CN117038870A - Preparation method of fast-charging anode material with high energy density - Google Patents
Preparation method of fast-charging anode material with high energy density Download PDFInfo
- Publication number
- CN117038870A CN117038870A CN202310425247.7A CN202310425247A CN117038870A CN 117038870 A CN117038870 A CN 117038870A CN 202310425247 A CN202310425247 A CN 202310425247A CN 117038870 A CN117038870 A CN 117038870A
- Authority
- CN
- China
- Prior art keywords
- graphite
- silicon
- fast
- anode material
- intercalation
- 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
- 239000010405 anode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 46
- 239000010439 graphite Substances 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 graphite compound Chemical class 0.000 claims abstract description 22
- 239000002210 silicon-based material Substances 0.000 claims abstract description 21
- 238000009830 intercalation Methods 0.000 claims abstract description 20
- 230000002687 intercalation Effects 0.000 claims abstract description 19
- 239000011162 core material Substances 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 239000010426 asphalt Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 238000001694 spray drying Methods 0.000 claims abstract description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 2
- 229940005991 chloric acid Drugs 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000007773 negative electrode material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910021383 artificial graphite Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002409 silicon-based active material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011239 graphite-silicon composite material Substances 0.000 description 1
- 229910003474 graphite-silicon composite material Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003860 storage Methods 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
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a high-energy-density fast-charge anode material, which comprises the following steps: dissolving graphite in an intercalation agent and an oxidant, stirring, reacting and drying to obtain an intercalation graphite compound; dissolving a silane coupling agent in toluene solution, adding a silicon oxide material, uniformly dispersing, then adding an intercalated graphite compound, uniformly dispersing, spray drying, and carbonizing to obtain a graphite core material; reacting inorganic aluminum salt compound, graphite core material, ammonia water and water-based polymer at 50-100 ℃ for 12-48h, filtering, carbonizing, and obtaining the porous alumina coated graphite silicon material. Melting metallic lithium at the dew point of-50 to-80 ℃ for 1-2 hours at 220-260 ℃, adding porous alumina coated graphite silicon material, uniformly mixing by a ball mill, adding into molten asphalt, uniformly stirring and dispersing, and heating to 500-800 ℃ under argon atmosphere for carbonization for 1-6 hours to obtain the composite material. The invention can improve the specific capacity and the multiplying power performance of the graphite cathode, and improve the first efficiency and the cycle performance of the material.
Description
Technical Field
The invention belongs to the field of preparation of lithium ion battery materials, and particularly relates to a preparation method of a fast-charging anode material with high energy density.
Background
The current marketized negative electrode material mainly comprises artificial graphite and natural graphite, the specific capacity of the negative electrode material reaches 360mAh/g, the specific capacity of the negative electrode material is close to the theoretical specific capacity of 372mAh/g, and the negative electrode material is difficult to be greatly improved. Although the silicon-based material has high specific capacity (1600-3000 mAh/g), the silicon-based material is required to be mixed with graphite for use because of higher expansion and poorer circulation, and if the expansion and the circulation improvement of the material are not large only by physically mixing the graphite and the silicon, the silicon-based material is because the silicon is easy to agglomerate because of the fact that the silicon is physically mixed and has smaller particle size, and the amorphous carbon coated on the surface of the silicon is easy to agglomerate, so that the silicon is exposed to cause more side reactions due to contact with electrolyte, and the circulation performance of the silicon-based material is reduced, and the electron and ion conductivity of the material such as amorphous carbon, a fast ion conductor and the like need to be coated on the surface of the negative electrode material of the silicon-based material. For example, patent application No. 202010389427.0 discloses a silicon anode material with a fluff structure and a preparation method thereof, wherein the silicon anode material comprises a silicon-based active material, a carbon nano tube, a carbon layer and a fast ion conductor layer, wherein the carbon nano tube is grown on the surface of the silicon-based active material in situ, the carbon layer is coated on the surfaces of the silicon-based active material and the carbon nano tube, and the fast ion conductor layer is coated on the surface of the carbon layer, so that the growth is carried out, and the material is ensured to still have the fluff structure finally.
Disclosure of Invention
The invention aims to overcome the defects and provide the preparation method of the high-energy-density fast-charging negative electrode material, which can improve the specific capacity and the multiplying power performance of the graphite negative electrode and the first efficiency and the cycle performance of the material.
The invention relates to a preparation method of a high-energy-density fast-charge anode material, which comprises the following steps:
step S1: graphite according to the mass ratio: intercalation agent: oxidant=100:50-100:50-100, dissolving graphite in an intercalation agent and an oxidant, stirring and reacting in a water bath (rotating speed of 100 rpm) for 600min, repeatedly washing the reaction product with water for 3 times, centrifuging (10000 r/min), and finally drying at 80 ℃ for 1h to obtain an intercalation graphite compound; intercalation graphite compound according to the mass ratio: silicon oxygen material: silane coupling agent: toluene solution=100:1-5:0.5-2: 500-1000, dissolving a silane coupling agent in toluene solution, adding a silicon oxide material, uniformly dispersing, then adding an intercalated graphite compound, uniformly dispersing, spray-drying (evaporation capacity is 10kg/h, time is 1 h), and carbonizing at 700-900 ℃ for 1-6h to obtain a graphite core material;
step S2: inorganic aluminum salt compound according to the mass ratio: graphite core material: ammonia water: the preparation method comprises the steps of preparing an inorganic aluminum salt compound with the mass concentration of 1-10wt% from water-based polymer=1-5:100:10-30:1-10, adding a graphite core material, ammonia water and the water-based polymer, reacting for 12-48h at the temperature of 50-100 ℃, filtering, and carbonizing at the temperature of 700-1100 ℃ to obtain the porous alumina-coated graphite silicon material.
Step S3: metal lithium according to the mass ratio: porous alumina coated graphite silicon material: pitch = 5-15:100:1-5, adding metal lithium into a melting reaction kettle at the dew point of minus 50 ℃ to minus 80 ℃ for 1-2 hours at the melting temperature of 220-260 ℃, adding a porous alumina coated graphite silicon material, uniformly mixing by a ball mill, adding the mixture into molten asphalt, uniformly stirring and dispersing, and then heating to 500-800 ℃ under the argon atmosphere for carbonization for 1-6 hours to obtain the high-energy density quick-charging anode material.
The intercalation agent in the step S1 is one of ammonium carbonate, ammonium oxalate or potassium carbonate; the oxidant is one of potassium permanganate, ferric chloride, hydrogen peroxide, chloric acid, hypochlorous acid, perchloric acid, nitric acid, potassium dichromate or sodium hypochlorite.
The inorganic aluminum salt compound in the step S1 is one of aluminum chloride, aluminum sulfate or aluminum nitrate.
The water-based polymer in the step S1 is one of polyacrylamide, polyvinyl alcohol, polyethylene glycol or polyvinylpyrrolidone.
The silane coupling agent in the step S1 is one of gamma-mercaptopropyl triethoxysilane, gamma-aminopropyl triethoxysilane or gamma- (2, 3-glycidoxy) propyl trimethoxysilane.
The softening point of the molten asphalt in the step S3 is 30-50 ℃.
Compared with the prior art, the invention has obvious beneficial effects, and the technical scheme can be adopted as follows: according to the invention, the intercalation compound is obtained by dissolving graphite in the intercalation agent and the oxidant, the intercalation compound has a defect structure introduced by sintering and de-intercalation, so that extra lithium storage space can be provided for the graphite, and the pores of the intercalation compound are filled with the silicon oxide material to improve the specific capacity of the material, reduce expansion of the material and improve the specific capacity and rate capability of the graphite cathode. The lithium metaaluminate coating can improve the wettability of graphite and electrolyte, thereby improving the multiplying power performance.
Description of the drawings:
fig. 1 is an SEM image of the lithium metaaluminate coated graphite silicon composite material prepared in example 1.
The specific embodiment is as follows:
example 1:
a preparation method of a fast-charge anode material with high energy density comprises the following steps:
step S1: dissolving 100g of artificial graphite in 80g of ammonium carbonate, 80g of potassium permanganate and 500g of deionized water, stirring and reacting in a water bath (rotating speed of 100 rpm) for 600min, repeatedly washing the reaction product with water for 3 times, centrifuging (10000 r/min), and finally drying at 80 ℃ for 1h to obtain an intercalated graphite compound; 1g of gamma-mercaptopropyl triethoxysilane is dissolved in 800g of ethanol solution of 5wt% toluene, 3g of silica material is added to disperse uniformly, 100g of intercalation graphite compound is added to disperse uniformly, spray drying (evaporation capacity is 10kg/h, time is 1 h) and carbonization is carried out at 800 ℃ for 3h, so as to obtain graphite core material;
step S2: 3g of aluminum chloride is added into 60g of deionized water to prepare an aluminum chloride compound with the mass concentration of 5wt%, then 100g of artificial graphite kernel material, 20g of ammonia water solution and 5g of polyacrylamide are added, and the mixture is reacted for 24 hours at the temperature of 80 ℃, filtered and carbonized for 3 hours at the temperature of 900 ℃ to obtain a porous aluminum oxide coated graphite silicon material; step S3: and adding 10g of metallic lithium into a melting reaction kettle at the dew point of-60 ℃ for 1.5 hours at the melting temperature of 250 ℃, adding 100g of porous alumina coated graphite silicon material, uniformly mixing by a ball mill, adding 3g of molten asphalt, uniformly stirring and dispersing, and heating to 600 ℃ under argon atmosphere for carbonization for 3 hours to obtain the high-energy density fast-charging anode material.
Example 2
A preparation method of a fast-charge anode material with high energy density comprises the following steps:
step S1: dissolving 100g of artificial graphite in 50g of ammonium oxalate, 50g of hydrogen peroxide and 500g of deionized water, stirring and reacting in a water bath (rotating speed of 100 rpm) for 600min, repeatedly washing the reaction product for 3 times, centrifuging (10000 r/min), and finally drying at 80 ℃ for 1h to obtain an intercalated graphite compound; dissolving 0.5g of gamma-aminopropyl triethoxysilane in 500g of ethanol solution of 1wt% toluene, adding 1g of silicon oxide material, uniformly dispersing, adding 100g of intercalated graphite compound, uniformly dispersing, spray drying, and carbonizing at 700 ℃ for 6 hours to obtain a graphite core material;
step S2: adding 1g of aluminum sulfate into 100g of deionized water to prepare an aluminum sulfate compound with the mass concentration of 1wt%, adding 100g of graphite core material, 10g of ammonia water solution and 1g of polyvinyl alcohol, reacting at 50 ℃ for 48 hours, filtering, and carbonizing at 700 ℃ for 6 hours to obtain the porous aluminum oxide coated graphite silicon material.
Step S3: and adding 5g of metallic lithium into a melting reaction kettle at the dew point of-80 ℃ for 2 hours at the melting temperature of 220 ℃, adding 100g of porous alumina coated graphite silicon material, uniformly mixing by a ball mill, adding 1g of molten asphalt, uniformly stirring and dispersing, and heating to 500 ℃ under argon atmosphere for carbonization for 6 hours to obtain the high-energy density fast-charging anode material.
Example 3
A preparation method of a fast-charge anode material with high energy density comprises the following steps:
step S1: dissolving 100g of artificial graphite in 100g of potassium carbonate, 100g of hypochlorous acid and 500g of deionized water, stirring and reacting in a water bath (rotating speed of 100 rpm) for 600min, repeatedly washing the reaction product with water for 3 times, centrifuging (10000 r/min), and finally drying at 80 ℃ for 1h to obtain an intercalated graphite compound; dissolving 2g of a silane coupling agent in 1000g of ethanol solution of 10wt% toluene, adding 2g of a silicon oxygen material, uniformly dispersing, adding 100g of an intercalated graphite compound, uniformly dispersing, spray-drying, and carbonizing at 900 ℃ for 1h to obtain a graphite core material;
step S2: 5g of aluminum nitrate is added into 50g of deionized water to prepare an aluminum nitrate solution with the mass concentration of 10wt%, then 100g of graphite core material, 30g of ammonia water solution and 10g of polyvinylpyrrolidone are added, and the mixture is reacted for 12 hours at the temperature of 100 ℃, filtered and carbonized for 1 hour at the temperature of 1100 ℃ to obtain the porous alumina-coated graphite silicon material.
Step S3: and adding 15g of metallic lithium into a melting reaction kettle at the dew point of-50 ℃ for 1 hour at the melting temperature of 260 ℃, adding 100g of porous alumina coated graphite silicon material, uniformly mixing by a ball mill, adding 5g of molten asphalt, uniformly stirring and dispersing, and heating to 800 ℃ under argon atmosphere for carbonization for 1 hour to obtain the high-energy density fast-charging anode material.
Comparative example 1:
a preparation method of a negative electrode material comprises the following steps:
unlike example 1, artificial graphite was used instead of the graphite core material, and the other was the same as in example 1.
Comparative example 2:
a preparation method of a negative electrode material comprises the following steps:
and (2) canceling the experimental step, namely replacing the porous alumina coated graphite silicon material with the graphite core material.
Comparative example 3:
a preparation method of a negative electrode material comprises the following steps:
unlike example 1, S3 was not performed.
Test example 1:
(1) SEM examination
SEM testing was performed on example 1, and the results are shown in fig. 1. From this, it was found that the high energy density obtained in example 1 was compatible with the rapid charging negative electrode material having a granular structure, and the particle size was uniform and ranged from 10 to 15. Mu.m.
(2) Powder conductivity test
Powder conductivity tests are carried out on the high-energy-density fast-charge anode materials prepared in the examples 1-3 and the anode materials prepared in the comparative examples 1-3, and the testing method comprises the following steps: powder was pressed into a block-like structure on a powder compaction densitometer with a pressure of 2T, and powder conductivity was tested using a four-probe tester, with the test results shown in table 1:
(3) Particle size, tap density, specific surface area, powder OI value test
The detection is carried out according to the detection method of national standard GB/T-24533-2019 lithium ion battery graphite anode material, and the detection result is shown in Table 1:
TABLE 1
| Project | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Tap density (g/cm) 3 ) | 1.19 | 1.14 | 1.20 | 1.04 | 1.06 | 1.11 |
| Specific surface area (m) 2 /g) | 1.89 | 1.82 | 1.91 | 1.52 | 1.35 | 1.71 |
| Conductivity (S/cm) | 9.82 | 8.45 | 9.99 | 4.23 | 5.67 | 6.95 |
| Powder OI value | 2.4 | 2.7 | 2.2 | 3.8 | 3.6 | 3.3 |
As can be seen from table 1, the high energy density fast-charge anode materials prepared in examples 1-3 have high tap density and specific surface area, and the reason is that the graphite core material is intercalation graphite, which can accommodate more specific capacity and tap density of the silicon-based material, and the porous alumina structure improves the specific surface area of the material.
(4) Button cell testing
The high energy density fast-charge anode materials prepared in examples 1-3 and the high energy density fast-charge anode materials prepared in comparative examples 1-3 are assembled into button cells A1, A2, A3, B1,B2 and B3, the assembly method is as follows: adding an adhesive, a conductive agent and a solvent into the graphite composite material, stirring and mixing uniformly to prepare negative electrode slurry, coating the negative electrode slurry on a copper foil, drying, rolling and cutting to prepare a negative electrode plate, wherein the adhesive is an LA132 adhesive, the conductive agent is an SP conductive agent, and the solvent is secondary distilled water; wherein the mass ratio of the graphite composite material to the SP conductive agent to the LA132 binder to the secondary distilled water is 95:1:4:220, and the electrolyte is LiPF 6 /EC+DEC(LiPF 6 The concentration of (2) was 1.3mol/L, the volume ratio of EC to DEC was 1:1), the metallic lithium sheet was the counter electrode, and the celegard2400 was the separator.
Specifically, the assembly of the button cell was performed in an argon-filled glove box, the electrochemical performance test was performed on a cell tester, the voltage range of charge and discharge was 0.005V-2.0V, the charge and discharge rate was 0.1C, and the discharge capacities thereof at 1C and 0.2C rates were tested, the rate performance (1C/0.1C) was calculated, and the cycle performance (0.2C/0.2C, 100 weeks) test results thereof were shown in table 2:
TABLE 2
As can be seen from table 2, the first discharge capacity and the first charge-discharge efficiency of the lithium ion battery prepared by adopting the high energy density fast-charge anode material of the embodiments 1-3 of the invention are obviously higher than those of the comparative example, which shows that the lithium ion transmission rate of the lithium metaaluminate lifting material coated on the surface of the graphite core reduces the loss of irreversible capacity of the material and improves the first charge-discharge efficiency; meanwhile, the porous alumina has the inert performance with lithium ions, no SEI film is formed, lithium ions are not consumed, and the first efficiency of the material is improved.
(4) Soft package battery test
Preparing a negative electrode by taking the high-energy-density compatible fast-charge negative electrode material of examples 1-3 and the high-energy-density compatible fast-charge negative electrode material of comparative examples 1-3 as negative electrode materials; with ternary material (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) As a positive electrode material, a positive electrode was prepared,by LiPF 6 Solution (EC+DEC solvent, volume ratio of 1:1, liPF) 6 1.3 mol/L) as an electrolyte and cellgard 2400 as a separator, 5Ah soft pack batteries A4, A5, A6, B4, B5, B6 were prepared, and then the cycle performance, the rate performance and the expansion performance in different states of the soft pack batteries were tested under the following test conditions:
1) Cycle performance test conditions: the charge and discharge current is 1C/1C, the voltage range is 2.8-4.2V, and the cycle number is 500.
2) Rate performance test conditions: charging multiplying power 1C/3C/5C/8C, discharging multiplying power 1C; the voltage range is 2.8-4.2V. The test results of the cycle performance are shown in table 3, and the test structures of the rate performance are shown in table 4.
TABLE 3 Table 3
From Table 3, after 500 times of circulation under the condition of charge-discharge current of 1C/1C, the circulation performance of the soft-packed battery prepared by adopting the high-energy density compatible fast-charge anode material of examples 1-3 is obviously better than that of the soft-packed battery prepared by adopting the comparative example, and the circulation performance is improved by coating the material surface with lithium metaaluminate to improve the transmission rate of lithium ions of the material and reducing the irreversible capacity of the material.
TABLE 4 Table 4
From table 4, it can be seen that under different charging rates, the soft-pack battery prepared from the composite materials of examples 1-3 has a better constant current ratio, which indicates that the lithium ion transmission rate and the high specific surface area of the lithium metaaluminate material coated on the surface of the graphite core improve the dynamic performance, and meanwhile, the electron conductivity of the material of the example is high, and the intercalation/deintercalation rate of lithium ions can be improved, thereby improving the rate charging performance.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (6)
1. A preparation method of a fast-charge anode material with high energy density comprises the following steps:
step S1: graphite according to the mass ratio: intercalation agent: oxidant=100:50-100:50-100, dissolving graphite in an intercalation agent and an oxidant, stirring and reacting in a water bath (rotating speed of 100 rpm) for 600min, repeatedly washing the reaction product with water for 3 times, centrifuging (10000 r/min), and finally drying at 80 ℃ for 1h to obtain an intercalation graphite compound; intercalation graphite compound according to the mass ratio: silicon oxygen material: silane coupling agent: toluene solution=100:1-5:0.5-2: 500-1000, dissolving a silane coupling agent in toluene solution, adding a silicon oxide material, uniformly dispersing, then adding an intercalated graphite compound, uniformly dispersing, spray-drying (evaporation capacity is 10kg/h, time is 1 h), and carbonizing at 700-900 ℃ for 1-6h to obtain a graphite core material;
step S2: inorganic aluminum salt compound according to the mass ratio: graphite core material: ammonia water: preparing an inorganic aluminum salt compound with the mass concentration of 1-10wt% by adding a graphite core material, ammonia water and a water-based polymer, reacting for 12-48 hours at the temperature of 50-100 ℃, filtering, and carbonizing at the temperature of 700-1100 ℃ to obtain a porous alumina-coated graphite silicon material;
step S3: metal lithium according to the mass ratio: porous alumina coated graphite silicon material: pitch = 5-15:100:1-5, adding metal lithium into a melting reaction kettle at the dew point of minus 50 ℃ to minus 80 ℃ for 1-2 hours at the melting temperature of 220-260 ℃, adding a porous alumina coated graphite silicon material, uniformly mixing by a ball mill, adding the mixture into molten asphalt, uniformly stirring and dispersing, and then heating to 500-800 ℃ under the argon atmosphere for carbonization for 1-6 hours to obtain the high-energy density quick-charging anode material.
2. The method for preparing the high-energy-density compatible fast-charge anode material according to claim 1, wherein: the intercalation agent in the step S1 is one of ammonium carbonate, ammonium oxalate or potassium carbonate; the oxidant is one of potassium permanganate, ferric chloride, hydrogen peroxide, chloric acid, hypochlorous acid, perchloric acid, nitric acid, potassium dichromate or sodium hypochlorite.
3. The method for preparing the high-energy-density compatible fast-charge anode material according to claim 1, wherein: the inorganic aluminum salt compound in the step S1 is one of aluminum chloride, aluminum sulfate or aluminum nitrate.
4. The method for preparing the high-energy-density compatible fast-charge anode material according to claim 1, wherein: the water-based polymer in the step S1 is one of polyacrylamide, polyvinyl alcohol, polyethylene glycol or polyvinylpyrrolidone.
5. The method for preparing the high-energy-density compatible fast-charge anode material according to claim 1, wherein: the silane coupling agent in the step S1 is one of gamma-mercaptopropyl triethoxysilane, gamma-aminopropyl triethoxysilane or gamma- (2, 3-glycidoxy) propyl trimethoxysilane.
6. The method for preparing the high-energy-density compatible fast-charge anode material according to claim 1, wherein: the softening point of the molten asphalt in the step S3 is 30-50 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310425247.7A CN117038870A (en) | 2023-04-20 | 2023-04-20 | Preparation method of fast-charging anode material with high energy density |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310425247.7A CN117038870A (en) | 2023-04-20 | 2023-04-20 | Preparation method of fast-charging anode material with high energy density |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117038870A true CN117038870A (en) | 2023-11-10 |
Family
ID=88625006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310425247.7A Pending CN117038870A (en) | 2023-04-20 | 2023-04-20 | Preparation method of fast-charging anode material with high energy density |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117038870A (en) |
-
2023
- 2023-04-20 CN CN202310425247.7A patent/CN117038870A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110071270B (en) | Nitrogen-doped silicon monoxide negative electrode material and preparation method and application thereof | |
| CN111193019A (en) | Lithium supplement additive, preparation method thereof and lithium ion battery | |
| CN111193018B (en) | Lithium battery positive active material and preparation method and application thereof | |
| CN110104677B (en) | Composite lithium titanate material and preparation method and application thereof | |
| CN115566170B (en) | Preparation method of high-energy-density quick-charging lithium ion battery anode material | |
| CN112110448A (en) | Nitrogen-doped carbon and nano-silicon composite anode material and preparation method thereof | |
| CN111129491A (en) | Lithium ion battery negative electrode active material, preparation method thereof and lithium ion battery | |
| CN108110226B (en) | Lithium ion battery, lithium ion battery anode material and preparation method thereof | |
| CN113328098A (en) | Negative plate and lithium ion battery comprising same | |
| CN114094068A (en) | Cobalt-coated positive electrode material, preparation method thereof, positive plate and lithium ion battery | |
| CN113889594A (en) | Preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material | |
| CN115974033A (en) | Nitrogen-doped mesoporous carbon-coated iron sodium phosphate pyrophosphate composite material and preparation method thereof | |
| CN117219777B (en) | Lithium supplementing agent, preparation method thereof, positive electrode plate and secondary battery | |
| CN114843483B (en) | Hard carbon composite material and preparation method and application thereof | |
| CN115249799A (en) | Rosin-based nitrogen-doped coated hard carbon negative electrode material of sodium ion battery and preparation method of rosin-based nitrogen-doped coated hard carbon negative electrode material | |
| CN115036458B (en) | Lithium ion battery | |
| CN114709398A (en) | Sulfur-containing fast ion conductor coated graphite composite material and preparation method thereof | |
| CN114784233A (en) | Negative electrode active material and preparation method and application thereof | |
| CN110098388B (en) | Silicon oxide composite material and preparation method and application thereof | |
| CN113594461A (en) | Carbon-silicon composite material and preparation method and application thereof | |
| CN117038870A (en) | Preparation method of fast-charging anode material with high energy density | |
| CN110931754A (en) | Negative electrode material, preparation method thereof, negative electrode plate and electrochemical device | |
| CN115974114B (en) | Quick-charging graphite composite material and preparation method thereof | |
| CN115036497B (en) | Graphite and ammonium polyphosphate co-modified silicon anode material and preparation method 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 |