CN111960410A - Preparation method of composite artificial graphite negative electrode material and lithium ion battery - Google Patents
Preparation method of composite artificial graphite negative electrode material and lithium ion battery Download PDFInfo
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- CN111960410A CN111960410A CN202010802311.5A CN202010802311A CN111960410A CN 111960410 A CN111960410 A CN 111960410A CN 202010802311 A CN202010802311 A CN 202010802311A CN 111960410 A CN111960410 A CN 111960410A
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- 229910021383 artificial graphite Inorganic materials 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 17
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 17
- 239000007773 negative electrode material Substances 0.000 title description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 32
- 239000010439 graphite Substances 0.000 claims abstract description 32
- 238000003763 carbonization Methods 0.000 claims abstract description 21
- 239000010406 cathode material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002006 petroleum coke Substances 0.000 claims abstract description 17
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 238000005469 granulation Methods 0.000 claims abstract description 6
- 230000003179 granulation Effects 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 27
- 239000011230 binding agent Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000011246 composite particle Substances 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000010426 asphalt Substances 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920001007 Nylon 4 Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 16
- 238000005253 cladding Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011331 needle coke Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 101150047356 dec-1 gene Proteins 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
- C01B32/21—After-treatment
-
- 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
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a preparation method of a composite artificial graphite cathode material, which takes graphitized petroleum coke and spherical graphite as raw materials to carry out composite granulation, and then carries out purification, cladding and carbonization to obtain the graphite cathode material. Compared with the prior art, the method has the advantages that the graphitized petroleum coke is used as the raw material, so that the raw material cost is greatly reduced, and meanwhile, the graphitizing process with higher cost is replaced by the carbonizing process, so that the obtained graphite cathode material has good multiplying power and cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a composite artificial graphite cathode material and a lithium ion battery containing the cathode material.
Background
Among the currently commercialized negative electrode materials for lithium ion batteries, lithium ion batteries using artificial graphite as the negative electrode material occupy the mainstream market. The preparation technology of the artificial graphite cathode material is relatively mature at present, but the problems of complex process, poor product stability, high cost, high price and the like still exist. Since the cost of the lithium ion battery accounts for more than 40% of the cost of the electric vehicle, the cost of the lithium ion battery also determines the cost of the electric vehicle purchased by the consumer and the competitiveness of the battery energy storage project in the electric power market. In order to reduce the overall cost of the battery, the core is to reduce the cost of the battery material. Therefore, a preparation method which has the advantages of low production cost and short production period and can obtain the cathode material with the performance equivalent to that of the traditional artificial graphite cathode material is needed.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the present invention is to provide a method for producing a composite artificial graphite negative electrode material, by which a graphite negative electrode material having low cost and excellent performance can be obtained.
A first object of the present invention is to provide a lithium ion battery containing the negative electrode material.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a preparation method of a composite artificial graphite cathode material, which comprises the following steps:
(1) mixing materials: fully mixing the graphitized petroleum coke and the spherical graphite to obtain a mixture;
preferably, the mass ratio of the graphitized petroleum coke to the spherical graphite is 1 (0.3-0.8).
(2) Crushing and shaping: crushing the mixture obtained in the step (1) to obtain powder;
preferably, the median particle diameter D50 of the powder is 3-10 μm.
(3) Coating and granulating: adding a binder into the powder obtained in the step (2), fully mixing to obtain a mixture, and then granulating to obtain graphite composite particles;
preferably, the binder is selected from at least one of asphalt, phenolic resin, glucose, polyacrylonitrile, polyvinyl alcohol, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyvinyl chloride.
Preferably, the mass ratio of the powder to the binder is 100 (5-20).
Preferably, the mixing is carried out in a high temperature mixing reaction stirred tank; the granulation is carried out in an inert gas atmosphere.
Preferably, the graphite composite particles are granulated and sieved to obtain the graphite composite particles with the median particle diameter D50 of 15-25 μm.
(4) Carbonizing: and (4) carrying out carbonization treatment on the graphite composite particles obtained in the step (3) to obtain the composite artificial graphite cathode material.
Preferably, the carbonization is carried out in an inert gas atmosphere, the carbonization temperature is 1200-1600 ℃, and the carbonization time is 6-20 hours.
The invention also relates to a lithium ion battery which comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte, wherein the negative pole piece contains the composite artificial graphite negative pole material provided by the invention.
The invention has the advantages of
The invention provides a preparation method of a composite artificial graphite cathode material, which takes graphitized petroleum coke and spherical graphite as raw materials to carry out composite granulation, and then carries out purification, cladding and carbonization to obtain the graphite cathode material. Compared with the prior art, the method has the advantages that the graphitized petroleum coke is used as the raw material, so that the raw material cost is greatly reduced, and meanwhile, the graphitizing process with higher cost is replaced by the carbonizing process, so that the obtained graphite cathode material has good multiplying power and cycle performance.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The embodiment of the invention relates to a preparation method of a composite artificial graphite cathode material, which comprises the following steps:
(1) mixing materials: fully mixing the graphitized petroleum coke and the spherical graphite to obtain a mixture;
in one embodiment of the invention, the mixing is performed in a mixer-blender. Of the two raw materials, the spherical graphite has high cost, and if the proportion of the spherical graphite is increased, the product circulation capacity is improved, but the raw material cost is greatly increased. The graphitized petroleum coke has lower cost, for example, the proportion of the graphitized petroleum coke is increased, and although the raw material cost is reduced, the product circulation capacity is reduced more. The mass ratio of the graphitized petroleum coke to the spherical graphite is preferably 1 (0.3-0.8). The mixing proportion can ensure the comprehensive performance of the cathode material and simultaneously has the lowest raw material cost. Compared with the artificial graphite cathode prepared by needle coke at present, the cost is reduced by more than 30%.
(2) Crushing and shaping: crushing the mixture obtained in the step (1) to obtain powder;
in one embodiment of the invention, the comminution is carried out in a combined plant in series of a mechanical crusher and an air classifier. The median particle diameter D50 of the obtained powder is 3-10 μm.
(3) Coating and granulating: adding a binder into the powder obtained in the step (2), fully mixing to obtain a mixture, and then granulating to obtain graphite composite particles;
in one embodiment of the present invention, the binder is selected from at least one of asphalt, phenolic resin, glucose, polyacrylonitrile, polyvinyl alcohol, polystyrene, polypyrrolidone, polyacrylic acid, polyvinyl chloride. The adhesive not only can play a role in adhering powder, but also can be fully carbonized after high-temperature treatment, and other impurities cannot be introduced.
In one embodiment of the invention, the mass ratio of the powder to the binder is 100 (5-20). If the amount of the powder added is too large, the binder does not function sufficiently, and the powder cannot be completely converted into a mixture having a relatively uniform particle size. If the addition amount of the powder is too small, the relative addition amount of the binder is large, so that the powder is excessively aggregated, and the particle size of the obtained mixture is large.
In one embodiment of the invention, the mixing of the powder and the binder is performed in a high temperature mixing reaction stirred tank. And granulating the mixture in an inert gas atmosphere of nitrogen or argon for 3-8 hours. And (4) sieving after granulation, namely performing vibration sieving treatment on the granulated mixture to obtain the graphite composite particles with the median particle size D50 of 15-25 mu m. If the particles are too large, they tend to swell during charging and discharging, and have a short cycle life, while small particles require more binder, which affects the energy density of the battery.
(4) Carbonizing: and (4) carrying out carbonization treatment on the graphite composite particles obtained in the step (3) to obtain the composite artificial graphite cathode material.
In one embodiment of the invention, the carbonization is carried out in an inert gas atmosphere of nitrogen or argon, the carbonization temperature is 1200-1600 ℃, and the carbonization time is 6-20 hours. The carbonization temperature is too high, the reaction of the binder is too fast, and holes are easy to appear in the coated carbon layer, so that the cycle performance of the material is influenced finally; the carbonization temperature is too low, the binder can not form a stable coating carbon layer, and the material capacity is low.
The invention also relates to a lithium ion battery which comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte, wherein the negative pole piece contains the composite artificial graphite negative pole material provided by the invention.
The lithium ion battery may be a wound or stacked lithium ion battery. The conventional preparation method of the lithium ion battery comprises the steps of sequentially stacking a positive pole piece, a diaphragm and a negative pole piece, then winding or tabletting to obtain a bare cell, then injecting electrolyte, and packaging to obtain the lithium ion battery.
Examples of the experiments
Preparation of composite artificial graphite cathode material
(1) Mixing materials: fully mixing the graphitized petroleum coke and the spherical graphite, wherein the mass ratio of the graphitized petroleum coke to the spherical graphite is shown in table 1, and obtaining a mixture;
(2) crushing and shaping: crushing the mixture obtained in the step (1) in a composite device with a mechanical crusher and an airflow classifier connected in series to obtain powder, wherein the median particle size D50 of the powder is 3-10 microns;
(3) coating and granulating: and (3) placing the powder obtained in the step (2) into a high-temperature mixing reaction stirring kettle and adding a binder. The specific type of binder, and the mass ratio of powder to binder are shown in table 1. Fully mixing to obtain a mixture, and then granulating and screening in an inert gas atmosphere to obtain graphite composite particles with the median particle size D50 of 15-25 mu m;
(4) carbonizing: and (4) carrying out carbonization treatment on the graphite composite particles obtained in the step (3) in an inert gas atmosphere, wherein the temperature and time of the carbonization treatment are shown in table 1, so as to obtain the composite artificial graphite cathode material.
Lithium ion battery preparation
And uniformly mixing the prepared composite artificial graphite negative electrode material, an N-methyl pyrrolidone solution containing 6-7% of polyvinylidene fluoride (PVDF) in volume fraction and 2% of conductive carbon black, coating the mixture on a copper foil, and putting the coated electrode piece into a vacuum drying oven at the temperature of 70 ℃ for vacuum drying for 4 hours to obtain a negative electrode piece.
The button cell is assembled in an argon-filled glove box, and the electrolyte is LiPF with 1M6A solution, wherein EC: volume ratio of DEC 1: 1. the metal lithium sheet is a counter electrode. The electrochemical performance test is carried out on a Wuhan blue battery tester under the following test conditions: the charging and discharging voltage range is 0 to 4V at 25 ℃, and the charging and discharging speed is 0.1C.
TABLE 1
On the basis of example 2, the types and the addition amounts of the components are changed, and the experimental conditions are changed to obtain comparative examples 1-8, wherein the specific setting mode is shown in table 2.
TABLE 2
Test example
The batteries prepared in the above examples and comparative examples were tested for the cycle capacity after 200 cycles at 25C with 0.1C constant current charge and discharge, and the manufacturing cost per ton of the negative electrode material prepared in the above examples and comparative examples, and the results are shown in table 2.
TABLE 2
In each embodiment, specific detailed selection of each component is not limited, and the selection made by a person skilled in the art according to the disclosure can be applied.
As can be seen from table 2:
the comparison of examples 1 to 5 shows that the cycle capacity of the battery gradually increases with the increase of the content of the spherical graphite, and that the performance of the negative electrode material is gradually improved. However, the manufacturing cost of each ton of the cathode material is also synchronously increased, and the trend of the change is consistent. In order to take account of the performance of the negative electrode material and the cost of the raw material, the mass ratio of the graphitized petroleum coke to the spherical graphite is limited to 1 (0.3-0.8).
It is understood from comparative examples 2, 6, 7, 10 and 11 that the performance of the negative electrode material is hardly affected by changing the type of the binder and the carbonization temperature, but the production cost varies depending on the type of the binder.
It is understood from comparative examples 2, 8 and 9 that, if the amount of the powder added is too small, the relative amount of the binder added becomes large, the powder excessively aggregates, and the particle size of the resulting mixture becomes large. If the amount of the powder added is too large, the binder does not function sufficiently, and the powder cannot be completely converted into a mixture having a relatively uniform particle size. May result in a decrease in the performance of the anode material. Therefore, the mass ratio of the powder to the binder is limited to 100 (5-20).
It can be seen from the comparison of example 2 and comparative examples 1 to 2 that, if petroleum coke is replaced by needle coke or pitch coke, the initial capacity of the obtained negative electrode material is about 200mAh/g, and the negative electrode material cannot be used after being circulated for dozens of times. Subsequent experiments of the applicant find that if a graphitization step of treating at 3000 ℃ for 24 hours is added after the carbonization treatment of the comparative examples 1 and 2, the capacity of the material is 335-345 mAh/g after 200 cycles, which is better than that of the material in the example 2. However, the manufacturing cost per ton is increased to 31000-38000 yuan, and the improvement of the cycle performance is not advantageous compared with the increase of the cost.
It can be seen from the comparison of example 2 and comparative examples 3 to 4 that the method in the prior art, that is, the needle coke and the asphalt are used as raw materials to prepare the negative electrode material, subsequent graphitization treatment is required, otherwise the material cannot meet the use requirements. The invention adopts graphitized petroleum coke and spherical graphite as raw materials, the cost of the raw materials is 12000 yuan/ton, the cost of carbonization is 12000 yuan/ton, and the comprehensive cost is 24000 yuan/ton. The cost of the needle coke raw material is 15000 yuan/ton, the graphitization cost is 14000-18000 yuan/ton, and the comprehensive cost is 38000 yuan/ton, so that the raw material cost and the manufacturing cost are greatly increased compared with the method.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. The preparation method of the composite artificial graphite cathode material is characterized by comprising the following steps of:
(1) mixing materials: fully mixing the graphitized petroleum coke and the spherical graphite to obtain a mixture;
(2) crushing and shaping: crushing the mixture obtained in the step (1) to obtain powder;
(3) coating and granulating: adding a binder into the powder obtained in the step (2), fully mixing to obtain a mixture, and then granulating to obtain graphite composite particles;
(4) carbonizing: and (4) carrying out carbonization treatment on the graphite composite particles obtained in the step (3) to obtain the composite artificial graphite cathode material.
2. The method according to claim 1, wherein in the step (1), the mass ratio of the graphitized petroleum coke to the spherical graphite is 1 (0.3-0.8).
3. The method according to claim 1, wherein in the step (2), the median particle diameter D50 of the powder is 3-10 μm.
4. The method according to claim 1, wherein in the step (3), the binder is at least one selected from asphalt, phenolic resin, glucose, polyacrylonitrile, polyvinyl alcohol, polystyrene, polypyrrolidone, polyacrylic acid, and polyvinyl chloride.
5. The method according to claim 1, wherein in the step (3), the mass ratio of the powder to the binder is 100 (5-20).
6. The method according to claim 1, wherein in step (3), the granulation is performed in an inert gas atmosphere.
7. The method according to claim 1, wherein in step (3), the granulation is followed by sieving.
8. The method according to claim 7, wherein the median particle diameter D50 of the graphite composite particles obtained after sieving is 15 to 25 μm.
9. The method according to claim 1, wherein in the step (4), the carbonization is performed in an inert gas atmosphere, and the carbonization temperature is 1200-1600 ℃ and the carbonization time is 6-20 hours.
10. A lithium ion battery comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte, and is characterized in that the negative pole piece contains the composite artificial graphite negative pole material prepared by the method of any one of claims 1 to 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114883546A (en) * | 2022-05-19 | 2022-08-09 | 江苏正力新能电池技术有限公司 | Silicon-carbon composite active material, preparation method thereof, negative plate and secondary battery |
| CN115650226A (en) * | 2022-12-22 | 2023-01-31 | 溧阳紫宸新材料科技有限公司 | Petroleum coke composite artificial graphite material and preparation method thereof |
| CN116314612A (en) * | 2023-05-11 | 2023-06-23 | 中创新航科技集团股份有限公司 | Negative electrode plate and application thereof |
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| CN102148355A (en) * | 2011-03-03 | 2011-08-10 | 江西正拓新能源科技有限公司 | Cathode material for lithium-ion power battery and preparation method thereof |
| CN102659091A (en) * | 2012-05-03 | 2012-09-12 | 天津市贝特瑞新能源科技有限公司 | High-capacity graphite material and preparation method as well as application thereof |
| CN105244485A (en) * | 2015-10-28 | 2016-01-13 | 东莞市凯金新能源科技有限公司 | High capacity and high magnification composite graphite material for lithium ion battery and preparation method thereof |
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| CN114883546A (en) * | 2022-05-19 | 2022-08-09 | 江苏正力新能电池技术有限公司 | Silicon-carbon composite active material, preparation method thereof, negative plate and secondary battery |
| CN115650226A (en) * | 2022-12-22 | 2023-01-31 | 溧阳紫宸新材料科技有限公司 | Petroleum coke composite artificial graphite material and preparation method thereof |
| CN116314612A (en) * | 2023-05-11 | 2023-06-23 | 中创新航科技集团股份有限公司 | Negative electrode plate and application thereof |
| CN116314612B (en) * | 2023-05-11 | 2023-08-18 | 中创新航科技集团股份有限公司 | Negative electrode plate and application thereof |
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