CN116281994A - Graphite negative electrode material, preparation method thereof and lithium ion battery - Google Patents
Graphite negative electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN116281994A CN116281994A CN202310267172.4A CN202310267172A CN116281994A CN 116281994 A CN116281994 A CN 116281994A CN 202310267172 A CN202310267172 A CN 202310267172A CN 116281994 A CN116281994 A CN 116281994A
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- copper
- graphite anode
- anode material
- coke
- containing complex
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 58
- 239000010439 graphite Substances 0.000 title claims abstract description 58
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007773 negative electrode material Substances 0.000 title description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000010405 anode material Substances 0.000 claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 claims abstract description 37
- 239000010949 copper Substances 0.000 claims abstract description 37
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 238000005087 graphitization Methods 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000000571 coke Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims description 53
- 238000002156 mixing Methods 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 22
- 239000011331 needle coke Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000003208 petroleum Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000010426 asphalt Substances 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- -1 for example Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 6
- 238000005056 compaction Methods 0.000 abstract description 6
- 238000003837 high-temperature calcination Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 239000008187 granular material Substances 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000004927 fusion Effects 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000007600 charging Methods 0.000 description 5
- 229910021383 artificial graphite Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses a graphite anode material, a preparation method thereof and a lithium ion battery. The preparation method of the graphite anode material comprises the following steps: calcining the mixture of the coke raw material and the copper-containing complex to prepare carbonized powder; then carrying out heat treatment and graphitization to prepare a graphite anode material; wherein the dosage of the copper-containing complex is 2-6%, and the percentage refers to the mass percentage of the copper-containing complex in the mixture. According to the invention, the copper-containing complex is added to modify the focus raw material, so that the prepared graphite anode material has good processability; the prepared pole piece has small rebound and high compaction density; the lithium ion battery prepared by the graphite cathode material has the performance of high energy density and high-rate discharge.
Description
Technical Field
The invention relates to a graphite anode material, a preparation method thereof and a lithium ion battery.
Background
One of the key technologies of lithium ion batteries is the selection and research of anode materials, and the quality of the anode materials directly influences the electrochemical performance of the batteries. Currently, carbon materials have become a commercial lithium ion battery negative electrode material; the artificial graphite has the advantages of high structural stability, excellent lithium intercalation performance, long cycle life, good pole piece processability and the like, is widely confirmed and used in the industry, but the compaction density and the energy density of the artificial graphite still cannot reach the level of natural graphite.
With miniaturization and high performance of electronic products, demands of the market for high energy density of lithium ion batteries are continuously increasing. Although the preparation technology of the current commercial lithium ion battery cathode material is mature, the requirements on energy density and fast charge are more and more severe due to the gradual improvement of the requirements, and the current charge-discharge multiplying power and energy density of graphite are difficult to meet the market demands. In order to improve the charge-discharge multiplying power, some manufacturers carry out modification treatment on the artificial graphite, for example, the carbon microspheres and the artificial graphite single particles are granulated and graphitized by Chinese patent CN201711333907.X, so that a high-capacity high-multiplying power composite graphite anode material is prepared; however, the charging rate can only reach 1-2C, the charging rate is still low, and the use requirement of higher rate is difficult to meet. In order to improve the energy density, some manufacturers adopt a mode of mixing a single-particle graphitized material and a secondary-particle graphitized material, for example, chinese patent CN201910987301.0 mixes the single-particle graphitized material and the secondary-particle graphitized material to obtain a single-particle and secondary-particle mixed high-energy-density graphite negative electrode material, but the capacity is only below 358mAh/g, and the requirement of high energy density cannot be met.
Disclosure of Invention
The invention aims to solve the technical problem that the graphite anode material in the prior art is difficult to simultaneously meet high-energy density and high-rate discharge, and provides a graphite anode material, a preparation method thereof and a lithium ion battery. According to the invention, the copper-containing complex is added to modify the focus raw material, so that the prepared graphite anode material has good processability; the prepared pole piece has small rebound and high compaction density; the lithium ion battery prepared by the graphite cathode material has the performance of high energy density and high-rate discharge.
The invention solves the technical problems through the following technical proposal.
The invention provides a preparation method of a graphite anode material, which comprises the following steps: calcining the mixture of the coke raw material and the copper-containing complex to prepare carbonized powder; then carrying out heat treatment and graphitization to prepare a graphite anode material;
wherein the dosage of the copper-containing complex is 2-6%, and the percentage refers to the mass percentage of the copper-containing complex in the mixture.
In the present invention, the types of the coke raw materials may be one or more of petroleum raw coke, petroleum raw needle coke, petroleum calcined raw coke, petroleum calcined needle coke, coal-based raw needle coke, coal-based calcined raw coke and coal-based calcined needle coke, for example, petroleum raw needle coke or coal-based raw needle coke.
In the present invention, the particle size of the coke-based raw material may be 4 to 10. Mu.m, preferably 6 to 8. Mu.m, for example 6 μm or 8. Mu.m.
In the present invention, the copper-containing complex may be an organic copper-containing complex such as EDTA chelated copper or copper tartrate.
In the present invention, the copper-containing complex is preferably used in an amount of 2 to 3%, for example 2% or 3%.
In the present invention, the mixture may be prepared by mixing the coke-based raw material and the copper-containing complex for 5 to 20 minutes. The mixing time is preferably 10min or 15min.
Wherein the mixing device may be a mechanoconfusion machine.
In the present invention, the temperature of the calcination may be 1000 to 1200 ℃, preferably 1100 to 1200 ℃, for example 1150 ℃ or 1200 ℃.
In the present invention, the calcination time may be 1 to 3 hours, for example, 1 hour or 2 hours.
In the present invention, the equipment for calcination may be conventional in the art, such as a carbonization kiln.
In the present invention, the calcination may be performed under an inert atmosphere. The inert atmosphere is not limited to inert gas, and may include nitrogen. The inert atmosphere may be nitrogen or helium.
In the present invention, the heat treatment is preferably preceded by an operation of mixing the carbonized powder material and the binder.
The binder may be of a type conventional in the art, such as asphalt.
Wherein the amount of the binder is preferably 6 to 10%, for example 6% or 10%, by mass% of the binder in the total mass.
In the present invention, the temperature of the heat treatment may be conventional in the art, preferably 300 to 700 ℃, for example 400 ℃.
In the present invention, the time of the heat treatment may be 0.75 to 1.5 hours, for example, 1 hour.
In the present invention, the graphitization temperature may be conventional in the art, preferably 3000 to 3200 ℃, for example 3100 ℃ or 3200 ℃.
In the present invention, the graphitization time may be conventional in the art, preferably 20 to 50 hours, for example 40 hours or 45 hours.
In the invention, the copper-containing complex is used as a pore-forming agent in the graphitization process after the process of calcination and heat treatment, so that the electron transmission rate is improved, the electrochemical performance is further improved, and finally the copper-containing complex volatilizes in the graphitization process. If an inorganic copper raw material is adopted, the combination of the inorganic copper raw material and a coke raw material is poor, the modification and catalysis effects are reduced, and finally the product performance is influenced.
In the invention, the graphitization can also comprise sieving operation.
In the invention, the particle diameter D of the graphite anode material v 50 may be 13 to 19 μm, for example 14 μm, 15 μm, or 16 μm.
The invention also provides a graphite anode material which is prepared by the preparation method.
The invention also provides a lithium ion battery, which comprises the graphite anode material.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
according to the invention, the copper-containing complex is added to modify the focus raw material, so that the prepared graphite anode material has higher energy density when being applied to a lithium ion battery, and simultaneously, the high-rate charge and discharge performance is considered. The preparation method has the advantages of simple process, convenient operation and less production equipment, thereby further reducing the cost, being convenient for popularization and application and being suitable for large-scale production.
The graphite anode material of the invention has good processability and high compaction density which can reach 1.9g/cm 3 The above; the prepared pole piece has small rebound, and the rebound rate is less than 10%. The first discharge capacity of the lithium ion battery prepared by the graphite anode material is more than 360 mAh/g; the rate performance is excellent, the charge and discharge of 3C-5C can be realized, the 3C capacity retention rate can reach more than 95%, and the 5C capacity retention rate can reach more than 85%.
Drawings
Fig. 1 is an SEM image of the graphite anode material prepared in example 2.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
In the following examples and comparative examples, copper chelated with petroleum needle coke EDTA and copper tartrate are commercially available.
Example 1
(1) Mixing material
Adding petroleum raw needle coke crushed to a particle size of 6 mu m and EDTA chelated copper into a mechanical fusion machine according to a mass ratio of 100:2, and treating for 10min to obtain a mixture material;
(2) High temperature calcination
Placing the mixture material obtained in the step (1) into a crucible, and placing the crucible into a carbonization kiln for calcination under the protection of nitrogen, wherein the calcination temperature is 1150 ℃ and the calcination time is 1h, so as to obtain carbonized powder;
(3) Mixing material
Mixing the carbonized powder material after high-temperature calcination with asphalt in a mixer according to a ratio of 100:8 to obtain a mixed material;
(4) Low temperature heat treatment
Loading the mixture material obtained in the step (3) into a reaction kettle for granulation, wherein the temperature is 400 ℃, and the time is 1h, so that graphite granulating materials are obtained;
(5) Graphitization of
Placing the graphite granules obtained in the step (4) into a graphitizing furnace for high-temperature graphitizing treatment at 3200 ℃ for 40h, and sieving to obtain the particle size D v 50 is 14 mu m, and the high-energy density and high-fast-charging graphite cathode material is obtained.
Example 2
(1) Mixing material
Adding petroleum raw needle coke crushed to 8 mu m in granularity and EDTA chelated copper into a mechanical fusion machine according to the mass ratio of 100:3, and treating for 15min to obtain a mixture material;
(2) High temperature calcination
Placing the mixture material obtained in the step (1) into a crucible, and placing the crucible into a carbonization kiln for calcination under the protection of nitrogen, wherein the calcination temperature is 1200 ℃ and the calcination time is 2 hours, so as to obtain carbonized powder;
(3) Mixing material
Mixing the carbonized powder material after high-temperature calcination with asphalt in a mixer according to a ratio of 100:6 to obtain a mixed material;
(4) Low temperature heat treatment
Loading the mixture material obtained in the step (3) into a reaction kettle for granulation, wherein the temperature is 400 ℃ and the time is 1.5h, so as to obtain graphite granules;
(5) Graphitization of
Placing the graphite granules obtained in the step (4) into a graphitization furnace to perform high-temperature graphitization treatment at 3100 ℃ for 45 hours, and sieving to obtain particle size D v 50 is 16 mu m, and the high energy density and high fast charge graphite cathode material is obtained, and an SEM image is shown in figure 1.
Example 3
(1) Mixing material
Adding petroleum raw needle coke crushed to 8 mu m in granularity and copper tartrate into a mechanical fusion machine according to the mass ratio of 100:3 for processing for 15min to obtain a mixture material;
(2) High temperature calcination
Placing the mixture material obtained in the step (1) into a crucible, and placing the crucible into a carbonization kiln for calcination under the protection of nitrogen, wherein the calcination temperature is 1200 ℃ and the calcination time is 2 hours, so as to obtain carbonized powder;
(3) Mixing material
Mixing the carbonized powder material after high-temperature calcination with asphalt in a mixer according to a ratio of 100:6 to obtain a mixed material;
(4) Low temperature heat treatment
Loading the mixture material obtained in the step (3) into a reaction kettle for granulation, wherein the temperature is 400 ℃ and the time is 1.5h, so as to obtain graphite granules;
(5) Graphitization of
Placing the graphite granules obtained in the step (4) into a graphitization furnace to perform high-temperature graphitization treatment at 3100 ℃ for 45 hours, and sieving to obtain particle size D v 50 is 15 mu m, and the high-energy density and high-fast-charging graphite cathode material is obtained.
Comparative example 1 (copper-containing Complex addition too little)
(1) Mixing material
Adding petroleum raw needle coke crushed to a particle size of 6 mu m and EDTA chelated copper into a mechanical fusion machine according to a mass ratio of 100:0.5, and treating for 10min to obtain a mixture material;
(2) High temperature calcination
Placing the mixture material obtained in the step (1) into a crucible, and placing the crucible into a carbonization kiln for calcination under the protection of nitrogen, wherein the calcination temperature is 1150 ℃ and the calcination time is 1h, so as to obtain carbonized powder;
(3) Mixing material
Mixing the carbonized powder material after high-temperature calcination with asphalt in a mixer according to a ratio of 100:8 to obtain a mixed material;
(4) Low temperature heat treatment
Loading the mixture material obtained in the step (3) into a reaction kettle for granulation, wherein the temperature is 400 ℃, and the time is 1h, so that graphite granulating materials are obtained;
(5) Graphitization of
Placing the graphite granules obtained in the step (4) into a graphitizing furnace for high-temperature graphitizing treatment at 3200 ℃ for 40h, and sieving to obtain the particle size D v The energy density and the quick charge performance of the obtained graphite anode material are poor, wherein 50 is 11 mu m.
Comparative example 2 (copper-containing Complex in too much amount)
(1) Mixing material
Adding petroleum raw needle coke crushed to a particle size of 6 mu m and EDTA chelated copper into a mechanical fusion machine according to a mass ratio of 100:10, and treating for 10min to obtain a mixture material;
(2) High temperature calcination
Placing the mixture material obtained in the step (1) into a crucible, and placing the crucible into a carbonization kiln for calcination under the protection of nitrogen, wherein the calcination temperature is 1150 ℃ and the calcination time is 1h, so as to obtain carbonized powder;
(3) Mixing material
Mixing the carbonized powder material after high-temperature calcination with asphalt in a mixer according to a ratio of 100:8 to obtain a mixed material;
(4) Low temperature heat treatment
Loading the mixture material obtained in the step (3) into a reaction kettle for granulation, wherein the temperature is 400 ℃, and the time is 1h, so that graphite granulating materials are obtained;
(5) Graphitization of
Placing the graphite granules obtained in the step (4) into a graphitizing furnace for high-temperature graphitizing treatment at 3200 ℃ for 40h, and sieving to obtain the particle size D v The energy density and the quick charge performance of the obtained graphite anode material are poor, wherein 50 is 13 mu m.
Comparative example 3 (addition of inorganic copper (CuSO) 4 ))
(1) Mixing material
Pulverizing needle Jiao Danyou raw needle coke with particle diameter of 6 μm and CuSO 4 Adding the mixture into a mechanical fusion machine according to the mass ratio of 100:2 for processing for 10min to obtain a mixture material;
(2) High temperature calcination
Placing the mixture material obtained in the step (1) into a crucible, and placing the crucible into a carbonization kiln for calcination under the protection of nitrogen, wherein the calcination temperature is 1150 ℃ and the calcination time is 1h, so as to obtain carbonized powder;
(3) Mixing material
Mixing the carbonized powder material after high-temperature calcination with asphalt in a mixer according to a ratio of 100:8 to obtain a mixed material;
(4) Low temperature heat treatment
Loading the mixture material obtained in the step (3) into a reaction kettle for granulation, wherein the temperature is 400 ℃, and the time is 1h, so that graphite granulating materials are obtained;
(5) Graphitization of
Placing the graphite granules obtained in the step (4) into a graphitizing furnace for high-temperature graphitizing treatment at 3200 ℃ for 40h, and sieving to obtain the particle size D v 50 is 12 mu m, and the obtained graphite anode material has poor energy density and quick charge performance.
Effect examples
Preparation of simulated button cell:
the graphite anode materials, the conductive carbon black SP, the sodium carboxymethylcellulose CMC and the styrene butadiene rubber SBR which are prepared in examples 1-3 and comparative examples 1-3 are respectively weighed according to the mass ratio of 94.5:1.5:1.5:1.5:1.5, uniformly stirred in water to prepare anode slurry, and uniformly coated on a copper foil by using a coater to prepare a pole piece. Placing the coated pole piece into a vacuum drying oven with the temperature of 110 ℃ for vacuum drying for 4 hours, and then pressing the pole piece to prepare a negative electrode; the simulated button cell assembly was performed in an argon filled German Braun glove box with an electrolyte of 1MLiPF 6 +ec: EMC: dmc=1:1:1 (volume ratio), metallic lithium flakes are counter electrodes.
1. Particle size and compacted density:
particle size testing: referring to GB/T19077-2016, the particle size of the graphite anode material was tested using a Mastersizer 3000 laser particle size analyzer, inc. of Markov instruments, UK.
Compaction density testing: testing the compacted density of the modified graphite material by adopting an FT-100F powder automatic compacted density meter; the graphite negative electrode material was pressed twice during the test.
2. Pole piece rebound rate:
rebound rate test: firstly, testing the average thickness of a pole piece to be D1 by adopting a thickness gauge, then placing the pole piece in a vacuum drying oven at 80 ℃ for drying for 48 hours, testing the thickness of the pole piece to be D2, and calculating according to the following formula: rebound rate= (D2-D1) ×100%/D1.
3. Electrochemical Properties
Gram capacity for first discharge: the prepared simulated button cell is subjected to electrochemical performance test on an ArbinBT2000 cell tester in the United states, and the test conditions are as follows: according to the charge and discharge of 0.1C constant current, the charge and discharge voltage range is as follows: 0.005-1.0V, the gram capacity of the first discharge is tested according to the conventional test method in the art.
Charge retention rate test: the prepared simulated button cell is subjected to electrochemical performance test on an ArbinBT2000 cell tester in the United states, and the test conditions are as follows: according to the constant current charging and discharging of 3C or 5C, the charging and discharging voltage range is as follows: 0.005 to 1.0V, and the charge retention rate is calculated from "charge retention rate=3c or 5C discharge capacity/first discharge capacity", according to a test method conventional in the art.
The graphite anode materials prepared in examples 1 to 3 and comparative examples 1 to 2 were tested, and the test results are shown in table 1.
TABLE 1
As can be seen from the comparison of examples 1 to 3 and comparative examples 1 to 3, if the amount of the copper-containing complex is too small or too large, or the copper-containing complex is changed into inorganic copper, the compaction density of the prepared pole piece is low, the rebound rate of the pole piece is greatly increased, and the initial discharge gram capacity and the charge retention rate of the assembled lithium ion battery are obviously reduced.
Claims (10)
1. The preparation method of the graphite anode material is characterized by comprising the following steps of: calcining the mixture of the coke raw material and the copper-containing complex to prepare carbonized powder; then carrying out heat treatment and graphitization to prepare a graphite anode material;
wherein the dosage of the copper-containing complex is 2-6%, and the percentage refers to the mass percentage of the copper-containing complex in the mixture.
2. The method for preparing a graphite anode material according to claim 1, wherein the type of the coke raw material is one or more of petroleum raw coke, petroleum raw needle coke, petroleum calcined raw coke, petroleum calcined needle coke, coal-based raw needle coke, coal-based calcined raw needle coke and coal-based calcined needle coke, for example, petroleum raw needle coke or coal-based raw needle coke;
and/or the particle size of the coke-based raw material is 4 to 10 μm, preferably 6 to 8 μm, for example 6 μm or 8 μm;
and/or the copper-containing complex is of the type that is an organic copper-containing complex, such as EDTA chelated copper or copper tartrate;
and/or the copper-containing complex is used in an amount of 2 to 3%, for example 2% or 3%.
3. The method for producing a graphite anode material according to claim 1, wherein the mixture is produced by mixing the coke-based raw material and the copper-containing complex for 5 to 20 minutes; the mixing time is preferably 10min or 15min.
4. The method of preparing a graphite anode material according to claim 1, wherein the calcination temperature is 1000-1200 ℃, preferably 1100-1200 ℃, such as 1150 ℃ or 1200 ℃;
and/or the calcination time is 1 to 3 hours, for example 1 hour or 2 hours;
and/or, the calcining is performed under an inert atmosphere; the inert atmosphere is preferably nitrogen or helium.
5. The method for preparing a graphite anode material according to claim 1, further comprising an operation of mixing the carbonized powder material with a binder before the heat treatment.
6. The method for preparing a graphite anode material according to claim 5, wherein the binder is asphalt;
and/or the binder is used in an amount of 6 to 10%, for example 6% or 10%, by mass% of the total mass.
7. The method of preparing a graphite anode material according to claim 1, wherein the temperature of the heat treatment is 300-700 ℃, such as 400 ℃;
and/or the heat treatment is for a period of 0.75 to 1.5 hours, for example 1 hour.
8. The method of preparing a graphite anode material according to claim 1, wherein the graphitization temperature is 3000-3200 ℃, such as 3100 ℃ or 3200 ℃;
and/or the graphitization time is 20 to 50 hours, for example 40 hours or 45 hours;
and/or, the graphitization further comprises sieving operation;
and/or the particle diameter D of the graphite anode material v 50 is 13 to 19 μm, for example 14 μm, 15 μm, or 16 μm.
9. A graphite anode material, characterized in that it is produced by the production method as claimed in claims 1 to 8.
10. A lithium ion battery comprising the graphite anode material of claim 9.
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