CN111620332A - Negative electrode material, preparation method thereof, negative plate and lithium ion battery - Google Patents
Negative electrode material, preparation method thereof, negative plate and lithium ion battery Download PDFInfo
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- CN111620332A CN111620332A CN202010514481.3A CN202010514481A CN111620332A CN 111620332 A CN111620332 A CN 111620332A CN 202010514481 A CN202010514481 A CN 202010514481A CN 111620332 A CN111620332 A CN 111620332A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
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Images
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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a negative electrode material, a preparation method thereof, a negative electrode sheet and a lithium ion battery. The method comprises the following steps: (1) mixing the coke material and hard carbon, adding a carbon-containing binder, and granulating to obtain a granulated product; (2) and graphitizing the granulated product to obtain the negative electrode material. The cathode material obtained by the method has high energy density, and excellent fast charge performance and high temperature performance.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a negative electrode material, a preparation method thereof, a negative electrode sheet and a lithium ion battery.
Background
The graphite material is used as a common material for the battery cathode and is widely applied to the field of power batteries and the field of consumer batteries. Meanwhile, the requirements of various products on the quick charging performance and the energy density of the battery core are higher and higher, and in the field of power batteries, the battery core is required to provide a long endurance mileage, and at least 70% of the charging amount of the battery can be completed within half an hour or even shorter time, so that the battery core is required to support high-rate charging; the consumption type battery cell tends to be miniaturized and light, and can be fully charged in a short time. In addition, with the rapid expansion of new energy vehicles, the rapidly increasing demand of lithium ion batteries has become a trend for a long time in the future, and two main factors that prevent new energy vehicles from replacing fuel vehicles are: on one hand, the battery cell can be charged in a short time; on the other hand, after the battery core is fully charged for one time, the endurance mileage of the battery core has advantages. The graphite is used as the main part of the negative electrode of the battery cell and plays a restrictive role in the volume energy density and the quick charging performance of the battery cell.
The energy density of the graphite negative electrode is generally increased as follows: 1. the graphite with higher gram capacity is selected, so that the use amount of a negative electrode material is reduced, for example, natural graphite or artificial graphite obtained by graphitizing petroleum coke, pitch coke and coal coke is selected, the natural graphite has poor compatibility with an electrolyte, the cycle performance of the battery cell is poor, the artificial graphite has large rebound, and a pole piece is easy to expand after the battery cell is charged and discharged; 2. the selection of graphite with small rebound resilience can improve the margin of the battery cell group and the volume energy density of the battery, and if needle coke raw materials are selected for graphitization to prepare graphite, the cost of the graphite is high and the multiplying power performance is poor; the way of improving the rate capability of the graphite negative electrode is generally as follows: 1. small-particle-size graphite is selected, so that the compacted density of the graphite is reduced; 2. the graphite material is coated with the bonding material and then carbonized, so that the processing cost of graphite is increased, and meanwhile, when the manufactured battery core is used under a high-temperature condition, the coating material is easy to generate side reaction of electrolyte, and the high-temperature performance of the battery core is deteriorated.
CN106025277A discloses a low-rebound high-energy density composite graphite negative electrode material and a preparation method thereof. The main raw material is graphite micro powder or carbon micro powder, the auxiliary raw material is coating agent, adhesive and organic solvent, the main raw material is pretreated, and then coating, compounding, grading, high-temperature carbonization and high-temperature graphitization are carried out.
CN103700808A discloses a lithium ion battery composite negative electrode plate, which includes a negative electrode current collector, wherein a first coating layer and a second coating layer are respectively coated on two sides of the negative electrode current collector, the coating slurry of the first coating layer is graphite slurry, and the coating slurry of the second coating layer is lithium titanate slurry.
CN109768247A discloses a preparation method of a high-energy-density negative electrode material with high compaction and excellent high-temperature performance, which comprises the steps of depositing organic alkane pyrolytic carbon in the internal pores and on the surface of natural spherical graphite, repairing the internal and surface defects of the natural spherical graphite, mixing with asphalt, stirring at a high speed for uniform dispersion, and carbonizing to obtain the negative electrode material with high compaction and high energy density.
However, the energy density, the fast charging performance and the high temperature performance of the graphite negative electrode material obtained by the method still need to be further improved.
Disclosure of Invention
In view of the above disadvantages in the prior art, the present invention aims to provide a negative electrode material, a preparation method thereof, a negative electrode sheet and a lithium ion battery. The cathode material provided by the invention has high energy density, and can improve the quick charge performance and the high temperature performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing an anode material, the method comprising the steps of:
(1) mixing the coke material and hard carbon, adding a carbon-containing binder, and granulating to obtain a granulated product;
(2) and (2) graphitizing the granulated product in the step (1) to obtain the negative electrode material.
According to the method provided by the invention, the coke material and the hard carbon are mixed for use, so that the synergistic relationship of the coke material and the hard carbon is well exerted, the gram volume of the hard carbon material is high, the volume of a secondary particle material formed by the hard carbon material and the coke material is increased, meanwhile, the rebound of the hard carbon material is small, the rebound of the coke material is reduced, and the production cost of the cathode material is reduced; meanwhile, the introduction of hard carbon enables the short distance of the secondary particle material to be more ordered, the orientation degree to be reduced, and the quick charging performance to be improved; the preparation method provided by the invention does not carry out any coating on the cathode material, so that the high-temperature performance of the material is improved.
The preparation method provided by the invention adopts the carbon-containing binder, has the effects of easy graphitization and excellent dynamic performance, and can better improve the performance of the product.
In the preparation method provided by the invention, the granulation process is adopted to combine hard carbon and coke raw materials, the synergistic effect between the hard carbon and coke raw materials can be better exerted, and the de-intercalation of lithium ions is facilitated.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In a preferred embodiment of the present invention, the coke-based material in the step (1) is a low-orientation degree coke-based material.
The low degree of orientation means a degree of orientation value of less than 5.
Preferably, the coke-based material in step (1) comprises any one or a combination of at least two of petroleum coke, pitch coke or coal coke.
Preferably, the coke-like material of step (1) is crushed and shaped prior to mixing. The crushing and shaping have the significance that the surface of the material is smoother, the orientation degree of the material is reduced, and the transmission channel of lithium ions in the material is favorably shortened, so that the dynamic performance of the material is improved; in addition, by the shaped material, the consumption of a granulation binder is less during granulation, the granulation appearance is more regular, and the orientation degree of the material is reduced.
Preferably, the particle size D50 of the coke-like material in step (1) is 4-15 μm, such as 4 μm, 6 μm, 8 μm, 10 μm, 12 μm or 14 μm.
As a preferable technical solution of the present invention, the hard carbon in step (1) includes any one or a combination of at least two of furfuryl ketone resin hard carbon, unsaturated polyester resin hard carbon, acrylic resin hard carbon, phenolic resin hard carbon, polyoxymethylene resin hard carbon, epoxy resin hard carbon, furfural resin hard carbon, or asphalt hard carbon;
preferably, the hard carbon of step (1) is crushed and shaped prior to mixing. The crushing and shaping have the significance that the surface of the material is smoother, the orientation degree of the material is reduced, and the transmission channel of lithium ions in the material is favorably shortened, so that the dynamic performance of the material is improved; in addition, by the shaped material, the consumption of a granulation binder is less during granulation, the granulation appearance is more regular, and the orientation degree of the material is reduced.
Preferably, the particle size D50 of the hard carbon in the step (1) is 10-20 μm, such as 10 μm, 12 μm, 14 μm, 16 μm, 18 μm or 20 μm.
In a preferred embodiment of the present invention, in the step (1), the mass of the hard carbon is 10 to 40% of the mass of the coke-based material, for example, 10%, 15%, 20%, 25%, 30%, 35%, or 40%. The range can improve the gram capacity of the new material and simultaneously improve the quick charging performance of the new material. The hard carbon material has low compacted density, large irreversible capacity loss, low coulombic efficiency, large gram capacity and obvious dynamic advantages.
If the hard carbon is too much relative to the coke material, the compacted density of the finally obtained negative electrode material is reduced, so that the energy density of a battery cell is reduced, and the coulomb efficiency of the negative electrode material is low; if the hard carbon is too little relative to the coke material, the gram volume of the finally obtained cathode material is not obviously improved, the dynamic performance cannot be obviously improved, and the conductivity of the material is lower.
Preferably, in step (1), the mixing time is 30-60min, such as 30min, 40min, 50min or 60 min.
Preferably, in the step (1), the mixing is carried out in a mixer, wherein the rotating speed of a cylinder of the mixer is 15-20r/min, and the rotating speed of a blade is 25-40 r/min.
In a preferred embodiment of the present invention, in step (1), the carbonaceous binder includes any one or a combination of at least two of pitch, coal tar, polypropylene, polyethylene, and acrylic acid. In the invention, the polypropylene can be emulsion, the polyethylene can be emulsion, and the acrylic acid can be solution.
Preferably, in step (1), the mass of the carbon-containing binder is 5-20% of the mass of the coke-based material, such as 5%, 10%, 15%, 20%, etc.
Preferably, the granulation in step (1) is mechanofusion granulation.
Preferably, the granulation time in step (1) is 2-6h, such as 2h, 3h, 4h, 5h or 6h, etc.
Preferably, the temperature for the granulation in step (1) is 500-700 ℃, such as 500 ℃, 550 ℃, 600 ℃, 650 ℃, or 700, etc.
Preferably, the temperature rise rate of the granulation in step (1) is 2-5 ℃/min, such as 2 ℃/min, 3 ℃/min, 4 ℃/min, or 5 ℃/min, and the like.
Preferably, the granulation of step (1) is carried out under a protective atmosphere.
Preferably, the protective atmosphere comprises any one of nitrogen, argon or helium or a combination of at least two thereof.
As a preferred embodiment of the present invention, the temperature for graphitization in step (2) is 2800-3500 ℃, for example 2800 ℃, 2900 ℃, 3000 ℃, 3100 ℃, 3200 ℃, 3300 ℃, 3400 ℃, 3500 ℃ or the like.
Preferably, the graphitization time in the step (2) is 36-60h, such as 36h, 42h, 48h, 54h or 60 h.
Preferably, the graphitization in the step (2) is performed under vacuum or protective atmosphere.
Preferably, the protective atmosphere comprises any one of gas, argon or helium or a combination of at least two thereof.
As a further preferable technical scheme of the preparation method, the method comprises the following steps:
(1) mixing the crushed and shaped coke material and the crushed and shaped hard carbon for 30-60min, adding a carbon-containing binder, heating to the temperature of 500-700 ℃ at the heating rate of 2-5 ℃/min in a protective atmosphere, and performing mechanical fusion granulation for 2-6h to obtain a granulated product;
wherein the mass of the hard carbon is 10-40% of that of the coke material, and the mass of the carbon-containing binder is 5-20% of that of the coke material;
(2) and (3) graphitizing the granulated product in the step (1) at 2800-3500 ℃ for 36-60h under vacuum pumping or protective atmosphere to obtain the negative electrode material.
In a second aspect, the present invention provides an anode material prepared by the method of the first aspect.
The cathode material provided by the invention is a graphite cathode material.
In a third aspect, the present invention provides a negative electrode sheet comprising the negative electrode material according to the second aspect.
The negative plate provided by the invention comprises a current collector and a negative active material layer arranged on the surface of the current collector.
The negative active material layer is obtained by coating a negative slurry on a current collector and drying.
The negative electrode slurry includes a solvent and a solid component dispersed in the solvent. The solid component includes the anode material of the second aspect, a binder, a dispersant, and a conductive agent.
The binder comprises at least one of styrene butadiene, polyacrylic acid, polyacrylate, styrene acrylate, polyacrylonitrile, polyacrylamide, polyimide or polyamide imide; the dispersing agent comprises at least one of sodium carboxymethylcellulose, polyacrylate or polyvinylpyrrolidone; the conductive agent comprises at least one of acetylene black, Ketjen black, porous carbon, graphene, single-walled or multi-walled conductive carbon nanotubes.
In a fourth aspect, the present invention provides a lithium ion battery comprising the negative electrode material according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method provided by the invention, the coke material and the hard carbon are mixed for use, so that the synergistic relationship of the coke material and the hard carbon is well exerted, the gram volume of the hard carbon material is high, the volume of a secondary particle material formed by the hard carbon material and the coke material is increased, meanwhile, the rebound of the hard carbon material is small, the rebound of the coke material is reduced, and the production cost of the cathode material is reduced; meanwhile, the introduction of hard carbon enables the short distance of the secondary particle material to be more ordered, the orientation degree to be reduced, and the quick charging performance to be improved; the preparation method provided by the invention does not carry out any coating on the cathode material, so that the high-temperature performance of the material is improved. The first-week coulombic efficiency of the negative electrode material provided by the invention is above 86.2%, the first-week specific capacity of the negative electrode is above 354.3mAh/g, the quick-charging performance (3C charging ratio) is above 79.8%, and the capacity retention rate after storage for 30 days at 60 ℃ is above 95.3%.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of the anode material provided in example 1.
Fig. 2 is a schematic flow chart of a method for manufacturing a lithium-ion secondary battery provided in example 1.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
The embodiment provides a preparation method of an anode material, which comprises the following specific steps:
(1) mixing a crushed and shaped coke material (petroleum coke) with D50 of 15 mu m and a crushed and shaped hard carbon (furfuryl ketone resin hard carbon) with D50 of 15 mu m in a horizontal mixer (a mixer with a cylinder volume of 200L and a maximum loading of 250kg of material, the rotating speed of the cylinder of 17r/min and the rotating speed of a blade of 35r/min) for 45min, adding a carbon-containing binder (asphalt), heating to 600 ℃ at a heating rate of 3 ℃/min in a nitrogen atmosphere, and mechanically fusing and granulating for 4h by using a horizontal kettle (the rotating speed frequency is 25Hz) to obtain a granulated product;
wherein the mass of the hard carbon is 20% of that of the coke material, and the mass of the carbon-containing binder is 15% of that of the coke material;
(2) and (3) graphitizing the granulated product in the step (1) for 45 hours at the temperature of 3100 ℃ by using an ultrahigh-temperature graphitizing furnace in a nitrogen atmosphere to obtain the negative electrode material.
A schematic flow chart of the preparation method of the anode material provided in this embodiment is shown in fig. 1.
The test results of the anode material provided in this example are shown in table 1.
The embodiment also provides a preparation method of the lithium ion secondary battery, the flow schematic diagram of which is shown in fig. 2, the negative electrode material, the conductive agent and the binder are dispersed by the solvent to form negative electrode slurry, the negative electrode slurry is coated on the current collector, and is dried to form the negative electrode sheet, and the negative electrode sheet, the positive electrode sheet, the diaphragm and the electrolyte are assembled to obtain the lithium ion secondary battery.
Example 2
The embodiment provides a preparation method of an anode material, which comprises the following specific steps:
(1) mixing a crushed and shaped coke material (petroleum coke and coal coke with a mass ratio of 1:1) with a D50 of 8 mu m and a crushed and shaped hard carbon (acrylic resin hard carbon) with a D50 of 18 mu m in a horizontal mixer (a mixer with a cylinder volume of 200L, the maximum charge of 250kg of material, the cylinder rotation speed of 17r/min and the blade rotation speed of 35r/min) for 35min, adding a carbon-containing binder (coal tar), heating to 550 ℃ at a heating rate of 4 ℃/min in a nitrogen atmosphere, and mechanically fusing and granulating for 3h by using a horizontal kettle (the rotation speed frequency of 25Hz) to obtain a granulated product;
wherein the mass of the hard carbon is 30% of that of the coke material, and the mass of the carbon-containing binder is 10% of that of the coke material;
(2) and (3) graphitizing the granulated product in the step (1) for 55 hours at 3000 ℃ by using an ultrahigh-temperature graphitizing furnace in a nitrogen atmosphere to obtain the negative electrode material.
The test results of the anode material provided in this example are shown in table 1.
Example 3
The embodiment provides a preparation method of an anode material, which comprises the following specific steps:
(1) mixing a crushed and shaped coke material (coal coke) with D50 of 10 mu m and a crushed and shaped hard carbon (phenolic resin hard carbon) with D50 of 10 mu m in a horizontal mixer (a mixer with a cylinder volume of 200L, the maximum charge of 250kg of material, the rotation speed of the cylinder of 15r/min and the rotation speed of a blade of 40r/min) for 30min, adding a carbon-containing binder (polypropylene emulsion), heating to 500 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere, and mechanically fusing and granulating for 6h by using a horizontal kettle (the rotation speed frequency is 10Hz) to obtain a granulated product;
wherein the mass of the hard carbon is 10% of that of the coke material, and the mass of the carbon-containing binder is 5% of that of the coke material;
(2) and (3) graphitizing the granulated product in the step (1) for 60 hours by using a vertical graphitization furnace at the temperature of 2800 ℃ under the condition of vacuumizing until the vacuum degree is 0.5Pa, so as to obtain the negative electrode material.
The test results of the anode material provided in this example are shown in table 1.
Example 4
The embodiment provides a preparation method of an anode material, which comprises the following specific steps:
(1) mixing a crushed and shaped coke material (asphalt coke) with D50 of 4 mu m and a crushed and shaped hard carbon (asphalt hard carbon) with D50 of 20 mu m in a horizontal mixer (a mixer with a cylinder volume of 200L and a maximum loading of 250kg of material, the rotating speed of the cylinder of 20r/min and the rotating speed of a blade of 25r/min) for 60min, adding a carbon-containing binder (acrylic acid solution), heating to 700 ℃ at a heating rate of 6 ℃/min in an argon atmosphere, and mechanically fusing and granulating for 2h by using a horizontal kettle (the rotating speed frequency is 40Hz) to obtain a granulated product;
wherein the mass of the hard carbon is 40% of that of the coke material, and the mass of the carbon-containing binder is 20% of that of the coke material;
(2) and (3) graphitizing the granulated product in the step (1) for 36 hours by using a horizontal graphitizing furnace at 3500 ℃ under the argon condition to obtain the negative electrode material.
The test results of the anode material provided in this example are shown in table 1.
Comparative example 1
The preparation method of the anode material provided by the comparative example is the same as the preparation method of the anode material provided by example 1 except that no coke-based material is added in step (1).
The test results of the negative electrode material provided in this comparative example are shown in table 1.
Comparative example 2
The method for preparing the anode material provided by this comparative example is the same as the method for preparing the anode material provided by example 1, except that hard carbon is not added in step (1).
The test results of the negative electrode material provided in this comparative example are shown in table 1.
Comparative example 3
The method for producing the anode material provided in this comparative example is the same as the method for producing the anode material provided in example 1, except that no carbonaceous binder is added in step (1).
The test results of the negative electrode material provided in this comparative example are shown in table 1.
Test method
The negative electrode materials provided by the examples and the comparative examples are used as active substances, SBR and CMC are used as binders, conductive carbon black is added, stirring and pulping are carried out, the mixture is coated on copper foil, and finally the negative electrode sheet is prepared by drying and rolling, wherein the active substances comprise 96 percent of conductive agent, SBR and 1.5 percent of CMC and 1.5 percent of conductive agent. The positive active material is NCM523, PVDF is used as a binder, conductive carbon black is added, stirring and pulping are carried out, the mixture is coated on an aluminum foil, and finally, the positive plate is prepared by drying and rolling, wherein the active material comprises a conductive agent, namely the binder (PVDF), 97%, 1.5% and 1.5%. PP as separator, LiPF6The method comprises the following steps of (1) assembling a test battery by taking/EC + DEC + DMC (EC, DEC and DMC in a volume ratio of 1:1:1) as an electrolyte, and performing electrochemical test by using a blue light tester, wherein the electrochemical test specifically comprises the following steps:
and (3) carrying out a charge-discharge test on the obtained battery at the temperature of 25 +/-2 ℃, wherein the charge-discharge voltage is 2.8V-4.2V, the charge-discharge current density is 0.2C, and the gram capacity and the first coulombic efficiency of the negative electrode material are tested. And (3) performing a charge-discharge test at the temperature of 25 +/-2 ℃, wherein the charge-discharge voltage is 2.8V-4.2V, the charge current density is 0.33C and 3C respectively, calculating the charge capacity at the rate of 3C divided by the charge capacity at the rate of 0.33C, and obtaining a percentage value, wherein the larger the vertical middle finger is, the better the quick charge performance is represented, thereby testing the quick charge performance of the cathode material. Under the condition of 25 +/-2 ℃, the charging and discharging voltage is 2.8V-4.2V, the battery cell is charged and discharged once by using 0.5C current, the discharging capacity of the battery cell is A1, and then the battery cell is fully charged according to the charging and discharging mechanism. And storing the fully charged cell for 30 days in an environment of 60 +/-2 ℃. And after the storage for 60 days, taking out the battery cell and cooling to the normal temperature. Under the condition of 25 +/-2 ℃, the charging and discharging voltage is 2.8V-4.2V, the battery cell is firstly discharged to 2.8V by using the multiplying power of 0.5C to obtain the battery cell capacity of A2, then the battery cell is charged to 4.2V by using the multiplying power of 0.5C to obtain the battery cell capacity of A3, the battery cell capacity retention rate is obtained by calculating A2/A1, and the battery cell capacity recovery rate is obtained by calculating A3/A1. The higher the capacity retention rate and the recovery rate, the better the high-temperature performance of the battery cell. The high temperature performance of the negative electrode material was tested by the above method.
The test results are given in the following table:
TABLE 1
It can be known from the above examples and comparative examples that the preparation method provided by the examples utilizes the coke material and the hard carbon as raw materials, and the synergistic relationship between the coke material and the hard carbon is well exerted, the gram volume of the hard carbon material is high, the volume of the secondary particle material formed by the hard carbon material and the coke material is increased, meanwhile, the rebound of the hard carbon material is small, the rebound of the coke material is reduced, and the production cost of the cathode material is reduced; meanwhile, the introduction of hard carbon enables the short distance of the secondary particle material to be more ordered, the orientation degree to be reduced, and the quick charging performance to be improved; in addition, the preparation method of the embodiment does not carry out any coating on the negative electrode material, so that the high-temperature performance of the material is improved.
Comparative example 1 no coke-type material was used, resulting in a material with a low first coulombic efficiency.
Comparative example 2 no hard carbon was used, resulting in a significant decrease in fast-fill performance.
Comparative example 3 no carbonaceous binder was used, resulting in poor fast-fill properties of the material.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a negative electrode material is characterized by comprising the following steps:
(1) mixing the coke material and hard carbon, adding a carbon-containing binder, and granulating to obtain a granulated product;
(2) and (2) graphitizing the granulated product in the step (1) to obtain the negative electrode material.
2. The method according to claim 1, wherein the coke-based material of step (1) is a low-degree-of-orientation coke-based material;
preferably, the coke-based material in step (1) comprises any one or a combination of at least two of petroleum coke, pitch coke or coal coke;
preferably, the coke-like material in the step (1) is crushed and shaped before being mixed;
preferably, the particle size D50 of the coke-like material in the step (1) is 4-15 μm.
3. The production method according to claim 1 or 2, characterized in that the hard carbon of step (1) comprises any one of or a combination of at least two of furfuryl ketone resin hard carbon, unsaturated polyester resin hard carbon, acrylic resin hard carbon, phenol resin hard carbon, polyoxymethylene resin hard carbon, epoxy resin hard carbon, furfural resin hard carbon, or pitch hard carbon;
preferably, the hard carbon of step (1) is crushed and shaped before mixing;
preferably, the particle size D50 of the hard carbon in the step (1) is 10-20 μm.
4. The production method according to any one of claims 1 to 3, wherein in the step (1), the mass of the hard carbon is 10 to 40% of the mass of the coke-based material;
preferably, in the step (1), the mixing time is 30-60 min;
preferably, in the step (1), the mixing is carried out in a mixer, wherein the rotating speed of a cylinder of the mixer is 15-20r/min, and the rotating speed of a blade is 25-40 r/min.
5. The method according to any one of claims 1 to 4, wherein in step (1), the carbonaceous binder comprises any one or a combination of at least two of pitch, coal tar, polypropylene, polyethylene, or acrylic acid;
preferably, in the step (1), the mass of the carbon-containing binder is 5-20% of the mass of the coke-based material;
preferably, the granulation in step (1) is mechanofusion granulation;
preferably, the granulation time of the step (1) is 2-6 h;
preferably, the temperature of the granulation in the step (1) is 500-700 ℃;
preferably, the temperature rise rate of the granulation in the step (1) is 2-5 ℃/min;
preferably, the granulation of step (1) is carried out under a protective atmosphere;
preferably, the protective atmosphere comprises any one of nitrogen, argon or helium or a combination of at least two thereof.
6. The method according to any one of claims 1 to 5, wherein the graphitization temperature in step (2) is 2800-3500 ℃;
preferably, the graphitization time of the step (2) is 36-60 h;
preferably, the graphitization in the step (2) is performed under vacuum or protective atmosphere;
preferably, the protective atmosphere comprises any one of gas, argon or helium or a combination of at least two thereof.
7. The method for preparing according to any one of claims 1 to 6, characterized in that it comprises the steps of:
(1) mixing the crushed and shaped coke material and the crushed and shaped hard carbon for 30-60min, adding a carbon-containing binder, heating to the temperature of 500-700 ℃ at the heating rate of 2-5 ℃/min in a protective atmosphere, and performing mechanical fusion granulation for 2-6h to obtain a granulated product;
wherein the mass of the hard carbon is 10-40% of that of the coke material, and the mass of the carbon-containing binder is 5-20% of that of the coke material;
(2) and (3) graphitizing the granulated product in the step (1) at 2800-3500 ℃ for 36-60h under vacuum pumping or protective atmosphere to obtain the negative electrode material.
8. The negative electrode material obtained by the production method according to claim 1.
9. A negative electrode sheet, characterized in that the negative electrode sheet comprises the negative electrode material according to claim 8.
10. A lithium ion battery comprising the negative electrode sheet according to claim 9.
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| CN114852991A (en) * | 2022-06-09 | 2022-08-05 | 广东凯金新能源科技股份有限公司 | Hard carbon and soft carbon co-modified artificial graphite anode material and preparation method thereof |
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