CN115020682B - Preparation method of high-energy-density quick-charging graphite cathode material - Google Patents
Preparation method of high-energy-density quick-charging graphite cathode material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 41
- 239000010439 graphite Substances 0.000 title claims abstract description 41
- 239000010406 cathode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000010426 asphalt Substances 0.000 claims abstract description 15
- 239000002006 petroleum coke Substances 0.000 claims abstract description 9
- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000000571 coke Substances 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 31
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 10
- -1 methyl tetrahydrophthalic acid monosodium salt Chemical compound 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 6
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000007773 negative electrode material Substances 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 11
- 239000006258 conductive agent Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000011267 electrode slurry Substances 0.000 description 5
- 229910003481 amorphous carbon Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
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- 238000005096 rolling process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 239000006256 anode slurry Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—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
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- 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
- H01M4/624—Electric conductive fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- 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
Abstract
The invention discloses a preparation method of high-energy density quick-charging graphite cathode materials, which comprises the steps of firstly preparing a titanium niobate compound, then uniformly mixing the titanium niobate compound with asphalt, petroleum coke or asphalt coke, adopting a plasma technology, and enabling the vacuum degree to be (1-5) multiplied by 10 ‑3 Pa, introducing 500-1000sccm chlorine trifluoride gas, and depositing at 50-100 ℃ for 10-60 min; and then coating the titanium niobate compound complex on the surface of the titanium niobate composite material by a liquid phase method to obtain the titanium niobate composite material. The invention can improve the energy density and the quick charging performance of the graphite cathode material and reduce the impedance.
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 high-energy-density quick-charging graphite cathode material.
Background
With the improvement of the energy density requirement of the electric automobile on the lithium ion battery, the fast charging performance of the material should be improved while the lithium ion battery cathode material is required to have high energy density. The current marketable negative electrode material mainly uses artificial graphite and natural graphite, and has the problem that energy density and quick charging performance cannot be considered, for example, the energy density of the material is improved through graphitization degree, but the material layer interval is reduced, and the charging rate is reduced. The metal oxide as a negative electrode material has high specific capacity (500-1000 mAh/g) and excellent electronic conductivity, but has the problems of large expansion and low first efficiency, can not be directly used as the negative electrode material, and needs to be coated on the surface of graphite to improve the energy density on one hand and improve the power performance on the other hand. For example, chinese patent publication No. CN108183039B discloses a method for preparing a carbon-modified titanium niobate material, a lithium ion capacitor, and a negative electrode slurry thereof, in which amorphous carbon is coated on the surface of titanium niobate by a liquid phase method, the uniformity is poor, the carbon source is ethanol or ethylene glycol, the impedance is large after carbonization of oxalic acid, the isotropy is poor, and the carbon-modified titanium niobate material is obtained by heat treatment between titanium niobate and amorphous carbon, and carbon and titanium niobate are merely bonded together by physical adsorption, and the bonding force is poor, thereby affecting the impedance.
Disclosure of Invention
The invention aims to overcome the defects and provides a preparation method of a high-energy-density quick-charging graphite cathode material, which can improve the energy density and the quick-charging performance of the graphite cathode material and reduce the resistance.
The invention relates to a preparation method of a high-energy-density quick-charging graphite cathode material, which comprises the following steps:
(1) Preparing titanium niobate: according to the weight ratio of Ti: weighing titanium dioxide and niobium pentoxide powder according to the Nb molar ratio of 1 (2-3), uniformly mixing with deionized water, putting into a ball mill for ball milling for 6h at a speed of 50r/min, spray drying for 1h at an air inlet temperature of 200 ℃, an air outlet temperature of 100 ℃, an evaporation amount of 100kg/h, and sintering for 3h at a high temperature of 700 ℃ to obtain a titanium niobate compound;
(2) According to the proportion of asphalt: the mass ratio of the petroleum coke or the asphalt coke is 1-10: 100, weighing asphalt, petroleum coke or asphalt coke, adding into a ball mill, grinding uniformly, transferring into a vacuum chamber, and vacuumizing to (1-5) x 10 -3 Pa, introducing 500-1000sccm chlorine trifluoride gas, and depositing at 50-100 ℃ for 10-60 min to obtain a graphite precursor material;
(3) Preparing titanium niobate: organic resin mixed solution: the mass ratio of the graphite precursor materials is (1-10): (10-30): 100, adding titanium niobate into an organic resin mixed solution, uniformly dispersing, adding a graphite precursor material, spray-drying for 1h at the air inlet temperature of 150 ℃, the air outlet temperature of 80 ℃ and the evaporation capacity of 50kg/h, and heating to 700-1100 ℃ under an inert atmosphere to carbonize for 1-6 h to obtain the graphite cathode material.
The preparation method of the high-energy-density quick-charging graphite cathode material comprises the following steps: the organic resin mixed solution in the step (3) is a mixture of 50-200 parts by mass of glycerol, 10-20 parts by mass of terephthalic acid, 1-10 parts by mass of pentaerythritol, 20-50 parts by mass of styrene, 1-10 parts by mass of acrylamide and 1-10 parts by mass of methyl tetrahydrophthalic acid monosodium salt.
Compared with the prior art, the invention has obvious beneficial effects, and the technical scheme can show that: according to the invention, the surface of the graphite is coated with the titanium niobate, and the transmission rate of lithium ions in the charging and discharging overcharge process is improved by utilizing the characteristics of stable structure and high ionic conductivity of the titanium niobate; meanwhile, the mixing of the titanium niobate and the amorphous carbon improves the processing difficulty of the titanium niobate on the one hand, and the power performance is improved by the characteristic of high electronic conductivity of the amorphous carbon. By adopting a plasma technology, chlorine trifluoride gas is decomposed and doped at high pressure, the rate of converting petroleum coke into graphite is increased, the defects on the surface of the material are reduced, and the first efficiency and the specific capacity of the material are improved; meanwhile, chlorine trifluoride is carried out on the surface of the graphite for surface modification, nano/micron holes can be left in the material, the lithium ion intercalation and deintercalation speed in the charge and discharge process is improved, and the multiplying power performance is improved. The specific capacity of the graphite cathode material prepared by the method is more than or equal to 355mAh/g, and the compaction density is more than or equal to 1.65g/cm 3 The OI value of the powder is less than or equal to 3, and the specific surface area is as follows: 1-2m 2 The graphitization degree is more than or equal to 95 percent per gram.
Drawings
FIG. 1 is an SEM image of a graphite composite material prepared in example 1;
the specific implementation mode is as follows:
example 1:
a preparation method of a high-energy-density quick-charging graphite cathode material comprises the following steps:
(1) Preparing titanium niobate: weighing 80g (1 mol) of titanium dioxide and 331g (1.25 mol) of niobium pentoxide powder, adding the titanium dioxide and the niobium pentoxide powder into 1000ml of deionized water, uniformly mixing, putting the mixture into a ball mill for ball milling (50 r/min,6 h), spray drying for 1h (air inlet temperature 200 ℃, air outlet temperature 100 ℃, evaporation amount 100 kg/h), and sintering at 700 ℃ for 3h to obtain a titanium niobate compound;
(2) Weighing 5g of asphalt and 100g of petroleum coke, adding into a ball mill, grinding uniformly, transferring into a vacuum chamber, and vacuumizing to 2 x 10 by adopting a plasma technology -3 Pa, introducing 800sccm chlorine trifluoride gas, and depositing at 80 ℃ for 30min to obtain a graphite precursor material;
(3) Preparation of organic resin solution: uniformly mixing 100g of glycerol, 5g of terephthalic acid, 5g of pentaerythritol, 30g of styrene, 5g of acrylamide and 5g of methyl tetrahydrophthalic acid monosodium salt to obtain an organic resin solution;
adding 5g of titanium niobate into 20g of organic resin mixed solution, uniformly dispersing, adding 100g of graphite precursor material, uniformly mixing, adding 500ml of ethanol to prepare a concentration of 20%, spray-drying for 1h (inlet air temperature of 150 ℃, outlet air temperature of 80 ℃, evaporation capacity of 50 kg/h), heating to 800 ℃ under an argon inert atmosphere, and carbonizing for 3h to obtain the graphite cathode material.
Example 2:
a preparation method of a high-energy-density quick-charging graphite cathode material comprises the following steps: (1) preparing titanium niobate: weighing 80g (1 mol) of titanium dioxide and 265g (1 mol) of niobium pentoxide powder, adding the weighed materials into 1000ml of deionized water, uniformly mixing, putting the mixture into a ball mill for ball milling (50 r/min,6 hours), spray drying for 1 hour (the air inlet temperature is 200 ℃, the air outlet temperature is 100 ℃, and the evaporation capacity is 100 kg/h), and sintering at the high temperature of 800 ℃ for 3 hours to obtain a titanium niobate compound;
(2) Weighing 1g of asphalt and 100g of asphalt coke, adding into a ball mill, grinding uniformly, transferring into a vacuum chamber, and vacuumizing to 1 × 10 by adopting a plasma technology -3 Pa, introducing 500sccm chlorine trifluoride gas, and depositing at 50 ℃ for 60min to obtain a graphite precursor material;
(3) Preparation of organic resin mixed solution: uniformly mixing 50g of glycerol, 20g of terephthalic acid, 1g of pentaerythritol, 20g of styrene, 1g of acrylamide and 1g of methyl tetrahydrophthalic acid monosodium salt to obtain an organic resin solution;
adding 1g of titanium niobate into 10g of organic resin mixed solution, uniformly dispersing, adding 100g of graphite precursor material, uniformly mixing, adding 1000ml of ethanol to prepare a 10% concentration, spray-drying for 1h (inlet air temperature 150 ℃, outlet air temperature 80 ℃, evaporation capacity 50 kg/h), and heating to 700 ℃ under an inert atmosphere for carbonization for 6h to obtain the graphite cathode material.
Example 3:
a preparation method of a high-energy-density quick-charging graphite cathode material comprises the following steps:
(1) Preparing titanium niobate: weighing 80g (1 mol) of titanium dioxide and 397g (1.5 mol) of niobium pentoxide powder, adding into 1000ml of deionized water, uniformly mixing, then putting into a ball mill for ball milling (50 r/min,6 h), spray drying for 1h (air inlet temperature 200 ℃, air outlet temperature 100 ℃, evaporation amount 100 kg/h), and sintering at high temperature of 800 ℃ for 3h to obtain a titanium niobate compound;
(2) Weighing 10g of asphalt and 100g of petroleum coke, adding into a ball mill, grinding uniformly, transferring into a vacuum chamber, and vacuumizing to 5 × 10 by adopting a plasma technology -3 Pa, introducing 1000sccm chlorine trifluoride gas, and depositing at 100 ℃ for 10min to obtain a graphite precursor material;
(3) Preparing organic resin mixed liquid: uniformly mixing 200g of glycerol, 10g of terephthalic acid, 10g of pentaerythritol, 50g of styrene, 10g of acrylamide and 10g of methyl tetrahydrophthalic acid monosodium salt to obtain an organic resin solution;
adding 10g of titanium niobate into 30g of organic resin mixed solution, uniformly dispersing, adding 100g of graphite precursor material, uniformly mixing, adding 270ml of ethanol to prepare a 30% concentration, spray-drying for 1h (inlet air temperature of 150 ℃, outlet air temperature of 80 ℃, evaporation capacity of 50 kg/h), and heating to 1100 ℃ under an argon inert atmosphere for carbonization for 1h to obtain the graphite cathode material.
Comparative example:
a preparation method of a graphite material comprises the following steps:
weighing 10g of asphalt and 100g of petroleum coke, adding into a ball mill, grinding uniformly, transferring into a tube furnace, heating to 750 ℃ in an argon inert atmosphere, keeping the temperature for 3 hours, cooling to room temperature in the argon inert atmosphere, and crushing to obtain the graphite material.
Experimental example:
(1) SEM test
The graphite composite anode material prepared in example 1 was subjected to SEM test, and the results are shown in fig. 1. As can be seen from FIG. 1, the obtained composite material is granular, has a particle size of 10-20 μm, and has uniform size distribution.
(2) Button cell test
The graphite composite negative electrode materials prepared in examples 1 to 3 and the negative electrode material of the comparative example were assembled into button cells, respectively, as follows:
adding a binder, a conductive agent and a solvent into the negative electrode material, stirring and mixing uniformly to prepare negative electrode slurry, coating the negative electrode slurry on copper foil, drying, rolling and cutting to prepare a negative electrode sheet. The binder is LA132 binder, the conductive agent is SP conductive agent, the solvent is secondary distilled water, and the weight ratio of the negative electrode material, the SP conductive agent, the LA132 binder and the secondary distilled water is 95. The lithium metal sheet is taken as a counter electrode, a Polyethylene (PE) film, a polypropylene (PP) film or a polyethylene propylene (PEP) composite film is taken as a diaphragm, and LiPF is taken 6 /EC+DEC(LiPF 6 With a concentration of 1.3mol/L, a volume ratio of EC to DEC of 1) as electrolyte, the cell assembly was carried out in a glove box filled with argon gas.
The prepared button cells are respectively arranged on a Wuhan blue CT2001A type cell tester, and are charged and discharged at 0.1C multiplying power, the charging and discharging voltage range is 0.005V-2.0V, and the first discharge capacity and the first discharge efficiency are measured. And tested for rate discharge capacity at 2C.
The powder conductivity, powder OI value, graphitization degree and specific surface area of the negative electrode material are tested according to the national standard GB/T-243333-2019 graphite negative electrode material of the lithium ion battery, and the test results are shown in Table 1:
TABLE 1 Properties of negative electrode materials in examples 1 to 3 and comparative example
As can be seen from Table 1, the discharge capacities of the composite anode materials prepared in examples 1 to 3 were significantly higher than those of the comparative examples; the reason for this is probably that the plasma technology is adopted in the preparation process of the graphite raw material to modify and activate the material surface by the trichloro-fluoride, so that the irreversible capacity and the defect degree of the material are reduced, and the specific capacity of the material is improved; meanwhile, the titanium niobate has inertia with electrolyte, so that lithium ions consumed by forming an SEI film are reduced, and the primary efficiency is improved; meanwhile, the titanium niobate has the characteristic of high lithium ion conductivity, so that the rate capability of the material is improved.
(3) Pouch cell testing
The negative electrode materials prepared in examples 1 to 3 and comparative example were used as negative electrodes, respectively, and a ternary material (LiNi) was used 1/3 Co 1/ 3 Mn 1/3 O 2 ) Preparing a positive electrode from a positive electrode material by using LiPF 6 (the solvent is EC + DEC, the volume ratio is 1, and the concentration is 1.3 mol/L) is used as an electrolyte, and Celegard2400 is used as a diaphragm to prepare the 2Ah flexible package battery.
When the negative electrode is prepared, the binder, the conductive agent and the solvent are added into the negative electrode material, the negative electrode slurry is prepared by stirring and mixing evenly, the slurry of the negative electrode slurry is coated on the copper foil, and the negative electrode sheet is prepared by drying, rolling and cutting. The binder is a LA132 binder, the conductive agent is an SP conductive agent, the solvent is secondary distilled water, and the weight ratio of the negative electrode material, the SP conductive agent, the LA132 binder and the secondary distilled water is 95.
When the anode is prepared, adding a binder, a conductive agent and a solvent into an anode material, stirring and mixing uniformly to prepare anode slurry, coating the anode slurry on an aluminum foil, drying, rolling and cutting to prepare an anode sheet, wherein the binder is PVDF, the conductive agent is carbon nano tubes and the solvent is N-methyl pyrrolidone. The weight ratio of the positive electrode material, the conductive agent, the binder and the solvent is 93.
3.1 Rate Performance test
The charging and discharging voltage range is 2.8-4.2V, the testing temperature is 25 +/-3.0 ℃, the charging is respectively carried out at 1.0C, 2.0C, 3.0C and 5.0C, the discharging is carried out at 1.0C, the constant current ratio and the temperature of the battery under different charging modes are tested, and the results are shown in Table 2:
TABLE 2 Rate Performance of examples 1-3 and comparative examples
As can be seen from Table 2, the rate charging performance of the battery pack of the invention is obviously superior to that of the comparative example, the charging time is shorter, and the composite negative electrode material of the invention has good quick charging performance. The reason may be that, because the battery needs the migration of lithium ions in the charging process, the surface of the material in the embodiment is coated with the titanium niobate with high ionic conductivity, which facilitates the insertion and extraction of the lithium ions and improves the rate performance of the lithium ions, and meanwhile, chlorine trifluoride is introduced in the preparation process of the material in the embodiment to modify the surface of the material to improve the insertion and extraction channels of the material, improve the rate performance and reduce the temperature rise.
3.2 cycle Performance test
The following experiment was performed on the pouch batteries manufactured using the negative electrode materials of examples 1 to 3 and comparative example: the capacity retention rate was measured by using a 2C/2C charge-discharge rate, a voltage range of 2.8-4.2V, and 500 charge-discharge cycles, and the results are shown in Table 3:
3.3 high temperature storage Performance test
Firstly, testing the discharge capacity Qa of a battery when the battery is charged to a 100% state, then placing the battery into a constant-temperature box at 55 ℃, storing the battery for 30 days, then testing the residual capacity QB of the battery, then testing the capacity QC when the battery is charged to a full-charge state, and then calculating the charge retention = QB/QA of the battery; capacity recovery = QC/QA.
Table 3 cycle and storage performance of the lithium ion batteries of examples 1-3 and comparative examples
As can be seen from table 3, the cycle performance of the lithium ion battery prepared from the composite negative electrode material prepared by the invention is superior to that of the comparative example, because the titanium niobate coated on the graphite surface has the characteristic of stable structure to improve the cycle performance; meanwhile, the side reaction of the titanium niobate and the electrolyte is not violent, so that the high-temperature storage performance is improved.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, they are not intended to limit the scope of the present invention. Various modifications and changes may be made by those skilled in the art, and any modifications, equivalents, and improvements made within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (1)
1. A preparation method of a high-energy-density quick-charging graphite cathode material comprises the following steps:
(1) Preparing titanium niobate: according to the weight ratio of Ti: weighing titanium dioxide and niobium pentoxide powder according to the Nb molar ratio of 1 (2-3), uniformly mixing with deionized water, putting into a ball mill for ball milling for 6h at a speed of 50r/min, spray drying for 1h at an air inlet temperature of 200 ℃, an air outlet temperature of 100 ℃, an evaporation amount of 100kg/h, and sintering for 3h at a high temperature of 700 ℃ to obtain a titanium niobate compound;
(2) According to the proportion of asphalt: the mass ratio of the petroleum coke or the asphalt coke is 1-10: 100, weighing asphalt, petroleum coke or asphalt coke, adding into a ball mill, grinding uniformly, transferring into a vacuum cavity, and vacuum-pumping to (1-5) × 10 -3 Pa, introducing 500-1000sccm chlorine trifluoride gas, and depositing at 50-100 ℃ for 10-60 min to obtain a graphite precursor material;
(3) Preparing titanium niobate: organic resin mixed solution: the mass ratio of the graphite precursor materials is (1-10): (10-30): 100, adding titanium niobate into an organic resin mixed solution, uniformly dispersing, adding a graphite precursor material, spray-drying for 1h at the air inlet temperature of 150 ℃, the air outlet temperature of 80 ℃ and the evaporation capacity of 50kg/h, and heating to 700-1100 ℃ under an inert atmosphere to carbonize for 1-6 h to obtain a graphite cathode material;
wherein: the organic resin mixed solution in the step (3) is a mixture of 50-200 parts by mass of glycerol, 10-20 parts by mass of terephthalic acid, 1-10 parts by mass of pentaerythritol, 20-50 parts by mass of styrene, 1-10 parts by mass of acrylamide and 1-10 parts by mass of methyl tetrahydrophthalic acid monosodium salt.
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Denomination of invention: A preparation method of high energy density fast charging graphite negative electrode material Effective date of registration: 20231122 Granted publication date: 20230203 Pledgee: Guiyang Branch of Shanghai Pudong Development Bank Co.,Ltd. Pledgor: Huiyang (Guizhou) new energy materials Co.,Ltd. Registration number: Y2023520000068 |