CN108483437B - Lithium battery carbon negative electrode material taking ethylene coke as raw material and preparation method thereof - Google Patents
Lithium battery carbon negative electrode material taking ethylene coke as raw material and preparation method thereof Download PDFInfo
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- CN108483437B CN108483437B CN201810224466.8A CN201810224466A CN108483437B CN 108483437 B CN108483437 B CN 108483437B CN 201810224466 A CN201810224466 A CN 201810224466A CN 108483437 B CN108483437 B CN 108483437B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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Abstract
The invention provides a preparation method of a lithium battery carbon negative electrode material taking ethylene coke as a raw material, belonging to the field of lithium ion batteries. The composite particle is characterized by comprising a composite particle of a primary particle and a secondary particle, wherein the primary particle is prepared by mixing ethylene coke calcined material with the average particle size D50 of 1-15 mu m and the secondary particle is prepared by mixing ethylene coke calcined material with the average particle size D50 of 1-10 mu m with asphalt according to the proportion of 5: 1-10: 1, and then carrying out solid-solid mixing and high-temperature reaction. The material prepared by the method has the advantages of high specific capacity and long cycle life, the specific capacity is up to 360mAh/g, the capacity retention rate is over 95 percent after 460 times of circulation, in addition, the isotropy is better, the compaction density is high, and particularly, the material has lower production cost and is expected to have good application prospect in the fields of power automobiles and the like.
Description
Technical Field
The invention relates to a lithium battery carbon negative electrode material and a preparation method thereof, in particular to a lithium battery carbon negative electrode material taking ethylene coke as a raw material and a preparation method thereof.
Background
The lithium ion battery cathode material mainly comprises carbon materials and mainly comprises artificial graphite and natural graphite. The raw materials of the artificial graphite comprise petroleum coke, pitch coke, needle coke, coal and the like, the negative electrode graphite taking the petroleum coke and the pitch coke as the raw materials has the advantages of low cost and good stability, but has the defect of low capacity, and the negative electrode graphite is mainly applied to medium-low-end power batteries. Other carbon negative electrode materials, such as mesocarbon microbeads, are extracted from pitch, have the advantages of good particle morphology, low irreversible capacity loss and stable cycle life, but also have the disadvantages of high production cost and low discharge capacity. The natural graphite raw material has low cost, but the flaky natural graphite has the defects of low tap density and high specific surface area, and is not suitable to be directly used as a negative electrode material. The loss of irreversible capacity of the natural graphite cathode material which is not modified for the first time is high and generally reaches 10 percent, and the problems of fast capacity attenuation and the like are caused due to the occurrence of solvent co-intercalation during circulation. The rounded and surface-treated natural graphite has the disadvantages of rapid capacity decay and high production cost, although the electrical properties are obviously improved.
Disclosure of Invention
The invention aims to solve the technical problem of greatly reducing the production cost on the basis of keeping various performance indexes of a product to reach the performance indexes of high-end cathode materials required by the market.
The invention provides a lithium ion battery cathode material prepared by taking high-quality ethylene coke as a raw material, which comprises composite particles of primary particles and secondary particles, and is characterized in that: the primary particles have an average particle diameter D50The ethylene coke calcined material with the particle size of 1-15 mu m adopts the average particle size D50The ethylene coke calcined material with the particle size of 1-10 mu m is mixed with asphalt to perform high-temperature reaction, wherein the secondary particles are prepared by the following steps after the ethylene coke and the asphalt are subjected to solid-solid mixing according to the proportion of 5: 1-10: 1:
1) carrying out polymerization reaction at the temperature of 200-700 ℃, wherein the reaction time is 300-600 minutes;
2) and carrying out carbonization treatment at the temperature of 900-1200 ℃.
The final product is prepared by solid-solid mixing of primary particles and secondary particles according to the proportion of 1: 4-4: 1 through the following steps:
1) carrying out graphitization treatment at 2700-3000 ℃;
2) and (5) sieving and demagnetizing.
A preparation method of a lithium battery carbon negative electrode material taking ethylene coke as a raw material comprises the following steps:
1. preparing the calcined ethylene coke into an average particle size D50Primary particles of 1 to 15 μm;
2. preparing the calcined ethylene coke into an average particle size D501-10 μm primary particles, solid-solid mixing with asphalt according to the proportion of 5: 1-10: 1, carrying out polymerization reaction at the temperature of 200-700 ℃, and the reaction time is 300-600 minutes；
3. Carrying out carbonization treatment at the temperature of 900-1200 ℃;
4. and (3) performing solid-solid mixing on the primary particles and the secondary particles according to the proportion of 1: 4-4: 1, performing graphitization treatment at the temperature of 2700-3000 ℃, screening, and demagnetizing.
The carbon negative electrode material obtained by the invention has the advantages of good isotropy, high specific capacity, high compaction density, long cycle life and the like, and particularly has lower production cost.
Description of the figures
Fig. 1 is a scanning electron microscope photograph of a carbon negative electrode prepared according to example 4 of the present invention.
Fig. 2 is a charge and discharge graph of a carbon negative electrode prepared according to example 4 of the present invention.
Detailed Description
The products of examples 1-10 were tested using the Q/TEZI01-2001 electrochemical capacity test standard, with the following results:
through detection, the product performance of the examples 1-10 reaches the index of a high-end artificial graphite cathode material sold in the market, and the production cost is greatly reduced due to the adoption of high-quality ethylene coke as a raw material.
Claims (2)
1. The carbon negative electrode material of the lithium battery comprises primary particles and secondary particles, and is characterized in that:
the primary particles are ethylene coke calcined materials with the average particle size D50 of 1-15 mu m, and the secondary particles are ethylene coke calcined materials with the average particle size D50Mixing 1-10 mu m ethylene coke calcined material and asphalt according to the proportion of 5: 1-10: 1, carrying out solid-solid mixing, and carrying out high-temperature reaction to obtain the asphalt, wherein the asphalt is one or a mixture of coal asphalt and petroleum asphalt, and secondary particles are obtained by the following stepsThe preparation method comprises the following steps:
1) carrying out polymerization reaction at the temperature of 450-700 ℃, wherein the reaction time is 300-600 minutes;
2) carbonizing at 1100-1200 ℃;
the final carbon negative electrode material of the lithium battery is prepared by solid-solid mixing of primary particles and secondary particles according to the proportion of 1: 4-4: 1 through the following steps:
1) carrying out graphitization treatment at 2700-3000 ℃;
2) and (5) sieving and demagnetizing.
2. A preparation method of a lithium battery carbon negative electrode material taking ethylene coke as a raw material comprises the following steps:
preparing the calcined ethylene coke into an average particle size D50Primary particles of 1 to 15 μm;
using the average particle diameter D50The ethylene coke calcined material with the particle size of 1-10 mu m is mixed with asphalt in a ratio of 5: 1-10: 1 for solid-solid mixing, polymerization is carried out at the temperature of 450-700 ℃, the reaction time is 300-600 minutes, and carbonization treatment is carried out at the temperature of 1100-1200 ℃ to prepare secondary particles;
and (3) performing solid-solid mixing on the primary particles and the secondary particles according to the proportion of 1: 4-4: 1, performing graphitization treatment at the temperature of 2700-3000 ℃, screening, and demagnetizing.
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| EP4265568A3 (en) * | 2020-03-27 | 2024-01-03 | Contemporary Amperex Technology Co., Limited | Process for preparing a secondary battery |
| CN115806289B (en) * | 2022-11-29 | 2024-07-05 | 江西紫宸科技有限公司 | Graphite negative electrode material with long cycle life and preparation method and application thereof |
Citations (5)
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| US6482547B1 (en) * | 1998-05-21 | 2002-11-19 | Samsung Display Devices Co., Ltd. | Negative active material for lithium secondary battery and lithium secondary battery using the same |
| CN101108729A (en) * | 2006-07-20 | 2008-01-23 | 天津市铁诚电池材料有限公司 | Method for manufacturing artificial plumbago negative pole material of lithium ion power cell |
| CN105489893A (en) * | 2015-10-28 | 2016-04-13 | 江西正拓新能源科技股份有限公司 | Graphite anode material for lithium-ion battery and preparation method of graphite anode material |
| CN105938906A (en) * | 2016-06-18 | 2016-09-14 | 湖南星城石墨科技股份有限公司 | Artificial graphite composite negative electrode material for lithium-ion battery and preparation method of artificial graphite composite negative electrode material |
| CN107758653A (en) * | 2016-08-17 | 2018-03-06 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of lithium ion battery composite particles graphite cathode material |
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- 2018-03-19 CN CN201810224466.8A patent/CN108483437B/en active Active
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| US6482547B1 (en) * | 1998-05-21 | 2002-11-19 | Samsung Display Devices Co., Ltd. | Negative active material for lithium secondary battery and lithium secondary battery using the same |
| CN101108729A (en) * | 2006-07-20 | 2008-01-23 | 天津市铁诚电池材料有限公司 | Method for manufacturing artificial plumbago negative pole material of lithium ion power cell |
| CN105489893A (en) * | 2015-10-28 | 2016-04-13 | 江西正拓新能源科技股份有限公司 | Graphite anode material for lithium-ion battery and preparation method of graphite anode material |
| CN105938906A (en) * | 2016-06-18 | 2016-09-14 | 湖南星城石墨科技股份有限公司 | Artificial graphite composite negative electrode material for lithium-ion battery and preparation method of artificial graphite composite negative electrode material |
| CN107758653A (en) * | 2016-08-17 | 2018-03-06 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of lithium ion battery composite particles graphite cathode material |
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| 乙烯裂解焦油综合利用新工艺技术及后续产品的开发利用;蒋小强;《广东化工》;20101231;第37卷(第12期);第67-68页 * |
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