CN114824233A - Preparation method of high-energy-density quick-charging graphite negative electrode material of lithium battery - Google Patents
Preparation method of high-energy-density quick-charging graphite negative electrode material of lithium battery Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 40
- 239000010439 graphite Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 18
- 239000007773 negative electrode material Substances 0.000 title claims description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 239000006258 conductive agent Substances 0.000 claims abstract description 37
- 238000005087 graphitization Methods 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 32
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000010406 cathode material Substances 0.000 claims abstract description 8
- -1 graphite alkene Chemical class 0.000 claims abstract description 4
- 239000011230 binding agent Substances 0.000 claims description 27
- 239000000571 coke Substances 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 23
- 238000000227 grinding Methods 0.000 claims description 18
- 238000000462 isostatic pressing Methods 0.000 claims description 16
- 239000010426 asphalt Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 230000004927 fusion Effects 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011331 needle coke Substances 0.000 claims description 7
- 239000002006 petroleum coke Substances 0.000 claims description 6
- 150000002506 iron compounds Chemical class 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 150000003377 silicon compounds Chemical class 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 102220043159 rs587780996 Human genes 0.000 claims 2
- 238000012986 modification Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000011247 coating layer Substances 0.000 abstract description 3
- 238000005469 granulation Methods 0.000 abstract description 3
- 230000003179 granulation Effects 0.000 abstract description 3
- 239000007770 graphite material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000010287 polarization Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
Abstract
The invention discloses a preparation method of a high-energy density quick-charging graphite cathode material of a lithium battery, which comprises the following steps: mixing materials, briquetting and graphitizing. The graphene for modification is uniformly distributed in the graphite phase, the contact performance of the graphene and the graphite phase is good, the conductivity of the graphite material and the coating layer of the graphite material is greatly enhanced, and the addition amount of a conductive agent can be reduced in the manufacturing process, so that more active substances are put into a limited battery space, and the energy density of the battery is increased; secondly, the capacity of the graphite can be improved to more than 360mAh/g by catalytic graphitization, and the energy density of the battery is further improved; the synergistic effect that graphite alkene modification and catalyst pore-forming brought has promoted fast filling performance, and graphite alkene has formed abundant electrically conductive network between graphite, granulation coating, reduces system impedance and battery polarization, promotes electric conductive property, strengthens the multiplying power characteristic of battery, and abundant hole can be left in catalyst volatilization, provides convenient route for lithium ion's diffusion, promotes fast filling performance.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a preparation method of a high-energy-density quick-charging graphite negative electrode material of a lithium battery.
Background
The lithium ion battery has the characteristics of high working voltage, high energy density, wide working temperature, long cycle life, no memory effect, environmental friendliness and the like, and is widely applied to the fields of power batteries of automobiles, electric bicycles and the like, the fields of energy storage of power grids, industrial energy storage, household energy storage, communication energy storage and the like, and the fields of 3C digital codes of smart phones, notebook computers, intelligent wearable equipment, mobile power supplies and the like.
The current commercialized negative electrode materials of lithium batteries are mainly modified natural graphite and artificial graphite, and although the preparation technology is quite mature, the requirements of the lithium ion batteries are gradually increased, and especially the requirements on energy density and quick charging are more and more strict. At present, the charge-discharge multiplying power of graphite is not high, and the energy density is low, in order to improve the charge-discharge multiplying power, some manufacturers modify the graphite, for example, in chinese patent No. cn201711333907.x, a composite graphite cathode material with high capacity and high multiplying power is prepared by granulating and graphitizing carbon microspheres and artificial graphite single particles, but the charge multiplying power can only reach 1-2C, and the charge multiplying power is still not high, so that the use requirement of higher multiplying power is difficult to meet; in order to improve the energy density of the lithium battery, some manufacturers adopt a mode of mixing a single-particle graphitized material and a secondary-particle graphitized material, for example, chinese patent CN 201910987301.0 mixes the single-particle graphitized material and the secondary-particle graphitized material to obtain a single-particle and secondary-particle mixed high-energy density graphite negative electrode material, but the capacity is only below 358mAh/g, and the requirement of high energy density cannot be met. Therefore, there is a need for an improved graphite negative electrode material for lithium batteries.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a graphite negative electrode material for a lithium battery, which has high energy density and fast charging, and the prepared graphite negative electrode material has the properties of high rate and high energy density, and can simultaneously meet the use requirements of high rate and high energy density.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a high-energy-density quick-charging graphite negative electrode material of a lithium battery comprises the following steps:
(1) mixing material
Adding the coke raw material, the catalyst, the conductive agent and the binder which are crushed to a certain particle size into a mechanical fusion machine according to a certain mass ratio, and treating for 5-20min to obtain a mixture material;
(2) pressing block
Putting the mixture material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 100-300MPa, so as to obtain an isostatic block;
(3) graphitization
And (3) placing the isostatic block obtained in the step (2) into a graphitization furnace for graphitization at the high temperature of 3000-3200 ℃, wherein the treatment time is 20-50h, and crushing and screening to obtain the high-energy-density quick-charging graphite cathode material.
As a preferable scheme, the mass ratio of the coke raw material, the catalyst, the conductive agent and the binder in the step (1) is 1 (0.05-0.1): (0.005-0.03): 0.05-0.15).
Preferably, the coke raw material in the step (1) is one or a mixture of pulverized petroleum coke and needle coke, D50 is 5-12 μm, and ash content is less than or equal to 0.5%.
Preferably, the binder in the step (1) is one or a mixture of coal-series asphalt and oil-series asphalt, and the softening point is 50-200 ℃.
Preferably, the conductive agent in the step (1) is graphene, the carbon content of the graphene is 99.5% or more, the number of layers is 1 to 10, and the sheet diameter D50 is 0.2 to 3 μm.
As a preferable scheme, the catalyst in the step (1) is one or more of silicon, silicon compounds, iron and iron compounds, and the purity of the catalyst is more than or equal to 95 percent.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and specifically, the technical scheme includes that:
according to the invention, the energy density is synergistically improved through graphene modification and catalytic graphitization, firstly, the graphene for modification is uniformly distributed in a graphite phase, the contact performance of the graphene and the graphite phase is good, the conductivity of a graphite material and a coating layer thereof is greatly enhanced, the addition amount of a conductive agent can be reduced in a battery manufacturing process, even the use of the conductive agent is completely omitted, so that more active substances can be put into a limited battery space, and the energy density of the battery is increased. Secondly, the capacity of graphite can be further improved to more than 360mAh/g by catalytic graphitization, so that the energy density of the battery is further improved. Simultaneously, the fast charging performance is improved through the synergistic effect brought by catalyst pore-forming in the graphene modification and catalytic graphitization processes: graphene has formed abundant electrically conductive network between graphite, granulation coating, reduces system impedance and battery polarization, promotes electric conductive property, strengthens the multiplying power characteristic of battery, and the catalyst can volatilize during graphitization and leave abundant hole, provides convenient route for lithium ion's diffusion, has further promoted fast and has filled the performance. The preparation method has the advantages of simple process, convenient operation and less production equipment, thereby further reducing the cost, being convenient for popularization and application and being suitable for large-scale production.
The present invention will be described in detail with reference to specific embodiments in order to more clearly illustrate the structural features and effects of the present invention.
Drawings
Fig. 1 is an SEM test chart of the high energy density compatible fast-charging graphite negative electrode material prepared in example 1.
Detailed Description
The invention discloses a preparation method of a high-energy-density quick-charging graphite negative electrode material of a lithium battery, which comprises the following steps of:
(1) mixing material
Adding the coke raw material, the catalyst, the conductive agent and the binder which are crushed to a certain particle size into a mechanical fusion machine according to a certain mass ratio, and treating for 5-20min to obtain a mixture material; the mass ratio of the coke raw material, the catalyst, the conductive agent and the binder is 1 (0.05-0.1) to 0.005-0.03 to 0.05-0.15; the coke raw material is one or two of pulverized petroleum coke and needle coke, D50 is 5-12 μm, and ash content is less than or equal to 0.5%; the binder is one or two of coal-series asphalt and oil-series asphalt which are mixed, and the softening point is 50-200 ℃; the conductive agent is graphene, the carbon content of the conductive agent is more than 99.5%, the number of layers is 1-10, and the sheet diameter D50 is 0.2-3 mu m; the catalyst is one or more of silicon, silicon compounds, iron and iron compounds, and the purity of the catalyst is more than or equal to 95%.
(2) Pressing block
And (2) putting the mixture material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 100-300MPa, so as to obtain an isostatic pressing block.
(3) Graphitization
And (3) placing the isostatic block obtained in the step (2) into a graphitization furnace for graphitization at the high temperature of 3000-3200 ℃, wherein the treatment time is 20-50h, and crushing and screening to obtain the high-energy-density quick-charging graphite cathode material.
The present invention will be described in detail with reference to specific examples.
Example 1
(1) Mixing material
Adding the coke raw material, the catalyst, the conductive agent and the binder which are crushed to a certain particle size into a mechanical fusion machine according to a certain mass ratio, and treating for 5min to obtain a mixture material; the mass ratio of the coke raw material to the catalyst to the conductive agent to the binder is 1:0.05:0.005: 0.15; the coke raw material is pulverized petroleum coke, D50 is 5-12 μm, and ash content is less than or equal to 0.5%; the binder is coal-series asphalt, and the softening point is 50-200 ℃; the conductive agent is graphene, the carbon content of the conductive agent is more than 99.5%, the number of layers is 1-10, and the sheet diameter D50 is 0.2-3 mu m; the catalyst is silicon, and the purity of the catalyst is more than or equal to 95 percent.
(2) Pressing block
And (2) putting the mixture material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 200MPa, so as to obtain an isostatic pressing block.
(3) Graphitization
And (3) placing the isostatic block obtained in the step (2) into a graphitization furnace for graphitization at a high temperature of 3100 ℃, wherein the treatment time is 30h, and crushing and screening to obtain the high-energy-density quick-charging graphite negative electrode material.
Example 2
(1) Mixing material
Adding the coke raw material, the catalyst, the conductive agent and the binder which are crushed to a certain granularity into a mechanical fusion machine according to a certain mass ratio, and treating for 20min to obtain a mixture material; the mass ratio of the coke raw material to the catalyst to the conductive agent to the binder is 1:0.1:0.03: 0.05; the coke raw material is pulverized needle coke, D50 is 5-12 μm, and ash content is less than or equal to 0.5%; the binder is oil-mixed asphalt, and the softening point is 50-200 ℃; the conductive agent is graphene, the carbon content of the conductive agent is more than 99.5%, the number of layers is 1-10, and the sheet diameter D50 is 0.2-3 mu m; the catalyst is a silicon compound, and the purity of the catalyst is more than or equal to 95 percent.
(2) Pressing block
And (2) putting the mixture material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 150MPa, so as to obtain an isostatic pressing block.
(3) Graphitization
And (3) placing the isostatic block obtained in the step (2) into a graphitization furnace for high-temperature graphitization at 3050 ℃, wherein the treatment time is 56 hours, and crushing and screening to obtain the high-energy-density quick-charging graphite negative electrode material.
Example 3
(1) Mixing material
Adding the coke raw material, the catalyst, the conductive agent and the binder which are crushed to a certain particle size into a mechanical fusion machine according to a certain mass ratio for treatment for 16min to obtain a mixture material; the mass ratio of the coke raw material to the catalyst to the conductive agent to the binder is 1:0.07:0.02: 0.1; the coke raw material is a mixture of pulverized petroleum coke and needle coke, D50 is 5-12 μm, and ash content is less than or equal to 0.5%; the binder is a mixture of coal-series asphalt and oil-series asphalt, and the softening point is 50-200 ℃; the conductive agent is graphene, the carbon content of the conductive agent is more than 99.5%, the number of layers is 1-10, and the sheet diameter D50 is 0.2-3 mu m; the catalyst is iron, and the purity of the catalyst is more than or equal to 95 percent.
(2) Pressing block
And (2) putting the mixture material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 100MPa, so as to obtain an isostatic pressing block.
(3) Graphitization
And (3) placing the isostatic block obtained in the step (2) into a graphitization furnace for graphitization at a high temperature of 3180 ℃, wherein the treatment time is 27h, and crushing and screening to obtain the high-energy-density quick-charging graphite negative electrode material.
Example 4
(1) Mixing material
Adding the coke raw material, the catalyst, the conductive agent and the binder which are crushed to a certain particle size into a mechanical fusion machine according to a certain mass ratio, and treating for 9min to obtain a mixture material; the mass ratio of the coke raw material to the catalyst to the conductive agent to the binder is 1:0.08:0.01: 0.15; the coke raw material is pulverized petroleum coke, D50 is 5-12 μm, and ash content is less than or equal to 0.5%; the binder is coal-series asphalt, and the softening point is 50-200 ℃; the conductive agent is graphene, the carbon content of the conductive agent is more than 99.5%, the number of layers is 1-10, and the sheet diameter D50 is 0.2-3 mu m; the catalyst is an iron compound, and the purity of the catalyst is more than or equal to 95%.
(2) Pressing block
And (2) putting the mixture material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 300MPa, so as to obtain an isostatic pressing block.
(3) Graphitization
And (3) placing the isostatic block obtained in the step (2) into a graphitization furnace for high-temperature graphitization treatment at 3080 ℃, wherein the treatment time is 33h, and crushing and screening to obtain the high-energy-density quick-charging graphite negative electrode material.
Example 5
(1) Mixing material
Adding the coke raw material, the catalyst, the conductive agent and the binder which are crushed to a certain particle size into a mechanical fusion machine according to a certain mass ratio, and treating for 12min to obtain a mixture material; the mass ratio of the coke raw material to the catalyst to the conductive agent to the binder is 1:0.09:0.018: 0.06; the coke raw material is pulverized needle coke, D50 is 5-12 μm, and ash content is less than or equal to 0.5%; the binder is oil-based asphalt, and the softening point is 50-200 ℃; the conductive agent is graphene, the carbon content of the conductive agent is more than 99.5%, the number of layers is 1-10, and the sheet diameter D50 is 0.2-3 mu m; the catalyst is silicon, and the purity of the catalyst is more than or equal to 95 percent.
(2) Pressing block
And (2) putting the mixture material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 265MPa, so as to obtain an isostatic pressing block.
(3) Graphitization
And (3) placing the isostatic block obtained in the step (2) into a graphitization furnace for graphitization at a high temperature of 3000 ℃ for 50h, and crushing and screening to obtain the high-energy-density quick-charging graphite negative electrode material.
Example 6
(1) Mixing material
Adding the coke raw material, the catalyst, the conductive agent and the binder which are crushed to a certain particle size into a mechanical fusion machine according to a certain mass ratio for treatment for 18min to obtain a mixture material; the mass ratio of the coke raw material, the catalyst, the conductive agent and the binder is 1:0.1: 0.02: 0.12; the coke raw material is pulverized needle coke, D50 is 5-12 μm, and ash content is less than or equal to 0.5%; the binder is coal-series asphalt, and the softening point is 50-200 ℃; the conductive agent is graphene, the carbon content of the conductive agent is more than 99.5%, the number of layers is 1-10, and the sheet diameter D50 is 0.2-3 mu m; the catalyst is an iron compound, and the purity of the catalyst is more than or equal to 95%.
(2) Pressing block
And (2) putting the mixture material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 285MPa, so that an isostatic pressing block is obtained.
(3) Graphitization
And (3) placing the isostatic block obtained in the step (2) into a graphitization furnace for high-temperature graphitization at 3200 ℃, wherein the treatment time is 50h, and crushing and screening to obtain the high-energy-density quick-charging graphite negative electrode material.
Comparative example 1
Graphene was not added in step (1), and the other conditions were the same as in example 1.
Comparative example 2
No catalyst was added in step (1), and the other conditions were the same as in example 1.
The products obtained in the above examples and comparative examples were subjected to the following performance tests.
SEM test
The SEM of Hitachi SU1510 was used for the product prepared in example 1.
Electrochemical performance test
In order to test the performance of the lithium ion battery cathode material of the invention, the above examples and comparative examples were tested by a half-cell test method, and the cathode material of the above examples and comparative examples, SBR (solid content 50%), CMC, Super-p (weight ratio) 95.5: 2: 1.5: 1, was mixed with a proper amount of deionized water to form a slurry, coated on a copper foil and dried in a vacuum drying oven for 12 hours to prepare a cathode sheet, and the electrolyte was 1M LiPF 6 And the/EC + DEC + DMC is 1: 1, the polypropylene microporous membrane is a diaphragm, the counter electrode is a lithium sheet, and the battery is assembled. Performing constant current charge and discharge experiment in LAND battery test system with charge and discharge voltage limited to 0.01-3.0VAnd the charge and discharge cabinet controlled by the computer collects and controls data and measures the rebound of the pole piece under full power. The test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the prepared lithium ion battery cathode material has excellent capacity performance, cycle performance, first charge-discharge efficiency and rate capability. Meanwhile, as can be seen from fig. 1, graphene is uniformly distributed between graphite and the granulation coating layer and serves as a conductive network, and the surface porosity is caused by volatilization of the catalyst, so that the appearance of the porosity and the modification effect of the graphene synergistically promote the excellent fast-charging performance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (6)
1. A preparation method of a high-energy-density quick-charging graphite negative electrode material of a lithium battery is characterized by comprising the following steps of: the method comprises the following steps:
(1) mixing material
Adding the coke raw material, the catalyst, the conductive agent and the binder which are crushed to a certain particle size into a mechanical fusion machine according to a certain mass ratio, and treating for 5-20min to obtain a mixture material;
(2) pressing block
Putting the mixture material obtained in the step (1) into a rubber grinding tool, and putting the rubber grinding tool into an isostatic pressing forming machine for forming, wherein the pressure is 100-300MPa, so as to obtain an isostatic block;
(3) graphitization
And (3) placing the isostatic block obtained in the step (2) into a graphitization furnace for graphitization at the high temperature of 3000-3200 ℃, wherein the treatment time is 20-50h, and crushing and screening to obtain the high-energy-density quick-charging graphite cathode material.
2. The preparation method of the high energy density quick-charging graphite negative electrode material for the lithium battery as claimed in claim 1, wherein the preparation method comprises the following steps: the mass ratio of the coke raw material, the catalyst, the conductive agent and the binder in the step (1) is 1 (0.05-0.1): (0.005-0.03): 0.05-0.15).
3. The preparation method of the high energy density quick-charging graphite negative electrode material for the lithium battery as claimed in claim 1, wherein the preparation method comprises the following steps: the coke raw material in the step (1) is one or two of pulverized petroleum coke and needle coke, D50=5-12 μm, and ash content is less than or equal to 0.5%.
4. The preparation method of the high energy density quick-charging graphite negative electrode material for the lithium battery as claimed in claim 1, wherein the preparation method comprises the following steps: the binder in the step (1) is one or a mixture of coal-series asphalt and oil-series asphalt, and the softening point is 50-200 ℃.
5. The preparation method of the high energy density quick-charging graphite negative electrode material for the lithium battery as claimed in claim 1, wherein the preparation method comprises the following steps: the conductive agent in the step (1) is graphene, the carbon content of the graphene is more than 99.5%, the number of layers is 1-10, and the sheet diameter D50=0.2-3 μm.
6. The preparation method of the high energy density quick-charging graphite negative electrode material for the lithium battery as claimed in claim 1, wherein the preparation method comprises the following steps: the catalyst in the step (1) is one or more of silicon, silicon compounds, iron and iron compounds, and the purity of the catalyst is more than or equal to 95%.
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