CN115536019B - Artificial graphite material, preparation thereof and application thereof in lithium secondary battery - Google Patents
Artificial graphite material, preparation thereof and application thereof in lithium secondary battery Download PDFInfo
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- CN115536019B CN115536019B CN202211201843.9A CN202211201843A CN115536019B CN 115536019 B CN115536019 B CN 115536019B CN 202211201843 A CN202211201843 A CN 202211201843A CN 115536019 B CN115536019 B CN 115536019B
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- 229910021383 artificial graphite Inorganic materials 0.000 title claims abstract description 53
- 239000007770 graphite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 title claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 14
- 239000000571 coke Substances 0.000 claims abstract description 156
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000012986 modification Methods 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 229910021384 soft carbon Inorganic materials 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 39
- 239000010426 asphalt Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000009818 secondary granulation Methods 0.000 claims description 9
- 239000002006 petroleum coke Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011331 needle coke Substances 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000009656 pre-carbonization Methods 0.000 claims description 5
- 239000011163 secondary particle Substances 0.000 claims description 5
- 238000005087 graphitization Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 6
- 239000000463 material Substances 0.000 abstract description 18
- 229910002804 graphite Inorganic materials 0.000 abstract description 6
- 239000010439 graphite Substances 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 description 63
- 230000014759 maintenance of location Effects 0.000 description 42
- 239000000843 powder Substances 0.000 description 34
- 238000001816 cooling Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000010405 anode material Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000007493 shaping process Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000011294 coal tar pitch Substances 0.000 description 3
- 239000002010 green coke Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002391 graphite-based active material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
-
- 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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- 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of graphite cathodes, and particularly relates to a preparation method of an artificial graphite material, which is used for obtaining coke A, coke B and coke C; the coke A is raw coke; the coke B is a product obtained by heat treatment of the coke A at 300-400 ℃; the coke C is a product of thermal modification of the coke A at 800-1000 ℃; mixing the coke A, the coke B, the coke C and a soft carbon source, and granulating for the second time to obtain a precursor A; pre-carbonizing the precursor A, coating a carbon source, and graphitizing and roasting to obtain the artificial graphite material. The preparation method disclosed by the invention can synergistically improve the electrochemical performance of the material, and particularly can synchronously improve the capacity and the multiplying power performance of the material and the cycling stability at low temperature.
Description
Technical Field
The invention belongs to the field of battery materials, and particularly relates to the field of graphite anode materials.
Background
The lithium ion battery has been widely used in the fields of consumer electronics, new energy automobiles and large-scale energy storage due to the advantages of high working voltage, high energy density, long cycle life and the like. The negative electrode material is one of four key materials of the lithium ion battery, and is mainly divided into two types of carbon materials and non-carbon materials, and graphite in the carbon materials can be specifically divided into natural graphite and artificial graphite. The natural graphite has the advantages of lower cost and high specific capacity, the artificial graphite has more excellent performance in cycle performance, safety performance and charge-discharge multiplying power, and the raw materials are widely available, the technology and industry are matched and mature, and the artificial graphite is the main stream of the current lithium ion battery cathode material.
The raw materials of the artificial graphite mainly comprise petroleum coke and needle coke, and single-particle anode materials can be obtained through the procedures of crushing, grading, graphitizing and the like, and have higher specific capacity and good cycle performance, but due to different orientation degrees of single particles in all directions, certain defects still exist in the electrochemical performance, such as low initial coulomb efficiency and poor multiplying power performance, which are unfavorable for industrial application. In the prior art, the problem of single particles is solved by adopting secondary granulation, and the performance of the anode material is improved. The secondary granulation process is to crush the coke into small-particle primary particles, use asphalt as a binder, carry out secondary granulation in a reaction kettle to obtain target particle size, and then carry out graphitization, screening and other processes to obtain the secondary particle anode material consisting of the primary particles. The secondary granulation process can improve the compaction density and the processability of the material, increase the channels for inserting and extracting lithium ions in the particles, solve the problem of anisotropy of single-particle materials, and is beneficial to obtaining the negative electrode material with high first coulomb efficiency and high rate performance. However, the secondary granulation process has high complexity and great control difficulty, and secondary particles are easily depolymerized in a long-cycle process to affect the cycle life, so that the preparation process of the secondary particles needs to be improved to improve the comprehensive electrochemical performance of the anode material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of an artificial graphite material, which aims to prepare the artificial graphite material with high capacity and high multiplying power and excellent cycle characteristics.
The second object of the invention is to provide the artificial graphite material prepared by the preparation method.
The third object of the invention is to provide the application of the artificial graphite material prepared by the preparation method in the lithium secondary battery.
A fourth object of the present invention is to provide a lithium secondary battery including the artificial graphite material prepared by the preparation method, and a negative electrode material thereof.
The preparation method of the artificial graphite material comprises the following steps:
step (1):
obtaining coke A, coke B and coke C;
the coke A is raw coke;
the coke B is a product obtained by heat treatment of the coke A at 300-400 ℃;
the coke C is a product of thermal modification of the coke A at 800-1000 ℃;
step (2):
mixing the coke A, the coke B, the coke C and a soft carbon source, and granulating for the second time to obtain a precursor A;
step (3):
pre-carbonizing the precursor A, coating a carbon source, and graphitizing and roasting to obtain the artificial graphite material.
The invention innovatively adopts the combination of the coke B and the coke C which are modified at a special temperature and further combines with the coke A, can realize the synergy, can accidentally improve the suitability between particles and interfaces, reduce the impedance of the particles and the interfaces, and can also adapt to the storage and the intercalation-deintercalation of lithium ions and improve the electron and ion conduction network. The preparation method disclosed by the invention can synergistically improve the electrochemical performance of the material, and particularly can synchronously improve the capacity and the multiplying power performance of the material and the cycling stability at low temperature.
The coke A is at least one raw coke of petroleum coke and needle coke;
preferably, the D50 of the coke A is 6-20 μm, preferably 6-12 μm;
preferably, the volatile matter of the coke A is 8-25%, preferably 15-22%.
In the invention, the pretreatment mode and condition combination of the coke B and the coke C and further the combination of the coke A are key to synergistically improve the electrochemical performance of the prepared artificial graphite material.
In the invention, in the coke B, the heat treatment atmosphere is a protective atmosphere; the protective atmosphere is at least one of nitrogen and inert gas.
Preferably, the heat treatment is carried out for a period of time of 350 to 400 ℃, more preferably 350 to 360 ℃.
Preferably, the heat treatment time is 1 to 3 hours;
preferably, the coke A is prepared by quenching the hot coke A in an aqueous solution after heat treatment. The research of the invention also discovers that the coke A is innovatively subjected to heat treatment at the temperature and quenched in a water system, which is favorable for further improving the particle and level suitability of the coke B, the coke A and the coke C, reducing the impedance, improving the network and the path adapting to lithium ion transmission and improving the electrochemical performance of lithium batteries.
Preferably, the aqueous solution is water or an aqueous solution of a transition metal. The transition metal water solution is preferably water soluble salt water solution of iron, nickel, cobalt, molybdenum, tin, copper and vanadium.
Preferably, the D50 of the coke B is from 5 to 16. Mu.m. Preferably, D50 of coke B is 80-90% of D50 of coke A.
Preferably, in the coke C, the atmosphere in the thermal modification stage is C 1 ～C 4 At least one of alcohol, ammonia, oxygen, carbon dioxide, gaseous water.
In the invention, under the combination of the atmosphere and the temperature of the coke C pretreatment, the synergistic effect of coke A and coke C is further synergistically improved, the particle and level impedance is further reduced, the ion and battery transmission paths and networks are improved, and the electrochemical performance of the material is further synergistically improved.
Preferably, the temperature of the thermal modification is 900 to 950 ℃.
Preferably, the time of thermal modification is 2-4 hours;
preferably, the D50 of the coke C is 4-12 μm; the particle size is preferably 65 to 75% of the D50 of the coke A.
Preferably, the weight ratio of the coke A, the coke B and the coke C is 60-80: 10-20: 10 to 20, preferably 60 to 70: 15-20: 15-20.
According to the invention, under the combination of the pretreatment process and parameters of the coke B and the coke C, the coke B and the coke C are further synergistically combined with the coke A, so that the synergy can be realized, and on the basis, the capacity, multiplying power and other performances of the prepared material can be further synergistically improved by further matching with a two-stage coating process.
Preferably, the soft carbon source is at least one of petroleum asphalt or coal asphalt; the softening point is 95-250 ℃.
Preferably, the weight ratio of the total weight of the coke A, the coke B and the coke C to the soft carbon source is 100:1-5;
preferably, the secondary granulation is carried out at a temperature of 600 to 800 ℃;
preferably, the D50 particle size of the secondary granulation is 10 to 30. Mu.m, preferably 13 to 20. Mu.m;
preferably, the temperature of the pre-carbonization is 950-1250 ℃, preferably 1150-1200 ℃;
preferably, the pre-carbonization stage is carried out under an oxygen-free atmosphere, for example at least one of nitrogen, inert gases;
preferably, the pre-carbonization time is 1 to 3 hours.
Preferably, the carbon source is at least one of petroleum asphalt or coal asphalt;
preferably, the carbon source is pitch with a softening point of 65-90 ℃; preferably, the secondary particles are mixed in a carbon source in a liquid state, followed by cooling to obtain a carbon-coated precursor;
preferably, the graphitization temperature is 2800 to 3200 ℃.
Preferably, the graphitization time is 24 to 48 hours, preferably 30 to 40 hours.
The invention also provides the artificial graphite prepared by the preparation method.
The preparation method can endow the material with special microstructure and structural characteristics, and the special material prepared by the preparation method has excellent electrochemical performance.
The invention also provides an application of the artificial graphite prepared by the preparation method, which is used as a negative electrode active material for preparing a lithium secondary battery;
preferably, it is prepared as a negative electrode of a lithium secondary battery;
preferably, it is used to prepare a negative electrode material for a lithium secondary battery.
According to the invention, the artificial graphite material prepared by the preparation method can be prepared into a lithium secondary battery and a negative electrode material thereof based on the existing means.
The invention also provides a lithium secondary battery cathode which comprises the artificial graphite prepared by the preparation method.
The invention also provides a lithium secondary battery comprising the negative electrode.
The invention has the beneficial effects that:
the invention innovatively adopts the combination of the coke B and the coke C which are modified at a special temperature and further combines with the coke A, can realize the cooperation, can accidentally improve the suitability between particles and interfaces, reduce the impedance of the particles and the interfaces, improve the impedance, and can also adapt to the storage and the intercalation-deintercalation of lithium ions and improve the electron and ion conduction network. The preparation method disclosed by the invention can synergistically improve the electrochemical performance of the material, and particularly can synchronously improve the capacity, the multiplying power performance and the low-temperature cycle performance of the material.
In the invention, the coke B, the coke A and the coke C which are prepared by adopting a 300-400-water system quenching process are combined, so that the synergistic effect of combined treatment can be further improved unexpectedly. And/or will contain C 1 ～C 4 The coke C prepared by thermal modification under the atmosphere of alcohol, ammonia, oxygen, carbon dioxide and gaseous water, and the combination of the coke C, the coke B and the coke A can further realize a combined synergistic effect, and is beneficial to further improving the performance of the artificial graphite prepared in a combined way.
The technical scheme provided by the invention has the advantages of wide sources of raw materials and auxiliary materials, simple and convenient process and good industrial production benefit and practical application value.
Drawings
FIG. 1 is an SEM image of a graphite anode material prepared in example 1;
FIG. 2 is a graph of electrochemical data for the graphite anode material prepared in example 1;
Detailed Description
The invention is further illustrated below in connection with specific examples, which are not to be construed as limiting in any way.
The raw materials adopted in the examples and the comparative examples are coal-based needle Jiao Shengjiao, which is from Liaoning Anshan, and the volatile of the raw materials is 15%; or low sulfur petroleum coke green coke from Shandong sunshine, volatile component of 22% and sulfur content of 1.9%.
With the artificial graphite electrode (comprising artificial graphite active material (prepared in each case), conductive carbon black and PVDF, the weight ratio of F to Li is 90:5:5) is a working electrode, lithium metal is a negative electrode, and 1mol/L LiPF 6 The CR2025 button cell is assembled in a dry glove box filled with argon by taking an electrolyte solution and a PE-PP composite film as a diaphragm (volume ratio of 1:1:1), and the button cell charge and discharge detection is carried out at 0.25C and 2C respectively under the voltage interval of 0.001-1.5V at room temperature (25 ℃) and low temperature (-20 ℃).
Example 1
Step 1: the needle Jiao Shengjiao is used as raw material to prepare the following 3 kinds of needle coke powder:
powder 1 (coke a): needle Jiao Shengjiao is ground and shaped to a D50 of 8 μm and a volatile fraction of 15%;
powder 2 (coke B): needle Jiao Shengjiao (coke a) was calcined in a nitrogen atmosphere at 350 ℃ (labeled T1) for 2h, cooled with the oven and then milled and shaped to D50 of 7 μm;
powder 3 (coke C): needle Jiao Shengjiao (coke a) was calcined in a nitrogen atmosphere at 900 ℃ (labeled T2) for 2h, then milled and shaped to D50 of 6 μm;
step 2: the three powders are uniformly mixed with high-temperature coal tar pitch powder with granularity of 2 mu m and softening point of 120 ℃, and the mass ratio of the A/B/C powder is 60:20:20, the addition amount of the high-temperature asphalt is 3% of the total mass of the three powders; then placing the mixture into a vertical reaction kettle, granulating the mixture at 700 ℃ for 2 hours, and shaping the mixture to obtain the particle size D50 of 15 mu m;
step 3: the granulated powder is placed in a roller kiln and pre-carbonized for 2 hours in an oxygen-isolated environment (Ar) with the temperature of 1150 ℃ (marked as T3), so that the volatile matter is less than 1 percent;
step 4: melting medium-temperature petroleum asphalt with a softening point of 80 ℃ at 180 ℃, adding medium-temperature liquid asphalt with an amount of 3% of the amount of the powder into the powder under the condition of stirring, cooling, stirring and mixing for 1h, and cooling to room temperature after stirring and mixing are finished to obtain coke powder wrapped with asphalt;
step 5: and (3) placing the powder into an Acheson crucible furnace, and graphitizing for 36h at 3000 ℃ (marked as T4), thus obtaining the graphite anode material product.
The prepared artificial graphite material product is subjected to electrochemical performance test, wherein the first reversible capacity is 356mAh/g at 0.25C multiplying power, the first coulomb efficiency is 95.6%, the reversible capacity retention rate at 2C multiplying power is 95%, and the reversible capacity retention rate at-20 ℃ is 72%.
Example 2
The only difference compared to example 1 is that the manner of obtaining coke B is changed, specifically:
a first group: the temperature is 300 ℃;
second group: the temperature is 400 ℃;
third group: heat-preserving at 350 ℃ and then directly placing the heat-preserved material in normal-temperature pure water (the dosage is 10-15 ml/g) for quenching, and then drying to obtain modified coke B;
fourth group: heat-preserving at 350 ℃ and then directly placing in a normal-temperature 0.3M nickel sulfate aqueous solution (the dosage is 10-15 ml/g) for quenching while hot, and then drying to obtain modified coke B;
electrochemical performance was measured by the method of example 1, and the results were:
a first group: the first reversible capacity is 349mAh/g at 0.25C rate, the first coulomb efficiency is 93.8%, the reversible capacity retention rate is 92% at 2C rate, and the reversible capacity retention rate is 67% at-20 ℃.
Second group: the first reversible capacity is 352mAh/g at 0.25C, the first coulomb efficiency is 94.5%, the reversible capacity retention rate is 93% at 2C, and the reversible capacity retention rate is 70% at-20 ℃.
Third group: the first reversible capacity is 360mAh/g at 0.25C multiplying power, the first coulomb efficiency is 94.7%, the reversible capacity retention rate is 96% at 2C multiplying power, and the reversible capacity retention rate is 75% at-20 ℃.
Fourth group: the first reversible capacity is 362mAh/g at 0.25C rate, the first coulomb efficiency is 95.3%, the reversible capacity retention rate at 2C rate is 97%, and the reversible capacity retention rate at-20 ℃ is 79%.
Compared with the embodiment 1, the performance can be improved by adopting the thermal modification at 300-400 ℃, particularly the quenching treatment is carried out after the thermal treatment, which is favorable for further improving the electrochemical performance, particularly the low-temperature stability.
Example 3
The only difference compared to example 1 is that the way of obtaining coke C is changed, in particular:
a first group: the temperature of T2 is 800 ℃;
second group: setting the temperature of T2 to 1000 ℃;
third group: immersing the coke A in saturated ammonia water solution, and then carrying out heat preservation treatment in T2;
fourth group: heat-insulating the coke A in a mixed atmosphere containing ethanol-Ar in T2, wherein the content of ethanol is 5% by volume;
other operations and parameters were the same as in example 1, and electrochemical performance was measured by the method of example 1, with the results of:
a first group: at 0.25C multiplying power, the first reversible capacity is 343mAh/g, the first coulomb efficiency is 92.5%, the reversible capacity retention rate at 2C multiplying power is 90%, and the reversible capacity retention rate at-20 ℃ is 66%;
second group: the first reversible capacity is 350mAh/g under the 0.25C multiplying power, the first coulomb efficiency is 93.8%, the reversible capacity retention rate under the 2C multiplying power is 93%, and the reversible capacity retention rate under the minus 20 ℃ is 69%;
third group: at 0.25C multiplying power, the first reversible capacity is 361mAh/g, the first coulomb efficiency is 95.7%, the reversible capacity retention rate at 2C multiplying power is 95%, and the reversible capacity retention rate at-20 ℃ is 80%;
fourth group: the first reversible capacity is 358mAh/g under the 0.25C multiplying power, the first coulomb efficiency is 95.9%, the reversible capacity retention rate under the 2C multiplying power is 96%, and the reversible capacity retention rate under the minus 20 ℃ is 78%;
it is evident from examples 1 and 3 that the treatment of focus C helps to improve the properties of the prepared material in combination with focus B and focus A, in particular by performing the thermal modification treatment in a system comprising N and an alcohol, helps to further improve the combined synergy with other components, helps to further improve the properties of the prepared material, in particular the low temperature properties.
Example 4
The only difference compared with example 1 is that the mass ratio of the three powders of coke A, coke B and coke C is changed to 80:10:10, other operations and parameters are the same as in example 1.
Electrochemical performance was measured by the method of example 1, and the result was: the first reversible capacity is 346mAh/g at 0.25C rate, the first coulomb efficiency is 93.2%, the reversible capacity retention rate at 2C rate is 92%, and the reversible capacity retention rate at-20 ℃ is 69%.
Example 5
Step 1: the needle Jiao Shengjiao is used as raw material to prepare the following 3 kinds of needle coke powder:
powder 1 (coke a): needle Jiao Shengjiao is ground and shaped to a D50 of 12 μm and a volatile fraction of 15%;
powder 2 (coke B): calcining needle Jiao Shengjiao (coke A) in nitrogen atmosphere at 350deg.C for 3 hr, cooling with furnace, pulverizing, and shaping to D50 of 10 μm;
powder 3 (coke C): needle Jiao Shengjiao (coke A) was calcined at 900℃for 3h under nitrogen atmosphere, then milled and shaped to a D50 of 8. Mu.m;
step 2: uniformly mixing the three kinds of powder with high-temperature coal tar pitch powder with granularity of 3 mu m and softening point of 150 ℃, wherein the mass ratio of the three kinds of powder is 60:20:20, the addition amount of the high-temperature asphalt is 5% of the total mass of the three powders; then placing the mixture into a vertical reaction kettle, granulating the mixture at 800 ℃ for 1 hour, and shaping the mixture to obtain the particle size D50 of 20 mu m;
step 3: the granulated powder is placed in a roller kiln and pre-carbonized in an oxygen-isolated environment (Ar) at 1250 ℃ for 2 hours, so that the volatile matters are less than 1 percent;
step 4: melting medium-temperature petroleum asphalt with a softening point of 90 ℃ at 200 ℃, adding medium-temperature liquid asphalt with an amount of 5% of the amount of the powder into the powder under the condition of stirring, cooling, stirring and mixing for 2 hours, and cooling to room temperature after stirring and mixing are finished to obtain coke powder wrapped with asphalt;
step 5: and (3) placing the powder into an Acheson crucible furnace, and graphitizing at 3200 ℃ for 30 hours to obtain the product.
Electrochemical performance was measured by the method of example 1, and the result was: the first reversible capacity is 348mAh/g at 0.25C rate, the first coulomb efficiency is 94.4%, the reversible capacity retention rate is 90% at 2C rate, and the reversible capacity retention rate is 68% at-20 ℃.
Example 6
Step 1: the following 3 needle coke powder bodies are prepared by taking petroleum coke raw coke as a raw material:
powder 1 (coke a): grinding and shaping the petroleum coke raw coke until the D50 is 6 mu m and the volatile component is 22%;
powder 2 (coke B): calcining petroleum coke green coke (coke A) in nitrogen atmosphere at 350 ℃ for 1h, cooling along with a furnace, grinding and shaping until the D50 is 5 mu m;
powder 3 (coke C): calcining petroleum coke green coke (coke A) at Ar and 900 ℃ for 1h, grinding and shaping until the D50 is 4 mu m;
step 2: uniformly mixing the three kinds of powder with high-temperature coal tar pitch powder with granularity of 1 mu m and softening point of 180 ℃, wherein the mass ratio of the three kinds of powder is 60:20:20, the addition amount of the high-temperature asphalt is 1% of the total mass of the three powders; then placing the mixture into a vertical reaction kettle, granulating the mixture at 600 ℃ for 1 hour, and shaping the mixture to obtain the particle size D50 of 13 mu m;
step 3: the granulated powder is placed in a roller kiln and pre-carbonized in an oxygen-isolated environment (Ar) at 950 ℃ for 2 hours, so that the volatile matters are less than 1 percent;
step 4: melting medium-temperature petroleum asphalt with a softening point of 65 ℃ at 150 ℃, adding medium-temperature liquid asphalt with an amount of 1% of the amount of the powder into the powder under the condition of stirring, cooling, stirring and mixing for 0.5h, and cooling to room temperature after the stirring and mixing are finished to obtain coke powder wrapped with asphalt;
step 5: and (3) placing the powder into an Acheson crucible furnace, and graphitizing at 2800 ℃ for 40 hours to obtain the product.
Electrochemical performance was measured by the method of example 1, and the result was: the first reversible capacity is 355mAh/g at 0.25C rate, the first coulomb efficiency is 94.8%, the reversible capacity retention rate is 93% at 2C rate, and the reversible capacity retention rate is 72% at-20 ℃.
Comparative example 1:
the only difference compared to example 1 is that the coke raw materials were changed as follows:
a first group: coke A alone in the same amounts as the total of coke A, coke B and coke C of example 1:
second group: coke B alone in the same amounts as the total of coke A, coke B and coke C of example 1:
third group: coke C alone in the same amount as the total amount of coke a, coke B and coke C of example 1;
fourth group: coke A+coke C, and the mass ratio is 60:40, the total amount being the same as the total amount of coke A, coke B and coke C of example 1;
fifth group: coke A+coke B, and the mass ratio is 60:40, the total amount being the same as the total amount of coke A, coke B and coke C of example 1;
electrochemical performance was measured by the method of example 1, and the results were:
a first group: the first reversible capacity is 320mAh/g at 0.25C rate, the first coulomb efficiency is 88.7%, the reversible capacity retention rate at 2C rate is 72%, and the reversible capacity retention rate at-20 ℃ is 52%.
Second group: the first reversible capacity is 316mAh/g at 0.25C rate, the first coulomb efficiency is 87.9%, the reversible capacity retention rate is 75% at 2C rate, and the reversible capacity retention rate is 56% at-20 ℃.
Third group: the first reversible capacity is 325mAh/g at 0.25C rate, the first coulomb efficiency is 90.1%, the reversible capacity retention rate at 2C rate is 76%, and the reversible capacity retention rate at-20 ℃ is 60%.
Fourth group: the first reversible capacity is 330mAh/g at 0.25C rate, the first coulomb efficiency is 91.2%, the reversible capacity retention rate at 2C rate is 80%, and the reversible capacity retention rate at-20 ℃ is 62%.
Fifth group: the first reversible capacity is 327mAh/g at 0.25C multiplying power, the first coulomb efficiency is 90.5%, the reversible capacity retention rate is 78% at 2C multiplying power, and the reversible capacity retention rate is 61% at-20 ℃.
Comparative example 2
The only difference compared to example 1 is that the modification temperature of coke B is changed by:
a: changing the temperature of the section T1 to 200 ℃; the other operations are the same as in example 1.
B: changing the temperature of the T1 section to 500 ℃; the other operations are the same as in example 1.
Electrochemical performance was measured by the method of example 1, and the results were:
a: the first reversible capacity is 334mAh/g at 0.25C rate, the first coulomb efficiency is 91.5%, the reversible capacity retention rate is 81% at 2C rate, and the reversible capacity retention rate is 64% at-20 ℃.
B: the first reversible capacity is 331mAh/g at 0.25C rate, the first coulomb efficiency is 91.3%, the reversible capacity retention rate is 82% at 2C rate, and the reversible capacity retention rate is 63% at-20 ℃.
Comparative example 3
The only difference compared to example 1 is that the modification temperature of coke C is changed by:
a: changing the temperature of the T2 section to 600 ℃; the other operations are the same as in example 1.
B: changing the temperature of the T2 section to 1200 ℃; the other operations are the same as in example 1.
Electrochemical performance was measured by the method of example 1, and the results were:
a: the first reversible capacity is 325mAh/g at 0.25C rate, the first coulomb efficiency is 90.8%, the reversible capacity retention rate at 2C rate is 79%, and the reversible capacity retention rate at-20 ℃ is 61%.
B: the first reversible capacity is 328mAh/g at 0.25C, the first coulomb efficiency is 91.1%, the reversible capacity retention rate is 80% at 2C, and the reversible capacity retention rate is 62% at-20 ℃.
Claims (29)
1. A preparation method of an artificial graphite material is characterized by comprising the following steps: the method comprises the following steps:
step (1):
obtaining coke A, coke B and coke C;
the coke A is raw coke;
the coke B is a product obtained by heat treatment of the coke A at 300-400 ℃;
the coke C is a product of thermal modification of the coke A at 800-1000 ℃;
step (2):
mixing the coke A, the coke B, the coke C and a soft carbon source, and granulating for the second time to obtain a precursor A; the weight ratio of the coke A to the coke B to the coke C is 60-80: 10-20: 10-20 parts of a base;
step (3):
pre-carbonizing the precursor A, coating a carbon source, and graphitizing and roasting to obtain the artificial graphite material.
2. The method for preparing the artificial graphite material according to claim 1, wherein: the coke A is at least one of petroleum coke and needle coke.
3. A method of preparing an artificial graphite material as claimed in claim 2, wherein: the D50 of the coke A is 6-20 mu m.
4. A method of preparing an artificial graphite material as claimed in claim 2, wherein: the volatile matter of the coke A is 8-25%.
5. The method for preparing the artificial graphite material according to claim 1, wherein: in the coke B, the atmosphere of heat treatment is a protective atmosphere.
6. The method for preparing the artificial graphite material according to claim 1, wherein: the heat treatment time is 1-3 h.
7. The method for preparing the artificial graphite material according to claim 1, wherein: and (3) after heat treatment, placing the obtained product in an aqueous solution while the obtained product is hot, and performing quenching treatment to obtain the coke B.
8. The method for preparing the artificial graphite material according to claim 7, wherein: the aqueous solution is water or transition metal aqueous solution.
9. The method for preparing the artificial graphite material according to claim 7, wherein: the D50 of the coke B is 5-16 μm.
10. The method of making an artificial graphite material as claimed in claim 9, wherein: the D50 of the coke B is 80-90% of the D50 of the coke A.
11. The method for preparing the artificial graphite material according to claim 1, wherein: in the coke C, the atmosphere of the thermal modification stage is C 1 ~C 4 At least one of alcohol, ammonia, oxygen, carbon dioxide, gaseous water.
12. The method of making an artificial graphite material as claimed in claim 11, wherein: the thermal modification time is 2-4 hours.
13. The method for preparing the artificial graphite material according to claim 1, wherein: the D50 of the coke C is 4-12 μm.
14. The method of making an artificial graphite material as claimed in claim 13, wherein: the particle size of the coke C is 65-75% of the D50 of the coke A.
15. The method for preparing the artificial graphite material according to claim 1, wherein: the weight ratio of the coke A to the coke B to the coke C is 60-70: 15-20: 15-20.
16. The method for preparing the artificial graphite material according to claim 1, wherein: the soft carbon source is at least one of petroleum asphalt or coal asphalt, and the softening point is 95-250 ℃.
17. The method for preparing the artificial graphite material according to claim 1, wherein: the weight ratio of the total weight of the coke A, the coke B and the coke C to the soft carbon source is 100:1-5.
18. The method for preparing the artificial graphite material according to claim 1, wherein: and carrying out secondary granulation at the temperature of 600-800 ℃.
19. The method for preparing the artificial graphite material according to claim 1, wherein: the D50 particle size of the secondary granulation is 10-30 mu m.
20. The method for preparing the artificial graphite material according to claim 1, wherein: the pre-carbonization temperature is 950-1250 ℃.
21. The method for preparing the artificial graphite material according to claim 1, wherein: the pre-carbonization stage is carried out in an oxygen-free atmosphere.
22. The method for preparing the artificial graphite material according to claim 1, wherein: the carbon source is at least one of petroleum asphalt or coal asphalt.
23. The method for preparing the artificial graphite material according to claim 1, wherein: the carbon source is asphalt with a softening point of 65-90 ℃.
24. The method for preparing the artificial graphite material according to claim 1, wherein: the secondary particles are mixed in a carbon source in a liquid state and then cooled to obtain a carbon-coated precursor.
25. The method for preparing the artificial graphite material according to claim 1, wherein: the graphitization temperature is 2800-3200 ℃.
26. An artificial graphite produced by the production process of any one of claims 1 to 25.
27. Use of the artificial graphite produced by the production method according to any one of claims 1 to 25 as a negative electrode active material for producing a lithium secondary battery.
28. A negative electrode for a lithium secondary battery, comprising the artificial graphite produced by the production method according to any one of claims 1 to 25.
29. A lithium secondary battery comprising the negative electrode of claim 28.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108328613A (en) * | 2017-12-15 | 2018-07-27 | 大同新成新材料股份有限公司 | A kind of method and negative material producing graphite cathode material using needle coke |
| CN108550850A (en) * | 2018-05-08 | 2018-09-18 | 中航锂电（洛阳）有限公司 | A kind of high power capacity high-pressure solid artificial plumbago negative pole material and preparation method thereof, lithium ion battery |
| WO2021217617A1 (en) * | 2020-04-30 | 2021-11-04 | 宁德时代新能源科技股份有限公司 | Negative electrode active material, manufacturing method therefor, secondary battery, and device comprising secondary battery |
| CN114538423A (en) * | 2022-03-15 | 2022-05-27 | 上海杉杉科技有限公司 | Artificial graphite material and preparation method and application thereof |
| CN114597361A (en) * | 2022-03-02 | 2022-06-07 | 广东东岛新能源股份有限公司 | Artificial graphite composite negative electrode material for lithium ion battery and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108328613A (en) * | 2017-12-15 | 2018-07-27 | 大同新成新材料股份有限公司 | A kind of method and negative material producing graphite cathode material using needle coke |
| CN108550850A (en) * | 2018-05-08 | 2018-09-18 | 中航锂电（洛阳）有限公司 | A kind of high power capacity high-pressure solid artificial plumbago negative pole material and preparation method thereof, lithium ion battery |
| WO2021217617A1 (en) * | 2020-04-30 | 2021-11-04 | 宁德时代新能源科技股份有限公司 | Negative electrode active material, manufacturing method therefor, secondary battery, and device comprising secondary battery |
| CN114597361A (en) * | 2022-03-02 | 2022-06-07 | 广东东岛新能源股份有限公司 | Artificial graphite composite negative electrode material for lithium ion battery and preparation method and application thereof |
| CN114538423A (en) * | 2022-03-15 | 2022-05-27 | 上海杉杉科技有限公司 | Artificial graphite material and preparation method and application thereof |
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