CN114933301B - Long-life artificial graphite negative electrode material for energy storage and preparation method and application thereof - Google Patents
Long-life artificial graphite negative electrode material for energy storage and preparation method and application thereof Download PDFInfo
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- CN114933301B CN114933301B CN202210552076.XA CN202210552076A CN114933301B CN 114933301 B CN114933301 B CN 114933301B CN 202210552076 A CN202210552076 A CN 202210552076A CN 114933301 B CN114933301 B CN 114933301B
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- 229910021383 artificial graphite Inorganic materials 0.000 title claims abstract description 41
- 238000004146 energy storage Methods 0.000 title claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000010405 anode material Substances 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000571 coke Substances 0.000 claims abstract description 14
- 238000007493 shaping process Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims description 45
- 239000010426 asphalt Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 26
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 24
- 229910002804 graphite Inorganic materials 0.000 claims description 24
- 239000010439 graphite Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 18
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- 238000005087 graphitization Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000009694 cold isostatic pressing Methods 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000002006 petroleum coke Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007770 graphite material Substances 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- 239000011335 coal coke Substances 0.000 claims description 3
- 239000006253 pitch coke Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000010298 pulverizing process Methods 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012719 thermal polymerization Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011331 needle coke Substances 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000001291 vacuum drying 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
- C01B32/205—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
-
- 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
Abstract
The invention provides a long-life artificial graphite negative electrode material for energy storage, a preparation method and application thereof; in the preparation method of the invention, firstly, the technologies of crushing, shaping and grading are adopted. Control of small particles in the isotropic focus (D 10 ) And large particles (D) 90 ) To prepare coke powder with narrow particle size distribution, and small particles (D 10 Not less than 2 μm) isotropic coke is favorable for improving the first charge and discharge efficiency of the artificial graphite anode material, and large particles (D) 90 And less than or equal to 12 mu m), the isotropic coke is beneficial to reducing the unidirectional mechanical stress field of the artificial graphite anode material in the circulation process, and can improve the circulation performance of the artificial graphite anode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a long-life artificial graphite cathode material for energy storage, and a preparation method and application thereof.
Background
Lithium ion secondary batteries (LIBs) as energy storage devices have been the focus of research in the energy storage field because of their advantages of high energy density, long cycle life, stable charge and discharge platforms, wide operating temperature ranges, environmental friendliness, and the like. The domestic carbon materials for manufacturing the lithium ion battery cathode material are mainly divided into two types, namely artificial graphite and natural graphite, wherein the natural graphite has low intercalation potential and excellent intercalation and deintercalation performance, and is a good lithium ion battery cathode material. However, the disadvantage is that the graphite layers are combined with weak intermolecular force, i.e. van der Waals force, and when charged, the layers are peeled off and form new surfaces along with the intercalation of solvated lithium ions, and the electrolyte is continuously reduced and decomposed on the newly formed surfaces to form new SEI films, so that a large amount of lithium ions are consumed, the first irreversible capacity loss is increased, and meanwhile, the volume expansion and shrinkage of graphite particles are caused by the intercalation and deintercalation of solvated lithium ions, so that the electrified network part among the particles is interrupted, and the cycle life is poor. Therefore, the prior art generally adopts needle coke as a raw material, and prepares the artificial graphite cathode through procedures such as crushing, granulating, graphitizing and the like, so that the cycle performance of the lithium ion battery can be remarkably improved. However, needle coke has a fibrous or needle-like texture, and particles have a large aspect ratio and are anisotropic, and a granulation step is required to improve isotropy in the preparation of a negative electrode material. In addition, needle coke is costly.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a long-life artificial graphite anode material for energy storage, and a preparation method and application thereof.
The invention provides a preparation method of an artificial graphite anode material, which comprises the following steps:
(1) Sequentially crushing, shaping and grading the isotropic coke to obtain micro powder 1;
(2) Kneading the micro powder 1 obtained in the step (1) with asphalt, and profiling to obtain graphite blocks;
(3) Scattering the graphite blocks obtained in the step (2), and then performing heat treatment at 350-500 ℃ to obtain micro powder 2;
(4) Graphitizing the micro powder 2 obtained in the step (3) at 2200-2400 ℃ to obtain graphite micro powder;
(5) Purifying the graphite micropowder obtained in the step (4) by using hydrofluoric acid aqueous solution, and washing and drying to obtain the artificial graphite anode material.
According to the invention, in the step (1), the isotropic coke is one or more of low sulfur petroleum coke, pitch coke, coal coke, metallurgical coke and the like.
According to the present invention, in the step (1), the apparatus used for the pulverization is not particularly limited, and apparatuses known in the art such as an impact pulverizer, a jet mill, a high-pressure pulverizer, or a bar-type mechanical pulverizer may be selected.
According to the present invention, in the step (1), the shaping equipment is not particularly limited, and equipment known in the art, such as a mechanical shaper or an airflow shaper, may be used.
According to the present invention, in the step (1), the apparatus used for the classification is not particularly limited, and an apparatus known in the art, such as an air classifier, may be used.
According to the present invention, in the step (1), the particle size of the fine powder 1 satisfies: d (D) 10 ≥2μm，6μm≤D 50 ≤8μm，D 90 ≤12μm。
According to the invention, in the step (2), the mass ratio of the micro powder 1 to the asphalt is 100 (8-20), such as 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, 100:15, 100:16, 100:17, 100:18, 100:19, 100:20.
According to the invention, in the step (2), the kneading is performed under rolling stirring, the micro powder 1 can be fully contacted with asphalt, particularly asphalt in a molten state or a softened state, the asphalt is coated on the surface of the micro powder 1, the kneading temperature is more than 10 ℃ higher than the softening point temperature of the asphalt, for example more than 20 ℃, and the kneading time is 30-120 min.
According to the invention, in the step (2), the asphalt is any one or a mixture of two of petroleum asphalt, coal tar asphalt and natural asphalt, the softening point of the asphalt is 60-90 ℃, and the quinoline insoluble content is less than or equal to 1%.
According to the invention, in step (2), the profiling is performed by cold isostatic pressing, the pressure is 80-300 MPa, preferably 100-250 MPa, and exemplary 100MPa, 150MPa, 200MPa, 250MPa, and the dwell time is 10-40 min.
According to the present invention, in the step (3), the apparatus used for the dispersion is not particularly limited, and any apparatus known in the art may be used, for example, selected from turbine-type dispersion machines and air-type dispersion machines.
According to the present invention, in the step (3), the particle size of the fine powder 2 satisfies: d (D) 10 ≥2μm，6μm≤D 50 ≤8μm，D 90 ≤12μm。
According to the present invention, in the step (3), the particle size of the fine powder 2 is 0.1 μm to 1 μm larger than the particle size of the fine powder 1.
According to the invention, in step (3), the heating rate of the heat treatment is 1-10 ℃/min, preferably 2-5 ℃/min, such as 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min or 7 ℃/min; the temperature of the heat treatment is 390 ℃ to 450 ℃, preferably 410 ℃ to 430 ℃, for example 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃ or 450 ℃; the heat treatment is carried out for a period of time of 1 to 10 hours, preferably 4 to 8 hours, for example 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours.
According to the present invention, in step (3), the heat treatment may convert the low carbon residue pitch into a high carbon residue mesophase pitch.
According to the present invention, in the step (4), the graphitization treatment is performed at a temperature of 2200 ℃, 2300 ℃, 2350 ℃ or 2400 ℃. Further, the graphitization treatment is for 2 to 10 hours, for example, 4 to 8 hours, and exemplary is 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours. Wherein, the graphitization treatment adopts a conventional graphitization processing furnace. The graphitization treatment is carried out at normal pressure.
According to the invention, in the step (5), the process of purifying hydrofluoric acid is as follows: placing the graphite micro powder obtained in the step (4) into a reaction kettle, adding hydrofluoric acid aqueous solution, heating the reaction kettle to 80-90 ℃, fully reacting for 2-12 h, and then carrying out solid-liquid separation; rinsing the obtained acid filter cake with deionized water, centrifuging until a neutral filter cake is obtained, and finally drying.
According to the invention, in the step (5), the mass concentration of the hydrofluoric acid aqueous solution is 5-10wt%.
The invention also provides the artificial graphite anode material prepared by the method.
According to the invention, the first reversible capacity of the artificial graphite anode material is 290-320 mAh/g, and is exemplified by 292.6mAh/g, 304.2mAh/g, 310.7mAh/g and 315.6mAh/g.
According to the invention, the first charge-discharge efficiency of the artificial graphite anode material is more than or equal to 88.6%, and is exemplified by 88.6%, 88.9%, 89.1% and 89.5%.
According to the invention, the capacity retention rate of the artificial graphite anode material at the normal temperature of 0.5C charge-discharge cycle of 3000 weeks is over 94 percent, and the exemplary capacity retention rate is 94.2 percent, 95.6 percent, 96.2 percent and 96.5 percent.
The invention also provides application of the artificial graphite material in a lithium ion battery, and the artificial graphite material is preferably used as a negative electrode material of a lithium ion high-end energy storage battery.
The invention has the beneficial effects that:
the invention provides a long-life artificial graphite negative electrode material for energy storage, a preparation method and application thereof; in the preparation method of the invention, firstly, the technologies of crushing, shaping and grading are adopted. Control of small particles in the isotropic focus (D 10 ) And large particles (D) 90 ) To prepare coke powder with narrow particle size distribution, and small particles (D 10 Not less than 2 μm) isotropic coke is favorable for improving the first charge and discharge efficiency of the artificial graphite anode material, and large particles (D) 90 And less than or equal to 12 mu m), the isotropic coke is beneficial to reducing the unidirectional mechanical stress field of the artificial graphite anode material in the circulation process, and can improve the circulation performance of the artificial graphite anode material.
And filling the low-softening-point asphalt into pores in the isotropic coke powder by adopting an isostatic pressing technology, and forming an asphalt coating layer on the surface of the low-softening-point asphalt. In the high-temperature heating polymerization reaction, the low-softening-point asphalt is converted into mesophase asphalt, so that the residual carbon quantity is improved, the internal pores of the isotropic coke powder can be quickly densified, a uniform and compact carbon coating layer can be formed on the surface of the isotropic coke powder, the specific surface area of the artificial graphite cathode material is reduced, and the first charge and discharge efficiency and the cycle performance of the battery are improved. Graphitization treatment is carried out at 2200-2400 ℃, the graphitization degree is controlled at 85-89%, the obtained artificial graphite layers have larger interlayer spacing, the graphite layers are difficult to peel off in the charge-discharge cycle process, and the cycle performance of the artificial graphite negative electrode material is improved.
The first reversible capacity of the artificial graphite anode material prepared by the method is 290-320 mAh/g, the first charge-discharge efficiency is more than or equal to 88.6%, the capacity retention rate of the artificial graphite anode material at room temperature of 0.5C charge-discharge cycle of 3000 weeks is more than or equal to 94%, and the artificial graphite anode material prepared by the method has high first charge-discharge efficiency and long service life, and can meet the requirements of the high-end energy storage field and the low-end lithium ion power battery.
The method adopts isotropic coke which is low-sulfur petroleum coke, asphalt coke, coal coke, metallurgical coke and the like as raw materials for producing the anode material of the lithium ion battery, thereby saving resources, reducing cost, having simple process flow and reducing energy consumption.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
Example 1
Pulverizing petroleum coke in impact pulverizer, shaping, and grading to obtain micropowder 1 (D) 10 ：2μm，D 50 6 μm, D 90 :9 μm); adding asphalt (softening point 70 ℃ and quinoline insoluble content 0.06%) and micro powder 1 into a kneader according to a mass ratio of 16:100, mixing for 100min at 95 ℃, then treating for 30min under 100MPa by using cold isostatic pressing equipment to obtain a block, and finally scattering the block by using an airflow scattering machine. Heating the scattered coke powder to 410 ℃ according to the heating rate of 5 ℃/min for thermal polymerization reaction for 10 hours, and cooling to room temperature to obtain micro powder 2; carrying out graphitization high-temperature (2200 ℃) treatment on the micro powder 2 for 8 hours, and cooling to room temperature to obtain graphite micro powder; finally, graphite micropowder and hydrofluoric acid water are mixedMixing the solutions (5 wt%) and placing the mixture into a reaction kettle, heating the reaction kettle to 90 ℃, fully reacting for 4 hours, and then carrying out solid-liquid separation; rinsing the obtained acid filter cake with deionized water, centrifuging until a neutral filter cake is obtained, and finally drying.
Example 2
Pulverizing pitch coke in impact pulverizer, shaping, and grading to obtain micropowder 1 (D) 10 ：3μm，D 50 7 μm, D 90 :10 μm); adding asphalt (softening point 75 ℃ and quinoline insoluble content 0.06%) and micro powder 1 into a kneader according to a mass ratio of 14:100, mixing for 80min at 100 ℃, then treating for 20min under 200MPa by using cold isostatic pressing equipment to obtain a block, and finally scattering the block by using an airflow scattering machine. Heating the scattered coke powder to 430 ℃ according to a heating rate of 5 ℃/min for thermal polymerization reaction for 7 hours, and cooling to room temperature to obtain micro powder 2; carrying out graphitization high-temperature (2300 ℃) treatment on the micro powder 2 for 6 hours, and cooling to room temperature to obtain graphite micro powder; finally, mixing graphite micropowder and hydrofluoric acid aqueous solution (7 wt%) and placing them into a reaction kettle, heating the reaction kettle to 80 deg.C, fully reacting for 8 hr, then making solid-liquid separation; rinsing the obtained acid filter cake with deionized water, centrifuging until a neutral filter cake is obtained, and finally drying.
Example 3
The char was pulverized in an impact pulverizer, and then shaped and classified to obtain fine powder 1 (D) 10 ：4μm，D 50 8 μm, D 90 :11 μm); adding asphalt (softening point 80 ℃ and quinoline insoluble content 0.06%) and micro powder 1 into a kneader according to a mass ratio of 12:100, mixing for 40min at 105 ℃, then treating for 100min by using cold isostatic pressing equipment under 100MPa to obtain a block, and finally scattering the block by using an airflow scattering machine. Heating the scattered coke powder to 430 ℃ according to a heating rate of 5 ℃/min for thermal polymerization reaction for 4 hours, and cooling to room temperature to obtain micro powder 2; graphitizing the micro powder 2 at high temperature (2400 ℃) for 4 hours, and cooling to room temperature to obtain graphite micro powder; finally, mixing graphite micropowder and hydrofluoric acid aqueous solution (8 wt%) and placing them into a reaction kettle, heating the reaction kettle to 80 deg.C, fully reacting for 10 hr, and making solid-liquid separation;rinsing the obtained acid filter cake with deionized water, centrifuging until a neutral filter cake is obtained, and finally drying.
Example 4
Pulverizing metallurgical coke in impact pulverizer, shaping, and grading to obtain micropowder 1 (D) 10 ：3.5μm，D 50 6 μm, D 90 :10 μm); adding asphalt (softening point 70 ℃ and quinoline insoluble content 0.06%) and graphite micropowder into a kneader according to a mass ratio of 10:100, mixing for 40min at 95 ℃, then treating for 30min under 100MPa by using cold isostatic pressing equipment to obtain a block, and finally scattering the block by using an airflow scattering machine. Heating the scattered coke powder to 410 ℃ according to the heating rate of 5 ℃/min for thermal polymerization reaction for 10 hours, and cooling to room temperature to obtain micro powder 2; graphitizing the micro powder 2 at high temperature (2400 ℃) for 8 hours, and cooling to room temperature to obtain graphite micro powder; finally, mixing graphite micropowder and hydrofluoric acid aqueous solution (9 wt%) and placing them into a reaction kettle, heating the reaction kettle to 85 deg.C, fully reacting for 10 hr, and making solid-liquid separation; rinsing the obtained acid filter cake with deionized water, centrifuging until a neutral filter cake is obtained, and finally drying.
Comparative example 1
Pulverizing petroleum coke in impact pulverizer, shaping, and grading to obtain micropowder 1 (D) 10 ：2μm，D 50 6 μm, D 90 :9 μm); adding asphalt (with a softening point of 70 ℃ and a quinoline insoluble content of 0.06%) and micro powder 1 into a kneader according to a mass ratio of 16:100, mixing for 100min at 95 ℃, then treating for 30min under 100MPa by using cold isostatic pressing equipment to obtain a block, and finally scattering the block by using an airflow scattering machine to obtain micro powder 2; and (3) carrying out graphitization high-temperature (2900 ℃) treatment on the micro powder 2 for 8 hours, and cooling to room temperature to obtain the artificial graphite anode material.
Comparative example 2
Pulverizing petroleum coke in impact pulverizer, shaping, and grading to obtain micropowder 1 (D) 10 ：2μm，D 50 6 μm, D 90 :9 μm); adding asphalt (softening point 70 ℃ C., quinoline insoluble content 0.06%) and micropowder 1 into the mixture according to a mass ratio of 16:100Mixing at 95deg.C for 100min, treating with cold isostatic pressing equipment under 100MPa for 30min to obtain block, and dispersing with air-flow type dispersing machine to obtain micropowder 2; carrying out graphitization high-temperature (2200 ℃) treatment on the micro powder 2 for 8 hours, and cooling to room temperature to obtain graphite micro powder; finally, mixing graphite micropowder and hydrofluoric acid aqueous solution (5 wt%) and placing them into a reaction kettle, heating the reaction kettle to 90 deg.C, fully reacting for 4 hr, and making solid-liquid separation; rinsing the obtained acid filter cake with deionized water, centrifuging until a neutral filter cake is obtained, and finally drying.
The physicochemical indexes of the artificial graphite anode materials of the above examples 1-4 and comparative examples 1-2 were tested as follows: the particle size distribution of the samples was tested using a laser particle sizer.
Electrochemical performance test
Half-electric test method: the artificial graphite anode materials prepared in examples 1 to 4 and comparative examples 1 to 2 were prepared by uniformly mixing conductive carbon black (SP) carboxymethylcellulose (CMC) Styrene Butadiene Rubber (SBR) =95:1:1.5:2.5 (mass ratio), coating the mixture on copper foil, and drying the coated electrode sheet in a vacuum drying oven at 120 ℃ for 12 hours. Simulated battery assembly was performed in an argon-protected Braun glove box with electrolyte 1M-LiPF 6 +EC: DEC: DMC (volume ratio is 1:1:1), metal lithium sheet is counter electrode, simulation battery test is carried out in a 5V, 10mA new Wei battery test cabinet, charging and discharging voltage is 0.01-1.5V, charging and discharging rate is 0.5C, and the first reversible capacity and first charging and discharging efficiency obtained by the test are shown in Table 1.
The full battery test method comprises the following steps: the artificial graphite anode materials prepared in examples 1-4 and comparative examples 1-2 were used as the anode, lithium iron phosphate was used as the cathode, and 1M-LiPF 6 +EC: DEC: DMC (volume ratio 1:1:1) solution as electrolyte to complete battery, charge and discharge at normal temperature at 0.5C, voltage range of 3.0-4.2V, and cycle properties obtained by the test are shown in Table 1.
TABLE 1 electrochemical Performance test results
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A method for preparing an artificial graphite anode material, the method comprising the steps of:
(1) Sequentially crushing, shaping and grading the isotropic coke to obtain micro powder 1;
(2) Kneading the micro powder 1 obtained in the step (1) with asphalt, and profiling to obtain graphite blocks;
(3) Scattering the graphite blocks obtained in the step (2), and then performing heat treatment at 390-450 ℃ to obtain micro powder 2;
(4) Graphitizing the micro powder 2 obtained in the step (3) at 2200-2400 ℃ to obtain graphite micro powder;
(5) Purifying the graphite micropowder obtained in the step (4) by using hydrofluoric acid aqueous solution, and washing and drying to obtain an artificial graphite negative electrode material;
in the step (1), the particle size of the micro powder 1 satisfies the following conditions: d (D) 10 ≥2μm，6μm≤D 50 ≤8μm，D 90 ≤12μm；
In the step (2), the mass ratio of the micro powder 1 to the asphalt is 100 (8-20);
in the step (2), cold isostatic pressing is adopted for molding, the pressure is 80MPa-300MPa, and the dwell time is 10min-40min;
in the step (3), the particle size of the fine powder 2 satisfies the following conditions: d (D) 10 ≥2μm，6μm≤D 50 ≤8μm，D 90 ≤12μm。
2. The method of claim 1, wherein in step (1), the isotropic coke is one or more of low sulfur petroleum coke, pitch coke, coal coke, metallurgical coke.
3. The production method according to claim 1, wherein in the step (2), the kneading is performed under rolling stirring, the kneading is performed at a temperature of 10 ℃ or higher than the softening point temperature of asphalt, and the kneading is performed for 30min to 120min;
and/or in the step (2), the asphalt is any one or a mixture of two of petroleum asphalt, coal tar asphalt and natural asphalt, the softening point of the asphalt is 60-90 ℃, and the content of quinoline insoluble matters is less than or equal to 1%.
4. The process according to claim 1, wherein in the step (3), the particle size of the fine powder 2 is 0.1 μm to 1 μm larger than the particle size of the fine powder 1.
5. The production method according to claim 1, wherein in the step (3), the heating rate of the heat treatment is 1 to 10 ℃/min; the heat treatment has a heat preservation time of 1-10 hours.
6. The production method according to claim 1, wherein in the step (4), the graphitization treatment is performed for a period of 2 to 10 hours.
7. The production method according to any one of claims 1 to 6, wherein in the step (5), the process of purifying hydrofluoric acid is: placing the graphite micro powder obtained in the step (4) into a reaction kettle, adding hydrofluoric acid aqueous solution, heating the reaction kettle to 80-90 ℃, fully reacting for 2-12 h, and then carrying out solid-liquid separation; rinsing the obtained acid filter cake with deionized water, centrifuging until a neutral filter cake is obtained, and finally drying.
8. An artificial graphite anode material prepared by the method of any one of claims 1 to 7.
9. The artificial graphite anode material of claim 8, wherein the first reversible capacity of the artificial graphite anode material is 290-320 mAh/g;
and/or the first charge-discharge efficiency of the artificial graphite anode material is more than or equal to 88.6%;
and/or the capacity retention rate of the artificial graphite anode material at 3000 weeks of 0.5C charge-discharge cycle under normal temperature is over 94 percent.
10. Use of the artificial graphite material of claim 8 or 9 in a lithium ion battery.
11. The use according to claim 10, wherein the artificial graphite material is used as a negative electrode material of a lithium ion high-end energy storage battery.
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