CN116902973A - Graphite negative electrode material of lithium ion battery and preparation method thereof - Google Patents
Graphite negative electrode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN116902973A CN116902973A CN202310775610.8A CN202310775610A CN116902973A CN 116902973 A CN116902973 A CN 116902973A CN 202310775610 A CN202310775610 A CN 202310775610A CN 116902973 A CN116902973 A CN 116902973A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 35
- 239000010439 graphite Substances 0.000 title claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 120
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000010406 cathode material Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000007493 shaping process Methods 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 7
- 230000001070 adhesive effect Effects 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- 239000010405 anode material Substances 0.000 claims description 17
- 239000010426 asphalt Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002006 petroleum coke Substances 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 6
- 238000005087 graphitization Methods 0.000 claims description 5
- 238000009656 pre-carbonization Methods 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011331 needle coke Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 16
- 239000011248 coating agent Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 239000002245 particle Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005469 granulation Methods 0.000 description 10
- 230000003179 granulation Effects 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000005056 compaction Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 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
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 239000011261 inert gas 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
- 239000012982 microporous membrane Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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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
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
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Abstract
The invention discloses a graphite cathode material of a lithium ion battery and a preparation method thereof, wherein the method comprises the following steps: the method comprises the steps of (1) carrying out coarse crushing on raw materials to obtain a material A; (2) crushing the material A to obtain a material C; (3) Classifying the material C to obtain a material D, wherein DV50 of the material D is 11-12 mu m, DV10 of the material D is 4.0-4.5 mu m or 4.5-5.0 mu m; (4) mixing the material D with an adhesive to obtain a material E; (5) Granulating the material E to obtain a material F, wherein the granulating equipment adopts one of a horizontal kettle or a vertical kettle; (6) shaping the material F to obtain a material G; (7) pre-carbonizing the material G to obtain a material H; and (8) graphitizing the material H to obtain graphitized material. The graphite negative electrode material of the lithium ion battery has the advantages of high tap density, small specific surface area and high capacity, and has the characteristics of good compatibility with electrolyte, excellent cycle performance and good battery coating processability.
Description
Technical Field
The invention relates to the technical field of graphite material preparation, in particular to a graphite negative electrode material of a lithium ion battery and a preparation method thereof.
Background
At present, the new energy lithium ion battery cathode material mainly takes natural graphite and artificial graphite as main materials; the negative electrode material is an important component of the lithium ion battery, and the performance of the negative electrode material influences key indexes such as the safety, specific capacity, multiplying power performance, cycle life, high-low temperature performance and the like of the lithium ion battery. The artificial graphite has good compatibility with electrolyte, good cycle performance and good rate capability, and is the preferred negative electrode material of the lithium ion battery. Currently, the artificial graphitized secondary particle process comprises coarse crushing, grading, coating, shaping, pre-carbonization and graphitization. The process has the following defects: because the content of the fine powder is not completely removed after the raw materials are crushed and graded, the aggregate and the fine powder are bonded together in a coating process, so that the graphitized vibration density is low, the specific surface area is large, the capacity is low, and the problems of poor compatibility with electrolyte, poor multiplying power performance and poor cycle performance are caused after the graphitized vibration density is manufactured into a lithium ion battery.
Therefore, it is necessary to provide a graphite negative electrode material with high tap density for lithium ion batteries and a preparation method thereof to solve the current defects.
Disclosure of Invention
In view of the problems in the prior art that the content of fine powder is not completely removed after the raw materials are crushed and graded, and the aggregate and the fine powder are bonded together in the coating process, the graphitized negative electrode material has the problems of low tap density, large specific surface area, low capacity and the like. The invention aims to provide a graphite negative electrode material of a lithium ion battery, which has the characteristics of high tap density, small specific surface area and high capacity, and the graphite negative electrode material has the characteristics of good compatibility with electrolyte, excellent cycle performance and good battery coating processability.
In order to achieve the above purpose, the invention provides a preparation method of a graphite anode material of a lithium ion battery, comprising the following steps:
(1) Coarse crushing the raw materials to obtain a material A;
(2) Crushing the material A to obtain a material C;
(3) Classifying the material C to obtain a material D, wherein DV50 of the material D is 11-12 mu m, DV10 of the material D is 4.0-4.5 mu m or 4.5-5.0 mu m;
(4) Mixing the material D with an adhesive to obtain a material E;
(5) Granulating the material E to obtain a material F, wherein the granulating equipment adopts one of a horizontal kettle or a vertical kettle;
(6) Shaping the material F to obtain a material G;
(7) Pre-carbonizing the material G to obtain a material H;
(8) Graphitizing the material H to obtain graphitized material.
In the prior art, the range of particle size generally adopted in the classification stage is larger in span, and fine powder is contained, for example, 3.5-4.5 mu m is adopted, so that the content of the fine powder in the subsequent process is not completely removed, aggregate in the coating process is bonded with the fine powder, and the graphitized negative electrode material has the problems of low tap density, large specific surface area, low capacity and the like. The inventor finds that the DV10 of the material in the step is controlled to be 4.0-4.5 mu m or 4.5-5.0 mu m by reducing the grain size span range, properly increasing the grain size, removing part of fine powder with small grain size and grading, thereby improving the capacity after graphitization and reducing the specific surface area after graphitization. Meanwhile, the inventor also discovers that in the process, the continuous kettle coating granulation process is adopted, the performances of relatively good specific surface area, tap density, compaction, gram capacity, oil absorption value and the like cannot be realized, a specific horizontal kettle or vertical kettle granulation device is selected for the granulation process, and the graded particle size arrangement of the invention is matched, so that the product particles can be made to present a small number of single particles in secondary particles, the particle size distribution is more reasonable, the tap density and the compaction density are improved, the expansion is reduced, the cycle performance is improved, and the prepared negative electrode material has the characteristics of high capacity, high compaction, good compatibility with electrolyte, excellent cycle performance and good battery coating processing performance.
In some embodiments, the feedstock is at least one selected from petroleum coke, coal-based coke, needle coke, semicoke, as an example, but not limited to, petroleum coke green coke.
In some embodiments, the DV50 of the material C is 10-11 μm, the DV10 is 2.8-3.5 μm, but not limited thereto.
In some embodiments, the binder is at least one selected from high temperature asphalt, resin, and liquid asphalt, but not limited thereto.
In some embodiments, the apparatus for blending uses one of a horizontal ribbon blender or a VC3000 blender.
In some embodiments, the apparatus for the batch process is a horizontal ribbon blender and the temperature profile of the horizontal ribbon blender is controlled to rise from room temperature to 300 ℃ within 1 hour, then to 650 ℃ within 3 hours, and held for 3 hours, N 2 The flow rate is 0.5-1.0m 3 /h。
In some embodiments, the temperature of the pre-carbonization is 800-1200 ℃.
In some embodiments, the pre-carbonization device is selected from one of a low temperature carbonization furnace, a shuttle furnace.
In some embodiments, the graphitization temperature is 2900-3200 ℃.
In some embodiments, the graphitizing device is selected from one of an acheson, a box furnace, and an inner strand furnace.
Correspondingly, the invention also provides a graphite anode material of the lithium ion battery, which is prepared by adopting the preparation method, and has the characteristics of high capacity, high compaction, good compatibility with electrolyte, excellent cycle performance and good battery coating processability.
Drawings
Fig. 1 is an SEM image of a graphite negative electrode material of a lithium ion battery according to example 2 of the present invention.
Fig. 2 shows capacity retention curves of batteries made of the negative electrode materials of examples and comparative examples after 500 weeks of cycling.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
A graphite cathode material of a lithium ion battery comprises the following steps:
(1) Coarse crushing raw material petroleum coke by a jaw crusher to obtain a material A1 with the particle size of 0-5 mm;
(2) Crushing the material A1 by a crusher (260 mechanical mill) to obtain a material C1 with the particle diameter DV50 of 10-11 mu m and DV10 of 2.8-3.5 mu m;
(3) Classifying the material C1 by an air classifier to obtain a material D1 with DV50 of 11-12 mu m and DV10 of 4.0-4.5 mu m;
(4) Mixing the material D1 and the adhesive high-temperature asphalt in a horizontal spiral ribbon mixing machine for 120 min/kettle, wherein each kettle is 2T/kettle, and the rotation number is 28r/min to obtain a material E1;
(5) Granulating the material E1 by a horizontal kettle of a coating device, heating to 300 ℃ from room temperature within 1 hour, heating to 650 ℃ within 3 hours, and preserving heat for 3 hours, wherein the temperature is N 2 The flow rate is 0.5-1.0m 3 And/h, obtaining a material F1;
(6) Shaping the material F1 by an 80 shaper to realize total material collection and obtain a material G1;
(7) Pre-carbonizing the material G1 by a low-temperature carbonization furnace to obtain a material H1;
(8) Graphitizing the material H1 by an Acheson furnace to obtain a graphitized material, namely a graphite anode material.
Example 2
A graphite cathode material of a lithium ion battery comprises the following steps:
(1) Coarse crushing raw material petroleum coke by a jaw crusher to obtain a material A2 with the particle size of 0-5 mm;
(2) Crushing the material A2 by a crusher (260 mechanical mill) to obtain a material C2 with the particle diameter DV50 of 10-11 mu m and DV10 of 2.8-3.5 mu m;
(3) Classifying the material C2 by an air classifier to obtain a material D2 with DV50 of 11-12 mu m and DV10 of 4.5-5.0 mu m;
(4) Mixing the material D2 and the adhesive high-temperature asphalt in a horizontal spiral ribbon mixing machine for 120 min/kettle, wherein each kettle is 2T/kettle, and the rotation number is 28r/min to obtain a material E2;
(5) Granulating the material E2 by a vertical kettle of a coating device, heating to 300 ℃ from room temperature within 1 hour, heating to 650 ℃ within 3 hours, and preserving heat for 3 hours, wherein the temperature is N 2 The flow rate is 0.5-1.0m 3 And/h, obtaining a material F2;
(6) Shaping the material F2 by an 80 shaper to realize total material collection and obtain a material G2;
(7) Pre-carbonizing the material G2 by a low-temperature carbonization furnace to obtain a material H2;
(8) Graphitizing the material H2 by an Acheson furnace to obtain a graphitized material, namely a graphite anode material.
Comparative example 1
A graphite cathode material of a lithium ion battery comprises the following steps:
(1) Coarse crushing raw material petroleum coke by a jaw crusher to obtain a material A3 with the particle size of 0-5 mm;
(2) Crushing the material A3 by a crusher (260 mechanical mill) to obtain a material C3 with the particle diameter DV50 of 10-11 mu m and DV10 of 2.8-3.5 mu m;
(3) Classifying the material C3 by an air classifier to obtain a material D3 with DV50 of 11-12 mu m and DV10 of 4.5-5.0 mu m;
(4) Mixing the material D3 and the adhesive high-temperature asphalt in a horizontal spiral ribbon mixing machine for 120 min/kettle, wherein each kettle is 2T/kettle, and the rotation number is 28r/min to obtain a material E3;
(5) Granulating the material E3 by continuous kettle granulation of a coating device, wherein the temperature rise curve is that the room temperature is raised to 300 ℃ within 1 hour, then the temperature is raised to 650 ℃ within 3 hours, and the temperature is kept for 3 hours, N 2 The flow rate is 0.5-1.0m 3 And/h, obtaining a material F3;
(6) Shaping the material F3 by an 80 shaper to realize total material collection and obtain a material G3;
(7) Pre-carbonizing the material G3 by a low-temperature carbonization furnace to obtain a material H3;
(8) Graphitizing the material H3 by an Acheson furnace to obtain a graphitized material, namely a graphite anode material.
Comparative example 2
A graphite cathode material of a lithium ion battery comprises the following steps:
(1) Coarse crushing raw material petroleum coke by a jaw crusher to obtain a material A4 with the particle size of 0-5 mm;
(2) Crushing the material A4 by a crusher (260 mechanical mill) to obtain a material C4 with the particle diameter DV50 of 10-11 mu m and DV10 of 2.8-3.5 mu m;
(3) Classifying the material C4 by an air classifier to obtain a material D4 with DV50 of 11-12 mu m and DV10 of 3.5-4.5 mu m;
(4) Mixing the material D4 and the adhesive high-temperature asphalt in a horizontal spiral ribbon mixing machine for 120 min/kettle, wherein each kettle is 2T/kettle, and the rotation number is 28r/min to obtain a material E4;
(5) Granulating the material E4 by a vertical kettle of a coating device, heating to 300 ℃ from room temperature within 1 hour, heating to 650 ℃ within 3 hours, and preserving heat for 3 hours, wherein the temperature is N 2 The flow rate is 0.5-1.0m 3 And/h, obtaining a material F4;
(6) Shaping the material F4 by an 80 shaper, wherein the material yield is 95% to obtain a material G4;
(7) Pre-carbonizing the material G4 by a low-temperature carbonization furnace to obtain a material H4;
(8) Graphitizing the material H4 by an Acheson furnace to obtain a graphitized material, namely a graphite anode material.
Fig. 1 shows an SEM image of the graphite anode material of example 2, and it can be seen from the image that the particle structure shows that the secondary particles contain a small amount of single particles, and the wider the particle size distribution, the smaller particles can fill gaps among the large particles under the same volume space, so that the tap density is correspondingly increased, and the slurry with high tap density has low viscosity, high solid content and easier coating processing.
The graphite anode materials prepared in examples and comparative examples were subjected to particle diameter DV50 (test equipment: mastersizer3000, test standard: GB/T19077-2016), specific surface area (test equipment: trist ii 3020, test standard: GB/T24533-2009), tap density 20KN (BT-302, GB/T5162-2006), compaction density (test equipment: samsung longitudinal and transverse UTM7305, test standard: GB/T24533-2019), oil absorption value (test equipment: S-500 oil absorption tester, test standard: GB/T3780.2-2007), gram capacity detection (test equipment: blue electric buckling test system, test standard: GB/T24533-2009), and the results are shown in table 1.
The graphite cathode materials prepared in the examples and the comparative examples are used as cathode materials of lithium ion batteries, are mixed with a binder polyvinylidene fluoride (PVDF) and a conductive agent (Super-P) according to the mass ratio of 91:7:2, are added with a proper amount of N-methylpyrrolidone (NMP) as a solvent to prepare slurry, are coated on copper foil, and are subjected to vacuum drying and rolling to prepare a cathode plate; a metal lithium sheet was used as a counter electrode, and 1mol/L LiPF was used 6 And the electrolyte mixed by the three components according to the ratio of EC: DMC: emc=1:1:1 (v/v) is assembled into the CR2430 button cell in a glove box filled with inert gas by adopting a polypropylene microporous membrane as a diaphragm. The charge and discharge test of the button cell was performed on a blue cell test system of Guangdong Jin Xin energy technologies Co., ltd, under normal temperature conditions, 0.02C was discharged 300min,0.05C was discharged to 0.005V, standing 10min,0.05mA was discharged to 0.005V, standing 5min,0.01mA was discharged to 0.005V, and 0.1C was charged to 2V, and the results are shown in Table 1.
Table 1 test results
As is clear from the results of table 1, the graphite anode materials of examples 1-2 have more excellent tap density, specific surface area, and capacity properties than those of comparative examples 1-2. Specifically, the coating equipment in comparative example 1 adopts continuous kettle granulation for granulation, and the specific surface area, tap density, compaction density, gram capacity and oil absorption value of the graphitized anode material are all worse than those of example 2, so that a horizontal kettle or a vertical kettle is more advantageous in the system; in comparative example 2, although the vertical kettle is adopted for granulation, a lot of fine powder exists in the material with larger grain size span after the grading treatment, namely, more grains with smaller grain size exist, the specific surface area, tap density, compaction density, gram capacity and oil absorption value are all inferior to those of example 2, the vertical kettle granulation equipment is selected for granulation process in example 2, the grain size after the grading is matched with the vertical kettle for granulation process, the fine powder is less and the grain size span is not great, and after the subsequent process, the product grains can be made to present secondary grains to contain a small amount of single grains, so that the grain size distribution is more reasonable, and the tap density, the compaction density, the expansion and the cycle performance are improved.
Fig. 2 shows capacity retention curves of batteries made of the negative electrode materials of examples and comparative examples after 500 weeks of cycling. As can be seen from FIG. 2, the cycle performance of comparative examples 1-2 is not as good as that of examples 1-2, specifically example 2, and the cycle performance of comparative example 1 is the worst.
In conclusion, the graphite anode material of the lithium ion battery prepared by the invention has the characteristics of high capacity, high compaction, good compatibility with electrolyte, excellent cycle performance and good battery coating processability.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (11)
1. The preparation method of the graphite cathode material of the lithium ion battery is characterized by comprising the following steps:
(1) Coarse crushing the raw materials to obtain a material A;
(2) Crushing the material A to obtain a material C;
(3) Classifying the material C to obtain a material D, wherein DV50 of the material D is 11-12 mu m, DV10 of the material D is 4.0-4.5 mu m or 4.5-5.0 mu m;
(4) Mixing the material D with an adhesive to obtain a material E;
(5) Granulating the material E to obtain a material F, wherein the granulating equipment adopts one of a horizontal kettle or a vertical kettle;
(6) Shaping the material F to obtain a material G;
(7) Pre-carbonizing the material G to obtain a material H;
(8) Graphitizing the material H to obtain graphitized material.
2. The graphite anode material of lithium ion battery according to claim 1, wherein the raw material is at least one selected from petroleum coke, coal-based coke, needle coke and semicoke.
3. The graphite anode material of lithium ion battery according to claim 1, wherein DV50 of material C is 10-11 μm and DV10 is 2.8-3.5 μm.
4. The graphite negative electrode material for lithium ion batteries according to claim 1, wherein the binder is at least one selected from the group consisting of high-temperature asphalt, resin, and liquid asphalt.
5. The lithium ion battery graphite anode material of claim 1, wherein the batching equipment adopts one of a horizontal ribbon blender or a VC3000 blender.
6. The graphite cathode material for lithium ion battery according to claim 5, wherein the equipment for mixing and batching is a horizontal ribbon mixer, and the heating curve of the horizontal ribbon mixer is controlled to be raised from room temperature to 3 within 1 hour00 ℃ and then rise to 650 ℃ within 3 hours, keep the temperature for 3 hours, N 2 The flow rate is 0.5-1.0m 3 /h。
7. The lithium ion battery graphite anode material according to claim 1, wherein the pre-carbonization temperature is 800-1200 ℃.
8. The graphite negative electrode material for lithium ion batteries according to claim 1, wherein the pre-carbonization equipment is one selected from the group consisting of a low-temperature carbonization furnace and a shuttle furnace.
9. The lithium ion battery graphite anode material of claim 1, wherein the graphitization temperature is 2900-3200 ℃.
10. The graphite anode material for lithium ion batteries according to claim 1, wherein the graphitizing equipment is one selected from the group consisting of acheson, box furnaces and inner series furnaces.
11. A graphite negative electrode material for a lithium ion battery, which is characterized by being prepared by the preparation method of any one of claims 1-10.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310775610.8A CN116902973A (en) | 2023-06-27 | 2023-06-27 | Graphite negative electrode material of lithium ion battery and preparation method thereof |
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| CN202310775610.8A CN116902973A (en) | 2023-06-27 | 2023-06-27 | Graphite negative electrode material of lithium ion battery and preparation method thereof |
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| CN118263401A (en) * | 2024-05-30 | 2024-06-28 | 宁德时代新能源科技股份有限公司 | Battery, preparation method thereof and electricity utilization device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058304A (en) * | 2016-08-10 | 2016-10-26 | 广东东岛新能源股份有限公司 | Artificial graphite negative electrode material used for lithium ion power batteries, and preparation method thereof |
| CN107369823A (en) * | 2017-07-25 | 2017-11-21 | 广东海洋大学 | A kind of lithium ion battery artificial composite cathode material of silicon/carbon/graphite and preparation method thereof |
| CN116239382A (en) * | 2022-12-23 | 2023-06-09 | 合肥国轩新材料科技有限公司 | Preparation method of high-pressure compact composite graphite and lithium ion battery |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058304A (en) * | 2016-08-10 | 2016-10-26 | 广东东岛新能源股份有限公司 | Artificial graphite negative electrode material used for lithium ion power batteries, and preparation method thereof |
| CN107369823A (en) * | 2017-07-25 | 2017-11-21 | 广东海洋大学 | A kind of lithium ion battery artificial composite cathode material of silicon/carbon/graphite and preparation method thereof |
| CN116239382A (en) * | 2022-12-23 | 2023-06-09 | 合肥国轩新材料科技有限公司 | Preparation method of high-pressure compact composite graphite and lithium ion battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118263401A (en) * | 2024-05-30 | 2024-06-28 | 宁德时代新能源科技股份有限公司 | Battery, preparation method thereof and electricity utilization device |
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