CN114300646A - Composite graphite negative electrode material and preparation method and application thereof - Google Patents
Composite graphite negative electrode material and preparation method and application thereof Download PDFInfo
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- CN114300646A CN114300646A CN202111526083.4A CN202111526083A CN114300646A CN 114300646 A CN114300646 A CN 114300646A CN 202111526083 A CN202111526083 A CN 202111526083A CN 114300646 A CN114300646 A CN 114300646A
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Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a composite graphite cathode material as well as a preparation method and an application thereof, wherein the preparation method comprises the following steps: step S1, crushing, grinding and grading the calcined coke to obtain calcined coke aggregate; step S2, crushing, grinding and grading the raw coke to obtain raw coke aggregate; step S3, mixing the cooked coke aggregate and the raw coke aggregate, adding asphalt, heating, granulating and graphitizing to obtain a first material; and step S4, adding the first material and the coating agent into a fusion machine for fusion coating, and carbonizing to obtain the composite graphite cathode material. According to the method, the calcined coke and the green coke are used in a matched manner, the asphalt is added for granulation, the coating agent is added for fusion coating, and then carbonization is carried out to obtain the composite graphite cathode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a composite graphite negative electrode material and a preparation method and application thereof.
Background
The lithium ion battery has the characteristics of higher energy density, long cycle life, no memory effect and the like, and is widely applied to the field of 3C consumer batteries and power batteries. Graphite, which is the most suitable negative electrode material for lithium ion batteries, has not been replaced by other materials for a short period of time. However, as consumers demand high specific capacity and also demand fast-charging lithium ion batteries increasingly, the conventional graphite negative electrode material needs to be upgraded.
The general graphite material with high specific capacity and high compaction density adopts needle-shaped coke as a raw material, but has limited dynamic performance. The good dynamic graphite material is generally petroleum green coke or needle-shaped green coke, but is limited by low compaction density and low capacity. Therefore, how to obtain the graphite material which has high capacity and quick charging performance simultaneously is significant. The existing method generally adopts the blending of graphite secondary particles and single particles to improve the quick charging capacity and the specific capacity, but the performance of the graphite secondary particles and the performance of the single particles and the specific capacity are difficult to be considered simultaneously, and the problem of the blending uniformity of the single particles and the secondary particles is also existed, thus causing adverse effects on the homogenization and the coating in the later period. Therefore, a graphite negative electrode material with high compaction density and high specific capacity and simultaneously considering the quick charging performance is urgently needed to be designed.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the preparation method of the composite graphite cathode material is provided, and the problem that the graphite cathode material with high compaction density, high specific capacity and quick charging performance cannot be prepared is solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite graphite anode material comprising the steps of:
step S1, crushing, grinding and grading the calcined coke to obtain calcined coke aggregate;
step S2, crushing, grinding and grading the raw coke to obtain raw coke aggregate;
step S3, mixing the cooked coke aggregate in the step S1 and the raw coke aggregate in the step S2, adding asphalt, heating for granulation, and graphitizing to obtain a first material;
and S4, adding the first material and the coating agent in the step S3 into a fusion machine for fusion and coating, and carbonizing to obtain the composite graphite cathode material.
According to the method, the calcined coke and the green coke are used in a matched manner, the asphalt is added for granulation, the coating agent is added for fusion coating, and then carbonization is carried out to obtain the composite graphite cathode material. The coke can be classified into needle coke, sponge coke, shot coke (shot coke) and coke breeze according to morphology, and the coke obtained by the method comprises needle coke and coke with a high length-diameter ratio. The raw coke of the invention comprises graphite raw coke and needle-shaped raw coke with 15 to 25 percent of volatile component content. The needle coke has the characteristics of high specific capacity and high compacted density, the particle size of the aggregate is controlled in a proper range, excessive compacted density and capacity are not lost, and certain charging capacity is ensured.
Preferably, the particle diameter D of the cooked coke aggregate in the step S1506 to 7 μm, particle diameter D of the green coke aggregate in step S2504 to 6 μm. The cooked coke is more brittle and hard compared with the raw coke, the edge defects of the surface of the ground coke are more, and the smaller the particle size is, the more defects are, and the electrochemical performance of the material is influenced. According to the invention, the calcined coke aggregate and the green coke aggregate are designed within the range, so that excessive compaction density and capacity are not lost, a certain charging capacity is ensured, the material performance is better exerted, and the material has dynamic performance, high compaction density and high specific capacity.
Preferably, the volatile content of the green coke is 15% to 25%. According to the volatile matter content in the coke, the maturity of the coke can be judged, and the volatile matter content of the raw coke is higher than that of the common raw coke, so that the rate capability of the material is improved.
Preferably, the weight part ratio of the cooked coke aggregate to the raw coke aggregate is 75-85: 15-25. The reasonable matching of the cooked coke and the raw coke ensures that the material not only does not lose excessive compaction density and capacity, but also ensures the charging capacity, good rate capability and quick charging performance.
Preferably, the weight part ratio of the cooked coke aggregate to the green coke aggregate to the asphalt is 75-85: 15-25: 5-10. The asphalt comprises low-temperature asphalt, medium-temperature asphalt and high-temperature asphalt, the medium-temperature asphalt with the softening point of 90-110 ℃ is used in the invention, and the asphalt can keep good fluidity and wettability when mixed with aggregate, can provide a certain coking value and enhances the bonding strength.
Preferably, the graphitization temperature in the step S3 is 2900 ℃ to 3200 ℃, and the graphitization degree is 92.5% to 100%.
Preferably, the softening point of the asphalt in the step S3 is 90-110 ℃. The invention uses medium temperature asphalt to be mixed with aggregate, which can keep good fluidity and wetting property, provide a certain coking value and enhance the bonding strength.
Preferably, the temperature of the carbonization in the step S4 is 1000 to 1200 ℃. The coating agent is used for carbonization, a carbonized layer is formed on the surface, and the conductivity of the material is improved.
Preferably, the coating agent comprises one or a mixture of several of resin materials, asphalt materials and conductive agents. The coating agent is liquid-phase fusion coating, one or more of liquid-phase resin materials and asphalt polymer materials are mixed, and oils such as coal tar, castor oil, anthracene oil and the like are used as solvents to be dispersed and then mixed with graphitized materials for fusion coating. Preferably, the coating agent further comprises a conductive agent for coating, so that the conductivity of the material can be improved, and the conductive agent comprises carbon nanotubes, carbon fibers and graphene. Preferably, the solid-liquid ratio of the coating agent is controlled to be 30-35%.
The second purpose of the invention is: aiming at the defects of the prior art, the composite graphite negative electrode material has good compacted density, specific capacity and rate capability, and can be charged quickly.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite graphite cathode material is prepared by the preparation method of the composite graphite cathode material.
The third purpose of the invention is that: aiming at the defects of the prior art, the negative plate has good compaction density, specific capacity and rate capability and can be charged quickly.
In order to achieve the purpose, the invention adopts the following technical scheme:
a negative plate comprises the composite graphite negative electrode material.
The fourth purpose of the invention is that: in order to overcome the defects of the prior art, the negative plate comprises the composite graphite negative electrode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium ion battery comprises the negative plate. Specifically, the lithium ion battery comprises a positive plate, a negative plate, a diaphragm, electrolyte and a shell, wherein the diaphragm separates the positive plate from the negative plate, and the shell is used for installing the positive plate, the negative plate, the diaphragm and the electrolyte.
Compared with the prior art, the invention has the beneficial effects that: according to the method, the calcined coke and the green coke are used in a matched manner, the asphalt is added for granulation, the coating agent is added for fusion coating, and then carbonization is carried out to obtain the composite graphite cathode material.
Drawings
Fig. 1 is an SEM image of the composite graphite anode material prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the composite graphite anode material prepared in example 2 of the present invention.
Fig. 3 is an SEM image of the anode material prepared in comparative example 1.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
1) 480kg of needle-shaped calcined coke is crushed, ground and classified to obtain calcined coke aggregate with Dv50 of 7 mu m, and 120kg of petroleum raw coke is crushed, ground and classified to obtain raw coke aggregate with Dv50 of 6 mu m; wherein the volatile content of the raw coke is 18%.
2) Uniformly mixing the cooked coke aggregate and the raw coke aggregate according to a proportion of 80:20 by weight, adding 8 parts by weight of 48kg of medium temperature asphalt, stirring and dynamically granulating in a horizontal kettle, wherein the reaction kettle is in an inert atmosphere. The heat treatment stirring speed is as follows; 25Hz, controlling the temperature rise speed at 2-3 ℃/min, wherein the heat preservation time at 350 ℃ is 90min, and the heat preservation time at 600 ℃ is 80 min; wherein the softening point of the medium-temperature asphalt is 95 ℃;
3) screening the granulated product, and then loading the screened product into a graphite crucible for graphitization to obtain a first material, wherein the graphitization atmosphere is inert gas protection, the graphitization temperature is 3200 ℃, the graphitization time is 50h, and the graphitization degree is 95%;
4) 1.2g of phenolic resin is swelled in 2g of coal tar with the solid-to-liquid ratio of 30%, and 0.3% of 0.05g of nano conductive agent is added to obtain a coating agent; the weight portion ratio of the phenolic resin to the coal tar to the nano conductive agent is 12:20: 0.5.
5) Adding the first material and the coating agent accounting for 5 wt% of the first material into a fusion machine for fusion and coating, wherein the stirring speed is controlled to be 30Hz, and the fusion time is 4 min;
6) and (3) putting the fused material into a graphite crucible, sending the fused material into a roller kiln for carbonization at 1150 ℃, directly screening and demagnetizing the carbonized material to obtain the composite graphite cathode material, wherein the composite graphite cathode material is shown in figure 1 and is an SEM image of the prepared composite graphite cathode material.
Example 2
1) Crushing, grinding and grading 420kg of needle-shaped calcined coke to obtain calcined coke aggregate with Dv50 of 7 mu m; 180kg of petroleum green coke is crushed, ground and classified to obtain green coke aggregate with Dv50 of 4 mu m.
2) Mixing the cooked coke aggregate and the raw coke aggregate according to the weight ratio of 70: mixing evenly in proportion of 30, adding 48kg of medium temperature asphalt, stirring and dynamically granulating in a horizontal kettle, wherein the reaction kettle is in inert atmosphere. The heat treatment stirring speed is as follows; 25Hz, controlling the temperature rise speed at 2-3 ℃/min, wherein the heat preservation time at 350 ℃ is 90min, and the heat preservation time at 600 ℃ is 80 min;
3) screening the granulated product, and then loading the screened product into a graphite crucible for graphitization to obtain a first material, wherein the graphitization atmosphere is inert gas protection, the graphitization temperature is 3200 ℃, and the graphitization time is 50 h;
4) swelling phenolic resin in coal tar with a solid-to-liquid ratio of 30%, and adding 0.3% of nano conductive agent to obtain a coating agent;
5) adding the first material and a coating agent accounting for 5 wt% of the first material into a fusion machine, controlling the stirring speed to be 30Hz, and controlling the fusion time to be 4 min;
6) and putting the fused material into a graphite crucible, sending the fused material into a roller kiln for carbonization, wherein the highest carbonization temperature is 1150 ℃, directly screening and demagnetizing the carbonized material to obtain the composite graphite cathode material, and as shown in figure 2, the SEM image of the prepared composite graphite cathode material is shown.
Example 3
The difference from example 1 is that: the weight portion ratio of the cooked coke aggregate to the green coke aggregate to the asphalt is 75:20: 8.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The difference from example 1 is that: the weight portion ratio of the cooked coke aggregate to the green coke aggregate to the asphalt is 85:20: 8.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
The difference from example 1 is that: the weight portion ratio of the cooked coke aggregate to the green coke aggregate to the asphalt is 80:15: 8.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
The difference from example 1 is that: the weight portion ratio of the cooked coke aggregate to the green coke aggregate to the asphalt is 80:25: 8.
The rest is the same as embodiment 1, and the description is omitted here.
Example 7
The difference from example 1 is that: the weight portion ratio of the cooked coke aggregate to the green coke aggregate to the asphalt is 80:20: 5.
The rest is the same as embodiment 1, and the description is omitted here.
Example 8
The difference from example 1 is that: the particle diameter D of the calcined coke aggregate507 μm, particle diameter D of green coke aggregate506 μm, the volatile content of the green coke is 18%.
The rest is the same as embodiment 1, and the description is omitted here.
Example 9
The difference from example 1 is that: the particle diameter D of the calcined coke aggregate506 μm, particle diameter D of green coke aggregate506 μm, the volatile content of the green coke is 16%. .
The rest is the same as embodiment 1, and the description is omitted here.
Example 10
The difference from example 1 is that: the particle diameter D of the calcined coke aggregate506 μm, particle diameter D of green coke aggregate505 μm, the volatile content of the green coke was 19%. .
The rest is the same as embodiment 1, and the description is omitted here.
Example 11
The difference from example 1 is that: the particle diameter D of the calcined coke aggregate507 μm, particle diameter D of green coke aggregate506 μm, the volatile content of the green coke is 25%. .
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
The difference from example 1 is that: only the needle-like coke was crushed, ground and classified to obtain an aggregate having a Dv50 of 7 μm. The SEM image of the finally obtained composite material is shown in fig. 3.
The rest is the same as embodiment 1, and the description is omitted here.
And (3) performance testing: the negative electrode materials prepared in the above examples 1 to 11 and comparative example 1 were subjected to performance tests, and the gram capacity of graphite, the compacted density of the negative electrode sheet, and the rebound test results are recorded in table 1, and the room-temperature charging lithium deposition window test results of the battery cell are recorded in table 2.
TABLE 1
TABLE 2
The table 1 shows that the composite graphite negative electrode material has higher compaction density and specific capacity and quick charge performance compared with the negative electrode material in the prior art, and is quick to charge, easy to precipitate lithium and long in service life. Compared with the examples 1 and 3-7, the prepared composite graphite cathode material has better performance when the weight part ratio of the cooked coke aggregate to the raw coke aggregate to the asphalt is 80:20:8, because the compaction density and the dynamic relationship can be balanced under the mixture ratio, the two are considered and the optimal performance is obtained. From comparison of examples 1, 8 to 11, it is found that when the particle diameter D of the cooked coke aggregate is set507 μm, particle diameter D of green coke aggregate50At 6 μm, when the volatile content of the green coke is 18% (i.e., example 1), the prepared composite graphite anode material has better compacted density, specific capacity, rate capability and dynamic performance, because the compacted density is enabled by reasonable matching of the cooked coke aggregate and the green coke aggregateThe method has the advantages that the electrochemical performance is improved greatly, the volatile content of the raw coke is high, the defect of needle coke with large long diameter after grinding can be overcome, the defect of surface edges and corners after grinding is reduced, the compaction density is improved, and the material performance is improved.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (12)
1. The preparation method of the composite graphite negative electrode material is characterized by comprising the following steps of:
step S1, crushing, grinding and grading the calcined coke to obtain calcined coke aggregate;
step S2, crushing, grinding and grading the raw coke to obtain raw coke aggregate;
step S3, mixing the cooked coke aggregate in the step S1 and the raw coke aggregate in the step S2, adding asphalt, heating for granulation, and graphitizing to obtain a first material;
and S4, adding the first material and the coating agent in the step S3 into a fusion machine for fusion and coating, and carbonizing to obtain the composite graphite cathode material.
2. The method for producing the composite graphite anode material according to claim 1, wherein the particle diameter D of the calcined coke aggregate in the step S1506 to 7 μm, particle diameter D of the green coke aggregate in step S2504 to 6 μm.
3. The composite graphite anode material according to claim 1 or 2, wherein the volatile content of the raw coke in the step S2 is 15% to 25%.
4. The preparation method of the composite graphite anode material according to claim 1, wherein the weight part ratio of the cooked coke aggregate to the green coke aggregate is 75-85: 15-25.
5. The preparation method of the composite graphite anode material according to claim 1 or 4, wherein the weight part ratio of the cooked coke aggregate, the green coke aggregate and the asphalt is 75-85: 15-25: 5-10.
6. The method for preparing the composite graphite anode material according to claim 1, wherein the graphitization temperature in the step S3 is 2900-3200 ℃, and the graphitization degree is 92.5-100%.
7. The method for preparing the composite graphite anode material according to claim 1, wherein the softening point of the pitch in the step S3 is 90 ℃ to 110 ℃.
8. The method for preparing the composite graphite anode material according to claim 1, wherein the temperature for carbonization in the step S4 is 1000 ℃ to 1200 ℃.
9. The preparation method of the composite graphite anode material as claimed in claim 1, wherein the coating agent comprises one or a mixture of a resin material, an asphalt material and a conductive agent.
10. A composite graphite negative electrode material produced by the method for producing a composite graphite negative electrode material according to any one of claims 1 to 9.
11. A negative electrode sheet comprising the composite graphite negative electrode material according to claim 10.
12. A lithium ion battery comprising the negative electrode sheet according to claim 11.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI816598B (en) * | 2022-11-03 | 2023-09-21 | 台灣中油股份有限公司 | Method for producing negative electrode carbon material and its lithium ion secondary battery |
| CN117658123A (en) * | 2023-11-28 | 2024-03-08 | 安徽科达新材料有限公司 | Preparation method of artificial graphite anode material |
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| CN113371707A (en) * | 2021-06-30 | 2021-09-10 | 惠州亿纬锂能股份有限公司 | Artificial graphite negative electrode material and preparation method and application thereof |
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Patent Citations (4)
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| CN107706387A (en) * | 2017-10-09 | 2018-02-16 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of composite negative pole material, its preparation method and lithium ion battery |
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| CN117658123A (en) * | 2023-11-28 | 2024-03-08 | 安徽科达新材料有限公司 | Preparation method of artificial graphite anode material |
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