CN117393724A - High-magnification artificial graphite composite negative electrode material and preparation method and application thereof - Google Patents
High-magnification artificial graphite composite negative electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN117393724A CN117393724A CN202311431087.3A CN202311431087A CN117393724A CN 117393724 A CN117393724 A CN 117393724A CN 202311431087 A CN202311431087 A CN 202311431087A CN 117393724 A CN117393724 A CN 117393724A
- Authority
- CN
- China
- Prior art keywords
- artificial graphite
- magnification
- negative electrode
- particle
- graphite composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910021383 artificial graphite Inorganic materials 0.000 title claims abstract description 117
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 70
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000010405 anode material Substances 0.000 claims abstract description 43
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 37
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 37
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 229920001568 phenolic resin Polymers 0.000 claims description 16
- 239000005011 phenolic resin Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- -1 transition metal salt Chemical class 0.000 claims description 14
- 238000005087 graphitization Methods 0.000 claims description 12
- 229910052723 transition metal Inorganic materials 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 11
- 238000007731 hot pressing Methods 0.000 claims description 10
- 239000002006 petroleum coke Substances 0.000 claims description 10
- 238000007493 shaping process Methods 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011331 needle coke Substances 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000006253 pitch coke Substances 0.000 claims description 2
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 239000011163 secondary particle Substances 0.000 abstract description 6
- 230000006872 improvement Effects 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000008569 process Effects 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910000314 transition metal oxide Inorganic materials 0.000 description 8
- 229910003481 amorphous carbon Inorganic materials 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 6
- 238000000462 isostatic pressing Methods 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000006183 anode active material Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000009818 secondary granulation Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000001192 hot extrusion Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a high-magnification artificial graphite composite negative electrode material, a preparation method and application thereof, wherein the high-magnification artificial graphite composite negative electrode material comprises small-particle artificial graphite, hard carbon and carbon nano tubes, the hard carbon is coated on the surface of the small-particle artificial graphite and is bonded into large-particle artificial graphite, and the carbon nano tubes are distributed in the hard carbon; the composite anode material has the characteristic of secondary particle structure, so that the transmission path of lithium ions can be shortened, the transmission channel of the lithium ions can be increased, and the improvement of quick charge performance can be realized; meanwhile, the carbon nano tube can improve the conductivity and the dynamic performance of the composite anode material, so that the composite anode material has higher rate capability.
Description
Technical Field
The invention belongs to the technical field of carbon cathode materials of lithium ion batteries, and particularly relates to a high-magnification artificial graphite composite cathode material, and a preparation method and application thereof.
Background
The lithium ion battery is a new generation secondary battery after the nickel-hydrogen battery in the nineties of the last century because of the advantages of high working voltage, high energy density, long cycle life, small self-discharge, no memory effect and the like.
In recent years, as electronic products and vehicle-mounted and energy storage devices are increasingly required to be miniaturized, light-weighted, multifunctional, and driven for a long time, requirements for high energy density and high rate performance of lithium ion batteries are increasingly increasing. Research shows that the ways for improving the multiplying power performance of the graphite anode material comprise particle design and surface coating, wherein the particle design comprises small granulation and secondary granulation, and the improvement of the quick charge performance is mainly realized by shortening the transmission path of lithium ions and increasing the transmission channel of the lithium ions.
In the prior art, it has been reported that a graphite anode material with a secondary particle structure (formed by bonding small particles) is obtained by mixing, granulating and graphitizing a small particle graphite precursor and a binder (asphalt or resin), but asphalt is used as a soft carbon precursor, and is easy to graphitize in the high-temperature graphitization process, and the prepared graphite anode material has poor multiplying power performance and can only support charging and discharging of 1C multiplying power at most; the resin is used as a hard carbon precursor, and hard carbon with larger interlayer spacing is formed after graphitization, so that more excellent quick charge performance (highest energy supports charge and discharge of 3C multiplying power) can be obtained, but the conductive performance of the hard carbon is poor, secondary particles are limited to be used under higher multiplying power, in addition, the surface defects of the hard carbon are more, and the first coulomb efficiency of the anode material is extremely easy to cause.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a high-magnification artificial graphite composite negative electrode material, a preparation method and application thereof, wherein the high-magnification artificial graphite composite negative electrode material comprises small-particle artificial graphite, hard carbon and carbon nano tubes, the hard carbon is coated on the surface of the small-particle artificial graphite and bonded into large-particle artificial graphite, and the carbon nano tubes are distributed in the hard carbon; the composite anode material has the characteristic of secondary particle structure, so that the transmission path of lithium ions can be shortened, the transmission channel of the lithium ions can be increased, and the improvement of quick charge performance can be realized; meanwhile, the carbon nano tube can improve the conductivity and the dynamic performance of the composite anode material, so that the composite anode material has higher rate capability.
Specifically, the invention provides the following technical scheme:
a preparation method of a high-magnification artificial graphite composite anode material, which comprises the following steps:
(1) Dissolving transition metal salt in absolute ethyl alcohol, then mixing with phenolic resin, and curing to prepare modified phenolic resin;
(2) Mixing the modified phenolic resin in the step (1) with an artificial graphite precursor, and carrying out hot pressing treatment to obtain a block;
(3) Carbonizing the block in the step (2) to obtain a carbonized product;
(4) And (3) graphitizing the carbonized product in the step (3), cooling, and crushing, shaping and screening to obtain the high-magnification artificial graphite composite anode material.
According to an embodiment of the present invention, in step (1), the transition metal salt is selected from transition metal nitrates, for example, at least one selected from ferric nitrate, nickel nitrate, cobalt nitrate, and the like.
According to an embodiment of the invention, in step (1), 90-200mg of the transition metal salt is dissolved per ml of absolute ethanol, such as 90mg, 100mg, 110mg, 120mg, 130mg, 140mg, 150mg, 160mg, 170mg, 180mg, 190mg or 200mg of the transition metal salt is dissolved per ml of absolute ethanol.
According to an embodiment of the invention, in step (1), the mass ratio of transition metal salt to phenolic resin is (5-10): 100, for example 5:100, 6:100, 7:100, 8:100, 9:100 or 10:100.
According to an embodiment of the present invention, in the step (1), the curing temperature is 120 to 200 ℃, and the curing time is 8 to 24 hours.
According to the embodiment of the invention, in the step (1), the removal of the absolute ethyl alcohol can be realized in the curing process. In the curing process, the transition metal salt is decomposed into metal oxide particles, and the metal oxide modified phenolic resin is obtained after crushing.
According to an embodiment of the present invention, in the step (1), a step of pulverizing treatment is further included after the completion of the curing, and the modified phenolic resin having a particle size of 3 to 5 μm can be obtained by the pulverizing treatment.
According to an embodiment of the present invention, in step (2), the artificial graphite precursor is selected from at least one of petroleum coke, needle coke, pitch coke, and the like.
According to an embodiment of the invention, in step (2), the mass ratio of the modified phenolic resin to the artificial graphite precursor particles is (10-30): 100, for example 10:100, 15:100, 20:100, 25:100, 30:100.
According to an embodiment of the present invention, in step (2), the artificial graphite precursor has an average particle diameter of 5 to 8 μm.
According to an embodiment of the invention, in step (2), the pressure of the autoclave treatment is 5-10MPa, such as 5MPa, 6MPa, 7MPa, 8MPa, 9MPa or 10MPa; the hot pressing treatment temperature is 100-200deg.C, such as 100deg.C, 110deg.C, 120deg.C, 130deg.C, 140deg.C, 150deg.C, 160deg.C, 170deg.C, 180deg.C, 190 deg.C or 200deg.C; the hot pressing treatment time is 3-10min, such as 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min.
According to the embodiment of the invention, in the step (2), the purpose of the hot pressing treatment is to press the modified phenolic resin and the artificial graphite precursor into a block-shaped structure, which can effectively inhibit the escape of carbon-containing gas in the carbonization process and ensure that more carbon-containing gas forms carbon nanotubes in situ under the catalysis of the transition metal oxide.
According to an embodiment of the present invention, in the step (2), the hot pressing treatment may be at least one of hot pressing, hot isostatic pressing, hot extrusion, and the like.
According to an embodiment of the present invention, in step (2), the block may be a rectangular block or a square block. Preferably square blocks, the side length of said blocks being 20-50cm.
According to the embodiment of the invention, in the step (3), the carbonization treatment is performed by heating to 600-800 ℃ at a heating rate of 1-5 ℃/min, preserving heat for 1-6 hours, and then heating to 1000-1200 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 2-6 hours. In the carbonization process, on one hand, amorphous carbon formed by phenolic resin carbonization can be ensured to be coated on the surface of the artificial graphite precursor and firmly bonded, and on the other hand, carbon-containing gases released when the phenolic resin forms amorphous carbon can be ensured to catalyze the carbon-containing gases to form carbon nanotubes in situ in the amorphous carbon in transition metal oxide.
According to an embodiment of the present invention, in step (3), the carbonization treatment is performed under an inert atmosphere such as nitrogen and/or argon.
According to an embodiment of the present invention, in the step (4), the temperature of the graphitization treatment is 2800 to 3000 ℃, and the time of the graphitization treatment is 12 to 48 hours. The transition metal oxide particles have the effect of catalyzing graphitization on the hard carbon in the graphitization treatment process, so that a hard carbon coating layer with a more regular and ordered graphite-like layer microcrystalline structure can be obtained, the defect of the hard carbon coating layer is reduced, and the first coulomb efficiency of the composite anode material is further improved.
According to an embodiment of the present invention, in the step (4), the pulverizing, shaping, sieving are performed as conventional procedures and processes in the art.
According to an embodiment of the present invention, in step (4), the artificial graphite composite anode material has an average particle diameter D 50 Is 12-18 μm.
The invention also provides the high-magnification artificial graphite composite anode material prepared by the method.
According to the embodiment of the invention, the high-magnification artificial graphite composite anode material comprises small-particle artificial graphite, hard carbon and carbon nano tubes, wherein the hard carbon is coated on the surface of the small-particle artificial graphite and is bonded into large-particle artificial graphite, and the carbon nano tubes are distributed in the hard carbon.
According to an embodiment of the present invention, the small-particle artificial graphite has an average particle diameter of 5 to 8 μm.
According to an embodiment of the present invention, the large-particle artificial graphite has an average particle diameter of 12 to 18 μm.
According to the embodiment of the invention, the carbon nano tube can improve the conductivity and the dynamic performance of the composite anode material, so that the composite anode material has higher rate capability.
According to an embodiment of the invention, the mass ratio of the carbon nanotubes to the small particle artificial graphite is (2-6): 100, for example, 2:100, 3:100, 4:100, 5:100 or 6:100.
According to an embodiment of the invention, the mass ratio of hard carbon to small particle artificial graphite is (8-15): 100, for example 8:100, 9:100, 10:100, 11:100, 12:100, 13:100, 14:100 or 15:100.
According to the embodiment of the invention, the high-rate artificial graphite composite negative electrode material has good charge and discharge performance under high current, and the maximum charge and discharge rate can reach 8 ℃.
The invention also provides a negative plate which comprises the high-rate artificial graphite composite negative material.
According to an embodiment of the present invention, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer disposed on at least one side surface of the negative electrode current collector, the negative electrode active material layer including the above-described high-rate artificial graphite composite negative electrode material.
According to an embodiment of the present invention, the anode active material layer further includes a binder and a conductive agent.
According to an embodiment of the present invention, the high-rate artificial graphite composite anode material is contained in an amount of 85 to 98wt%, for example, 85wt%, 86wt%, 87wt%, 88wt%, 89wt%, 90wt%, 91wt%, 92wt%, 93wt%, 94wt%, 95wt%, 96wt%, 97wt% or 98% of the total mass of the anode active material layer.
According to an embodiment of the present invention, the binder is contained in an amount of 1 to 5wt%, for example, 1wt%, 2wt%, 3wt%, 4wt%, or 5wt% based on the total mass of the anode active material layer.
According to an embodiment of the present invention, the content of the conductive agent is 1 to 5wt%, for example, 1wt%, 2wt%, 3wt%, 4wt%, or 5wt% of the total mass of the anode active material layer.
The invention also provides a battery, which comprises the high-rate artificial graphite composite anode material, or comprises the anode plate.
The invention has the beneficial effects that:
according to the invention, after the transition metal salt and the phenolic resin are uniformly mixed, in the curing process, the transition metal salt is decomposed into metal oxide particles, the metal oxide particles are crushed to obtain transition metal oxide modified phenolic resin, then the transition metal oxide modified phenolic resin and small particle artificial graphite precursors are pressed into blocks, in the carbonization process, amorphous carbon formed by carbonization of the phenolic resin is coated on the surface of the artificial graphite precursors and firmly bonded, carbon-containing gas escapes while the phenolic resin forms amorphous carbon, but the bulk structure inhibits the escape of most of carbon-containing gas, and the transition metal oxide can catalyze the carbon-containing gas to form carbon nanotubes in the amorphous carbon in situ; after high-temperature graphitization, the artificial graphite precursor is converted into artificial graphite, amorphous carbon is converted into hard carbon, the carbon nano tube still exists in the form of carbon nano tube, transition metal oxide is volatilized, graphitized blocks are broken to obtain large-particle artificial graphite, and in the large-particle artificial graphite, the hard carbon embedded with the carbon nano tube is uniformly coated on the surface of small-particle artificial graphite, so that the conductivity and the dynamics performance of the composite anode material can be obviously improved, and the composite anode material has higher rate capability. In addition, the transition metal oxide particles have the function of catalyzing graphitization on hard carbon in the high-temperature graphitization process, so that a hard carbon coating layer with a more regular and ordered graphite-like layer microcrystalline structure can be obtained, the defect of the hard carbon coating layer is reduced, and the first coulomb efficiency of the composite anode material is further improved.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
Example 1
(1) 7gFe (NO) 3 ) 3 Dissolving in 50ml absolute ethyl alcohol, adding the absolute ethyl alcohol into 100g phenolic resin, uniformly stirring, curing at 120 ℃ for 16 hours to remove the absolute ethyl alcohol, and crushing to obtain modified phenolic resin;
(2) 20g of the modified phenolic resin of step (1) and 100g of petroleum coke (D) 50 6 μm), placing the mixture into a rubber mold, placing the mold into an isostatic pressing machine, pressurizing to 6MPa, heating to 150 ℃, maintaining the pressure and preserving heat for 5min, cooling to room temperature, and pressing to form square blocks of 30cm multiplied by 30 cm;
(3) Heating the block in the step (2) to 700 ℃ at a speed of 1 ℃/min under nitrogen for 6 hours, heating to 1000 ℃ at a speed of 5 ℃/min for 3 hours, and cooling to room temperature to obtain a carbonized product;
(4) Graphitizing the carbonized product in the step (3) for 24 hours at 3000 ℃, naturally cooling to room temperature, crushing, shaping and screening to obtain the high-magnification artificial graphite composite anode material.
The high-magnification artificial graphite composite negative electrode material comprises small-particle artificial graphite, hard carbon and carbon nano tubes, wherein the hard carbon is coated on the surface of the small-particle artificial graphite and is bonded into large-particle artificial graphite, and the carbon nano tubes are distributed in the hard carbon. The carbon nano tube in the high-magnification artificial graphite composite anode material comprises the following components: hard carbon: the mass ratio of the artificial graphite is 2.7:5.3:100.
Example 2
(1) Will 5gNi (NO) 3 ) 3 Dissolving in 50ml absolute ethyl alcohol, adding the mixture into 100g phenolic resin, uniformly stirring, curing at 160 ℃ for 10 hours, removing the absolute ethyl alcohol, and crushing to obtain the modified phenolic resin.
(2) Mixing 15g of the modified phenolic resin from the step (1) with 100g of needle coke (D 50 6 μm), placing the mixture into a rubber mold, placing the mold into an isostatic pressing machine, pressurizing to 4MPa, heating to 150 ℃, maintaining the pressure and preserving heat for 3min, cooling to room temperature, and pressing to form a rectangular block body with the thickness of 30cm multiplied by 40cm multiplied by 45 cm;
(3) Heating the block in the step (2) to 680 ℃ at a speed of 1 ℃/min under nitrogen for 4 hours, heating to 1100 ℃ at a speed of 5 ℃/min for 5 hours, and cooling to room temperature to obtain a carbonized product;
(4) Graphitizing the carbonized product in the step (3) at 2900 ℃ for 24 hours, naturally cooling to room temperature, crushing, shaping and screening to obtain the high-magnification artificial graphite composite anode material.
The high-magnification artificial graphite composite negative electrode material comprises small-particle artificial graphite, hard carbon and carbon nano tubes, wherein the hard carbon is coated on the surface of the small-particle artificial graphite and is bonded into large-particle artificial graphite, and the carbon nano tubes are distributed in the hard carbon. The carbon nano tube in the high-magnification artificial graphite composite anode material comprises the following components: hard carbon: the mass ratio of the artificial graphite is 1.4:4.6:100.
Example 3
(1) 5g of Fe (NO) 3 ) 3 Dissolving in 50ml absolute ethyl alcohol, adding the mixture into 100g phenolic resin, uniformly stirring, solidifying at 140 ℃ for 12 hours to remove the absolute ethyl alcohol, and crushing to obtain the modified phenolic resin.
(2) Mixing 25g of the modified phenolic resin obtained in the step (1) with 100g of petroleum coke (D) 50 7 μm), placing the mixture into a rubber mold, placing the mold into an isostatic pressing machine, pressurizing to 5MPa, heating to 120 ℃, maintaining the pressure and preserving heat for 5min, cooling to room temperature, and pressing to form square blocks of 40cm multiplied by 40 cm;
(3) Heating the block in the step (2) to 700 ℃ at a speed of 1 ℃/min under nitrogen for 4 hours, heating to 1200 ℃ at a speed of 5 ℃/min for 3 hours, and cooling to room temperature to obtain a carbonized product;
(4) Graphitizing the carbonized product in the step (3) at 2850 ℃ for 24 hours, naturally cooling to room temperature, crushing, shaping and screening to obtain the high-magnification artificial graphite composite anode material.
The high-magnification artificial graphite composite negative electrode material comprises small-particle artificial graphite, hard carbon and carbon nano tubes, wherein the hard carbon is coated on the surface of the small-particle artificial graphite and is bonded into large-particle artificial graphite, and the carbon nano tubes are distributed in the hard carbon. The carbon nano tube in the high-magnification artificial graphite composite anode material comprises the following components: hard carbon: the mass ratio of the artificial graphite is 2.4:7.6:100.
Example 4
(1) 10g of Fe (NO) 3 ) 3 Dissolving in 50ml absolute ethyl alcohol, adding the mixture into 100g phenolic resin, uniformly stirring, curing at 150 ℃ for 8 hours, removing the absolute ethyl alcohol, and crushing to obtain the modified phenolic resin.
(2) Mixing 30g of the modified phenolic resin from the step (1) with 100g of needle coke (D 50 8 μm), placing the mixture into a rubber mold, placing the mold into an isostatic pressing machine, pressurizing to 6MPa, heating to 120 ℃, maintaining the pressure and preserving heat for 5min, cooling to room temperature, and pressing to form a rectangular block body with the thickness of 30cm multiplied by 40 cm;
(3) Heating the block in the step (3) to 750 ℃ at 1 ℃/min under nitrogen for 4 hours, heating to 1200 ℃ at 5 ℃/min for 3 hours, and cooling to room temperature to obtain a carbonized product;
(4) Graphitizing the carbonized product in the step (3) at 2850 ℃ for 24 hours, naturally cooling to room temperature, crushing, shaping and screening to obtain the high-magnification artificial graphite composite anode material.
The high-magnification artificial graphite composite negative electrode material comprises small-particle artificial graphite, hard carbon and carbon nano tubes, wherein the hard carbon is coated on the surface of the small-particle artificial graphite and is bonded into large-particle artificial graphite, and the carbon nano tubes are distributed in the hard carbon. The carbon nano tube in the high-magnification artificial graphite composite anode material comprises the following components: hard carbon: the mass ratio of the artificial graphite is 3.8:8.2:100.
Comparative example 1
(1) 7gFe (NO) 3 ) 3 Dissolving in 50ml absolute ethyl alcohol, adding the absolute ethyl alcohol into 100g phenolic resin, uniformly stirring, curing at 120 ℃ for 16 hours to remove the absolute ethyl alcohol, and crushing to obtain modified phenolic resin;
(2) 20g of the modified phenolic resin of step (1) and 100g of petroleum coke (D) 50 6 μm), granulating in a reaction kettle, heating to 700 ℃ at 1 ℃/min under nitrogen for 6 hours, heating to 1000 ℃ at 5 ℃/min for 3 hours, and cooling to room temperature to obtain secondary particles;
(3) And (3) graphitizing the secondary particles in the step (2) for 24 hours at 3000 ℃, naturally cooling to room temperature, and crushing, shaping and screening to obtain the high-magnification artificial graphite composite anode material. The high-magnification artificial graphite composite negative electrode material comprises small-particle artificial graphite and hard carbon, wherein the hard carbon is coated on the surface of the small-particle artificial graphite and is bonded into large-particle artificial graphite. Hard carbon in the high-magnification artificial graphite composite anode material: the mass ratio of the artificial graphite is 8:100.
Comparative example 2
(1) 20g of phenolic resin was reacted with 100g of petroleum coke (D 50 6 μm), placing the mixture into a rubber mold, placing the mold into an isostatic pressing machine, pressurizing to 6MPa, heating to 150 ℃, maintaining the pressure and preserving heat for 5min, cooling to room temperature, and pressing to form square blocks of 30cm multiplied by 30 cm;
(2) Heating the block in the step (1) to 700 ℃ at a speed of 1 ℃/min under nitrogen for 6 hours, heating to 1000 ℃ at a speed of 5 ℃/min for 3 hours, and cooling to room temperature to obtain a carbonized product;
(3) Graphitizing the carbonized product in the step (2) for 24 hours at 3000 ℃, naturally cooling to room temperature, crushing, shaping and screening to obtain the high-magnification artificial graphite composite anode material. The high-magnification artificial graphite composite negative electrode material comprises small-particle artificial graphite and hard carbon, wherein the hard carbon is coated on the surface of the small-particle artificial graphite and is bonded into large-particle artificial graphite. Hard carbon in the high-magnification artificial graphite composite anode material: the mass ratio of the artificial graphite is 8:100.
Comparative example 3
(1) 7gFe (NO) 3 ) 3 Dissolving in 50ml absolute ethyl alcohol, adding the absolute ethyl alcohol into 100g phenolic resin, uniformly stirring, curing at 120 ℃ for 16 hours to remove the absolute ethyl alcohol, and crushing to obtain modified phenolic resin;
(2) 20g of the modified phenolic resin of step (1) and 100g of petroleum coke (D) 50 6 μm), placing the mixture into a rubber mold, placing the mold into an isostatic pressing machine, pressurizing to 6MPa, heating to 150 ℃, maintaining the pressure and preserving heat for 5min, cooling to room temperature, and pressing to form square blocks of 30cm multiplied by 30 cm;
(3) Heating the block in the step (2) to 1000 ℃ at a speed of 5 ℃/min under nitrogen, preserving heat for 3 hours, and cooling to room temperature to obtain a carbonized product;
(4) Graphitizing the carbonized product in the step (3) for 24 hours at 3000 ℃, naturally cooling to room temperature, crushing, shaping and screening to obtain the high-magnification artificial graphite composite anode material.
The high-magnification artificial graphite composite negative electrode material comprises small-particle artificial graphite, hard carbon and carbon nano tubes, wherein the hard carbon is coated on the surface of the small-particle artificial graphite and is bonded into large-particle artificial graphite, and the carbon nano tubes are distributed in the hard carbon. The carbon nano tube in the high-magnification artificial graphite composite anode material comprises the following components: hard carbon: the mass ratio of the artificial graphite is 0.3:7.7:100.
Test example 1
(1) The particle size distribution of the samples was tested using a laser particle sizer.
(2) Electrochemical performance test
Half-electric test method: the composite anode materials prepared in examples 1 to 4 and comparative examples 1 to 3 were uniformly mixed with conductive carbon black (SP) carboxymethylcellulose (CMC) Styrene Butadiene Rubber (SBR) =95:1:1.5:2.5 (mass ratio), coated on copper foil, and the coated electrode sheet was dried in a vacuum oven at 120 ℃ for 12 hours. Simulated battery assembly was performed in an argon-protected Braun glove box with electrolyte 1M-LiPF 6 +EC: DEC: DMC (volume ratio 1:1:1), metallic lithium sheet as counter electrode, performing simulated battery test in a 5V, 10mA New Wei battery test cabinet,the charge-discharge voltage is 0.01-1.5V, the charge-discharge rate is 0.1C, and the first discharge capacity and the first coulombic efficiency are tested.
The full battery test method comprises the following steps: the graphite materials prepared in examples 1 to 4 and comparative examples 1 to 3 were used as negative electrodes, lithium cobaltate was used as positive electrode, and 1M-LiPF 6 And (3) using a +EC:DEC:DMC (volume ratio of 1:1:1) solution as an electrolyte to assemble a full battery, charging and discharging at normal temperature at the multiplying power of 1C and 3C, wherein the voltage range is 3.0-4.2V, and testing the obtained cycle performance.
(3) The maximum rate test method for charging comprises the following steps:
and respectively charging the battery cells to 100% SOC at different multiplying powers, disassembling the battery cells under a low-temperature and low-humidity environment, and observing the lithium precipitation condition of the negative electrode plate.
TABLE 1 electrochemical Performance test results
As can be seen from Table 1, the artificial graphite composite negative electrode material prepared by the invention has better first coulombic efficiency and rate capability. However, the artificial graphite composite anode materials of comparative examples 1 to 3 cannot obtain better rate performance mainly due to the following:
in comparative example 1, after the modified phenolic resin and the petroleum coke particles are mixed, secondary granulation is performed, and the obtained artificial graphite composite negative electrode material has high primary efficiency, but has poor multiplying power performance due to the fact that no carbon nano tube is generated. In comparative example 2, after phenolic resin and petroleum coke particles are directly mixed, briquetting, carbonization and graphitization are performed, and the obtained artificial graphite composite negative electrode material has poor initial coulombic efficiency and rate capability, mainly because the generated hard carbon has a large number of defects and no carbon nano tube is generated. In comparative example 3, after the modified phenolic resin and the petroleum coke particles are mixed, briquetting, carbonization and graphitization are performed, but the obtained artificial graphite composite negative electrode material has poor multiplying power performance, mainly because the temperature rising speed is high during carbonization, carbon-containing gas generated by the phenolic resin rapidly escapes from a block body, only a small amount of carbon nano tubes can be generated, and the conductivity of the composite negative electrode material cannot be effectively improved.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-magnification artificial graphite composite anode material, which comprises the following steps:
(1) Dissolving transition metal salt in absolute ethyl alcohol, then mixing with phenolic resin, and curing to prepare modified phenolic resin;
(2) Mixing the modified phenolic resin in the step (1) with an artificial graphite precursor, and carrying out hot pressing treatment to obtain a block;
(3) Carbonizing the block in the step (2) to obtain a carbonized product;
(4) And (3) graphitizing the carbonized product in the step (3), cooling, and crushing, shaping and screening to obtain the high-magnification artificial graphite composite anode material.
2. The production method according to claim 1, wherein in the step (1), the transition metal salt is selected from a transition metal nitrate selected from at least one of ferric nitrate, nickel nitrate, and cobalt nitrate;
and/or, in the step (1), 90-200mg of transition metal salt is dissolved in each milliliter of absolute ethyl alcohol;
and/or in the step (1), the mass ratio of the transition metal salt to the phenolic resin is (5-10): 100;
and/or in the step (1), the curing temperature is 120-200 ℃, and the curing time is 8-24 hours.
3. The production method according to claim 1 or 2, wherein in the step (2), the artificial graphite precursor is selected from at least one of petroleum coke, needle coke, pitch coke, and the like;
and/or in the step (2), the mass ratio of the modified phenolic resin to the artificial graphite precursor particles is (10-30): 100;
and/or, in the step (2), the average particle size of the artificial graphite precursor is 5-8 μm;
and/or, in the step (2), the pressure of the hot pressing treatment is 5-10MPa; the temperature of the hot pressing treatment is 100-200 ℃; the hot pressing treatment time is 3-10min.
4. A production method according to any one of claims 1 to 3, wherein in the step (3), the carbonization treatment is performed by heating up to 600 to 800 ℃ at a heating rate of 1 to 5 ℃/min, holding for 1 to 6 hours, and then heating up to 1000 to 1200 ℃ at a heating rate of 5 to 10 ℃/min, holding for 2 to 6 hours.
5. The production method according to claim 1, wherein in the step (4), the graphitization treatment is performed at a temperature of 2800 to 3000 ℃ for a time of 12 to 48 hours;
and/or, in the step (4), the average particle diameter D of the artificial graphite composite anode material 50 Is 12-18 μm.
6. A high-rate artificial graphite composite negative electrode material prepared by the method of any one of claims 1 to 5.
7. The high-magnification artificial graphite composite negative electrode material according to claim 6, wherein the high-magnification artificial graphite composite negative electrode material comprises small-particle artificial graphite, hard carbon and carbon nanotubes, wherein the hard carbon is coated on the surface of the small-particle artificial graphite and is bonded into large-particle artificial graphite, and the carbon nanotubes are distributed in the hard carbon.
8. The high-magnification artificial graphite composite anode material according to claim 6 or 7, wherein the small-particle artificial graphite has an average particle diameter of 5-8 μm;
and/or the average particle size of the large-particle artificial graphite is 12-18 mu m;
and/or the mass ratio of the carbon nano tube to the small-particle artificial graphite is (2-6): 100;
and/or the mass ratio of the hard carbon to the small-particle artificial graphite is (8-15): 100.
9. A negative electrode sheet comprising the high-magnification artificial graphite composite negative electrode material according to any one of claims 6 to 8.
10. A battery comprising the high-rate artificial graphite composite negative electrode material according to any one of claims 6 to 8, or the negative electrode sheet according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311431087.3A CN117393724A (en) | 2023-10-31 | 2023-10-31 | High-magnification artificial graphite composite negative electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311431087.3A CN117393724A (en) | 2023-10-31 | 2023-10-31 | High-magnification artificial graphite composite negative electrode material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117393724A true CN117393724A (en) | 2024-01-12 |
Family
ID=89464702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311431087.3A Pending CN117393724A (en) | 2023-10-31 | 2023-10-31 | High-magnification artificial graphite composite negative electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117393724A (en) |
-
2023
- 2023-10-31 CN CN202311431087.3A patent/CN117393724A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110642247B (en) | Artificial graphite negative electrode material, preparation method thereof and lithium ion battery | |
| US11929484B2 (en) | Compound, preparation method therefore, and use in lithium ion secondary battery | |
| WO2022121136A1 (en) | Artificial graphite negative electrode material for high-rate lithium ion battery and preparation method therefor | |
| CN106654235B (en) | Composite graphite material, preparation method thereof and lithium ion battery containing composite graphite material | |
| CN110615423A (en) | Preparation method of silicon-based composite negative electrode material of lithium battery | |
| CN112645300B (en) | Hard carbon negative electrode material, lithium ion battery, and preparation method and application of hard carbon negative electrode material | |
| CN109888284B (en) | Lithium ion battery cathode material, lithium ion battery cathode, lithium ion battery, battery pack and battery power vehicle | |
| WO2023173772A1 (en) | Preparation method for and use of hard carbon negative electrode material | |
| CN104300148B (en) | A kind of graphite negative material of lithium ion battery and preparation method thereof | |
| CN114314580A (en) | Composite graphite negative electrode material and preparation method and application thereof | |
| CN106532010B (en) | Silicon-silicon nitride-carbon composite material and preparation method and application method thereof | |
| CN117219777B (en) | Lithium supplementing agent, preparation method thereof, positive electrode plate and secondary battery | |
| CN114551871A (en) | Spherical hard carbon composite material and preparation method and application thereof | |
| CN108075110A (en) | Negative electrode for lithium ion battery composite material and lithium ion battery | |
| CN113644243A (en) | Nitrogen-doped hollow-structure graphite microsphere, composite negative electrode material and preparation method of composite negative electrode material | |
| CN110970599B (en) | Graphene-based composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN114937758B (en) | Negative electrode active material, negative electrode plate containing same and battery | |
| CN116514100A (en) | Hard carbon anode material and preparation method and application thereof | |
| CN115432699A (en) | Waste negative electrode base regenerated graphite material and preparation and application thereof | |
| CN114156471B (en) | Graphite negative electrode material and preparation method and application thereof | |
| CN114203979B (en) | Graphite negative electrode material and preparation method and application thereof | |
| CN117393724A (en) | High-magnification artificial graphite composite negative electrode material and preparation method and application thereof | |
| CN110911643B (en) | Diatomite-based lithium ion battery anode material and preparation method thereof | |
| CN111348685A (en) | Graphene-based composite material and preparation method and application thereof | |
| CN115911306B (en) | High-energy-density graphite composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |