CN117154044A - High-power graphite composite material and preparation method and application thereof - Google Patents
High-power graphite composite material and preparation method and application thereof Download PDFInfo
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- CN117154044A CN117154044A CN202311138660.1A CN202311138660A CN117154044A CN 117154044 A CN117154044 A CN 117154044A CN 202311138660 A CN202311138660 A CN 202311138660A CN 117154044 A CN117154044 A CN 117154044A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 52
- 239000010439 graphite Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 239000002184 metal Substances 0.000 claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 36
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 18
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 17
- 239000007770 graphite material Substances 0.000 claims abstract description 16
- -1 saccharide compound Chemical class 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000010426 asphalt Substances 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 41
- 238000003860 storage Methods 0.000 abstract description 6
- 239000003575 carbonaceous material Substances 0.000 abstract description 5
- 150000002642 lithium compounds Chemical class 0.000 abstract description 5
- 230000002427 irreversible effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910021383 artificial graphite Inorganic materials 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 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
- C01B32/20—Graphite
- C01B32/21—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
-
- 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
-
- 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
- H01M4/626—Metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of secondary battery materials, in particular to a high-power graphite composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, carrying out blending reaction on the pretreated metal powder, a silane coupling agent, active particles and an organic solution to obtain modified metal powder; s2, carrying out blending reaction on the modified metal powder, the saccharide compound, the graphite and the magnetic oxide to obtain a hard carbon and metal coated graphite material; s3, blending and reacting the hard carbon and metal coated graphite material with asphalt, organic lithium salt and organic solvent to obtain the graphite composite material. The electronic conductivity and strength of the material are improved by doping metal powder in the graphite shell, and the orientation of the carbon material is changed by the magnetic oxide so as to improve the ion embedding channel of the material and improve the power performance; meanwhile, the lithium compound coated on the outer layer reduces the irreversible capacity of the material, and improves the first efficiency, the cycle performance and the high-temperature storage performance of the material.
Description
Technical Field
The invention relates to the technical field of secondary battery materials, in particular to a high-power graphite composite material and a preparation method and application thereof.
Background
The current marketed lithium ion battery cathode material mainly uses artificial graphite, and because the interlayer spacing of graphite is smaller than the crystal plane interlayer spacing of a graphite intercalation lithium compound, the interlayer spacing of graphite is changed in the charge and discharge process, the graphite is easy to peel off and pulverize, and the graphite is of a lamellar structure, so that the intercalation and deintercalation path of lithium ions in the charge and discharge process is longer, the isotropy is lower, and the rate performance is deviated. Although the electron conductivity of the material can be improved by coating and doping graphene and amorphous carbon with high electron conductivity, the ionic conductivity of the material is not improved, and the rate capability of the material is not obvious. The metal is used as a material with high electronic conductivity, and the doping of the metal in graphite can improve the electronic conductivity of the material, but the metal has the problems of poor high-temperature storage and the like, and the surface of the metal is often coated with lithium salt to improve the high-temperature storage performance of the material. For example, patent application number cn20151438421. X discloses a method for producing an artificial graphite negative electrode material of a high-capacity lithium ion battery, which takes petroleum coke coarse powder as a raw material A, asphalt micro powder as a raw material B and single transition metal micro powder or mixed micro powder of multiple transition metals as a raw material C; and taking the raw material A and the raw material C, and carrying out graphitization and other processes to obtain the anode material. The graphitization degree of the material is improved by adding metal elements, namely the material capacity is improved, but the nano holes remained after graphitization are gasified by transition metal micro powder, so that the electronic conductivity of the material is reduced, and the power performance is reduced.
Therefore, the negative electrode material prepared in the prior art is difficult to achieve the power performance, the first efficiency and the multiplying power performance of graphite.
Disclosure of Invention
In order to improve the power performance of graphite, the invention improves the electronic conductivity of the material and changes the orientation of the carbon-based material by doping metal and magnetic oxide in the shell, improves the electronic conductivity and the isotropy of the coating layer, improves the power performance, and simultaneously improves the first efficiency and the multiplying power performance of the material by doping lithium salt with high ionic conductivity in the shell.
The first aspect of the invention provides a preparation method of a high-power graphite composite material, which comprises the following steps:
s1, carrying out blending reaction on the pretreated metal powder, a silane coupling agent, active particles and an organic solution to obtain modified metal powder;
s2, carrying out blending reaction on the modified metal powder, the saccharide compound, the graphite and the magnetic oxide to obtain a hard carbon and metal coated graphite material;
s3, blending and reacting the hard carbon and metal coated graphite material with asphalt, organic lithium salt and organic solvent to obtain the graphite composite material.
In some embodiments, the metal powder comprises at least one of silver powder, copper powder, nickel powder, cobalt powder, iron powder.
Further, the particle size of the metal powder is 80-120nm.
Further, the pretreatment of the metal powder comprises ultrasonic washing of the metal powder with ethanol and drying.
In some embodiments, the mass ratio of the metal powder to the silane coupling agent, the active particles, the organic solution is 100: (1-10): (0.5-2): (500-1000).
Further, the silane coupling agent may be selected from some kinds commonly used in the art, including but not limited to, gamma-aminopropyl methyl diethoxy silane, gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma-mercaptopropyl trimethoxy silane, gamma-mercaptopropyl triethoxy silane, gamma-methacryloxypropyl trimethoxy silane, gamma- (2, 3-glycidoxy) propyl trimethoxy silane.
In some embodiments, the active particles comprise at least one of silver chloride, cobalt chloride, palladium chloride, nickel chloride.
Further, the organic solution may be selected from the common classes in the art including, but not limited to, at least one of n-hexane, xylene, carbon disulfide, carbon tetrachloride.
According to the invention, the metal powder is modified by using the silane coupling agent and the active particles, so that the activity of the material can be improved, the intercalation and deintercalation of lithium ions in the charge and discharge process of the composite material are facilitated, meanwhile, the silane coupling agent is coated on the surface of the material, the structural stability of the material can be improved, and the specific capacity of the material can be improved by forming the silicon oxide compound after carbonization, especially when the mass ratio of the metal powder to the silane coupling agent, the active particles and the organic solution is 100: (1-10): (0.5-2): (500-1000), the material has better dynamic performance and tap density effect, and the content of the silane coupling agent and the active particles is too high, so that the cycle performance and the storage performance of the material are reduced, and the dynamic performance of the material is not greatly improved when the content of the silane coupling agent and the active particles is too low.
In some embodiments, the mass ratio of the modified metal powder to the saccharide compound, graphite, magnetic oxide is (1-5): (10-20): 100: (0.5-2).
Further, the saccharide compound comprises at least one of glucose, sucrose, lignin, starch and cellulose.
In some embodiments, the magnetic oxide includes at least one of ferroferric oxide, tricobalt tetraoxide, and tricobalt tetraoxide.
When the mass ratio of the modified metal powder to the saccharide compound, the graphite and the magnetic oxide is (1-5): (10-20): 100: (0.5-2), the material has better multiplying power performance, pole piece adhesion and specific capacity; if the mass ratio is too high, the magnetic oxide is more, the activity is stronger, the high-temperature storage performance is reduced, the self-discharge is larger, if the mass ratio is too low, the magnetic oxide is less, the carbon-based material arrangement is more regular, the OI value is larger, and the dynamics is poorer.
In some embodiments, the mass ratio of the hard carbon and metal coated graphite material to pitch, organolithium salt, organic solvent is 100: (1-30): (1-5): (500-1000).
In some embodiments, the organolithium salt includes at least one of lithium tetrafluoroborate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium difluorobisoxalato phosphate, lithium tetrafluorooxalato phosphate.
The composite material disclosed by the invention is coated with the organic lithium salt on the metal surface, has high compatibility with electrolyte, has firm binding force of a coating layer, reduces the electron rate of the material, has a higher lithium ion diffusion rate under a low-temperature condition, and improves the low-temperature performance of the material.
The second aspect of the invention provides a high-power graphite composite material, which is obtained by the preparation method.
The third aspect of the invention provides application of the high-power graphite composite material in preparing a secondary battery anode material.
Compared with the prior art, the invention has the following beneficial effects: the electronic conductivity and strength of the material are improved by doping metal powder in the graphite shell, and the orientation of the carbon material is changed by the magnetic oxide so as to improve the ion embedding channel of the material and improve the power performance; meanwhile, the lithium compound coated on the outer layer reduces the irreversible capacity of the material, and improves the first efficiency, the cycle performance and the high-temperature storage performance of the material.
Drawings
Fig. 1 is an SEM image of the high power graphite composite material prepared in example 1.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a high-power graphite composite material, and the preparation method comprises the following steps:
s1, washing 100g of silver powder (with the particle size of 100 nm) with ethanol, ultrasonic cleaning, drying, uniformly dispersing with 5g of gamma-aminopropyl methyl diethoxy silane, 1g of silver chloride and 800g of toluene organic solution, transferring into a high-pressure reaction kettle, and reacting for 120min at the temperature of 100 ℃ to obtain modified metal powder;
s2, adding 3g of modified metal powder into 150g of 10wt% glucose aqueous solution, adding 100g of artificial graphite and 1g of ferroferric oxide, uniformly dispersing, transferring into a high-pressure reaction kettle, reacting for 3 hours at 200 ℃, filtering, vacuum drying for 24 hours at 80 ℃, and heating to 1300 ℃ for carbonization for 3 hours to obtain a hard carbon and metal coated graphite material;
s3, adding 20g of petroleum asphalt into 800g of normal hexane organic solvent for uniform dispersion, adding 3g of lithium tetrafluoroborate for uniform dispersion, adding 100g of hard carbon and metal coated graphite material for uniform ultrasonic dispersion, reacting for 3 hours at 150 ℃, filtering, vacuum drying for 24 hours at 80 ℃, transferring into a tubular furnace, and heating to 900 ℃ for carbonization for 3 hours at a heating rate of 5 ℃/min under an inert argon atmosphere to obtain the graphite composite material.
Example 2
The embodiment provides a high-power graphite composite material, and the preparation method comprises the following steps:
s1, washing 100g of copper powder (with the particle size of 100 nm) with ethanol, ultrasonic cleaning, drying, uniformly dispersing with 1g of gamma-aminopropyl trimethoxy silane, 0.5g of nickel chloride and 500g of xylene organic solution, transferring into a high-pressure reaction kettle, and reacting for 300min at the temperature of 50 ℃ to obtain modified metal powder;
s2, adding 1g of modified metal powder into 100g of 10wt% sucrose aqueous solution, adding 100g of artificial graphite and 0.5g of trinickel tetroxide, uniformly dispersing, transferring into a high-pressure reaction kettle, reacting for 6 hours at 150 ℃, filtering, vacuum drying for 24 hours at 80 ℃, and heating to 1200 ℃ for carbonization for 6 hours to obtain a hard carbon and metal coated graphite material;
s3, adding 10g of coal tar pitch into 500g of xylene organic solvent for uniform dispersion, adding 1g of lithium bisoxalato borate for uniform dispersion, adding 100g of hard carbon and metal coated graphite material for uniform ultrasonic dispersion, reacting for 6 hours at the temperature of 100 ℃, filtering, vacuum drying for 24 hours at the temperature of 80 ℃, transferring into a tubular furnace, and carbonizing for 6 hours at the temperature of 700 ℃ at the temperature rising rate of 1 ℃/min under the inert atmosphere of argon to obtain the graphite composite material.
Example 3
The embodiment provides a high-power graphite composite material, and the preparation method comprises the following steps:
s1, washing 100g of cobalt powder (with the particle size of 100 nm) with ethanol, ultrasonic cleaning, drying, reacting with 10g of gamma-aminopropyl triethoxysilane, 2g of cobalt chloride and 1000g of carbon tetrachloride organic solution at the temperature of 150 ℃ for 30min to obtain modified metal powder;
s2, adding 5g of modified metal powder into 200g of 10wt% starch aqueous solution, adding 100g of artificial graphite and 2g of cobaltosic oxide, uniformly dispersing, transferring into a high-pressure reaction kettle, reacting at 250 ℃ for 1h, filtering, vacuum drying at 80 ℃ for 24h, and heating to 1500 ℃ for carbonization for 1h to obtain a hard carbon and metal coated graphite material;
s3, adding 30g of petroleum asphalt into 1000g of carbon tetrachloride organic solvent for uniform dispersion, adding 5g of lithium difluorooxalate borate for uniform dispersion, adding 100g of hard carbon and metal coated graphite material for uniform ultrasonic dispersion, reacting for 1h at 200 ℃, filtering, vacuum drying for 24h at 80 ℃, transferring into a tubular furnace, and heating to 1200 ℃ for carbonization for 1h under the inert atmosphere of argon at the heating rate of 10 ℃/min to obtain the graphite composite material.
Comparative example 1
This comparative example provides a high power graphite composite material, the specific embodiment being the same as example 1, except,
s1, adding 3g of copper powder (with the particle size of 100 nm) into 150g of 10wt% glucose aqueous solution, adding 100g of artificial graphite and 1g of ferroferric oxide, uniformly dispersing, transferring into a high-pressure reaction kettle, reacting for 3 hours at the temperature of 200 ℃, filtering, vacuum drying for 24 hours at the temperature of 80 ℃, and heating to 1300 ℃ for carbonization for 3 hours to obtain a hard carbon and metal coated graphite material;
s2, adding 20g of petroleum asphalt into 800g of normal hexane organic solvent for uniform dispersion, adding 3g of lithium tetrafluoroborate for uniform dispersion, adding 100g of hard carbon and metal coated graphite material for uniform ultrasonic dispersion, reacting for 3 hours at 150 ℃, filtering, vacuum drying for 24 hours at 80 ℃, transferring into a tubular furnace, and heating to 900 ℃ for carbonization for 3 hours at a heating rate of 5 ℃/min under an inert argon atmosphere to obtain the graphite composite material.
Comparative example 2
This comparative example provides a high power graphite composite, the specific embodiment being the same as example 1 except that the lithium tetrafluoroborate is 0g.
Comparative example 3
This comparative example provides a high power graphite composite, the specific embodiment being the same as example 1 except that the silver chloride is 13g.
Comparative example 4
This comparative example provides a high power graphite composite, the specific embodiment being the same as example 1, except that the ferroferric oxide is 5g.
Performance testing
1. SEM test of the high-power graphite composite material prepared in example 1 shows that the graphite composite material prepared in example 1 has a spheroidal structure with uniform size distribution and particle size of 10-15 μm as shown in FIG. 1.
2. Physical and chemical properties and button cell testing
The graphite composite materials prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to particle size, tap density, specific surface area, powder OI value and specific capacity test. The testing method comprises the following steps: GBT-24533-2019 lithium ion battery graphite anode material, and the powder OI value is tested by XRD, and the OI value of the material is calculated.
The graphite composite materials obtained in examples 1 to 3 and comparative examples 1 to 4 were assembled into button cells, respectively; the preparation method comprises the following steps: adding binder, conductive agent and solvent into the cathode material, stirring to slurry, coating on copper foil, oven drying, and rolling. The binder used is LA132 binder, conductive agent SP, and the negative electrode material is hard carbon material prepared in examples 1-3 and comparative examples 1-4, the solvent is secondary distilled water, and the proportions are: negative electrode material: SP: LA132: secondary distilled water = 94g:2g:4g:220mL, and preparing a negative pole piece; the electrolyte is LiPF 6 EC+DEC (volume ratio 1:1, concentration 1.1 mol/L), metal lithium sheet is counter electrode, diaphragm adopts polyethylene PE, polypropylene PP or polyethylene propylene PEP composite film, simulated battery is assembled in glove box filled with argon gas, electrochemical performance is tested in Wuhan blue electric CT2001A type batteryThe charging and discharging voltage ranges from 0.005V to 2.0V, and the charging and discharging rate is 0.1C. The rate (1C/0.1C), cycle performance (0.2C/0.2C, 100 times) and charged DCR (50% SOC) of the button cell were simultaneously tested, and the diffusion coefficients of the example and comparative example materials were tested by GITT, with the test results shown in Table 1 below:
TABLE 1
As can be seen from table 1, compared with comparative example 1, the graphite composite materials prepared in examples 1 to 3 are significantly improved in first discharge capacity and first efficiency, rate capability and cycle performance, because doping metal sheets in the graphite shell improves the electronic conductivity of the material, improves the rate capability, and improves gram capacity exertion of the material; meanwhile, the lithium compound coated on the outer layer reduces the irreversible capacity of the material, and improves the first efficiency of the material.
3. Soft package battery test:
graphite composite materials prepared in examples 1 to 3 and comparative examples 1 to 4 were used as negative electrodes, respectively, and ternary materials (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) Preparation of positive electrode for positive electrode material with LiPF 6 (the solvent is EC+DEC, the volume ratio is 1:1, the concentration is 1.3 mol/L) is electrolyte, and the cellgard 2400 is a diaphragm to prepare the 2Ah soft package battery.
3.1 rate Performance test
The charge-discharge voltage ranges from 2.8V to 4.2V, the test temperature is 25+/-3.0 ℃, the charge is respectively carried out at 1.0C, 2.0C, 3.0C and 5.0C, the discharge is carried out at 1.0C, the constant current ratio of the battery in different charging modes is tested, and the results are shown in Table 2:
TABLE 2
| Multiplying power | 1C | 2C | 3C | 5C | |
| Example 1 | Constant current ratio (%) | 95.78 | 92.79 | 87.39 | 79.45 |
| Example 2 | Constant current ratio (%) | 94.13 | 91.35 | 86.82 | 78.28 |
| Example 3 | Constant current ratio (%) | 96.92 | 93.94 | 88.56 | 80.23 |
| Comparative example 1 | Constant current ratio (%) | 91.68 | 88.37 | 83.23 | 68.98 |
| Comparative example 2 | Constant current ratio (%) | 90.33 | 87.58 | 82.22 | 66.56 |
| Comparative example 3 | Constant current ratio (%) | 92.13 | 89.89 | 85.21 | 70.34 |
| Comparative example 4 | Constant current ratio (%) | 92.10 | 88.98 | 85.13 | 69.87 |
As can be seen from Table 2, the rate charging performance of the battery pack of the invention is significantly better than that of the comparative example, and the charging time is shorter, which indicates that the composite anode material of the invention has good quick charging performance. The reason may be that the embodiment material has a lower OI value to improve the dynamic performance of the material, and simultaneously has a high specific surface area to improve the multiplying power performance of the material.
3.2 cycle Performance test
The following experiments were performed on the flexible battery fabricated using the graphite composite materials of examples 1 to 3 and comparative example: the capacity retention was tested at a charge/discharge rate of 1C/1C, a voltage range of 2.8-4.2V, and 500 charge/discharge cycles were performed, and the charging DCR after 500 cycles was also tested, and the results are shown in table 3.
TABLE 3 Table 3
As can be seen from table 3, the cycle performance of the lithium ion battery prepared from the graphite composite anode material prepared by the invention is superior to that of the comparative example, because the graphite surface is coated with the lithium compound to improve the cycle performance in the process of charging and discharging by improving the transmission quantity of lithium ions; while the example has excellent diffusion coefficient, DCR is reduced.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the high-power graphite composite material is characterized by comprising the following steps of:
s1, carrying out blending reaction on the pretreated metal powder, a silane coupling agent, active particles and an organic solution to obtain modified metal powder;
s2, carrying out blending reaction on the modified metal powder, the saccharide compound, the graphite and the magnetic oxide to obtain a hard carbon and metal coated graphite material;
s3, blending and reacting the hard carbon and metal coated graphite material with asphalt, organic lithium salt and organic solvent to obtain the graphite composite material.
2. The method of claim 1, wherein the metal powder comprises at least one of silver powder, copper powder, nickel powder, cobalt powder, and iron powder.
3. The preparation method according to claim 1, wherein the mass ratio of the metal powder to the silane coupling agent, the active particles and the organic solution is 100: (1-10): (0.5-2): (500-1000).
4. The method of claim 1, wherein the active particles comprise at least one of silver chloride, cobalt chloride, palladium chloride, nickel chloride.
5. The preparation method according to claim 1, wherein the mass ratio of the modified metal powder to the saccharide compound, graphite and magnetic oxide is (1-5): (10-20): 100: (0.5-2).
6. The method according to claim 1, wherein the magnetic oxide comprises at least one of ferroferric oxide, tricobalt tetraoxide, and tricobalt tetraoxide.
7. The preparation method according to claim 1, wherein the mass ratio of the hard carbon and metal coated graphite material to asphalt, organic lithium salt and organic solvent is 100: (1-30): (1-5): (500-1000).
8. The method according to claim 1, wherein the organic lithium salt comprises at least one of lithium tetrafluoroborate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium difluorobisoxalato phosphate, and lithium tetrafluorooxalato phosphate.
9. A high power graphite composite material, characterized in that it is obtained by the preparation method according to any one of claims 1-8.
10. The use of the high-power graphite composite material as claimed in claim 9 for preparing a negative electrode material of a secondary battery.
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