CN115417405A - Preparation method of resistance material and negative electrode material for Acheson graphitizing furnace - Google Patents
Preparation method of resistance material and negative electrode material for Acheson graphitizing furnace Download PDFInfo
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- CN115417405A CN115417405A CN202211185643.9A CN202211185643A CN115417405A CN 115417405 A CN115417405 A CN 115417405A CN 202211185643 A CN202211185643 A CN 202211185643A CN 115417405 A CN115417405 A CN 115417405A
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- 239000000463 material Substances 0.000 title claims abstract description 88
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 40
- 239000010439 graphite Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000005087 graphitization Methods 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 229910021382 natural graphite Inorganic materials 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 239000010426 asphalt Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011331 needle coke Substances 0.000 claims description 4
- 239000002006 petroleum coke Substances 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000002931 mesocarbon microbead Substances 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 239000006253 pitch coke Substances 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 1
- 229920001568 phenolic resin Polymers 0.000 claims 1
- 239000000571 coke Substances 0.000 abstract description 18
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000010406 cathode material Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000012216 screening Methods 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007790 solid phase Substances 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
-
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention belongs to the technical field of carbon material production, and particularly relates to a preparation method of a resistance material and a negative electrode material for an Acheson type graphitization furnace. The method adopts the microcrystalline graphite as a substitute material of the resistance material in the Acheson graphitizing furnace, and the use of the microcrystalline graphite can ensure that the graphitizing process is carried out under the condition of higher transformer parameters, so the power of the transformer can be more effectively utilized, the effect is greatly superior to that of various resistance materials such as metallurgical coke, graphitized coke, mixed coke and the like which are widely used at present, and the method has the remarkable technical progress of high thermal efficiency, high strength, good compactness, small environmental pollution and the like.
Description
Technical Field
The invention belongs to the technical field of carbon material production, and particularly relates to a preparation method of a resistance material and a negative electrode material for an Acheson type graphitization furnace.
Background
When the Acheson type graphitization furnace is charged, the space between charging electrode arrays is filled with granular carbon materials, the granular carbon materials are called resistance materials, the main function of the granular carbon materials is to improve the effective resistance of the furnace core and ensure uniform heat supply to graphitized products, and the quantity of the granular carbon materials accounts for about 20% of the volume of the furnace core. The electric heating process in the furnace core is mainly carried out in the electric resistance material, and the total resistance of the furnace core can be improved only if the electric resistance material has higher resistivity, so that the power of the furnace core is increased, the graphitization period is greatly shortened, and the productivity is improved. On the other hand, if the resistivity of the electrical resistance material is too high, a large difference in electrical resistance occurs between the electrical resistance material and the graphitized article, and the temperature difference between the furnace core and each part is too large, thereby increasing cracks of the graphitized article. The nature and method of use of the resistor thus determines to a large extent the progress and end result of the graphitization process.
The current commonly used electric resistance materials mainly comprise three types: metallurgical coke, graphitized coke, and mixed coke of the metallurgical coke and the graphitized coke in different proportions. In practice, as the effective resistance of the furnace core is increased, the power factor of the graphitization furnace equipment is increased, so that the productivity of the graphitization furnace is improved and the power consumption is reduced. However, the conventional resistance materials (especially metallurgical coke) such as metallurgical coke, graphitized coke and mixed coke need to be continuously supplemented under the high temperature condition due to the defects of high ash content, high sulfur content, low true density, high specific resistance and the like and the problem of large burning loss (about 30-40% burning loss), which not only increases the production cost, but also limits the improvement of the effective resistance of the furnace core. In addition, the resistance materials generally have larger difference between the resistivity and the resistance material of the graphitized product, so that the temperature difference of each part of the furnace core is overlarge, cracks of the graphitized product are increased, and the quality of the graphitized product is greatly influenced. Therefore, there is a need to develop alternative materials to existing resistive materials with superior properties.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide a preparation method of a resistance material and a negative electrode material for an Acheson type graphitization furnace, and the invention uses microcrystalline graphite to replace the existing resistance material (including metallurgical coke, graphitized coke and mixed coke) for the Acheson type graphitization furnace, and a method for producing a natural graphite negative electrode material by using the microcrystalline graphite.
The purpose of the invention is realized by the following technical scheme:
the invention provides application of microcrystalline graphite serving as a resistance material of an Acheson type graphitization furnace.
According to an embodiment of the present invention, the fixed carbon content of the microcrystalline graphite is 95wt% or more.
According to an embodiment of the present invention, the microcrystalline graphite may be prepared by a method known in the art, or may be obtained after being purchased from a commercial source.
According to an embodiment of the present invention, the diameter or particle size of the microcrystalline graphite is 3mm to 50mm, more preferably 5mm to 45mm.
The invention provides a preparation method of a resistance material for an Acheson type graphitizing furnace, which comprises the following steps:
(1) Mixing microcrystalline graphite with a binder, and granulating to obtain granules;
(2) And (3) roasting the granulated material obtained in the step (2) to obtain the resistor material.
According to the embodiment of the invention, in the step (1), the fixed carbon content of the microcrystalline graphite is more than or equal to 95wt%.
According to an embodiment of the present invention, in step (1), the microcrystalline graphite may be prepared by a method known in the art, or may be obtained after being purchased from a commercial source.
According to an embodiment of the present invention, in the step (1), the binder is at least one selected from the group consisting of asphalt, epoxy resin, phenol resin, petroleum resin, and tar. The binder is used for granulation, namely, microcrystalline graphite with small granularity is bonded into a granulated material with large granularity, so that the resistor material with proper granularity can be conveniently obtained.
According to an embodiment of the present invention, in step (1), the mass ratio of the microcrystalline graphite to the binder is 100 (5 to 20), and is, for example, 100.
According to an embodiment of the present invention, in the step (1), the microcrystalline graphite has a particle size of 5 μm to 20 μm, for example, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or 20 μm.
According to an embodiment of the present invention, in the step (1), the granulation is performed at 100 to 200 ℃.
According to an embodiment of the present invention, in the step (1), the pellet is pressed in a disk pelletizer, a roll pelletizer, an extrusion pelletizer, or the like.
According to the embodiment of the present invention, in the step (1), the shape of the granulated material may be selected according to actual needs, and may be circular, columnar and/or block.
According to an embodiment of the present invention, in the step (1), the diameter or particle size of the granulated material is preferably 3mm to 50mm, more preferably 5mm to 45mm.
According to an embodiment of the present invention, in the step (1), the mixing is performed under stirring conditions, and the stirring speed and time may be optional, i.e., the mixing can be uniform.
According to an embodiment of the present invention, in the step (2), the firing is performed in an air atmosphere, and after the firing, the binder for binding the fine-grained graphite is carbonized to form amorphous carbon capable of firmly binding the fine-grained graphite together. Meanwhile, the ash content, the volatile content and the sulfur content of the microcrystalline graphite can be reduced in the roasting process, and the requirements of the ash content, the volatile content and the sulfur content of the resistor material are met.
According to an embodiment of the present invention, in the step (2), the temperature of the roasting is 800 ℃ to 1200 ℃, for example, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ or 1200 ℃; the roasting time is 1h to 8h, such as 1h, 2h, 3h, 4h, 5h, 6h or 8h.
According to an embodiment of the invention, the method further comprises: and (4) sieving the roasted resistance material to obtain the particle size of the resistance material meeting the requirements of various graphitization furnaces.
The invention also provides the resistance material for the Acheson type graphitization furnace, which is prepared by the method.
According to the embodiment of the invention, the performance indexes of the electric resistance material are as follows: the content of fixed carbon is more than or equal to 98 percent, the content of ash is less than 0.5 percent, the content of volatile components is less than 1 percent, and the content of sulfur is less than 0.5 percent.
The invention also provides a preparation method of the negative electrode material for the lithium ion battery, which comprises the following steps:
(a) Mixing the resistance material and a graphitized product to be roasted in an Acheson graphitizing furnace, roasting for 90-120 h at 2800-3200 ℃, cooling the graphitized product and the resistance material, and separating out the graphitized resistance material;
(b) And (3) scattering the graphitized resistance material, then carrying out carbon coating and sintering treatment to obtain the negative electrode material for the lithium ion battery.
According to an embodiment of the present invention, in the step (a), the temperature of firing (i.e., graphitization) is 2800 ℃, 2850 ℃, 2900 ℃, 2950 ℃, 3000 ℃, 3050 ℃, 3100 ℃, 3150 ℃, or 3200 ℃. The time for calcination (i.e. graphitization) is 90h, 95h, 100h, 105h, 110h, 115h or 120h.
According to an embodiment of the present invention, in the step (a), the graphitized product to be fired is, for example, at least one of needle coke, petroleum coke, pitch coke, mesocarbon microbeads, natural graphite, and the like.
According to an embodiment of the present invention, in the step (a), the firing is performed under an argon or nitrogen atmosphere.
According to the embodiment of the invention, in the step (b), the fixed carbon content of the graphitized resistor material is more than or equal to 99%.
According to an embodiment of the present invention, in the step (b), the carbon coating and sintering process is a method known to those skilled in the art. The carbon coating method includes, but is not limited to, any one of chemical vapor deposition, solid-phase mixing of carbon source, or liquid-phase mixing of carbon source.
Illustratively, the carbon coating method comprises the steps of uniformly mixing the loosened graphitized resistance material with asphalt (such as asphalt with a softening point temperature of not less than 150 ℃) (the mass ratio of the graphitized resistance material to the asphalt is 100.5-2), and coating the asphalt on the surface of the graphitized resistance material to obtain a mixture.
Illustratively, the carbon coating method is to put the loosened graphitized resistor material into a rotary furnace and introduce a gas-phase carbon source (methane, ethane, propane, acetylene, etc.) under heating conditions.
According to the embodiment of the invention, in the step (b), the sintering method is to perform carbonization treatment on the carbon-coated mixture, cool the carbon-coated mixture, and perform screening treatment to obtain the negative electrode material for the lithium ion battery.
Illustratively, the atmosphere of the carbonization is a nitrogen atmosphere or an argon atmosphere; the temperature of the carbonization is 800-2400 ℃, and the carbonization time is 2-6 hours.
The invention also provides the negative electrode material of the lithium ion battery prepared by the method.
The invention has no special requirements on the size of the microcrystalline graphite, if the microcrystalline graphite with small particle size (5-20 μm) is selected, the microcrystalline graphite can be mixed and granulated through a binder, and a resistor material with proper particle size and better performance can be obtained by matching with a further roasting treatment mode (the ash content, the volatile content and the sulfur content of the microcrystalline graphite can be reduced in the roasting process, so that the requirements on the ash content, the volatile content and the sulfur content of the resistor material are met), and the natural graphite cathode material with proper particle size can be obtained without further crushing treatment after the graphitization treatment of the resistor material obtained by the method; if the microcrystalline graphite with large particle size (5-45 mm) is selected, the microcrystalline graphite can be directly used as a resistance material without granulation and roasting treatment, but the natural graphite cathode material with proper particle size can be obtained by further crushing treatment after graphitization treatment. In order to avoid introducing excessive impurities during the pulverization, microcrystalline graphite (5 μm to 20 μm) having a small particle size is preferable.
The invention has the beneficial effects that:
the method adopts the microcrystalline graphite as a substitute material of the resistance material in the Acheson graphitizing furnace, and the use of the microcrystalline graphite can ensure that the graphitization process is carried out under the condition of higher transformer parameters, so that the power of the transformer can be more effectively utilized, the effect is greatly superior to that of various resistance materials such as metallurgical coke, graphitized coke, mixed coke and the like which are widely used at present, and the method has the remarkable technical progress of high thermal efficiency, high strength, good compactness, small environmental pollution and the like. Meanwhile, when the resistance material is graphitized in the Acheson graphitizing furnace by adopting the microcrystalline graphite, the quality of the graphitized product can be obviously improved because the temperature field in the graphitizing furnace is more uniform. In addition, as the furnace temperature in the graphitizing furnace can reach more than 2800 ℃, the microcrystalline graphite can also be used for preparing a natural graphite cathode material after graphitization while playing a role of a resistance material, so that the product additional value of the resistance material is improved, and the defect that the resistance material is wasted when other resistance materials are used for graphitization is avoided.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Mixing 15g of asphalt (with a softening point of 80 ℃) and 100g of microcrystalline graphite with a fixed carbon content of 97.5wt%, stirring at a rotating speed of 100r/min for 60min, granulating at 120 ℃ in a disc granulator, finally heating to 800 ℃ in air, preserving heat for 1 hour, and cooling to room temperature to obtain the electric resistance material. The resistance material and the graphitized product to be roasted (needle coke) are mixed in an Acheson graphitizing furnace and then are put inRoasting for 120h at 2800 ℃, then cooling the graphitized product and the resistor material, and separating the graphitized resistor material. The graphitized resistance material is scattered, and then is mixed with high-softening-point asphalt (the granularity is 3 mu m) with the softening point of 200 ℃ according to the mass ratio of 100 2 Processing for 4 hours at 1200 ℃ under protection, cooling to room temperature, screening and demagnetizing to obtain the natural graphite cathode material. The performance indexes of the resistance material obtained after roasting are as follows: fixed carbon content: 98.6%, ash content: 0.35%, volatile content: 0.6%, sulfur content: 0.45 percent and the granularity of 8mm. The first specific capacity of the natural graphite negative electrode material is 360mAh/g, and the first efficiency is 92.2%.
Example 2
Mixing 15g of epoxy resin and 100g of microcrystalline graphite with the fixed carbon content of 95.2wt%, stirring at 160r/min for 60min, granulating at 150 ℃ in a rolling granulator, heating to 900 ℃ in air, keeping the temperature for 3 hours, and cooling to room temperature to obtain the resistance material. The resistance material and a graphitized product (petroleum coke) to be roasted are mixed in an Acheson graphitizing furnace and then roasted for 110h at 3200 ℃, and then the graphitized product and the resistance material are cooled and separated to obtain the graphitized resistance material. And (3) scattering the graphitized resistance material, putting the resistor material into a rotary furnace, introducing methane at the flow rate of 1L/min in an argon atmosphere with the flow rate of 100L/min and at the temperature of 800 ℃, continuing for 2 hours, switching to introducing argon, cooling to room temperature, screening and demagnetizing to obtain the natural graphite cathode material. The performance indexes of the resistance material obtained after roasting are as follows: fixed carbon content: 98.8%, ash content: 0.4%, volatile content: 0.76%, sulfur content: 0.4 percent and the granularity of 15mm. The first specific capacity of the natural graphite anode material is 362.6mAh/g, and the first efficiency is 91.6%.
Example 3
10g of asphalt (with the softening point of 130 ℃) and 100g of microcrystalline graphite with the fixed carbon content of 96.5wt% are mixed, stirred for 100min at the speed of 120r/min, granulated in a disc granulator at the temperature of 160 ℃, finally heated to 1000 ℃ in air, kept warm for 6 hours, and cooled to room temperature to obtain the resistance material. The resistance material and a graphitized product (petroleum coke) to be roasted are mixed in an Acheson graphitizing furnace and then roasted for 100h at the temperature of 2980 ℃, and then the graphitized product and the resistance material are cooled and separated to obtain the graphitized resistance material. And (3) scattering the graphitized resistance material, putting the resistor material into a rotary furnace, introducing methane at the flow rate of 1L/min in an argon atmosphere with the flow rate of 100L/min and at the temperature of 800 ℃, continuing for 2 hours, switching to introducing argon, cooling to room temperature, screening and demagnetizing to obtain the natural graphite cathode material. The performance indexes of the resistance material obtained after roasting are as follows: fixed carbon content: 98.4%, ash content: 0.4%, volatile content: 0.78%, sulfur content: 0.42 percent and the granularity of 38mm. The first specific capacity of the natural graphite anode material is 362.5mAh/g, and the first efficiency is 92.4%.
Example 4
14g of petroleum resin and 100g of microcrystalline graphite with the fixed carbon content of 96.8wt% are mixed, stirred for 100min at 120r/min, granulated in a disc granulator at 160 ℃, heated to 800 ℃ in air, kept warm for 8 hours, and cooled to room temperature to obtain the electric resistance material. The resistance material and the graphitized product to be roasted (needle coke) are mixed in an Acheson graphitizing furnace and then roasted for 100 hours at the temperature of 2800 ℃, and then the graphitized product and the resistance material are cooled and separated to obtain the graphitized resistance material. The graphitized resistance material is scattered, and then mixed with high-softening-point asphalt (the particle size is 3 mu m) with the softening point of 220 ℃ according to the mass ratio of 100 2 Processing for 4 hours at 2000 ℃ under protection, cooling to room temperature, screening and demagnetizing to obtain the natural graphite cathode material. The performance indexes of the resistance material obtained after roasting are as follows: fixed carbon content: 98.55%, ash content: 0.42%, volatile content: 0.6%, sulfur content: 0.43 percent and the granularity of 30mm. The first specific capacity of the natural graphite negative electrode material is 360mAh/g, and the first efficiency is 93.2%.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The application of the microcrystalline graphite is characterized in that the microcrystalline graphite is used as a resistance material of an Acheson type graphitization furnace.
2. The use according to claim 1, wherein the fixed carbon content of the microcrystalline graphite is not less than 95wt%;
and/or the diameter or the granularity of the microcrystalline graphite is 3 mm-50 mm.
3. A preparation method of a resistance material for an Acheson type graphitizing furnace comprises the following steps:
(1) Mixing microcrystalline graphite with a binder, and granulating to obtain granules;
(2) And (3) roasting the granulated material obtained in the step (2) to obtain the resistor material.
4. The preparation method according to claim 3, wherein in the step (1), the fixed carbon content of the microcrystalline graphite is more than or equal to 95wt%;
and/or in the step (1), the binder is selected from at least one of asphalt, epoxy resin, phenolic resin, petroleum resin and tar;
and/or in the step (1), the mass ratio of the microcrystalline graphite to the binder is 100 (5-20);
and/or in the step (1), the grain size of the microcrystalline graphite is 5-20 μm;
and/or, in the step (1), the granulation is carried out at 100-200 ℃;
and/or, in the step (1), the diameter or the particle size of the granulating material is 3 mm-50 mm.
5. The production method according to claim 3 or 4, wherein in the step (2), the baking is performed in an air atmosphere;
and/or in the step (2), the roasting temperature is 800-1200 ℃; the roasting time is 1-8 h.
6. A resistor for an Acheson-type graphitization furnace prepared by the method of any one of claims 3-5.
7. The electric resistance material according to claim 6, characterized in that the performance indexes of the electric resistance material are as follows: the content of fixed carbon is more than or equal to 98 percent, the content of ash is less than 0.5 percent, the content of volatile components is less than 1 percent, and the content of sulfur is less than 0.5 percent.
8. A preparation method of a negative electrode material for a lithium ion battery comprises the following steps:
(a) Mixing the resistor material of claim 5 or 6 with a graphitized product to be fired in an Acheson graphitizing furnace, firing the mixture for 90 to 120 hours at 2800 to 3200 ℃, cooling the graphitized product and the resistor material, and separating the graphitized resistor material;
(b) And (3) scattering the graphitized resistance material, then carrying out carbon coating and sintering treatment to obtain the negative electrode material for the lithium ion battery.
9. The preparation method according to claim 8, wherein in the step (a), the graphitized product to be calcined is at least one of needle coke, petroleum coke, pitch coke, mesocarbon microbeads and natural graphite;
and/or, in step (a), the calcination is carried out under an argon or nitrogen atmosphere;
and/or in the step (b), the fixed carbon content of the graphitized resistor material is not less than 99%.
10. A negative electrode material for a lithium ion battery prepared by the method of claim 8 or 9.
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Application publication date: 20221202 |