CN115974066A - Method for preparing artificial graphite by using high-sulfur coke - Google Patents

Method for preparing artificial graphite by using high-sulfur coke Download PDF

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CN115974066A
CN115974066A CN202211704638.4A CN202211704638A CN115974066A CN 115974066 A CN115974066 A CN 115974066A CN 202211704638 A CN202211704638 A CN 202211704638A CN 115974066 A CN115974066 A CN 115974066A
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artificial graphite
intermediate material
sulfur coke
preparing artificial
sulfur
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常元钦
慈蒙蒙
江国庆
王如秀
路鹏飞
黄升政
刘超
何慧娟
严烁
王莉
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Hefei Guoxuan New Material Technology Co ltd
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Hefei Guoxuan New Material Technology Co ltd
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    • YGENERAL 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
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10Energy storage using batteries

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Abstract

The invention discloses a method for preparing artificial graphite by using high-sulfur coke, which comprises the following steps: s1, carrying out pre-carbonization treatment on the coarsely crushed high-sulfur coke, and then crushing to obtain an intermediate material 1 with 10-13wt% of volatile matter; s2, shaping the intermediate material 1, then uniformly mixing the intermediate material with a binder, and granulating to obtain an intermediate material 2; and S3, shaping the intermediate material 2, then graphitizing, and demagnetizing and screening to obtain the artificial graphite. The invention adopts high-sulfur coke as a raw material, reduces the cost, and selects a proper preparation process to ensure that the prepared artificial graphite has good tap density and electrical property.

Description

Method for preparing artificial graphite by using high-sulfur coke
Technical Field
The invention relates to the technical field of artificial graphite, in particular to a method for preparing artificial graphite by using high-sulfur coke.
Background
The anode material is one of the key factors determining the performance of the lithium ion battery, and the artificial graphite is a commonly used raw material of the anode material of the lithium ion battery. The artificial graphite is mainly obtained by graphitizing a coke material at a high temperature, and part of products are also subjected to surface modification. The coke material mainly comprises petroleum coke, needle coke and the like.
The needle coke has low contents of elements such as sulfur, nitrogen and the like, has higher graphitization degree, excellent conductivity and larger lithium storage capacity, and is often used as a raw material for preparing artificial graphite. However, the price of the needle coke is high, about 10000 yuan/ton, and the needle coke is directly purchased for use, so that the cost is high.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a method for preparing artificial graphite by using high-sulfur coke, the high-sulfur coke is used as a raw material, the cost is reduced, and the prepared artificial graphite has good tap density and electrical property by selecting a proper preparation process.
The invention provides a method for preparing artificial graphite by using high-sulfur coke, which comprises the following steps:
s1, carrying out pre-carbonization treatment on the coarsely crushed high-sulfur coke, and then crushing to obtain an intermediate material 1 with 10-13wt% of volatile components;
s2, shaping the intermediate material 1, then uniformly mixing the intermediate material with a binder, and granulating to obtain an intermediate material 2;
and S3, shaping the intermediate material 2, then graphitizing, and demagnetizing and screening to obtain the artificial graphite.
The invention selects high-sulfur coke as raw material, the price of the high-sulfur coke is about 4000 yuan/ton, which is far lower than that of needle coke, and the production cost can be reduced; but the high-sulfur coke has high content of impurities and volatile components, which can reduce the performance of the artificial graphite, and the proper pre-carbonization process is selected in the invention, so that the content of the volatile components and the sulfur in the high-sulfur coke can be reduced; then crushing and screening the intermediate material 1 with proper particle size distribution, so that the tap density of the artificial graphite can be improved, and the electrical property of the artificial graphite is further improved.
Preferably, in S1, the pre-carbonization temperature is 900-1200 ℃ and the pre-carbonization time is 4-5h.
Preferably, in S1, the particle diameter D of the intermediate charge 1 10 ≥3μm、D 50 8-10 μm, D 90 ≤18μm、D 99 ≤35μm。
Preferably, in S2, the amount of the intermediate material 1 is 7-8% of the weight of the binder; the binder is asphalt; the binder is preferably medium temperature coal tar pitch.
Preferably, in S2, the granulation temperature is 900-1200 ℃ and the granulation time is 5-6h.
Preferably, in S2, the particle size D of the intermediate charge 2 10 ≥7.5μm、D 50 16.3-18.7 μm, D 90 ≤28μm、D 99 ≤48μm。
The tap density and graphitization degree of the artificial graphite can be further improved by selecting a proper granulation process and screening the intermediate material 2 with proper particle size distribution.
Preferably, in S3, the graphitization temperature is 2800-3200 ℃, and the graphitization time is 7-8h.
Preferably, the pre-carbonization, granulation, graphitization is performed in an inert gas atmosphere.
Preferably, pre-carbonizing and granulating in a nitrogen atmosphere; graphitization was performed in an argon atmosphere.
Preferably, the precarbonization and granulation are carried out in a tunnel kiln.
The tunnel kiln is used for replacing the traditional vertical kettle, the yield of batch production can be improved, and the tunnel kiln can be used for pre-carbonizing and granulating at a higher temperature, so that the purity of raw materials is improved, and the contents of impurities such as sulfur element, volatile component and the like are reduced; thereby improving the electrical property of the artificial graphite.
Preferably, in S3, the screen is 100-500 mesh.
Has the advantages that:
the invention selects the high-sulfur coke as the raw material, which can reduce the production cost; proper pre-carbonization and granulation processes are selected, so that the volatile content and the sulfur content in the high-sulfur coke can be reduced; the intermediate material 1 and the intermediate material 2 with proper particle size distribution are screened, so that the tap density of the artificial graphite can be improved, and the electrical property of the artificial graphite is further improved; replace traditional vertical cauldron with the tunnel cave, can improve batch production's output, use the tunnel cave moreover and can carry out carbonization and granulation in advance under higher temperature, improve the purity of raw materials, reduce the content of impurity such as sulphur element, volatile, prolong the energy storage life, improve the electrical property of artificial graphite.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A method for preparing artificial graphite by using high-sulfur coke comprises the following steps:
s1, putting coarsely crushed high-sulfur coke into a tunnel kiln, pre-carbonizing at 1100 ℃ for 4.5 hours in a nitrogen atmosphere, and then crushing to obtain an intermediate material 1 with 10wt% of volatile matter;
particle diameter D of intermediate Material 1 10 ≥3μm、D 50 Is 8-10 μm, D 90 ≤18μm、D 99 ≤35μm;
S2, shaping the intermediate material 1, then uniformly mixing the intermediate material with asphalt, and granulating for 5.5 hours at 1100 ℃ in a tunnel kiln in a nitrogen atmosphere to obtain an intermediate material 2; the using amount of the intermediate material 1 is 7.5 percent of the weight of the asphalt;
particle diameter D of intermediate Material 2 10 ≥7.5μm、D 50 16.3-18.7 μm, D 90 ≤28μm、D 99 ≤48μm;
And S3, shaping the intermediate material 2, graphitizing for 7.5h at 3000 ℃ in an argon atmosphere in a graphitizing furnace, demagnetizing, and sieving by using a 100-500-mesh vibrating screen to obtain the artificial graphite.
Example 2
A method for preparing artificial graphite by using high-sulfur coke comprises the following steps:
s1, putting coarsely crushed high-sulfur coke into a tunnel kiln, pre-carbonizing for 5 hours at 900 ℃ in a nitrogen atmosphere, and then crushing to obtain an intermediate material 1 with 13wt% of volatile components;
particle diameter D of intermediate Material 1 10 ≥3μm、D 50 8-10 μm, D 90 ≤18μm、D 99 ≤35μm;
S2, shaping the intermediate material 1, then uniformly mixing the intermediate material with asphalt, and granulating for 6 hours at 900 ℃ in a tunnel kiln in a nitrogen atmosphere to obtain an intermediate material 2; the using amount of the intermediate material 1 is 7 percent of the weight of the asphalt;
particle diameter D of intermediate Material 2 10 ≥7.5μm、D 50 16.3-18.7 μm, D 90 ≤28μm、D 99 ≤48μm;
And S3, shaping the intermediate material 2, graphitizing for 8 hours at 2800 ℃ in an argon atmosphere in a graphitizing furnace, demagnetizing, and sieving by using a 100-500-mesh vibrating screen to obtain the artificial graphite.
Example 3
A method for preparing artificial graphite by using high-sulfur coke comprises the following steps:
s1, putting coarsely crushed high-sulfur coke into a tunnel kiln, pre-carbonizing for 4 hours at 1200 ℃ in a nitrogen atmosphere, and then crushing to obtain an intermediate material 1 with 11wt% of volatile matter;
particle diameter D of intermediate Material 1 10 ≥3μm、D 50 8-10 μm, D 90 ≤18μm、D 99 ≤35μm;
S2, shaping the intermediate material 1, then uniformly mixing the intermediate material with asphalt, and granulating for 5 hours at 1200 ℃ in a tunnel kiln in a nitrogen atmosphere to obtain an intermediate material 2; the using amount of the intermediate material 1 is 8 percent of the weight of the asphalt;
particle diameter D of intermediate Material 2 10 ≥7.5μm、D 50 16.3-18.7 mu m, D 90 ≤28μm、D 99 ≤48μm;
And S3, shaping the intermediate material 2, graphitizing for 7 hours at 3200 ℃ in an argon atmosphere in a graphitizing furnace, demagnetizing, and screening by using a 100-500-mesh vibrating screen to obtain the artificial graphite.
Comparative example 1
The intermediate charge 1 was replaced with needle coke having the same particle size distribution, and the procedure was otherwise the same as in example 1.
Comparative example 2
Particle diameter D of intermediate Material 1 10 ≥1μm、D 50 Is 10-12 μm, D 90 ≤20μm、D 99 Less than or equal to 40 mu m; the rest is the same as example 1.
Comparative example 3
Particle diameter D of intermediate Material 2 10 ≥5μm、D 50 20-22 μm, D 90 ≤35μm、D 99 Less than or equal to 50 mu m; the rest is the same as example 1.
The artificial graphite prepared in examples 1 to 3 and comparative examples 1 to 3 were used to measure tap density, and button cells were prepared from the artificial graphite of each group and tested for performance, and the results are shown in table 1.
The preparation method of the button cell comprises the following steps: taking the artificial graphite prepared in the examples 1-3 and the comparative examples 1-3, and preparing anode slurry according to the weight ratio of the artificial graphite to the conductive agent to the binder of 95; respectively uniformly scraping and coating the negative electrode slurry on copper foil, and drying in vacuum at 60 ℃ to obtain a negative electrode plate; and respectively assembling the lithium sheet serving as a positive electrode and the 1mol/LLIPF6 solution serving as an electrolyte solution to obtain the button cell.
TABLE 1 test results
Figure SMS_1
As can be seen from Table 1, the artificial graphite prepared by using high-sulfur coke and combining with a proper preparation process has the performance close to that of the artificial graphite prepared by using needle coke, and the cost is low; and the intermediate material 1 and the intermediate material 2 with proper particle size distribution are selected, so that the tap density of the artificial graphite can be improved, and the performance of the lithium ion battery can be improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. A method for preparing artificial graphite by using high-sulfur coke is characterized by comprising the following steps:
s1, carrying out pre-carbonization treatment on the coarsely crushed high-sulfur coke, and then crushing to obtain an intermediate material 1 with 10-13wt% of volatile matter;
s2, shaping the intermediate material 1, then uniformly mixing the intermediate material with a binder, and granulating to obtain an intermediate material 2;
and S3, shaping the intermediate material 2, then graphitizing, and demagnetizing and screening to obtain the artificial graphite.
2. The method for preparing artificial graphite from high-sulfur coke according to claim 1, wherein the pre-carbonization temperature is 900 to 1200 ℃ and the pre-carbonization time is 4 to 5 hours in S1.
3. The method for preparing artificial graphite from high-sulfur coke according to claim 1 or 2, wherein in S1, the particle diameter D of the intermediate charge 1 10 ≥3μm、D 50 8-10 μm, D 90 ≤18μm、D 99 ≤35μm。
4. The method for preparing artificial graphite from high-sulfur coke according to claim 1 or 2, wherein in S2, the amount of the intermediate charge 1 is 7-8% by weight of the binder; the binder is asphalt.
5. The method for preparing artificial graphite from high-sulfur coke according to claim 1 or 2, wherein the granulation temperature is 900 to 1200 ℃ and the granulation time is 5 to 6 hours in S2.
6. The method for preparing artificial graphite from high-sulfur coke according to claim 1 or 2, wherein in S2, the particle diameter D of intermediate charge 2 10 ≥7.5μm、D 50 16.3-18.7 μm, D 90 ≤28μm、D 99 ≤48μm。
7. The method for preparing artificial graphite from high sulfur coke according to claim 1 or 2, wherein in S3, the graphitization temperature is 2800 to 3200 ℃ and the graphitization time is 7 to 8 hours.
8. The method for preparing artificial graphite from high-sulfur coke according to claim 1 or 2, wherein the pre-carbonization, granulation, and graphitization are performed in an inert gas atmosphere.
9. The method for preparing artificial graphite from high-sulfur coke according to claim 1 or 2, wherein the pre-carbonization and granulation are performed in a tunnel kiln.
10. The method for preparing artificial graphite from high-sulfur coke according to claim 1 or 2, wherein in S3, the mesh is 100 to 500 mesh.
CN202211704638.4A 2022-12-29 2022-12-29 Method for preparing artificial graphite by using high-sulfur coke Pending CN115974066A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108199043A (en) * 2018-01-15 2018-06-22 安徽科达洁能新材料有限公司 A kind of preparation method of high multiplying power lithium ion battery artificial plumbago negative pole material
CN109148852A (en) * 2018-08-17 2019-01-04 东莞市凯金新能源科技股份有限公司 A kind of preparation method and its material of the graphite cathode material improving covering property
CN109809399A (en) * 2017-11-22 2019-05-28 天津市贝特瑞新能源科技有限公司 A kind of preparation method of composite graphite negative electrode 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
CN114180564A (en) * 2021-11-08 2022-03-15 内蒙古斯诺新材料科技有限公司 Synthetic method of artificial graphite, negative electrode material and lithium ion battery
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
CN115520860A (en) * 2022-09-27 2022-12-27 大理宸宇储能新材料有限公司 High-sulfur Jiao Gaixing and method for preparing quick-charging graphite anode material and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109809399A (en) * 2017-11-22 2019-05-28 天津市贝特瑞新能源科技有限公司 A kind of preparation method of composite graphite negative electrode material
CN108199043A (en) * 2018-01-15 2018-06-22 安徽科达洁能新材料有限公司 A kind of preparation method of high multiplying power lithium ion battery artificial plumbago negative pole material
CN109148852A (en) * 2018-08-17 2019-01-04 东莞市凯金新能源科技股份有限公司 A kind of preparation method and its material of the graphite cathode material improving covering property
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
CN114180564A (en) * 2021-11-08 2022-03-15 内蒙古斯诺新材料科技有限公司 Synthetic method of artificial graphite, negative electrode material and lithium ion battery
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
CN115520860A (en) * 2022-09-27 2022-12-27 大理宸宇储能新材料有限公司 High-sulfur Jiao Gaixing and method for preparing quick-charging graphite anode material and application thereof

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