CN114122393A - Preparation method of high-power-density negative electrode material for lithium ion battery - Google Patents
Preparation method of high-power-density negative electrode material for lithium ion battery Download PDFInfo
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- CN114122393A CN114122393A CN202111331852.5A CN202111331852A CN114122393A CN 114122393 A CN114122393 A CN 114122393A CN 202111331852 A CN202111331852 A CN 202111331852A CN 114122393 A CN114122393 A CN 114122393A
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910021384 soft carbon Inorganic materials 0.000 claims abstract description 48
- 239000007833 carbon precursor Substances 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000006258 conductive agent Substances 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000012159 carrier gas Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000011331 needle coke Substances 0.000 claims description 39
- 239000002006 petroleum coke Substances 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- 239000010426 asphalt Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 239000011247 coating layer Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000004576 sand Substances 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 102220043159 rs587780996 Human genes 0.000 claims 1
- 238000000889 atomisation Methods 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 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
Classifications
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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
- H01M4/58—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
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a high-power-density negative electrode material for a lithium ion battery, which comprises the steps of pretreating a soft carbon precursor by strong acid or strong alkali to form a soft carbon precursor with a porous structure, putting the soft carbon precursor with the porous structure into a fluidized bed cavity, utilizing carrier gas to enable the soft carbon precursor with the porous structure to be in a fluidized state, and depositing a conductive agent on the surface of the soft carbon precursor with the porous structure in a liquid phase manner in an atomization manner, so that the interface impedance is further reduced, the high-current charging and discharging performance is improved, meanwhile, the residual carbon capacity can be within 2%, the inactive sites on the surface of the soft carbon are improved, the interface is improved, and the specific capacity, the first efficiency, the power performance and the cycle performance of the negative electrode material can be greatly improved.
Description
Technical Field
The invention relates to the technical field of negative electrode materials, in particular to a preparation method of a high-power-density negative electrode material for a lithium ion battery.
Background
The lithium ion battery has the advantages of high specific energy, high working voltage, wide application temperature range, low self-discharge rate, long cycle life, no pollution, good safety performance and the like, and is widely applied to various fields in recent years.
Most of traditional lithium batteries adopt graphite materials as negative electrode materials, and because the graphite materials are high in graphitization degree and have high layered structures, the lithium embedding space is small, so that the lithium embedding capacity of graphite is low, the charging and discharging efficiency of the lithium ion battery is low, and the cycle performance of graphite is poor. Therefore, there is a need to provide a new solution to improve the existing preparation method of high power density negative electrode material for lithium ion battery.
Disclosure of Invention
In view of the above, the present invention is directed to the defects existing in the prior art, and the main object of the present invention is to provide a method for preparing a high power density negative electrode material for a lithium ion battery, wherein the prepared lithium ion battery has excellent capacity performance, cycle performance, first charge-discharge efficiency and rate capability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a high-power-density cathode material for a lithium ion battery is characterized by comprising the following steps: the method comprises the following steps:
step (1): adding the binder, the conductive agent and the solvent into a sand mill according to a certain proportion, and grinding for 1-5 h at the grinding speed of 500-2500r/min to obtain a liquid conductive coating agent;
step (2): selecting a soft carbon precursor with small particle size to be mixed with 5-30 wt% of strong acid or strong base solution, stirring for 3-10h at the temperature of 120-150 ℃, filtering and fully cleaning to obtain the soft carbon precursor with a porous structure;
and (3): taking a proper amount of soft carbon precursor with a porous structure, and putting the soft carbon precursor into a fluidized bed cavity, wherein the binder: introducing carrier gas into the soft carbon precursor with the porous structure 3-6:100 to enable the soft carbon precursor to be in a fluidized state, atomizing and spraying the liquid conductive coating agent prepared in the step (1) at the atomizing speed of 1-10g/min to enable the liquid conductive coating agent to be uniformly coated on the surface of the soft carbon precursor with the porous structure to form a conductive coating layer, and obtaining the coated soft carbon precursor;
and (4): and (4) placing the coated soft carbon precursor obtained in the step (3) in a nitrogen atmosphere protective furnace for sintering, raising the temperature to 1600-2000 ℃ at the heating rate of 30-50 ℃/min, preserving the heat for 2-5 hours, and crushing and screening to obtain the high-power-density negative electrode material.
As a preferred scheme, the conductive agent is one or a mixture of carbon black, carbon nanotubes and graphene, and the carbon content of the conductive agent is more than 99%.
As a preferred scheme, the binder is one or a mixture of coal-series or oil-series asphalt, and the softening point of the binder is 50-200 ℃.
As a preferable scheme, the solvent is one or a mixture of benzene, toluene and xylene.
Preferably, the mass ratio of the binder to the conductive agent to the solvent is 1:0.05-0.5: 0.5-2.0.
Preferably, the soft carbon precursor is one or a mixture of pulverized petroleum coke and needle coke, and D50 is 3-6 μm.
Preferably, the carrier gas in step (3) is one or a mixture of nitrogen and argon, and the flow rate is 0.6-1.2m3The temperature is 160-200 ℃.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and specifically, the technical scheme includes that:
the soft carbon precursor with the porous structure is placed in the cavity of the fluidized bed, the soft carbon precursor with the porous structure is fluidized by utilizing the carrier gas, and the conductive agent is deposited on the surface of the soft carbon precursor with the porous structure in a liquid phase manner in an atomization manner, so that the interface impedance is further reduced, the high-current charging and discharging performance is improved, meanwhile, the residual carbon content can be within 2%, the surface inactive sites of the soft carbon are improved, the interface is improved, and the specific capacity, the first efficiency, the power performance and the cycle performance of the negative electrode material can be greatly improved.
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.
Detailed Description
The invention discloses a preparation method of a high-power-density cathode material for a lithium ion battery, which comprises the following steps of:
step (1): adding a binder, a conductive agent and a solvent into a sand mill according to a certain proportion, wherein the mass ratio of the binder to the conductive agent to the solvent is 1:0.05-0.5:0.5-2.0, the conductive agent is one or a mixture of carbon black, carbon nano tubes and graphene, the carbon content of the conductive agent is more than 99%, the binder is one or a mixture of coal-series or oil-series asphalt, the softening point of the binder is 50-200 ℃, the solvent is one or a mixture of benzene, toluene and xylene, grinding is carried out for 1-5 hours, and the grinding speed is 500-2500r/min, so as to obtain the liquid conductive coating agent.
Step (2): selecting a soft carbon precursor with small particle size and mixing the soft carbon precursor with 5-30 wt% of strong acid or strong base solution, wherein the soft carbon precursor is one or a mixture of pulverized petroleum coke or needle coke, D50 is 3-6 mu m, stirring the mixture for 3-10h at the temperature of 120-150 ℃, filtering and fully cleaning the mixture to obtain the soft carbon precursor with a porous structure.
And (3): taking a proper amount of soft carbon precursor with a porous structure, and putting the soft carbon precursor into a fluidized bed cavity, wherein the binder: 3-6:100 of soft carbon precursor with porous structure, and introducing carrier gas to fluidize the soft carbon precursor with porous structureIn the state that the carrier gas is one or the mixture of nitrogen and argon, the liquid conductive coating agent prepared in the step (1) is atomized and sprayed in, the atomization speed is 1-10g/min, and the flow speed is 0.6-1.2m3And/h, the temperature is 160-200 ℃, and the soft carbon precursor is uniformly coated on the surface of the soft carbon precursor with the porous structure to form a conductive coating layer, so that the coated soft carbon precursor is obtained.
And (4): and (4) placing the coated soft carbon precursor obtained in the step (3) in a nitrogen atmosphere protective furnace for sintering, raising the temperature to 1600-2000 ℃ at the heating rate of 30-50 ℃/min, preserving the heat for 2-5 hours, and crushing and screening to obtain the high-power-density negative electrode material.
The invention is illustrated below with specific examples and comparative examples.
Example 1
Step (1): adding the mixture of oil-based asphalt, carbon black and benzene and toluene into a sand mill according to a certain proportion, wherein the mass ratio of the mixture of oil-based asphalt, carbon black and benzene and toluene is 1:0.5:0.5, the softening point of the oil-based asphalt is 50-200 ℃, the carbon content of the carbon black is more than 99%, and grinding is carried out for 2h at the grinding speed of 2000r/min to obtain the liquid conductive coating agent.
Step (2): selecting and mixing pulverized petroleum coke with small particle size with 5 wt% of sodium hydroxide solution, wherein D50 of the petroleum coke is 3-6 mu m, stirring for 8h at 150 ℃, filtering and fully cleaning to obtain the soft carbon precursor with a porous structure.
And (3): taking a proper amount of petroleum coke with a porous structure, and putting the petroleum coke into a cavity of a fluidized bed, wherein the mass ratio of oil-series asphalt: 3:100 of petroleum coke with a porous structure, introducing mixed gas consisting of nitrogen and argon into the petroleum coke with the porous structure to enable the petroleum coke to be in a fluidized state, and atomizing and spraying the liquid conductive coating agent prepared in the step (1), wherein the atomizing speed is 1g/min, and the flow rate is 0.6m3And h, uniformly coating the petroleum coke on the surface of the petroleum coke with a porous structure at the temperature of 200 ℃ to form a conductive coating layer, thereby obtaining the coated petroleum coke.
And (4): and (4) placing the coated petroleum coke obtained in the step (3) in a nitrogen atmosphere protective furnace for sintering, raising the temperature to 1800 ℃ at a heating rate of 30 ℃/min, preserving the heat for 3 hours, and crushing and screening to obtain the high-power-density negative electrode material.
Example 2
Step (1): adding a mixture of oil-based asphalt, graphene, toluene and xylene into a sand mill according to a certain proportion, wherein the mass ratio of the mixture of oil-based asphalt, graphene, toluene and xylene is 1:0.05:2, the carbon content of graphene is more than 99%, the softening point of oil-based asphalt is 50-200 ℃, grinding is carried out for 1h, and the grinding speed is 2500r/min, so as to obtain the liquid conductive coating agent.
Step (2): selecting small-particle-size ground needle coke, mixing the needle coke with a 30 wt% sulfuric acid solution, wherein D50 of the needle coke is 3-6 mu m, stirring the needle coke at 120 ℃ for 10 hours, filtering and fully washing to obtain the needle coke with a porous structure.
And (3): taking a proper amount of needle coke with a porous structure and putting the needle coke into a cavity of a fluidized bed, wherein the oil-based asphalt: introducing nitrogen into the needle coke with the porous structure to ensure that the needle coke with the porous structure is in a fluidized state, and atomizing and spraying the liquid conductive coating agent prepared in the step (1) at the atomizing speed of 10g/min and the flow speed of 1.2m3And h, uniformly coating the needle coke on the surface of the needle coke with the porous structure at the temperature of 160 ℃ to form a conductive coating layer, thereby obtaining the coated needle coke.
And (4): and (4) sintering the coated needle coke obtained in the step (3) in a nitrogen atmosphere protection furnace, raising the temperature to 1800 ℃ at a heating rate of 40 ℃/min, preserving the heat for 4 hours, and crushing and screening to obtain the high-power-density negative electrode material.
Example 3
Step (1): adding a mixture of coal-series asphalt, carbon nano tubes and benzene into a sand mill according to a certain proportion, wherein the mass ratio of the mixture of the coal-series asphalt, the carbon nano tubes and the benzene is 1:0.5:0.5, the carbon content of the carbon nano tubes is more than 99%, the softening point of the coal-series asphalt is 50-200 ℃, and grinding is carried out for 5 hours at the grinding speed of 500r/min, so as to obtain the liquid conductive coating agent.
Step (2): selecting small-particle-size pulverized petroleum coke, mixing the small-particle-size pulverized petroleum coke with 10 wt% of sodium hydroxide solution, stirring the petroleum coke D50 being 3-6 mu m at 130 ℃ for 6 hours, filtering and fully cleaning to obtain the petroleum coke with a porous structure.
And (3): taking a proper amount of petroleum coke with a porous structure, and putting the petroleum coke into a cavity of a fluidized bed, wherein the mass ratio of coal-series asphalt: introducing argon gas into petroleum coke with a porous structure at a ratio of 4:100 to enable the petroleum coke to be in a fluidized state, and atomizing and spraying the liquid conductive coating agent prepared in the step (1) at an atomizing speed of 6g/min and a flow speed of 0.8m3And h, uniformly coating the petroleum coke on the surface of the petroleum coke with the porous structure at the temperature of 180 ℃ to form a conductive coating layer, thereby obtaining the coated petroleum coke.
And (4): and (4) sintering the coated petroleum coke obtained in the step (3) in a nitrogen atmosphere protective furnace, heating to 1600 ℃ at a heating rate of 50 ℃/min, preserving the heat for 5 hours, and crushing and screening to obtain the high-power-density negative electrode material.
Example 4
Step (1): adding the mixture of oil-based asphalt, the mixture of carbon black and graphene and toluene into a sand mill according to a certain proportion, wherein the mass ratio of the oil-based asphalt to the mixture of carbon black and graphene to the toluene is 1:0.1:1, the carbon content of the mixture of carbon black and graphene is more than 99%, the softening point of the oil-based asphalt is 50-200 ℃, and grinding is carried out for 3h at the grinding speed of 1500r/min, so as to obtain the liquid conductive coating agent.
Step (2): selecting small-particle-size ground needle coke, mixing the needle coke with a 20 wt% sulfuric acid solution, wherein D50 of the needle coke is 3-6 mu m, stirring for 3h at 130 ℃, filtering and fully cleaning to obtain the needle coke with a porous structure.
And (3): taking a proper amount of soft carbon precursor with a porous structure, and putting the soft carbon precursor into a fluidized bed cavity, wherein the oil pitch: introducing nitrogen into the needle coke with the porous structure at a ratio of 5:100 to ensure that the needle coke with the porous structure is in a fluidized state, and atomizing and spraying the liquid conductive coating agent prepared in the step (1) at an atomizing speed of 8g/min and a flow speed of 1.0m3And h, uniformly coating the needle coke on the surface of the needle coke with the porous structure at the temperature of 190 ℃ to form a conductive coating layer, thereby obtaining the coated needle coke.
And (4): and (4) sintering the coated needle coke obtained in the step (3) in a nitrogen atmosphere protection furnace, raising the temperature to 2000 ℃ at a heating rate of 35 ℃/min, preserving the heat for 2 hours, and crushing and screening to obtain the high-power-density negative electrode material.
Example 5
Step (1): adding a mixture of coal-series asphalt, graphene, benzene and toluene into a sand mill according to a certain proportion, wherein the mass ratio of the mixture of coal-series asphalt, carbon black, benzene and toluene is 1:0.3:1.5, the carbon content of the graphene is more than 99%, the softening point of the coal-series asphalt is 50-200 ℃, grinding is carried out for 2h, and the grinding speed is 2000r/min, so as to obtain the liquid conductive coating agent.
Step (2): selecting and mixing pulverized petroleum coke with small particle size with 5-30 wt% of sodium hydroxide solution, wherein D50 of the petroleum coke is 3-6 mu m, stirring for 8h at 125 ℃, filtering and fully cleaning to obtain the soft carbon precursor with a porous structure.
And (3): taking a proper amount of petroleum coke with a porous structure, and putting the petroleum coke into a cavity of a fluidized bed, wherein the mass ratio of coal-series asphalt: 3:100 of petroleum coke with a porous structure, introducing argon gas into the petroleum coke with the porous structure to enable the petroleum coke to be in a fluidized state, and atomizing and spraying the liquid conductive coating agent prepared in the step (1), wherein the atomizing speed is 3g/min, and the flow speed is 0.7m3And h, uniformly coating the petroleum coke on the surface of the petroleum coke with the porous structure at the temperature of 190 ℃ to form a conductive coating layer, thereby obtaining the coated petroleum coke.
And (4): and (4) sintering the coated petroleum coke obtained in the step (3) in a nitrogen atmosphere protective furnace, heating to 1700 ℃ at a heating rate of 35 ℃/min, preserving heat for 4 hours, and crushing and screening to obtain the high-power-density negative electrode material.
Example 6
Step (1): adding a mixture of coal-series asphalt, carbon nano tubes and xylene into a sand mill according to a certain proportion, wherein the mass ratio of the mixture of the coal-series asphalt, the carbon nano tubes and the xylene is 1:0.2:1.8, the carbon content of the carbon nano tubes is more than 99 percent, the softening point of the coal-series asphalt is 50-200 ℃, grinding is carried out for 3 hours, and the grinding speed is 1800r/min, so as to obtain the liquid conductive coating agent.
Step (2): selecting small-particle-size ground needle coke, mixing the needle coke with a 15 wt% sulfuric acid solution, wherein D50 of the needle coke is 3-6 mu m, stirring for 7 hours at 145 ℃, filtering and fully washing to obtain the needle coke with a porous structure.
And (3): taking a proper amount of needle coke with a porous structure and putting the needle coke into a cavity of a fluidized bed, wherein the mass ratio of coal-based asphalt: 3-6:100 of needle coke with a porous structure, introducing nitrogen into the needle coke with the porous structure to ensure that the needle coke with the porous structure is in a fluidized state, and atomizing and spraying the liquid conductive coating agent prepared in the step (1), wherein the atomization speed is 4g/min, and the flow speed is 0.9m3And h, uniformly coating the needle coke on the surface of the needle coke with the porous structure at the temperature of 190 ℃ to form a conductive coating layer, thereby obtaining the coated needle coke.
And (4): and (4) sintering the coated needle coke obtained in the step (3) in a nitrogen atmosphere protection furnace, raising the temperature to 1950 ℃ at the heating rate of 38 ℃/min, preserving the temperature for 3 hours, crushing and screening to obtain the high-power-density negative electrode material.
Comparative example 1
Adhesive: and (3) directly coating the soft carbon precursor with the ratio of 0.5-2:100, and then carbonizing to obtain the negative electrode material.
Comparative example 2
Negative electrode material obtained by coating soft carbon precursor without adding conductive agent
Electrochemical performance test
In order to test the performance of the lithium ion battery cathode material of the invention, a half-cell test method is used for testing, the cathode material of the above examples and comparative examples, SBR (solid content 50%), CMC and Super-p (weight ratio) are added with a proper amount of deionized water to be blended into slurry, the slurry is coated on a copper foil and dried in a vacuum drying oven for 12 hours to prepare a cathode piece, and the electrolyte is 1MLiPF6And 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. A constant-current charge and discharge experiment is carried out in a LAND battery test system, the charge and discharge voltage is controlled to be 0.01-3.00V, data collection and control are carried out by a charge and discharge cabinet controlled by a computer, and test results are shown in Table 1.
TABLE 1
According to the data in the table 1, the high-power-density negative electrode material prepared by the invention has excellent capacity performance, cycle performance, first charge-discharge efficiency and rate performance. The double-carbon layer structure formed by the conductive agent and the binder plays a very critical role, reduces the interface impedance and improves the performances in all aspects.
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 (7)
1. A preparation method of a high-power-density cathode material for a lithium ion battery is characterized by comprising the following steps: the method comprises the following steps:
step (1): adding the binder, the conductive agent and the solvent into a sand mill according to a certain proportion, and grinding for 1-5 h at the grinding speed of 500-2500r/min to obtain a liquid conductive coating agent;
step (2): selecting a soft carbon precursor with small particle size to be mixed with 5-30 wt% of strong acid or strong base solution, stirring for 3-10h at the temperature of 120-150 ℃, filtering and fully cleaning to obtain the soft carbon precursor with a porous structure;
and (3): taking a proper amount of soft carbon precursor with a porous structure, and putting the soft carbon precursor into a fluidized bed cavity, wherein the binder: introducing carrier gas into the soft carbon precursor =3-6:100 to enable the soft carbon precursor to be in a fluidized state, atomizing and spraying the liquid conductive coating agent prepared in the step (1) at the atomizing speed of 1-10g/min to enable the liquid conductive coating agent to be uniformly coated on the surface of the soft carbon precursor to form a conductive coating layer, and obtaining the coated soft carbon precursor;
and (4): and (4) placing the coated soft carbon precursor obtained in the step (3) in a nitrogen atmosphere protective furnace for sintering, raising the temperature to 1600-2000 ℃ at the heating rate of 30-50 ℃/min, preserving the heat for 2-5 hours, and crushing and screening to obtain the high-power-density negative electrode material.
2. The preparation method of the high power density negative electrode material for the lithium ion battery according to claim 1, characterized in that: the conductive agent is one or a mixture of carbon black, carbon nano tubes and graphene, and the carbon content of the conductive agent is more than 99%.
3. The preparation method of the high power density negative electrode material for the lithium ion battery according to claim 1, characterized in that: the binder is one or a mixture of coal-series or oil-series asphalt, and the softening point of the binder is 50-200 ℃.
4. The preparation method of the high power density negative electrode material for the lithium ion battery according to claim 1, characterized in that: the solvent is one or a mixture of benzene, toluene and xylene.
5. The preparation method of the high power density negative electrode material for the lithium ion battery according to claim 1, characterized in that: the mass ratio of the binder to the conductive agent to the solvent is 1:0.05-0.5: 0.5-2.0.
6. The preparation method of the high power density negative electrode material for the lithium ion battery according to claim 1, characterized in that: the soft carbon precursor is one or a mixture of more of pulverized petroleum coke or needle coke, and D50=3-6 μm.
7. The preparation method of the high power density negative electrode material for the lithium ion battery according to claim 1, characterized in that: the carrier gas in the step (3) is one or a mixture of nitrogen and argon, and the flow rate is 0.6-1.2m3The temperature is 160-200 ℃.
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