CN114188533B - Negative electrode material and preparation method and application thereof - Google Patents
Negative electrode material and preparation method and application thereof Download PDFInfo
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- CN114188533B CN114188533B CN202111564276.9A CN202111564276A CN114188533B CN 114188533 B CN114188533 B CN 114188533B CN 202111564276 A CN202111564276 A CN 202111564276A CN 114188533 B CN114188533 B CN 114188533B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- 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
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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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- 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
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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Abstract
The invention provides a negative electrode material, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Carrying out gas corrosion and pore-forming treatment on a graphite raw material to obtain a porous graphite precursor; (2) Performing vapor deposition coating carbonization treatment on the porous graphite precursor obtained in the step (1) and a nitrogen-containing polymer to obtain nitrogen-doped porous graphite; (3) Mixing the nitrogen doped porous graphite obtained in the step (2), a silicon source and a liquid phase coating agent, and performing heating treatment to obtain the negative electrode material. The material has the characteristics of low expansion, high capacity, high compaction and high rate capability.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a negative electrode material, a preparation method and application thereof.
Background
The exhaust emission of fuel vehicles causes atmospheric pollution, which is increasingly serious with the increase of the total quantity of the motor vehicles. Countries with high care on environmental pollution start to improve the energy use structure greatly, reduce emission and increase the development force of green energy. With the rapid development of new energy automobiles, lithium ion battery technology and markets have greatly developed as power sources of electric automobiles.
The lithium ion battery is widely applied to the automobile industry due to the advantages of high energy density, self-discharging capability, high charging efficiency and the like, however, the longer charging time and the lower endurance mileage make the electric automobile unable to completely meet the travel demands of people, so people need a battery with quick charging and long endurance mileage. Graphite is one of the main negative electrode materials of lithium ion batteries, and how to rapidly realize the rapid charging performance of graphite is one of the research hot spots in recent years.
CN109935793a discloses a preparation method of a high-capacity high-magnification composite graphene negative electrode material of a lithium ion battery, which coats part of graphene material on the surface of graphite, so that the magnification performance of the material is improved, but graphene preparation is difficult, and graphene is multilayer graphite in the current market, so-called graphene has poor consistency, and cannot meet sufficient production conditions.
CN111392723a discloses a preparation method of porous graphite, a product and application thereof, wherein graphite raw material is placed in corrosive gas for heat treatment to obtain porous graphite; the etching gas is selected from carbon dioxide, air or oxygen-containing atmosphere, but the crystal structure of the corroded graphite particles is destroyed, and the material energy density has an irreversible effect.
CN109437153a discloses a preparation method and application of a high-current pulsed electron beam of mesoporous carbon, which adopts the high-current pulsed electron beam to pore graphite, and also forms partial gaps in graphite crystals to improve the multiplying power performance of the material, but increases the specific surface area of the material, and has shorter storage life.
The anode material prepared by the scheme has the problems of poor consistency, poor energy density or short storage life, so that the development of the anode material with good consistency, good energy density and long storage life is necessary.
Disclosure of Invention
The invention aims to provide a negative electrode material, a preparation method and application thereof. The material has the characteristics of low expansion, high capacity, high compaction and high rate capability.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a negative electrode material, the method comprising the steps of:
(1) Carrying out gas corrosion and pore-forming treatment on a graphite raw material to obtain a porous graphite precursor;
(2) Performing vapor deposition coating carbonization treatment on the porous graphite precursor obtained in the step (1) and a nitrogen-containing polymer to obtain nitrogen-doped porous graphite;
(3) And (3) mixing the nitrogen-doped porous graphite obtained in the step (2), a silicon source and a liquid-phase coating agent, and performing heating treatment to obtain the anode material.
According to the invention, the graphite raw material is subjected to pore granulation, so that a lithium ion intercalation channel is provided, the multiplying power performance is greatly improved, meanwhile, nitrogen doping and vapor deposition coating carbonization are adopted, negative reactions caused by pores are less, and then the silicon oxide composite coating is adopted, so that the energy density of the material is improved.
Preferably, the graphite raw material in the step (1) comprises any one or a combination of at least two of petroleum coke, needle coke, pitch coke and flake graphite.
Preferably, the shaping treatment is performed on the graphite raw material before the pore-forming treatment.
Preferably, the particle size of the graphite raw material is 5 to 20 μm, for example: 5 μm, 8 μm, 10 μm, 15 μm or 20 μm, etc.
Preferably, the method of pore-forming treatment in step (1) comprises the following steps:
and dissolving the pore-forming agent in deionized water, adding the corroded graphite raw material, mixing by a fusion machine, and graphitizing the mixed graphite precursor at a high temperature.
According to the method, the graphite raw material is subjected to gas corrosion pore-forming, gas corrosion is adopted, pore-forming is uniform, materials are easy to obtain, and thus, gaps on the surfaces of particles are formed, channels for embedding and extracting lithium ions are provided, the inside of the particles are subjected to longitudinal pore-forming by adopting a pore-forming agent, and the speeds of embedding and extracting lithium ions are further improved through the penetration from the surface layer to the deep layer.
Preferably, the mass ratio of the pore-forming agent to the graphite raw material is 0.05-0.2:1, for example: 0.05:1, 0.08:1, 0.1:1, 0.15:1, or 0.2:1, etc.
Preferably, the high temperature graphitization temperature is 2600 to 3200 ℃, for example: 2600 ℃, 2700 ℃, 2800 ℃, 2900 ℃, 3000 ℃, 3100 ℃ or 3200 ℃ and the like.
Preferably, the specific surface area of the porous graphite precursor is 5-20 m 2 /g, for example: 5m 2 /g、8m 2 /g、10m 2 /g、15m 2 /g or 20m 2 /g, etc.
Preferably, the porous graphite precursor has a porosity of 10 to 20%, for example: 10%, 12%, 15%, 18% or 20%, etc.
Preferably, in the method of the vapor deposition coating carbonization treatment in the step (2), the porous graphite precursor and the nitrogen-containing polymer are mixed, coating gas is introduced, and the nitrogen-doped porous graphite is obtained through vapor deposition.
The invention repairs the pores by vapor deposition, the gas coating agent impregnates the inside of the particles to modify the pore structure, and the inside of the pores is an amorphous carbon structure.
Preferably, the nitrogen-containing polymer comprises any one or a combination of at least two of melamine, polyacrylonitrile, polyurethane, or polyaniline.
Preferably, the mass ratio of the nitrogen-containing polymer to the porous graphite precursor is 0.05-0.3:1, for example: 0.05:1, 0.1:1, 0.15:1, 0.2:1, or 0.3:1, etc.
Preferably, the sheath gas comprises any one or a combination of at least two of ethylene, acetylene or methane.
Preferably, the speed of introducing the covering gas is 100-1000 mL/min, for example: 100mL/min, 200mL/min, 500mL/min, 800mL/min, 1000mL/min, etc.
Preferably, the nitrogen-doped porous graphite has a pore carbon residue value of 0.5 to 5%, for example: 0.5%, 1%, 2%, 3%, 4% or 5%, etc.
Preferably, the silicon source of step (3) comprises spherical silica.
Preferably, the particle size of the spherical silica is 50 to 100nm, for example: 50nm, 60nm, 70nm, 80nm, 90nm or 100nm, etc.
Preferably, the liquid phase coating agent comprises any one or a combination of at least two of liquid asphalt, phenolic resin or heavy oil.
Preferably, the mass ratio of the nitrogen doped porous graphite, the silicon source and the liquid phase coating agent is 1 (0.005-0.1): (0.01-0.05), for example: 1:0.005:0.01, 1:0.01:0.002, 1:0.05:0.003, 1:0.08:0.004, or 1:0.1:0.05, etc.
Preferably, the temperature of the heating treatment is 1000 to 1300 ℃, for example: 1000 ℃, 1100 ℃, 1200 ℃, 1250 ℃, 1300 ℃, etc.
According to the invention, chemical doping and silicon-based material addition are adopted to carry out coating granulation, modification treatment is carried out on the surface of the graphite material, and liquid phase coating and granulation are adopted, so that silicon and graphite are perfectly compounded, the energy density of the material is improved, and the expansion of a silicon negative electrode is absorbed by utilizing the characteristic of a porous structure of the graphite, so that the integral expansion of the material is reduced.
In a second aspect, the present invention provides a negative electrode material, which is prepared by the method according to the first aspect, and comprises a core and a coating layer, wherein the thickness of the coating layer is 5-20 nm, for example: 5nm, 10nm, 15nm or 20nm, etc.
In the inner core of the negative electrode material, porous graphite particles and a nanoscale silicon oxide material are bonded together, and a coating layer is a layer of compact and uniform amorphous carbon.
In a third aspect, the present invention provides a negative electrode tab comprising a negative electrode material as described in the second aspect.
In a fourth aspect, the present invention provides a lithium ion battery comprising a negative electrode sheet according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the graphite raw material is subjected to pore granulation, so that a lithium ion intercalation channel is provided, the multiplying power performance is greatly improved, meanwhile, nitrogen doping and vapor deposition coating carbonization are adopted, negative reactions caused by pores are less, and then silicon oxide composite coating is adopted, so that the energy density of the material is improved.
(2) The specific surface area of the anode material of the invention can reach 8.24m 2 The gram capacity can reach more than 407.5mAh/g, the first efficiency can reach more than 89.9%, the charging constant current ratio of the 3C at 25 ℃ of the prepared battery can reach more than 91.8%, and the capacity retention rate of the 3C/1C at 25 ℃ for 500 weeks can reach more than 87.7%. Meets the requirement of high energy density of the material. Electrochemical tests show that the 3C charging constant current ratio is up to 96.4%, and the battery has excellent cycling stability under high current density, and remains after 500 cyclesHolding 92.3% of the capacity.
Drawings
Fig. 1 is a schematic structural view of a negative electrode material according to embodiment 1 of the present invention.
FIG. 2 is a schematic diagram of the structure of the nitrogen-doped and vapor-deposited coated porous graphite according to example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a negative electrode material, and the preparation method of the negative electrode material comprises the following steps:
(1) Crushing petroleum coke to 5 mu m, performing gas corrosion treatment, dissolving a pore-forming agent in deionized water, adding the pore-forming agent and the petroleum coke in a mass ratio of 0.1:1 into a corroded precursor, fully mixing by a fusion machine, and graphitizing at 3000 ℃ to obtain the product with a specific surface area of 10m 2 A porous graphite precursor having a porosity of 15%;
(2) Mixing the porous graphite precursor obtained in the step (1) with melamine according to the mass ratio of 1:0.05, placing the mixture into a vapor deposition carbonization furnace, introducing methane at the speed of 500mL/min, heating and stirring the mixture, and completing the vapor deposition carbonization process to obtain nitrogen-doped porous graphite, wherein the structural schematic diagram of the nitrogen-doped porous graphite is shown in figure 2;
(3) And (3) placing the mixture of the silicon oxide with the grain diameter of 100nm of the nitrogen-doped porous graphite obtained in the step (2) and the liquid asphalt in a heating VC machine according to the mass ratio of 1:0.05:0.003, and sintering at 1200 ℃ to obtain the negative electrode material with the coating layer thickness of 15nm, wherein the structural schematic diagram of the negative electrode material is shown in figure 1.
Example 2
The embodiment provides a negative electrode material, and the preparation method of the negative electrode material comprises the following steps:
(1) Crushing asphalt coke to 20 microns, gas etching, and dissolving pore forming agent in deionized waterWherein the mass ratio of the pore-forming agent to the pitch coke is 0.2:1, the pore-forming agent and the pitch coke are added into the corroded precursor, fully mixed by a fusion machine, graphitized at 2900 ℃ to obtain the porous ceramic material with the specific surface area of 12m 2 A porous graphite precursor having a porosity of 12%;
(2) Mixing the porous graphite precursor obtained in the step (1) with melamine according to the mass ratio of 1:0.3, placing the mixture into a vapor deposition carbonization furnace, introducing methane at the speed of 100mL/min, heating and stirring the mixture, and completing the vapor deposition carbonization process to obtain nitrogen-doped porous graphite;
(3) And (3) placing the mixture of the silicon oxide with the particle size of 100nm of the nitrogen-doped porous graphite obtained in the step (2) and the liquid asphalt in a heating VC machine according to the mass ratio of 1:0.05:0.1, and sintering at 1200 ℃ to obtain the anode material with the coating layer thickness of 12 nm.
Example 3
This example differs from example 1 only in that the mass ratio of pore-forming agent to graphite starting material in step (1) is 0.03:1, and other conditions and parameters are exactly the same as in example 1.
Example 4
This example differs from example 1 only in that the mass ratio of pore-forming agent to graphite starting material in step (1) is 0.25:1, and other conditions and parameters are exactly the same as in example 1.
Example 5
This example differs from example 1 only in that the mass ratio of the nitrogen-containing polymer and the porous graphite precursor in step (2) is 0.03:1, and other conditions and parameters are exactly the same as in example 1.
Example 6
This example differs from example 1 only in that the mass ratio of the nitrogen-containing polymer and the porous graphite precursor in step (2) is 0.35:1, and other conditions and parameters are exactly the same as in example 1.
Comparative example 1
This comparative example differs from example 1 only in that no nitrogen-containing polymer was added, and other conditions and parameters were exactly the same as in example 1.
Comparative example 2
This comparative example differs from example 1 only in that no vapor deposition coating is performed, and other conditions and parameters are exactly the same as example 1.
Comparative example 3
This comparative example differs from example 1 only in that no silica was added, and other conditions and parameters were exactly the same as example 1.
Performance test:
mixing the anode materials obtained in the examples 1-6 and the comparative examples 1-3 with conductive carbon black (SP), sodium carboxymethyl cellulose and styrene-butadiene rubber according to the mass ratio of 96.2:1.0:1.3:1.5 to obtain anode slurry, coating the anode slurry on copper foil to obtain an anode plate, mixing lithium iron phosphate, conductive carbon black (SP), polyvinylidene fluoride and carbon nano tubes according to the mass ratio of 96:0.5:2:0.7 to obtain anode slurry, and coating the anode slurry on aluminum foil to obtain an anode plate;
the prepared positive electrode and negative electrode are made into a 505070 lithium iron phosphate soft package battery, 3C current is adopted under the 25 ℃ environment, constant current and constant voltage are charged to 3.65V, and the charging capacity of a constant current section is recorded as C 1 Record total charge capacity as C 2 The constant current ratio can be expressed as C 1 /C 2 *100%. The 3C/1C cycle capacity retention rate at 25 ℃ specifically means that under the 25 ℃ environment, 3C current is adopted, constant current and constant voltage charge is adopted to reach 3.65V, the first week charge capacity is recorded as C3, then 1C current is adopted to discharge to reach 2.5V, the cycle is 500 weeks, the 500 th week constant current discharge capacity is recorded as C4, the 3C/1C cycle 500 week capacity retention rate at 25 ℃ is expressed as C4/C3 x 100%, and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, according to examples 1 to 6, the specific surface area of the anode material of the present invention can be 8.24m 2 The gram capacity can reach more than 407.5mAh/g below/g, and the first efficiency can reach89.9% or more, the charging constant current ratio of the battery at 25 ℃ 3C can reach 91.8% or more, and the capacity retention rate of the battery at 25 ℃ 3C/1C cycle 500 weeks can reach 87.7% or more.
The comparison between the embodiment 1 and the embodiment 3-4 shows that the mass ratio of the pore-forming agent to the graphite raw material can affect the performance of the prepared anode material, the mass ratio of the pore-forming agent to the graphite raw material is controlled to be 0.05-0.2:1, the prepared anode material has better performance, if the addition amount of the pore-forming agent is too large, the specific surface area of the anode material is larger, the exposed defects are more, the vapor deposition can not be completely modified, the contact area of the anode material and the electrolyte is larger, the side reaction is more, the cycle attenuation is faster, and if the addition amount of the pore-forming agent is too small, the pores of the anode material are less, lithium ions can not be quickly embedded into the center of graphite particles during high-rate charging, and the rate performance can not be satisfied.
As can be seen from comparison of examples 1 and examples 5 to 6, the mass ratio of the nitrogen-containing polymer to the porous graphite precursor affects the performance of the negative electrode material, the performance of the negative electrode material is better, if the addition amount of the nitrogen-containing polymer is too large, more defects are formed in the graphite crystal structure, on one hand, the defects become lithium storage units, the gram capacity of the material is increased, on the other hand, the more defects can aggravate side reactions with electrolyte, the cycle attenuation is faster, if the addition amount of the nitrogen-containing polymer is too small, the formed defect structure is smaller, the gram capacity and conductivity of the material are slightly insufficient, and the energy density and the rate performance of the material are relatively poor.
As can be obtained by comparing the example 1 with the comparative example 1, the invention can obviously improve the rate capability of the material by doping nitrogen into the anode material.
By comparing the embodiment 1 with the comparative example 2, the invention carries out vapor deposition coating on the graphite pores, can reduce the specific surface area of the material, increases the lithium storage position after the pores are filled, increases the gram capacity of the material, increases the first efficiency, and greatly increases the multiplying power performance of the material.
As can be obtained by comparing the example 1 with the comparative example 3, the invention composites the graphite material and the silicon oxide material, the gram capacity of the material is obviously increased, and the energy density requirement can be met.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (17)
1. A method for preparing a negative electrode material, comprising the steps of:
(1) Carrying out gas corrosion and pore-forming treatment on a graphite raw material to obtain a porous graphite precursor;
(2) Performing vapor deposition coating carbonization treatment on the porous graphite precursor obtained in the step (1) and a nitrogen-containing polymer to obtain nitrogen-doped porous graphite;
(3) Mixing the nitrogen-doped porous graphite obtained in the step (2), a silicon source and a liquid-phase coating agent, and performing heating treatment to obtain the anode material;
the method of the vapor deposition coating carbonization treatment in the step (2) comprises the steps of mixing a porous graphite precursor and a nitrogen-containing polymer, introducing coating gas, and obtaining nitrogen-doped porous graphite through vapor deposition, wherein the nitrogen-containing polymer comprises any one or a combination of at least two of melamine, polyacrylonitrile, polyurethane and polyaniline, and the coating gas comprises any one or a combination of at least two of ethylene, acetylene and methane;
the liquid phase coating agent in the step (3) comprises any one or a combination of at least two of liquid asphalt, phenolic resin and heavy oil, the temperature of the heating treatment is 1000-1300 ℃, and the silicon source is spherical silicon oxide.
2. The method of claim 1, wherein the graphite material of step (1) comprises any one or a combination of at least two of petroleum coke, needle coke, pitch coke, and flake graphite.
3. The method of claim 1, wherein the graphite material is shaped prior to the pore-forming treatment.
4. The method according to claim 1, wherein the graphite raw material has a particle diameter of 5 to 20. Mu.m.
5. The method of claim 1, wherein the pore-forming treatment in step (1) comprises:
and dissolving the pore-forming agent in deionized water, adding the corroded graphite raw material, mixing by a fusion machine, and graphitizing the mixed graphite precursor at a high temperature.
6. The method according to claim 5, wherein the mass ratio of the pore-forming agent to the graphite raw material is 0.05-0.2:1.
7. The method of claim 5, wherein the high temperature graphitization is at a temperature of 2600 ℃ to 3200 ℃.
8. The method according to claim 1, wherein the porous graphite precursor has a specific surface area of 5 to 20m 2 /g。
9. The method of claim 1, wherein the porous graphite precursor has a porosity of 10 to 20%.
10. The method of claim 1, wherein the mass ratio of the nitrogen-containing polymer to the porous graphite precursor is 0.05-0.3:1.
11. The method according to claim 1, wherein the velocity of the introducing the coating gas is 100 to 1000mL/min.
12. The method of claim 1, wherein the nitrogen-doped porous graphite has a pore carbon residue value of 0.5 to 5%.
13. The method according to claim 1, wherein the spherical silica has a particle diameter of 50 to 100nm.
14. The preparation method according to claim 1, wherein the mass ratio of the nitrogen-doped porous graphite, the silicon source and the liquid-phase cladding agent is 1 (0.005-0.1): 0.01-0.05.
15. A negative electrode material, characterized in that it is produced by the method according to any one of claims 1 to 14, comprising a core and a coating layer, the thickness of the coating layer being 5 to 20nm.
16. A negative electrode tab comprising the negative electrode material of claim 15.
17. A lithium ion battery comprising the negative electrode tab of claim 16.
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