CN114572978B - Preparation method of high-magnification graphite anode material, anode material and lithium battery - Google Patents
Preparation method of high-magnification graphite anode material, anode material and lithium battery Download PDFInfo
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- CN114572978B CN114572978B CN202210260274.9A CN202210260274A CN114572978B CN 114572978 B CN114572978 B CN 114572978B CN 202210260274 A CN202210260274 A CN 202210260274A CN 114572978 B CN114572978 B CN 114572978B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000010439 graphite Substances 0.000 title claims abstract description 102
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 102
- 239000010405 anode material Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 72
- 229920005989 resin Polymers 0.000 claims abstract description 69
- 239000011347 resin Substances 0.000 claims abstract description 69
- 238000010438 heat treatment Methods 0.000 claims abstract description 52
- 239000000571 coke Substances 0.000 claims abstract description 45
- 238000002156 mixing Methods 0.000 claims abstract description 40
- 239000011163 secondary particle Substances 0.000 claims abstract description 25
- 239000003208 petroleum Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 238000012216 screening Methods 0.000 claims abstract description 20
- 238000005303 weighing Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 10
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 8
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000012360 testing method Methods 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 14
- 238000001069 Raman spectroscopy Methods 0.000 claims description 13
- 239000007773 negative electrode material Substances 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- 239000011329 calcined coke Substances 0.000 claims description 9
- 238000005087 graphitization Methods 0.000 claims description 9
- 239000011331 needle coke Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000002006 petroleum coke Substances 0.000 claims description 8
- 230000007547 defect Effects 0.000 claims description 4
- 238000009396 hybridization Methods 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 239000006253 pitch coke Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 29
- 239000011248 coating agent Substances 0.000 description 27
- 238000000576 coating method Methods 0.000 description 27
- 229910021385 hard carbon Inorganic materials 0.000 description 17
- 238000009830 intercalation Methods 0.000 description 15
- 230000002687 intercalation Effects 0.000 description 15
- 238000000113 differential scanning calorimetry Methods 0.000 description 13
- 239000002131 composite material Substances 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 9
- 229910021384 soft carbon Inorganic materials 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 238000010000 carbonizing Methods 0.000 description 5
- 238000005253 cladding Methods 0.000 description 4
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 208000019901 Anxiety disease Diseases 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000036506 anxiety Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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 discloses a preparation method of a high-magnification graphite anode material, the anode material and a lithium battery, wherein the preparation method comprises the steps of weighing resin and raw coke according to a proportion, and fully and uniformly mixing to obtain a mixed raw material; the resin comprises: one or more combinations of C5 petroleum resins, C9 petroleum resins, C5 and C9 copolymer resins, hydrogenated petroleum resins, or coumarone resins; placing the mixed raw materials into a granulating furnace, setting a first heating curve under inert atmosphere to enable resin to be in a molten state, and under mechanical stirring, enabling particles of the mixed raw materials to be rubbed with each other, enabling the molten resin to be uniformly coated on the surface of raw coke, setting a second heating curve to enable the molten resin to be coked and solidified, and removing volatile matters of the raw coke to form secondary particles; placing the secondary particles into a graphitizing furnace for graphitizing to obtain graphitized materials; and scattering and uniformly mixing the graphitized material by mixing equipment, and screening to obtain the high-magnification graphite anode material.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a preparation method of a high-magnification graphite anode material, the anode material and a lithium battery.
Background
With the breakthrough development of battery technology and the improvement of battery energy density, the present electric automobile has greatly improved the mileage of endurance, five and six hundred kilometers of endurance are very popular, new energy automobiles are changed from the anxiety of the mileage to the anxiety of charging time, power battery factories and merchants are developing quick-charging batteries, and many manufacturers develop battery core projects with the quick-charging time of 10min-15 min.
The negative electrode material is used as a main material of the battery, and the main function of the negative electrode material is lithium storage in the charging process, and the lithium intercalation speed of the negative electrode material is one of the most important factors influencing the quick charge capacity of the battery. Graphite has good chemical stability and electrical property, is still a main current cathode material in the market at present, but because the graphite is of a lamellar structure, lithium ions can only be inserted into the graphite from the end face and cannot be inserted from the basal plane, and the lithium insertion speed of conventional graphite is low. The most common method for improving the quick charge performance of the graphite is to coat a layer of soft carbon on the surface of the graphite, wherein the layer spacing of the soft carbon is larger than that of the graphite, the disorder degree between the layers is higher, the lithium intercalation paths are more, the lithium ions on the basal plane of the graphite can be led to the end face for intercalation, and the quick charge performance of the graphite is improved. The current rising method for providing graphite fast charging performance is hard carbon coating, the interlayer spacing and disorder degree of the hard carbon are higher than those of soft carbon, and the fast charging performance is better than that of the soft carbon coating.
The traditional step of preparing the negative electrode material by coating graphite with soft carbon and hard carbon comprises the steps of firstly granulating to obtain secondary particles, graphitizing the granulating material, coating the granulating material with asphalt or resin, and then carbonizing, mixing, screening and the like to obtain the negative electrode material. Although the existing negative electrode material obtained by coating graphite with soft carbon and hard carbon can improve the quick charge performance to a certain extent, the preparation cost of the material can be greatly increased after the carbonization process of the granules of the soft carbon and the hard carbon, the energy consumption and the carbon emission are increased, the requirements of the market on the production cost reduction of the negative electrode material are not met, and the policy of carbon neutralization is also contrary. Therefore, a simpler and efficient preparation method is needed, and the energy consumption and the cost can be reduced while the quick-charge performance is improved.
Disclosure of Invention
The embodiment of the invention provides a preparation method, a material and an application of a high-rate graphite anode material, wherein the preparation method comprises the steps of heating to melt resin and uniformly coat the resin on the surface of raw coke, heating to coke the resin on the surface of the raw coke to form a hard carbon layer, graphitizing, scattering and sieving to obtain the hard carbon coated high-rate graphite anode material.
In a first aspect, an embodiment of the present invention provides a method for preparing a high-rate graphite anode material, where the method includes:
weighing resin and raw coke according to a proportion, and fully and uniformly mixing to obtain a mixed raw material; the resin comprises: one or more combinations of C5 petroleum resins, C9 petroleum resins, C5 and C9 copolymer resins, hydrogenated petroleum resins, or coumarone resins;
placing the mixed raw materials into a granulating furnace, carrying out first heating treatment under inert atmosphere to enable the resin to be in a molten state, and under mechanical stirring, enabling particles of the mixed raw materials to be rubbed with each other, enabling the molten resin to be uniformly coated on the surface of raw coke, then carrying out second heating treatment to enable the molten resin to be coked and solidified, and removing volatile matters of the raw coke to form secondary particles;
placing the secondary particles into a graphitizing furnace for graphitizing to obtain graphitized materials;
scattering and uniformly mixing the graphitized material by mixing equipment, and screening to obtain a high-magnification graphite anode material;
according to a Raman surface scanning test, the intensity ratio average value Id/Ig of a defect D peak belonging to a C atom lattice and an in-plane stretching vibration G peak belonging to C atom sp2 hybridization meets 0.1 Id/Ig less than or equal to 0.5; the absolute value of the intensity of the exothermic peak of the high-magnification graphite anode material is less than 2.0mW/mg at 600-1000 ℃.
Preferably, the resin is in a solid state at room temperature;
the raw coke comprises: one or more of petroleum coke, pitch coke, needle coke, calcined coke, coal, shot coke, metallurgical coke, graphitized resistor material or graphite crucible material; the medium particle diameter D50 of the raw coke is between 5 and 15 mu m;
the weight ratio of the resin to the raw coke is between 10:100 and 50:100.
Preferably, the medium grain diameter D50 of the grain diameter volume distribution of the high-rate graphite anode material is between 5 and 20 mu m.
Preferably, the inert atmosphere is a nitrogen atmosphere.
Preferably, the first temperature increasing process includes: heating to a temperature 50-150 ℃ higher than the softening point temperature of the resin at a heating rate of 1-8 ℃ per minute, and preserving heat for 2-6 hours;
the second temperature increasing process includes: continuously heating to 500-700 ℃ at a heating rate of 1-8 ℃/min, and preserving heat for 2-6 hours.
Preferably, the graphitization furnace comprises: one of an Acheson graphitizing furnace, an inner series graphitizing furnace or a box furnace; the graphitization temperature is set to 2500-3000 ℃.
Preferably, the mixing equipment comprises a stirrer, a high-speed dispersing machine, a ball mill or a grinding machine.
Preferably, the number of the screening meshes is 200-600 mesh.
In a second aspect, the embodiment of the invention provides a high-magnification graphite anode material prepared by the preparation method in the first aspect, which is characterized in that the intensity ratio average value Id/Ig of a defect D peak attributed to a C atom lattice and an in-plane stretching vibration G peak attributed to C atom sp2 hybridization meets 0.1-Id/Ig-0.5 through a Raman surface scanning test; the absolute value of the intensity of the exothermic peak of the high-magnification graphite anode material is less than 2.0mW/mg at 600-1000 ℃.
In a third aspect, an embodiment of the present invention provides a lithium battery, where the lithium battery includes the high-rate graphite negative electrode material described in the second aspect.
The invention provides a preparation method of a high-rate graphite anode material, which comprises the steps of heating to melt resin and uniformly coat the resin on the surface of raw coke, heating to enable the resin to coke on the surface of the raw coke to form a hard carbon layer, graphitizing, scattering and screening to obtain the hard carbon coated high-rate graphite anode material.
The invention uses the characteristic that hard carbon is difficult to graphitize, even though the graphitization temperature is 2500-3000 ℃, the characteristics of large interlayer spacing and high disorder degree are still maintained, the low crystallinity of the hard carbon coated on the surface can provide more lithium intercalation points, and meanwhile, the hard carbon coating ensures that the orientation degree of the pole piece is low, and the pole piece is Li + The embedding is convenient, and the quick charge performance of the graphite anode material is improved.
Drawings
The technical scheme of the embodiment of the invention is further described in detail through the drawings and the embodiments.
FIG. 1 is a flow chart of a preparation method of a high-rate graphite anode material provided by an embodiment of the invention;
FIG. 2 is a Differential Scanning Calorimetry (DSC) comparison of the high-magnification graphite anode material of example 1 of the present invention with the composite material of comparative example 1;
FIG. 3 is a DSC chart of the high-rate graphite anode material of example 2 of the present invention versus the composite material of comparative example 2;
FIG. 4 is a DSC chart of the high-rate graphite anode material of example 3 of the present invention versus the composite material of comparative example 3;
fig. 5 is a DSC comparison of the high-magnification graphite negative electrode material of example 4 of the present invention with the composite material of comparative example 4.
Detailed Description
The invention is described in further detail below with reference to the drawings and to specific examples, but it should be understood that these examples are for the purpose of more detailed description only and should not be construed as limiting the invention in any way, i.e. not as limiting the scope of the invention.
The embodiment of the invention provides a preparation method of a high-rate graphite anode material, which comprises the following specific steps as shown in fig. 1:
step 110, weighing resin and raw coke according to a proportion, and fully and uniformly mixing to obtain a mixed raw material;
the resin comprises: one or more combinations of C5 petroleum resins, C9 petroleum resins, C5 and C9 copolymer resins, hydrogenated petroleum resins, or coumarone resins; the resin is in a solid state at room temperature;
the raw coke comprises: one or more of petroleum coke, pitch coke, needle coke, calcined coke, coal, shot coke, metallurgical coke, graphitized resistor material or graphite crucible material; the medium grain diameter D50 of the raw coke is between 5 and 15 mu m;
the weight ratio of the resin to the raw coke is between 10:100 and 50:100.
Step 120, placing the mixed raw materials into a granulating furnace, performing first heating treatment under inert atmosphere to enable the resin to be in a molten state, rubbing the particles of the mixed raw materials with each other under mechanical stirring, uniformly coating the molten resin on the surface of raw coke, performing second heating treatment to enable the molten resin to be coked and solidified, and removing volatile components of the raw coke to form secondary particles;
wherein the inert atmosphere is a nitrogen atmosphere;
the first temperature raising process includes: heating to a temperature 50-150 ℃ higher than the softening point temperature of the resin at a heating rate of 1-8 ℃ per minute, and preserving heat for 2-6 hours;
the second temperature increasing treatment includes: continuously heating to 500-700 ℃ at a heating rate of 1-8 ℃/min, and preserving heat for 2-6 hours.
130, placing the secondary particles in a graphitizing furnace for graphitizing to obtain graphitized materials;
the graphitization furnace comprises: one of an Acheson graphitizing furnace, an inner series graphitizing furnace or a box furnace; the graphitization temperature is set to 2500-3000 ℃.
Step 140, scattering and uniformly mixing graphitized materials by mixing equipment, and screening to obtain a high-magnification graphite anode material;
the mixing equipment comprises a stirrer, a high-speed dispersing machine, a ball mill or a grinding machine;
the number of the screening meshes is 200-600 meshes;
the medium grain diameter D50 of the grain diameter volume distribution of the high-rate graphite anode material is between 5 and 20 mu m;
the high-magnification graphite anode material is subjected to Raman surface scanning test, and the average value Id/Ig of the intensity ratio of a defect D peak belonging to a C atom lattice to an in-plane stretching vibration G peak belonging to C atom sp2 hybridization is 0.1-0.5; DSC test is carried out on the high-magnification graphite anode material in argon atmosphere, and the absolute value of the intensity of an exothermic peak is less than 2.0mW/mg at 600-1000 ℃.
The embodiment of the invention provides a lithium battery, which comprises the high-rate graphite anode material prepared by the preparation method.
In order to better understand the technical scheme provided by the invention, the preparation process and the characteristics of the high-rate graphite anode material are respectively described in the following specific examples.
Example 1
The embodiment provides a preparation method of a high-rate graphite anode material, which comprises the following specific steps:
step 1: and weighing 3 microns of C5 petroleum resin and 5 microns of needle coke according to the weight ratio of 20:100, and uniformly mixing to obtain a mixed raw material.
Step 2: placing the mixed raw materials into a granulating furnace, heating to 200 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, preserving heat for 2 hours to enable the C5 petroleum resin to be in a molten state, and under mechanical stirring, enabling particles of the mixed raw materials to rub with each other, enabling the molten C5 petroleum resin to uniformly coat the surfaces of needle coke, heating to 500 ℃ at a heating rate of 5 ℃/min, preserving heat for 6 hours, enabling the molten C5 petroleum resin to be coked and solidified, and removing volatile matters of the needle coke to obtain secondary particles.
Step 3: and (3) placing the secondary particles in an Acheson graphitizing furnace, setting the temperature to 3000 ℃, and graphitizing the needle coke to obtain graphitized materials.
Step 4: and (3) scattering and uniformly mixing the graphitized material by a high-speed dispersing machine, and screening by a 500-mesh screen to obtain the high-magnification graphite anode material.
DSC test is carried out on the high-rate graphite anode material prepared in the embodiment under the argon atmosphere, and the test result is shown in figure 2.
The high-rate graphite anode material prepared in the embodiment is subjected to a Raman surface scanning test, and the average value of Id/Ig of the test results is shown in Table 1.
Example 2
The embodiment provides a preparation method of a high-rate graphite anode material, which comprises the following specific steps:
step 1: weighing 3 microns of C9 petroleum resin and 8 microns of calcined coke according to the weight ratio of 10:100, and uniformly mixing to obtain a mixed raw material;
step 2: placing the mixed raw materials into a granulating furnace, heating to 240 ℃ at a heating rate of 8 ℃/min under nitrogen atmosphere, preserving heat for 2 hours to enable the C9 petroleum resin to be in a molten state, and under mechanical stirring, enabling particles of the mixed raw materials to rub with each other, enabling the molten C9 petroleum resin to uniformly coat the surface of calcined coke, heating to 550 ℃ at a heating rate of 5 ℃/min, preserving heat for 4 hours, enabling the molten C9 petroleum resin to be coked and solidified, and removing volatile matters of the calcined coke to obtain secondary particles.
Step 3: and (3) placing the secondary particles in an Acheson graphitizing furnace, setting the temperature to 3000 ℃, and graphitizing the calcined coke to obtain graphitized materials.
Step 4: and (3) scattering and uniformly mixing the graphitized material by a high-speed dispersing machine, and screening by a 325-mesh screen to obtain the high-magnification graphite anode material.
DSC test is carried out on the high-rate graphite anode material prepared in the embodiment under the argon atmosphere, and the test result is shown in figure 3.
The high-rate graphite anode material prepared in the embodiment is subjected to a Raman surface scanning test, and the average value of Id/Ig of the test results is shown in Table 1.
Example 3
The embodiment provides a preparation method of a high-rate graphite anode material, which comprises the following specific steps:
step 1: and weighing 3 microns of C5 and C9 copolymer resin and 10 microns of petroleum coke according to the weight ratio of 30:100, and uniformly mixing to obtain a mixed raw material.
Step 2: placing the mixed raw materials into a granulating furnace, heating to 270 ℃ at a heating rate of 3 ℃/min under nitrogen atmosphere, preserving heat for 2 hours to enable the C5 and C9 copolymer resin to be in a molten state, and under mechanical stirring, enabling particles of the mixed raw materials to rub with each other, enabling the molten C5 and C9 copolymer resin to be uniformly coated on the surface of petroleum coke, heating to 600 ℃ at the heating rate of 3 ℃/min, preserving heat for 4 hours, enabling the molten C5 and C9 copolymer resin to be coked and solidified, and removing volatile components of the petroleum coke at the same time to obtain secondary particles.
Step 3: placing the secondary particles into an Acheson graphitizing furnace, setting the temperature to 3000 ℃, and graphitizing to obtain graphitized materials
Step 4: and (3) scattering and uniformly mixing the graphitized material by a high-speed dispersing machine, and screening by a 300-mesh screen to obtain the high-magnification graphite anode material.
DSC test is carried out on the high-rate graphite anode material prepared in the embodiment under the argon atmosphere, and the test result is shown in figure 4.
The high-rate graphite anode material prepared in the embodiment is subjected to a Raman surface scanning test, and the average value of Id/Ig of the test results is shown in Table 1.
Example 4
The embodiment provides a preparation method of a high-rate graphite anode material, which comprises the following specific steps:
step 1: weighing hydrogenated petroleum resin with the size of 3 microns and asphalt coke with the size of 15 microns according to the weight ratio of 15:100, and uniformly mixing to obtain a mixed raw material;
step 2: placing the mixed raw materials into a granulating furnace, heating to 200 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, preserving heat for 4 hours to enable the hydrogenated petroleum resin to be in a molten state, and under mechanical stirring, enabling particles of the mixed raw materials to rub with each other, enabling the molten hydrogenated petroleum resin to uniformly coat the surface of asphalt coke, heating to 600 ℃ at a heating rate of 5 ℃/min, preserving heat for 4 hours, enabling the molten hydrogenated petroleum resin to coke and solidify, and removing volatile components of the asphalt coke to obtain secondary particles.
Step 3: and (3) placing the secondary particles in an internal string graphitizing furnace, setting the temperature to 2800 ℃, and graphitizing the asphalt coke to obtain graphitized materials.
Step 4: and (3) scattering and uniformly mixing the graphitized material by a high-speed dispersing machine, and screening by a 270-mesh screen to obtain the high-magnification graphite anode material.
DSC test is carried out on the high-rate graphite anode material prepared in the embodiment under the argon atmosphere, and the test result is shown in figure 5.
The high-rate graphite anode material prepared in the embodiment is subjected to a Raman surface scanning test, and the average value of Id/Ig of the test results is shown in Table 1.
To better illustrate the effects of the embodiments of the present invention, the comparative examples are compared with the above embodiments.
Comparative example 1
The comparative example provides a preparation method of a graphite anode material, which comprises the following specific steps:
step 1: weighing asphalt with the diameter of 3 microns and needle coke with the diameter of 5 microns according to the weight ratio of 11:100, and uniformly mixing to obtain a first mixed material.
Step 2: and (3) placing the first mixed material into a granulating furnace, heating to 550 ℃ at a heating rate of 5 ℃/min under the nitrogen atmosphere, and then carrying out heat preservation for 4 hours to carry out granulation to obtain secondary particles.
Step 3: and (3) placing the secondary particles in an Acheson graphitizing furnace, setting the temperature to 3000 ℃, and graphitizing the needle coke to obtain the graphitized material. Scattering and uniformly mixing the graphitized material by a high-speed dispersing machine, and screening by a 500-mesh screen to obtain the graphitized material before coating;
carrying out a Raman scanning test on the graphitized material before coating, wherein the average value of Id/Ig of the test result is shown in Table 1;
batteries were prepared with the graphitized material before coating, and the lithium intercalation rate was measured, and the test results are shown in table 1.
Step 4: the graphitized material before coating and 3 microns of asphalt are mixed according to the mass ratio of 100:3, mixing to obtain a second mixed material.
Step 5: and carbonizing the second mixed material to obtain the asphalt graphite composite material.
Step 6: and scattering and uniformly mixing the asphalt graphite composite material by a high-speed dispersing machine, and screening by a 500-mesh screen to obtain the asphalt coated graphite anode material.
DSC test is carried out on the graphite anode material prepared in the comparative example under argon atmosphere, the test result is shown in figure 2, and compared with the high-magnification graphite anode material prepared in the example 1, the absolute value of the exothermic peak intensity of the example 1 at 600-1000 ℃ is less than 2.0mW/mg, and the absolute value of the exothermic peak intensity of the comparative example 1 at 600-1000 ℃ is more than 2.0mW/mg.
Batteries were prepared by using the asphalt coated graphite anode material prepared in this comparative example, and the lithium intercalation rate was measured, and the test results are shown in table 1.
Comparative example 2
The comparative example provides a preparation method of a graphite anode material, which comprises the following specific steps:
step 1: the weight ratio is 4:100, weighing asphalt with the diameter of 3 microns and calcined coke with the diameter of 8 microns, and uniformly mixing to obtain a first mixed material.
Step 2: and (3) placing the first mixed material into a granulating furnace, heating to 550 ℃ at a heating rate of 5 ℃/min under the nitrogen atmosphere, and granulating for 4 hours to obtain secondary particles.
Step 3: and (3) placing the secondary particles in an Acheson graphitizing furnace, setting the temperature to 3000 ℃, and graphitizing the calcined coke to obtain the graphitized material. Scattering and uniformly mixing the graphitized material by a high-speed dispersing machine, and screening by a 325-mesh screen to obtain the graphitized material before coating;
carrying out a Raman scanning test on the graphitized material before coating, wherein the average value of Id/Ig of the test result is shown in Table 1;
batteries were prepared with the graphitized material before coating, and the lithium intercalation rate was measured, and the test results are shown in table 1.
Step 4: the graphitized material before coating and 3 microns of asphalt are mixed according to the mass ratio of 100:3, mixing to obtain a second mixed material.
Step 5: and carbonizing the second mixed material to obtain the asphalt graphite composite material.
Step 6: and scattering and uniformly mixing the asphalt graphite composite material by a high-speed dispersing machine, and screening by a 325-mesh screen to obtain the asphalt coated graphite anode material.
DSC test is carried out on the asphalt coated graphite anode material prepared in the comparative example under argon atmosphere, the test result is shown in figure 3, and compared with the high-magnification graphite anode material prepared in the example 2, the absolute value of the exothermic peak intensity of the example 2 at 600-1000 ℃ is less than 2.0mW/mg, and the absolute value of the exothermic peak intensity of the comparative example 2 at 600-1000 ℃ is more than 2.0mW/mg.
Batteries were prepared by using the asphalt coated graphite anode material prepared in this comparative example, and the lithium intercalation rate was measured, and the test results are shown in table 1.
Comparative example 3
The comparative example provides a preparation method of a graphite anode material, which comprises the following specific steps:
step 1: the weight ratio of the components is 100: weighing asphalt with the diameter of 3 microns and petroleum coke with the diameter of 10 microns, and uniformly mixing to obtain a first mixed material;
step 2: and (3) placing the first mixed material into a granulating furnace, heating to 550 ℃ at a heating rate of 5 ℃/min under the nitrogen atmosphere, and then carrying out heat preservation for 4 hours to carry out granulation to obtain secondary particles.
Step 3: and (3) placing the secondary particles in an Acheson graphitizing furnace, setting the temperature to 3000 ℃, and graphitizing the petroleum coke to obtain the graphitized material. Scattering and uniformly mixing the graphitized material by a high-speed dispersing machine, and screening by a 300-mesh screen to obtain the graphitized material before coating;
carrying out a Raman scanning test on the graphitized material before coating, wherein the average value of Id/Ig of the test result is shown in Table 1;
batteries were prepared with the graphitized material before coating, and the lithium intercalation rate was measured, and the test results are shown in table 1.
Step 4: the graphitized material before coating and 3 microns of asphalt are mixed according to the mass ratio of 100:3, mixing to obtain a second mixed material.
Step 5: and carbonizing the second mixed material to obtain the asphalt graphite composite material.
Step 6: and scattering and uniformly mixing the asphalt graphite composite material by a high-speed dispersing machine, and screening by a 300-mesh screen to obtain the asphalt coated graphite anode material.
DSC test is carried out on the asphalt coated graphite anode material prepared in the comparative example under argon atmosphere, the test result is shown in figure 4, and compared with the high-magnification graphite anode material prepared in the example 3, the absolute value of the exothermic peak intensity of the example 3 at 600-1000 ℃ is less than 2.0mW/mg, and the absolute value of the exothermic peak intensity of the comparative example 2 at 600-1000 ℃ is more than 2.0mW/mg.
Batteries were prepared by using the asphalt coated graphite anode material prepared in this comparative example, and the lithium intercalation rate was measured, and the test results are shown in table 1.
Comparative example 4
The comparative example provides a preparation method of a graphite anode material, which comprises the following specific steps:
step 1: the weight ratio of the components is 100:9, weighing asphalt of 3 microns and asphalt coke of 15 microns, and uniformly mixing to obtain a first mixed material.
Step 2: and (3) placing the first mixed material into a granulating furnace, heating to 550 ℃ at a heating rate of 5 ℃/min under the nitrogen atmosphere, and then carrying out heat preservation for 4 hours to carry out granulation to obtain secondary particles.
Step 3: and (3) placing the secondary particles in an Acheson graphitizing furnace, setting the temperature to 3000 ℃, and graphitizing the asphalt coke to obtain the graphitized material. Scattering and uniformly mixing the graphitized material by a high-speed dispersing machine, and screening by a 270-mesh screen to obtain the graphitized material before coating;
carrying out a Raman scanning test on the graphitized material before coating, wherein the average value of Id/Ig of the test result is shown in Table 1;
batteries were prepared with the graphitized material before coating, and the lithium intercalation rate was measured, and the test results are shown in table 1.
Step 4: the graphitized material before coating and 3 microns of asphalt are mixed according to the mass ratio of 100:3, mixing to obtain a second mixed material.
Step 5: and carbonizing the second mixed material to obtain the asphalt graphite composite material.
Step 6: and scattering and uniformly mixing the asphalt graphite composite material by a high-speed dispersing machine, and screening by a 270-mesh screen to obtain the asphalt coated graphite anode material.
DSC test is carried out on the asphalt coated graphite anode material prepared in the comparative example under argon atmosphere, the test result is shown in figure 5, and compared with the high-magnification graphite anode material prepared in the example 4, the absolute value of the exothermic peak intensity of the example 4 at 600-1000 ℃ is less than 2.0mW/mg, and the absolute value of the exothermic peak intensity of the comparative example 4 at 600-1000 ℃ is more than 2.0mW/mg.
Batteries were prepared by using the asphalt coated graphite anode material prepared in this comparative example, and the lithium intercalation rate was measured, and the test results are shown in table 1.
TABLE 1
The high-rate graphite anode material prepared by the embodiment of the invention, the graphitized material before cladding and the graphite anode material after asphalt cladding prepared by the comparative example are respectively subjected to a Raman surface scanning test, and the battery prepared by the materials is subjected to a lithium intercalation rate test, and the test results are shown in Table 1.
As shown by test results, the Id/Ig average value of the high-rate graphite anode material prepared by the embodiment is one order of magnitude larger than that of the graphitized material before coating of the comparative example, and is similar to that of the graphite anode material after coating of asphalt.
The lithium intercalation rate of the battery prepared from the high-rate graphite anode material of the embodiment is larger than that of the battery prepared from the graphitized material before cladding of the comparative example, and is similar to that of the battery prepared from the graphite anode material after cladding of asphalt.
The invention adopts a two-time heating curve to lead the resin to be melted firstly under the first heating curve, evenly coated on the surface of raw coke, and then coked and solidified under the second heating curve, and is used as hard carbon to be coated on the surface of the raw coke, namely, the resin is used as a granulating binder and can be evenly coated on the surface of the raw coke, and after resin granulation, the characteristic that the hard carbon is difficult to graphitize is utilized, even though the graphitization temperature of 2500-3000 ℃ is passed, the characteristic that the interlayer spacing is large and the disorder degree is high is still maintained, the hard carbon coated on the surface has low crystallinity, more lithium intercalation points can be provided, and meanwhile, the hard carbon coating leads the pole pieceLow degree of orientation of Li + The embedding is convenient, and the quick charge performance of the graphite anode material is improved. In the comparative example, asphalt is used as a granulating binder, after high-temperature graphitization, the crystallinity of the surface of the graphite material is high, the carbon layer spacing is small, the multiplying power performance is poor, and the multiplying power performance can be improved only after a certain amount of asphalt is mixed for low-temperature carbonization coating.
In summary, the preparation method of the invention adopts resin as a granulating binder, and the resin is coated on the surface of the raw coke through a two-time heating curve, and the raw coke is graphitized to obtain the hard carbon coated high-magnification graphite negative electrode material.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The preparation method of the high-rate graphite anode material is characterized by comprising the following steps of:
weighing resin and raw coke according to a proportion, and fully and uniformly mixing to obtain a mixed raw material; the resin comprises: one or more combinations of C5 petroleum resins, C9 petroleum resins, C5 and C9 copolymer resins, hydrogenated petroleum resins, or coumarone resins;
placing the mixed raw materials into a granulating furnace, carrying out first heating treatment under inert atmosphere to enable the resin to be in a molten state, and under mechanical stirring, enabling particles of the mixed raw materials to be rubbed with each other, enabling the molten resin to be uniformly coated on the surface of raw coke, then carrying out second heating treatment to enable the molten resin to be coked and solidified, and removing volatile matters of the raw coke to form secondary particles;
placing the secondary particles into a graphitizing furnace for graphitizing to obtain graphitized materials;
scattering and uniformly mixing the graphitized material by mixing equipment, and screening to obtain a high-magnification graphite anode material;
according to a Raman surface scanning test, the intensity ratio average value Id/Ig of a defect D peak belonging to a C atom lattice and an in-plane stretching vibration G peak belonging to C atom sp2 hybridization meets 0.1 Id/Ig less than or equal to 0.5; the absolute value of the intensity of an exothermic peak of the high-magnification graphite anode material is less than 2.0mW/mg at 600-1000 ℃;
the resin is in a solid state at room temperature;
the first temperature increasing process includes: heating to a temperature 50-150 ℃ higher than the softening point temperature of the resin at a heating rate of 1-8 ℃ per minute, and preserving heat for 2-6 hours;
the second temperature increasing process includes: continuously heating to 500-700 ℃ at a heating rate of 1-8 ℃/min, and preserving heat for 2-6 hours;
the graphitization temperature is set to 2500-2800 ℃;
the raw coke comprises: one or more of petroleum coke, pitch coke, needle coke, calcined coke, coal, shot coke, metallurgical coke, graphitized resistor material or graphite crucible material; the medium particle diameter D50 of the raw coke is between 5 and 15 mu m, and the weight ratio of the resin to the raw coke is between 10:100 and 50:100;
the medium grain diameter D50 of the grain diameter volume distribution of the high-rate graphite anode material is between 5 and 20 mu m.
2. The method of claim 1, wherein the inert atmosphere is a nitrogen atmosphere.
3. The method of manufacturing according to claim 1, wherein the graphitization furnace comprises: one of an Acheson graphitizing furnace, an inner string graphitizing furnace or a box furnace.
4. The method according to claim 1, wherein the mixing device comprises a stirrer, a high-speed disperser, a ball mill, or a grinder.
5. The method of claim 1, wherein the screen mesh number of the screen is 200 mesh to 600 mesh.
6. A high-rate graphite anode material prepared by the preparation method of any one of claims 1 to 5.
7. A lithium battery comprising the high-rate graphite negative electrode material of claim 6.
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