CN114203978B - High-capacity graphite anode material and preparation method and application thereof - Google Patents
High-capacity graphite anode material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 111
- 239000010439 graphite Substances 0.000 title claims abstract description 111
- 239000010405 anode material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000011230 binding agent Substances 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 239000011268 mixed slurry Substances 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 16
- 238000001694 spray drying Methods 0.000 claims abstract description 8
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000012216 screening Methods 0.000 claims abstract description 6
- 239000007773 negative electrode material Substances 0.000 claims description 40
- 239000002194 amorphous carbon material Substances 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000007493 shaping process Methods 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000010426 asphalt Substances 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000000295 fuel oil Substances 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 21
- 239000003792 electrolyte Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000011300 coal pitch Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011294 coal tar pitch Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000006978 adaptation Effects 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000012360 testing method 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
- H01M4/58—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
-
- 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
-
- 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)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a high-capacity graphite anode material and a preparation method and application thereof, and the high-capacity graphite anode material comprises the following steps: preparing crystalline flake graphite, a doped compound, a binder and a solvent into mixed slurry, and performing spray drying, crushing and spheroidization to obtain spherical natural graphite with the inner and outer surfaces coated with the binder and the doped compound, carbonizing, demagnetizing and screening to obtain the high-capacity graphite anode material. The high-capacity graphite anode material prepared by the method has the advantages of high capacity, good cycle performance, good multiplying power performance and the like, and when the high-capacity graphite anode material is prepared into a working electrode for preparing a lithium ion battery, the cycle life of the lithium ion battery can be remarkably prolonged, and the high-capacity graphite anode material has high use value and good application prospect. The preparation method has the advantages of simple process, convenient operation, low cost, low energy consumption and the like, is suitable for large-scale production and is beneficial to technological application.
Description
Technical Field
The invention belongs to the field of negative electrode materials, and relates to a high-capacity graphite negative electrode material, and a preparation method and application thereof.
Background
The natural graphite has been widely used because of its advantages of high charge and discharge capacity, good charge and discharge platform, wide sources, low cost, etc. However, natural graphite has the defects of unstable structure, high internal pore, easiness in causing co-insertion of solvent molecules, falling and cracking of lamellar sheets in the charge and discharge process, exposing more surfaces capable of reacting with electrolyte, accelerating the reaction of natural graphite and electrolyte, causing the reduction of charge and discharge efficiency, poor cycle performance, poor safety and the like of a lithium ion battery, and directly reducing the cycle life of the lithium ion battery. In addition, natural graphite has the following disadvantages: the multiplying power performance can not meet the market demand; gram capacity has failed to meet the higher energy density requirements of batteries. In order to overcome the above-mentioned disadvantages of natural graphite, a layer of amorphous carbon material is generally coated on the surface of natural graphite, however, the existing coating method mainly comprises the steps of mixing natural graphite and a coating modifier in a physical mixing manner, and then flowing and self-coating the natural graphite by using the liquefaction process of the coating modifier in the carbonization process, so that the following disadvantages exist: the coating modifier cannot effectively cover the outer surface of the natural graphite, particularly, because the coating modifier is difficult to enter the internal pores of the spherical natural graphite, the coating modifier is difficult to effectively coat the inner surface of the spherical natural graphite, thus the amorphous carbon material is difficult to completely coat the natural graphite, finally, in the battery cycle process, electrolyte can gradually permeate to the surfaces of the uncoated natural graphite to continuously generate a Solid Electrolyte Interface (SEI) film, and the electrolyte is continuously embedded into the natural graphite layer structure, so that a large amount of active lithium is consumed and the natural graphite structure is damaged, and the capacity is continuously attenuated. In addition, a strategy for increasing the coating amount of the amorphous carbon material is proposed by those skilled in the art, and although the reaction of the natural graphite with the electrolyte can be prevented to some extent by increasing the coating amount of the amorphous carbon material, the capacity of the natural graphite is inevitably reduced, so that the energy density of the material cannot meet the use requirement.
Therefore, how to obtain a graphite anode material with high capacity and good cycle performance has great significance for improving the cycle life of the lithium ion battery.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and providing a high-capacity graphite anode material with high capacity and good cycle performance, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
The preparation method of the high-capacity graphite anode material comprises the following steps:
S1, mixing flake graphite, a doped compound, a binder and a solvent to prepare mixed slurry;
S2, spray drying the mixed slurry obtained in the step S1 to obtain a material of which the surface is coated with the binder and the doping compound in a mixing manner;
S3, crushing and spheroidizing the material obtained in the step S2 and coated on the surface of the crystalline flake graphite by mixing the binder and the doping compound to obtain spherical natural graphite with both the inner surface and the outer surface coated with the binder and the doping compound;
S4, carbonizing the spherical natural graphite with the inner and outer surfaces coated with the binder and the doping compound, and performing demagnetizing and screening to obtain the high-capacity graphite anode material.
In the preparation method, further improved, in the step S1, the solid content of the mixed slurry is 1% -25%.
In the preparation method, which is further improved, in the step S1, the mass ratio of the crystalline flake graphite, the doping compound and the binder in the mixed slurry is 55-94:1-15:5-30.
The preparation method is further improved, and the average particle size of the crystalline flake graphite is 3-45 mu m; the doping compound is one of phosphoric acid, phosphorus pentoxide, triphenylphosphine, boric acid, diboron trioxide and vanadium pentoxide; the binder is at least one of petroleum asphalt, coal asphalt, mesophase asphalt, phenolic resin, epoxy resin, petroleum resin, coal tar or heavy oil.
In a further improved preparation method, in the step S1, the solvent is one or more of acetone, diethyl ether, xylene, carbon tetrachloride, n-hexane or ethanol.
In the preparation method, the preparation method is further improved, and in the step S3, the spheroidization is carried out in a continuous shaping system formed by connecting 2-15 micro-nano particle shaping and coating systems in series; the technological parameters of the spheroidization are as follows: the feeding amount is 50 kg-200 kg/h, the rotating speed is 100 rpm-9000 rpm, and the time is 5 min-45 min.
In the preparation method, which is further improved, in the step S4, the carbonization is performed at 600-1500 ℃; the heat preservation time in the graphite carbonization process is 5-20 h.
The invention also provides a high-capacity graphite anode material which is prepared by the preparation method as a general technical conception.
The high-capacity graphite anode material is further improved, and comprises spherical natural graphite; the inner and outer surfaces of the spherical natural graphite are coated with amorphous carbon material layers to form an inner and outer coating structure which sequentially comprises the amorphous carbon material layers, the natural graphite layers and the amorphous carbon material layers from inside to outside; the amorphous carbon material layer is doped with at least one element of boron, phosphorus and vanadium.
As a general technical concept, the invention also provides application of the high-capacity graphite anode material in preparation of lithium ion batteries.
Compared with the prior art, the invention has the advantages that:
(1) The invention provides a preparation method of a high-capacity graphite cathode material, which is characterized in that crystalline flake graphite, a doped compound, a binder and a solvent are used as raw materials to prepare mixed slurry, the binder and the doped compound are uniformly coated on the surface of the crystalline flake graphite by a spray drying method, crystalline flake graphite which are mutually bonded together is dispersed by crushing, the crystalline flake graphite coated with the binder and the doped compound on the surface is spheroidized to form spherical natural graphite, the inner surface and the outer surface of the spherical natural graphite are uniformly coated with the binder and the doped compound, namely the spherical natural graphite coated with the binder and the doped compound on the inner surface and the outer surface is finally carbonized and demagnetized and screened to prepare the high-capacity graphite cathode material. In the invention, the binder and the doping compound can be uniformly coated on the inner and outer surfaces of the spherical natural graphite by adopting a method of combining spray drying, crushing and spheroidizing; based on the method, after carbonization, uniform amorphous carbon material layers are formed on the inner and outer surfaces of the spherical natural graphite, so that an inner and outer surface coating structure of the amorphous carbon material layers, the natural graphite layers and the amorphous carbon material layers is formed from inside to outside, and in the high-capacity graphite negative electrode material, the inner and outer surfaces of the spherical natural graphite are uniformly coated with the amorphous carbon material layers, so that electrolyte can be effectively prevented from contacting the natural graphite, the cycle performance of the material is improved, and meanwhile, the multiplying power performance of the natural graphite can be improved. In addition, in the carbonization process, the element doping of the amorphous carbon material is realized, the doped elements comprise boron, phosphorus, vanadium and the like, and the reversible charge-discharge capacity of the amorphous carbon material can be improved through doping, so that the gram capacity of the graphite composite material is improved, the energy density of the high-capacity graphite negative electrode material is obviously improved, and the application range of the high-capacity graphite negative electrode material is widened. Compared with the existing conventional natural graphite material, the graphite negative electrode material prepared by the preparation method has the advantages of high capacity, good cycle performance, good multiplying power performance and the like, and when the high-capacity graphite negative electrode material is prepared into a working electrode for preparing a lithium ion battery, the cycle life of the lithium ion battery can be remarkably prolonged, and the high-capacity graphite negative electrode material has high use value and good application prospect.
(2) In the preparation method, the solid content of the mixed slurry is optimized to be 1-25%, and the mixed slurry with proper viscosity is obtained by optimizing the solid content of the mixed slurry, so that the binder and the doped compound can be coated on the surface of the crystalline flake graphite more stably. The binder is not cured at high temperature and has strong binding effect, so that the binder and the doped compound are not separated in the spray drying, crushing and spheroidizing processes, and the coating layer of the binder and the doped compound is not damaged, which is the key point for preparing the amorphous carbon material layer uniformly coated on the inner and outer surfaces. Meanwhile, the application optimizes the mass ratio of the crystalline flake graphite, the doped compound and the binder in the mixed slurry to be 55-94:1-15:5-30, and obtains the mixed slurry with moderate binder content by optimizing the solid content of the mixed slurry and the dosage ratio of the raw materials, thereby being beneficial to forming the coating layers of the binder and the doped compound with proper thickness on the surface of the crystalline flake graphite, further being beneficial to forming compact amorphous carbon material layers with proper thickness on the inner and outer surfaces of the spherical natural graphite, and finally obtaining the high-capacity graphite anode material with higher capacity and better cycle performance. This is because if the content of the binder is too low, the amorphous carbon material layer generated in the graphite process is too thin and has poor thickness uniformity, so that the amorphous carbon material layer cannot be completely and effectively coated on the inner and outer surfaces of the natural graphite, the coating effect is poor, and the performance cycle of the high-capacity graphite negative electrode material is poor due to side reaction of the natural graphite and the electrolyte. If the content of the binder is too high, the coating layer becomes too thick, which affects the migration rate of lithium ions and deteriorates the rate performance.
(3) The preparation method has the advantages of simple process, convenient operation, low cost, low energy consumption and the like, does not need to adopt an organic solvent to wash off redundant binder on the surface of the natural graphite, does not need to use high-temperature and high-pressure equipment to heat and pressurize, is suitable for large-scale production, and is beneficial to technological application.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Fig. 1 is a flow chart of the preparation of the high capacity graphite negative electrode material in example 1 of the present invention.
Fig. 2 is an SEM image of the high-capacity graphite anode material prepared in example 1 of the present invention.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby.
The materials and instruments used in the examples below are all commercially available. In the examples of the present invention, unless otherwise specified, the process used was a conventional process, the equipment used was a conventional equipment, and the data obtained were all averages of three or more tests.
Example 1
The preparation method of the high-capacity graphite anode material is shown in fig. 1, and comprises the following steps:
(1) According to the mass ratio of the flake graphite, the doped compound and the binder of 80:5:15, adding the flake graphite, phosphoric acid (doped compound) and coal pitch (binder) with average particle size of 35 mu m into acetone, controlling the solid content to be 15%, and fully stirring and carrying out ultrasonic treatment to obtain the mixed slurry.
(2) And (3) spray drying the mixed slurry obtained in the step (1) to obtain a material of which the surface is coated with the mixture of coal tar pitch and phosphoric acid, namely the material of which the surface is coated with the mixture of the binder and the doping compound.
(3) Crushing the material obtained in the step (2) and obtained by mixing coal tar pitch and phosphoric acid and coating the material on the surface of the flake graphite, so that each flake graphite is dispersed, and controlling the granularity of the crushed material to be 35 mu m. The adhesive is not cured at high temperature, so that the adhesive has a strong adhesive effect, and the adhesive and the doped compound cannot fall off in the crushing process; meanwhile, due to the existence of the binder, the binder and the doping compound can be uniformly coated on the surface of the crystalline flake graphite.
(4) Spheroidizing the crushed product in the step (3), specifically: the crushed product is put into a continuous shaping system (developed by Zhexin New energy Co., ltd.) consisting of 6 micro-nano particle shaping cladding systems connected in series at a feeding amount of 100kg/h, and the crushed product is shaped (spheroidized) for 15min at a host rotation speed of 5000 rpm. In the spheroidizing process, the flake graphite is curled to form spherical natural graphite, and at the moment, the mixture of the binder and the doping compound is uniformly coated on the inner surface and the outer surface of the spherical natural graphite to obtain spherical natural graphite of which the inner surface and the outer surface are coated with coal pitch and phosphoric acid, namely the spherical natural graphite of which the inner surface and the outer surface are coated with the binder and the doping compound.
(5) Carbonizing spherical natural graphite with both the inner and outer surfaces coated with coal pitch and phosphoric acid obtained in the step (4), heating to 1000 ℃, and preserving heat for 12 hours, wherein in the carbonization process, the coal pitch coated on the inner and outer surfaces of the spherical natural graphite is converted into compact amorphous carbon materials, and the amorphous carbon materials are uniformly coated on the inner and outer surfaces of the spherical natural graphite, so that the spherical natural graphite with the inner and outer surfaces coated with the amorphous carbon materials is formed, and phosphorus elements are doped into the amorphous carbon materials in the carbonization process, so that the reversible mosaic lithium removal capacity of the amorphous carbon materials is improved, and the high-capacity graphite anode material is obtained by magnetic removal and screening.
In this embodiment, the prepared high-capacity graphite negative electrode material includes spherical natural graphite, wherein the inner and outer surfaces of the spherical natural graphite are coated with amorphous carbon material layers, so that an inner and outer coating structure which sequentially comprises the amorphous carbon material layers, the natural graphite layers and the amorphous carbon material layers from inside to outside is formed, and phosphorus elements are doped in the amorphous carbon material layers.
Fig. 2 is an SEM image of the high-capacity graphite anode material prepared in example 1 of the present invention.
The application of the high-capacity graphite anode material in preparing the lithium ion battery is that the high-capacity graphite anode material is made into a working electrode of the lithium ion battery and assembled into a button battery, and the method comprises the following steps:
the high-capacity graphite anode material prepared in example 1, CMC and SBR were uniformly mixed at a mass ratio of 96.5:1.5:2 to prepare a slurry, which was coated on a copper foil, and dried, rolled and punched to prepare a working electrode. The button cell assembly is carried out in a glove box filled with argon, a metal lithium foil is used as a counter electrode, a diaphragm is a polyethylene/propylene composite microporous membrane, and electrolyte is 1M LiPF 6/(EC: EMC) (3:7).
The application of the high-capacity graphite anode material in preparing the lithium ion battery is that the high-capacity graphite anode material is made into a working electrode of the lithium ion battery and assembled into a full battery, and the method comprises the following steps:
Mixing high-capacity graphite anode material, conductive agent (SP), CMC and SBR according to a mass ratio of 95:1.5:1.5:2, and coating on copper foil to obtain an anode pole piece. And uniformly mixing the positive active material LiCoO2, the conductive agent (SP) and the PVDF according to the mass ratio of 96.5:2:1.5, and coating the mixture on an aluminum foil to obtain the positive electrode plate. The electrolyte is 1mol/L LiPF6+EC+EMC, and the membrane is a polyethylene/propylene composite microporous membrane. They are assembled into a battery.
Electrochemical performance tests of button cells were performed on a cell tester with a charge-discharge rate of 0.1C and a voltage range of 0.005-2V, as shown in table 1.
The full cell was charged and discharged at normal temperature at a rate of 1C with a voltage range of 3.0 to 4.2V, and the cycle performance was tested as shown in table 1.
The results show that: the button cell assembled from the high-capacity graphite anode material prepared in example 1 had a first delithiation capacity of 382.2mAh/g and a coulombic efficiency of 92.1%; the full cell assembled from the high capacity graphite negative electrode material prepared in example 1 had a capacity retention of 93.2% at 500 weeks at room temperature 1C cycle and 86.8% at 1500 weeks at room temperature 1C cycle.
Comparative example 1
The preparation method of the graphite anode material comprises the following steps:
(1) Mixing flake graphite with average granularity of 35 μm with coal pitch according to the mass ratio of flake graphite to binder of 90:10 to obtain the mixture.
(2) Carbonizing the mixture obtained in the step (1), and heating to 1000 ℃ for 12 hours. And (3) carrying out demagnetizing and screening on the carbonized product to obtain the graphite anode material.
The graphite anode material prepared in comparative example 1 was prepared into a button cell battery and a full cell battery by the method of example 1, and electrochemical performance results are shown in table 1.
The results show that: in comparative example 1, the first lithium removal capacity was 360.1mAh/g, the coulombic efficiency was 90.7%, the capacity retention rate at 500 weeks at room temperature 1C cycle was 85.2% at most, and the capacity retention rate at 1500 weeks at room temperature 1C cycle was 75.6% at most.
Comparative example 2
The preparation method of the graphite anode material comprises the following steps:
(1) According to the mass ratio of the flake graphite to the binder of 85:15, adding the flake graphite with the average granularity of 35 mu m and coal pitch into acetone, controlling the solid content to be 15%, and fully stirring and carrying out ultrasonic treatment to obtain mixed slurry.
(2) And (3) carrying out spray drying on the mixed slurry obtained in the step (1) to obtain the material with coal tar pitch coated on the surface of the flake graphite.
(3) Crushing the material obtained in the step (2) and coated on the surface of the flake graphite, so that each flake graphite is dispersed, and controlling the granularity of the crushed material to be 35 mu m.
(4) Spheroidizing the crushed product in the step (3), specifically: the crushed product is put into a continuous shaping system (the system is developed by Zhexin New energy Co., ltd.) which is formed by connecting 6 micro-nano particle shaping cladding systems in series under the feeding amount of 100kg/h, and the crushed product is shaped (spheroidized) for 15min at the rotation speed of a main machine of 5000rpm, so that spherical natural graphite with coal tar pitch coated on the inner and outer surfaces is obtained.
(5) Carbonizing spherical natural graphite with coal tar pitch coated on the inner and outer surfaces obtained in the step (4), heating to 1000 ℃, preserving heat for 12 hours, and carrying out demagnetization and screening to obtain the graphite anode material.
The graphite anode material prepared in comparative example 2 was prepared into a button cell battery and a full cell battery by the method of example 1, and electrochemical performance results are shown in table 1.
Example 2
A method for preparing a high capacity graphite negative electrode material, which is substantially the same as in example 1, except that: in step (1) of example 2, the solid content of the mixed slurry was 1%.
The high capacity graphite negative electrode material prepared in example 2 was prepared as a button cell battery and a full cell battery according to the method of example 1, and electrochemical performance results are shown in table 1.
Example 3
A method for preparing a high capacity graphite negative electrode material, which is substantially the same as in example 1, except that: in step (1) of example 3, the solid content of the mixed slurry was 5%.
The high capacity graphite negative electrode material prepared in example 3 was prepared as a button cell battery and a full cell battery according to the method of example 1, and electrochemical performance results are shown in table 1.
Example 4
A method for preparing a high capacity graphite negative electrode material, which is substantially the same as in example 1, except that: in step (1) of example 4, the solid content of the mixed slurry was 10%.
The high capacity graphite negative electrode material prepared in example 4 was prepared as a button cell battery and a full cell battery according to the method of example 1, and electrochemical performance results are shown in table 1.
Example 5
A method for preparing a high capacity graphite negative electrode material, which is substantially the same as in example 1, except that: in step (1) of example 5, the solid content of the mixed slurry was 20%.
The high capacity graphite negative electrode material prepared in example 5 was prepared as a button cell battery and a full cell battery according to the method of example 1, and electrochemical performance results are shown in table 1.
Example 6
A method for preparing a high capacity graphite negative electrode material, which is substantially the same as in example 1, except that: in step (1) of example 6, the solid content of the mixed slurry was 25%.
The high capacity graphite negative electrode material prepared in example 6 was prepared as a button cell battery and a full cell battery according to the method of example 1, and electrochemical performance results are shown in table 1.
Example 7
A method for preparing a high capacity graphite negative electrode material, which is substantially the same as in example 1, except that: in the step (1) of the example 7, the mass ratio of the crystalline flake graphite, the doping compound and the binder is 85:5:10.
And, the spheroidization process parameters in the step (4) are as follows: and (3) putting the crushed products into a continuous shaping system consisting of 4 micro-nano particle shaping cladding systems connected in series under the feeding quantity of 100kg/h, and shaping (spheroidizing) the crushed products under the condition that the rotating speed of a main machine is 4000rpm for 5min.
The high capacity graphite negative electrode material prepared in example 7 was prepared as a button cell battery and a full cell battery according to the method of example 1, and electrochemical performance results are shown in table 1.
Example 8
A method for preparing a high capacity graphite negative electrode material, which is substantially the same as in example 1, except that: in the step (1) of the example 8, the mass ratio of the crystalline flake graphite, the doping compound and the binder is 85:5:10.
And (5) carbonizing process parameters are as follows: heating to 1200 ℃, and keeping the temperature for 12 hours.
Example 9
A method for preparing a high capacity graphite negative electrode material, which is substantially the same as in example 1, except that: in step (1) of example 9, the dopant compound is an organic compound of phosphorus, wherein the organic compound of phosphorus is triphenylphosphine.
The high capacity graphite negative electrode material prepared in example 9 was prepared as a button cell battery and a full cell battery according to the method of example 1, and electrochemical performance results are shown in table 1.
Example 10
A method for preparing a high capacity graphite negative electrode material, which is substantially the same as in example 1, except that: in step (1) of example 10, the dopant compound is boric acid.
The high capacity graphite negative electrode material prepared in example 10 was prepared as a button cell battery and a full cell battery according to the method of example 1, and electrochemical performance results are shown in table 1.
Example 11
A method for preparing a high capacity graphite negative electrode material, which is substantially the same as in example 1, except that: in step (1) of example 11, the dopant compound is boron oxide, wherein the boron oxide is diboron trioxide.
The high capacity graphite negative electrode material prepared in example 11 was prepared as a button cell battery and a full cell battery according to the method of example 1, and electrochemical performance results are shown in table 1.
Example 12
A method for preparing a high capacity graphite negative electrode material, which is substantially the same as in example 1, except that: in step (1) of example 12, the dopant compound is an oxide of vanadium, wherein the oxide of vanadium is vanadium pentoxide.
The high capacity graphite negative electrode material prepared in example 12 was prepared as a button cell battery and a full cell battery according to the method of example 1, and electrochemical performance results are shown in table 1.
TABLE 1 electrochemical performance test results for button cell and full cell made of different graphite negative electrode materials
As can be seen from the results, compared with the conventional natural graphite materials, the high-capacity graphite negative electrode material prepared by the method has the advantages of high capacity, good cycle performance, good multiplying power performance and the like, and when the negative electrode material serving as a working electrode is used for preparing a lithium ion battery, the cycle life of the lithium ion battery can be remarkably prolonged, and the high-capacity graphite negative electrode material has high use value and good application prospect.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the concept of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (10)
1. The preparation method of the high-capacity graphite anode material is characterized by comprising the following steps of:
s1, mixing flake graphite, a doped compound, a binder and a solvent to prepare mixed slurry; the doping compound is one of phosphoric acid, phosphorus pentoxide, triphenylphosphine, boric acid, diboron trioxide and vanadium pentoxide;
S2, spray drying the mixed slurry obtained in the step S1 to obtain a material of which the surface is coated with the binder and the doping compound in a mixing manner;
S3, crushing and spheroidizing the material obtained in the step S2 and coated on the surface of the crystalline flake graphite by mixing the binder and the doping compound to obtain spherical natural graphite with both the inner surface and the outer surface coated with the binder and the doping compound;
S4, carbonizing the spherical natural graphite with the inner and outer surfaces coated with the binder and the doping compound, and performing demagnetizing and screening to obtain the high-capacity graphite anode material.
2. The method according to claim 1, wherein in step S1, the solid content of the mixed slurry is 1% to 25%.
3. The preparation method according to claim 2, wherein in the step S1, the mass ratio of the flake graphite, the doped compound and the binder in the mixed slurry is 55-94:1-15:5-30.
4. A method of producing according to claim 3, wherein the flake graphite has an average particle size of 3 μm to 45 μm; the binder is at least one of petroleum asphalt, coal asphalt, mesophase asphalt, phenolic resin, epoxy resin, petroleum resin, coal tar or heavy oil.
5. The method according to claim 2, wherein in step S1, the solvent is one or more of acetone, diethyl ether, xylene, carbon tetrachloride, n-hexane, or ethanol.
6. The method according to any one of claims 1 to 5, wherein in step S3, the spheroidization is performed in a continuous type of shaping system consisting of 2 to 15 micro-nanoparticle shaping and coating systems in series; the technological parameters of the spheroidization are as follows: the feeding amount is 50 kg-200 kg/h, the rotating speed is 100 rpm-9000 rpm, and the time is 5-45 min.
7. The method according to any one of claims 1 to 5, wherein in step S4, the carbonization is performed at a temperature of 600 ℃ to 1500 ℃; the heat preservation time in the carbonization process is 5-20 h.
8. A high-capacity graphite anode material, characterized in that the high-capacity graphite anode material is prepared by the preparation method of any one of claims 1 to 7.
9. The high capacity graphite negative electrode material of claim 8, wherein the high capacity graphite negative electrode material comprises spherical natural graphite; the inner and outer surfaces of the spherical natural graphite are coated with amorphous carbon material layers to form an inner and outer coating structure which sequentially comprises the amorphous carbon material layers, the natural graphite layers and the amorphous carbon material layers from inside to outside; the amorphous carbon material layer is doped with at least one element of boron, phosphorus and vanadium.
10. Use of a high capacity graphite negative electrode material according to claim 8 or 9 in the preparation of a lithium ion battery.
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