circulation performance of the product.
Drawings
FIG. 1 is a 1000-fold SEM photograph of example 1 of the present invention;
FIG. 2 is a 1000-fold SEM photograph of example 2 of the present invention;
FIG. 3 is a 1000 SEM photograph of example 3 of the present invention;
fig. 4 is a cycle test curve of a full cell according to example 2 of the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless otherwise specified, the examples and comparative examples are parallel tests with the same components, component contents, preparation steps, preparation parameters. The pitch coke precursor is calcined pitch coke, and the manufacturer is Xinbang carbon; the softening point of the medium-temperature asphalt is 150 ℃, and the manufacturer is Liaoning Xinde; petroleum coke precursor A1, petroleum in the manufacturer; modified asphalt softening point 130, baoku of manufacturer; needle coke precursor B2, british Kangfen of manufacturer; the softening point of the high-temperature asphalt is 200 ℃, and the manufacturer Liaoning Xinde; anthracite ash content 3%, ningxia Shizushan. The type of the integer grader is 80 machines, and a manufacturer is a river-Yin Tianyuan.
Unless otherwise specified, the following component proportions are by weight. The inert gas is nitrogen.
Example 1
A preparation method of an artificial graphite negative electrode material with better cycle performance comprises the following steps:
placing the pitch coke precursor with the particle size of 7-8 μm and medium-temperature pitch into a mixer according to a ratio of 97 to 90min, and mixing at 30 ℃ at a rotating speed of 45r/min for 90min to obtain a mixed material;
putting the mixed material into a high-temperature reaction kettle, introducing inert gas for protection, heating to 600 ℃ at the rotating speed of 35r/min, keeping the temperature of 600 ℃ for 4 hours, and stirring while heating to obtain a granulated secondary particle material D50 with the particle size of 15.5 mu m;
and (3) depolymerizing and scattering the granulated secondary particles by a shaping classifier, wherein the host frequency is 35HZ, the feeding frequency is 25HZ, and the D50 after depolymerization and scattering is 14.5 mu m.
And heating the depolymerized and broken materials in a graphitization furnace to 2800 ℃ for graphitization heat treatment for 42 hours to obtain the long-cycle secondary particle artificial graphite cathode material.
Example 2
A preparation method of an artificial graphite negative electrode material with better cycle performance comprises the following steps:
placing a petroleum coke precursor with the particle size of 9-10 mu m and modified asphalt into a mixer according to a ratio of 97 to 90min, and mixing at 30 ℃ at a rotating speed of 45r/min to obtain a mixed material;
putting the mixed material into a high-temperature reaction kettle, introducing inert gas for protection, heating to 650 ℃ at the rotating speed of 32r/min, keeping the temperature of 650 ℃ for 4 hours, keeping the temperature for 4 hours again, and stirring while heating to obtain a granulated secondary granular material D50 with the particle size of 18 mu m;
and (3) depolymerizing and scattering the granulated secondary particles by a shaping classifier, wherein the host frequency is 15HZ, the feeding frequency is 20HZ, and the D50 after depolymerization and scattering is 17.5 mu m.
And heating the depolymerized and scattered materials in a graphitization furnace to 2800 ℃ for graphitization heat treatment for 43 hours to obtain the long-cycle secondary particle artificial graphite cathode material.
Example 3
A preparation method of an artificial graphite negative electrode material with better cycle performance comprises the following steps:
placing a needle coke precursor with the particle size of 10-11 microns and high-temperature asphalt into a mixer according to the ratio of 90;
putting the mixed material into a high-temperature reaction kettle, introducing inert gas for protection, heating to 650 ℃ at the rotating speed of 30r/min, keeping the temperature of 650 ℃ for 4 hours, and stirring while heating to obtain a granulated secondary particle material D50 with the particle size of 17 microns;
and (3) depolymerizing and scattering the granulated secondary particles by a shaping classifier, wherein the host frequency is 10HZ, the feeding frequency is 20HZ, and the D50 after depolymerization and scattering is 16 mu m.
Heating the depolymerized and broken materials in a graphitization furnace to 3000 ℃ and carrying out graphitization heat treatment for 45 hours to obtain the long-cycle secondary particle artificial graphite cathode material.
Example 4
A preparation method of an artificial graphite negative electrode material with better cycle performance comprises the following steps:
placing the anthracite precursor with the particle size of 10.5-11.5 microns and phenolic resin in a mixer according to the formula of 87, and mixing for 30min at the rotation speed of 180r/min at the temperature of 30 ℃ to obtain a mixed material;
putting the mixed material into a high-temperature reaction kettle, introducing inert gas for protection, heating to 600 ℃ at the rotating speed of 30r/min, keeping the temperature of 600 ℃ for 4 hours, and stirring while heating to obtain a granulated secondary particle material D50 of 20 microns;
and (3) depolymerizing and scattering the granulated secondary particles by a shaping classifier, wherein the host frequency is 30HZ, the feeding frequency is 20HZ, and the D50 after depolymerization and scattering is 18 mu m.
And performing graphitization heat treatment on the depolymerized and scattered materials at 2800 ℃ for 42 hours to obtain the long-cycle secondary particle artificial graphite cathode material.
Example 5
A preparation method of an artificial graphite negative electrode material with better cycle performance comprises the following steps:
putting a petroleum coke precursor with the particle size of 10-11 microns and phenolic resin into a mixer according to the mixing ratio of 90;
putting the mixed material into a high-temperature reaction kettle, introducing inert gas for protection, heating to 600 ℃ at the rotating speed of 32r/min, keeping the temperature of 600 ℃ for 4 hours, and stirring while heating to obtain a granulated secondary particle material D50 of 22 mu m;
and (3) depolymerizing and scattering the granulated secondary particles by a shaping classifier, wherein the host frequency is 15HZ, the feeding frequency is 20HZ, and the D50 after depolymerization and scattering is 19 mu m.
And heating the depolymerized and scattered materials in a graphitization furnace to 2800 ℃ for graphitization heat treatment for 43 hours to obtain the long-cycle secondary particle artificial graphite cathode material.
Example 6
The preparation method of the artificial graphite cathode material with better cycle performance is different from the embodiment 1 in that the detection is carried out through automatic image identification in the granulation and depolymerization scattering processes, and comprises a definition judgment step, which specifically comprises the following steps:
(1) Presetting clear pictures with different sizes and resolutions
Collecting particle pictures with different definition degrees, wherein the content of the particle pictures is the same, the resolution is the same, and calculating the NSRR of the image;
wherein n is the number of images;
wherein u is x 、u y Representing the mean, σ, of the different images x and y x 2 、σ y 2 Representing the variance, σ, of different images x and y, respectively xy Representing the covariance of the different images x and y. c1= (k) 1 L) 2 ，c2＝(k 2 L) 2 Are all constants to maintain a steady state. Where L refers to the dynamic range of pixel values, typically k1=0.010-0.015, and k2=0.030-0.035. The larger the value, the better the quality of the graph.
(2) Acquiring images in real time, and calculating NSRR:
(3) Analyzing and judging, and if the definition reaches a threshold value, carrying out the next automatic identification step; if the threshold value is not reached, the image is acquired again;
in the research, the values of k1 and k2 are found to be more accurate when the values conform to the following formula in the processes of granulation, depolymerization and scattering:
wherein, b is a constant and takes a value of 0.8-0.9; when D50 is below 15 μm, a is 0.09-0.10; when the D50 is more than 15 μm, the value of a is 0.11-0.12.
In the image automatic identification step of the embodiment, the problem of insufficient definition in image acquisition is solved by pre-judging the definition of the acquired image, so that the identification rate is improved, and unnecessary image acquisition is reduced.
In the image automatic identification step of the embodiment, different definition calculation coefficients are adopted for the sizes of different particles in the granulating and deagglomerating and scattering processes, so that the accuracy is higher.
Comparative example
The precursors of examples 1 to 2 were mixed by adding 2% of the phenol resin, and the other processes were the same as those of examples to obtain comparative examples 1 to 2.
The precursors of examples 3 to 4 were mixed by adding 16% of high temperature pitch, and the other processes were the same as those of examples to obtain comparative examples 3 to 4.
Other processes are the same as example 5 except that the particle size of the precursor of example 5 is controlled to 3-4um to thereby obtain comparative example 5.
And (3) performance testing:
secondary particle artificial graphite anode materials obtained in examples 1 to 3 are shown in fig. 1 to 3, respectively, in SEM images at 1000 times.
The physical properties of the products obtained in each example and comparative example were measured by a malvern 3000 precision particle sizer, a bestsden true densitometer, a hectometer, and a full-automatic powder compaction densitometer, and the physical properties are shown in table 1.
TABLE 1 physical Properties of Secondary particle Artificial graphite negative electrode Material
The products obtained in each example and each comparative example are manufactured into a button cell, and a blue test system is used for testing the first discharge capacity and the first efficiency. Each example and comparative example were also made to a 4.0Ah pouch cell test cycle. The electrochemical test results are shown in table 2.
TABLE 2 Electrical Properties of Secondary particle Artificial graphite cathode Material
The negative electrode of the lithium ion battery obtained in example 2 was prepared as a soft-packed lithium ion battery, and the results of the cycle measurement by the 1C/1C method were shown in fig. 1.
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the embodiments and examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. The artificial graphite cathode material with better cycle performance is characterized in that the preparation raw materials comprise the following components in parts by weight:
85-97 parts of precursor and 3-15 parts of binding material.
2. The artificial graphite negative electrode material according to claim 1, wherein the precursor is at least one selected from the group consisting of petroleum coke, needle coke, pitch coke, and anthracite.
3. The artificial graphite anode material according to claim 1 or 2, wherein the binder is at least one selected from the group consisting of a resin, a modified pitch, a high-temperature pitch, and a medium-temperature pitch.
4. The artificial graphite anode material according to any one of claims 1 to 3, wherein the D50 of the particles of the precursor and the binder are each 5 to 12 μm.
5. The preparation method of the artificial graphite anode material with better cycle performance according to any one of claims 1 to 4, characterized by comprising the following steps:
s01, mixing the precursor with a bonding material to obtain a mixed material;
s02, introducing inert gas into the mixed material for protection, and granulating to obtain a granulated secondary granular material;
and S03, under the protection of inert gas, cooling the granulated secondary particle material, scattering and depolymerizing, and then carrying out graphitization heat treatment to obtain the long-cycle secondary particle artificial graphite cathode material, namely the artificial graphite cathode material with better cycle performance.
6. The method according to claim 5, wherein the mixing in S01 is performed at 60 ℃ or lower.
7. The method according to claim 5 or 6, wherein in S02, the granulation is carried out at 0-650 ℃ for 5-8 hours.
8. The production method according to any one of claims 5 to 7, wherein in S02, the particles D50 of the secondary particulate material are 15 to 30 μm;
and/or in S03, the D50 of the particles after deagglomeration and scattering is 13-25 mu m.
9. The production method according to any one of claims 5 to 8, wherein in S03, the cooling is to room temperature, the graphitization heat treatment is at a temperature of 2500 to 3000 ℃, and the treatment time is 30 to 50 hours.
10. The method according to any one of claims 5 to 9, wherein in S02 and/or S03, the inert gas is selected from one or more of nitrogen, argon, helium and neon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211588865.5A CN115784221A (en) | 2022-12-09 | 2022-12-09 | Artificial graphite negative electrode material with better cycle performance and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211588865.5A CN115784221A (en) | 2022-12-09 | 2022-12-09 | Artificial graphite negative electrode material with better cycle performance and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115784221A true CN115784221A (en) | 2023-03-14 |
Family
ID=85419220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211588865.5A Pending CN115784221A (en) | 2022-12-09 | 2022-12-09 | Artificial graphite negative electrode material with better cycle performance and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115784221A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106486669A (en) * | 2015-11-17 | 2017-03-08 | 上海杉杉科技有限公司 | A kind of high-discharge-rate lithium ion battery graphite cathode material and preparation method thereof |
| CN110921659A (en) * | 2019-12-11 | 2020-03-27 | 内蒙古三信新材料科技有限公司 | Preparation method of high-capacity artificial graphite negative electrode material |
| CN112670472A (en) * | 2020-12-22 | 2021-04-16 | 宁波杉杉新材料科技有限公司 | Graphite negative electrode material, lithium ion battery, preparation method and application |
| CN113213470A (en) * | 2021-05-07 | 2021-08-06 | 上海杉杉新材料有限公司 | Artificial graphite secondary particle, coating agent, preparation method and application thereof |
| CN113422024A (en) * | 2021-06-25 | 2021-09-21 | 洛阳月星新能源科技有限公司 | Preparation method of high-compaction-density composite negative electrode graphite material |
| CN113526500A (en) * | 2021-07-20 | 2021-10-22 | 安徽科达新材料有限公司 | Preparation method of high-performance artificial graphite negative electrode material |
| CN114933301A (en) * | 2022-05-18 | 2022-08-23 | 广东东岛新能源股份有限公司 | Long-life artificial graphite negative electrode material for energy storage and preparation method and application thereof |
| CN114956069A (en) * | 2022-07-07 | 2022-08-30 | 王辅志 | Device for preparing artificial graphite cathode material for lithium ion battery and preparation method thereof |
| CN115347176A (en) * | 2022-09-05 | 2022-11-15 | 湛江市聚鑫新能源有限公司 | Graphite-based composite negative electrode material and preparation method and application thereof |
| CN115432698A (en) * | 2022-09-30 | 2022-12-06 | 贝特瑞新材料集团股份有限公司 | Carbon secondary particle and preparation method thereof, artificial graphite and preparation method thereof, lithium ion battery cathode material and lithium ion battery |
-
2022
- 2022-12-09 CN CN202211588865.5A patent/CN115784221A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106486669A (en) * | 2015-11-17 | 2017-03-08 | 上海杉杉科技有限公司 | A kind of high-discharge-rate lithium ion battery graphite cathode material and preparation method thereof |
| CN110921659A (en) * | 2019-12-11 | 2020-03-27 | 内蒙古三信新材料科技有限公司 | Preparation method of high-capacity artificial graphite negative electrode material |
| CN112670472A (en) * | 2020-12-22 | 2021-04-16 | 宁波杉杉新材料科技有限公司 | Graphite negative electrode material, lithium ion battery, preparation method and application |
| CN113213470A (en) * | 2021-05-07 | 2021-08-06 | 上海杉杉新材料有限公司 | Artificial graphite secondary particle, coating agent, preparation method and application thereof |
| CN113422024A (en) * | 2021-06-25 | 2021-09-21 | 洛阳月星新能源科技有限公司 | Preparation method of high-compaction-density composite negative electrode graphite material |
| CN113526500A (en) * | 2021-07-20 | 2021-10-22 | 安徽科达新材料有限公司 | Preparation method of high-performance artificial graphite negative electrode material |
| CN114933301A (en) * | 2022-05-18 | 2022-08-23 | 广东东岛新能源股份有限公司 | Long-life artificial graphite negative electrode material for energy storage and preparation method and application thereof |
| CN114956069A (en) * | 2022-07-07 | 2022-08-30 | 王辅志 | Device for preparing artificial graphite cathode material for lithium ion battery and preparation method thereof |
| CN115347176A (en) * | 2022-09-05 | 2022-11-15 | 湛江市聚鑫新能源有限公司 | Graphite-based composite negative electrode material and preparation method and application thereof |
| CN115432698A (en) * | 2022-09-30 | 2022-12-06 | 贝特瑞新材料集团股份有限公司 | Carbon secondary particle and preparation method thereof, artificial graphite and preparation method thereof, lithium ion battery cathode material and lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112751029B (en) | Silicon-oxygen composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN102593434B (en) | Composite graphite particles for lithium secondary battery and preparation method thereof | |
| CN112670466B (en) | Composite graphite negative electrode material, preparation method thereof and lithium ion battery | |
| CN111029578B (en) | Modified hard carbon negative electrode material and preparation method thereof | |
| CN110518251A (en) | A kind of three-dimensional grapheme powder body material and preparation method thereof | |
| CN112645300A (en) | Hard carbon negative electrode material, lithium ion battery and preparation method and application thereof | |
| CN106532009A (en) | Preparation method of high capacity lithium ion battery hard carbon composite negative electrode material | |
| CN106486652A (en) | A kind of graphite negative material of lithium ion battery and preparation method thereof | |
| CN111232971A (en) | Long-circulation natural graphite-based modified composite material and preparation method and application thereof | |
| CN113666368B (en) | Artificial graphite negative electrode material and preparation method thereof | |
| CN103311519A (en) | Composite hard carbon negative electrode material, and preparation method and application thereof | |
| CN103311520A (en) | Composite graphite negative electrode material of lithium ion battery and preparation method thereof | |
| CN111370654A (en) | Composite graphite negative electrode material, lithium ion battery and preparation method and application thereof | |
| CN103855395B (en) | A kind of natural graphite cathode material of lithium ion battery and preparation method thereof | |
| CN112054165B (en) | Mesocarbon microbeads, graphite negative electrode material, preparation method of mesocarbon microbeads and graphite negative electrode material, and lithium ion battery | |
| CN115084513A (en) | Hard carbon negative electrode material, preparation method thereof and lithium ion battery | |
| CN106477569A (en) | A kind of preprocess method of artificial graphite material and products obtained therefrom and application | |
| CN110518203A (en) | Compound soft carbon negative electrode material and preparation method thereof, lithium ion battery | |
| CN112938960B (en) | Preparation method of high-compaction-density and low-specific-surface-area negative electrode material | |
| CN113023724A (en) | Preparation method of high-rate graphite negative electrode material for lithium ion power battery | |
| CN111072012B (en) | Microcrystalline graphite graphene-doped negative electrode material of lithium ion battery and preparation method thereof | |
| CN112670459B (en) | Graphite negative electrode material and preparation and application thereof | |
| CN103219520B (en) | Graphite cathode material of lithium ion battery and preparation method thereof | |
| CN111232969B (en) | Composite intermediate phase negative electrode material, lithium ion secondary battery, preparation method and application | |
| CN115784221A (en) | Artificial graphite negative electrode material with better cycle performance 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 |