CN116741952A - Preparation method of conductive polymer coated pre-lithiated graphite negative electrode composite material, product and application thereof - Google Patents
Preparation method of conductive polymer coated pre-lithiated graphite negative electrode composite material, product and application thereof Download PDFInfo
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- CN116741952A CN116741952A CN202211344032.4A CN202211344032A CN116741952A CN 116741952 A CN116741952 A CN 116741952A CN 202211344032 A CN202211344032 A CN 202211344032A CN 116741952 A CN116741952 A CN 116741952A
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- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 46
- 239000010439 graphite Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 57
- 238000011282 treatment Methods 0.000 claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 238000006138 lithiation reaction Methods 0.000 claims abstract description 19
- 239000007770 graphite material Substances 0.000 claims abstract description 18
- 229910021384 soft carbon Inorganic materials 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000010426 asphalt Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 10
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005056 compaction Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 230000000630 rising effect Effects 0.000 claims description 6
- 229960003638 dopamine Drugs 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000011280 coal tar Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 239000011331 needle coke Substances 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 15
- 230000000052 comparative effect Effects 0.000 description 17
- 239000010405 anode material Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
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- 239000000463 material Substances 0.000 description 6
- 102220043159 rs587780996 Human genes 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 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
- 230000032798 delamination Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- 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 a conductive polymer coated prelithiation graphite negative electrode composite material, which comprises the following steps: (1) Mixing natural graphite, conductive polymer monomer, oxidant and dispersant with solvent, and obtaining conductive polymer coated natural graphite material through polymerization reaction; (2) Uniformly mixing a natural graphite material coated by a conductive polymer, soft carbon and a pre-lithiation reagent to obtain a composite material precursor; (3) And carbonizing the precursor, cooling and then performing post-treatment to obtain the conductive polymer coated pre-lithiated graphite negative electrode composite material. According to the preparation method disclosed by the invention, after a series of coating and pre-lithiation treatments, the problems of uneven coating on the surface of natural graphite, large specific surface area and low tap density are solved, and the lithium ion battery assembled by the graphite negative electrode composite material prepared by the invention has high initial efficiency, high capacity and excellent cycle stability.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a conductive polymer coated prelithiation graphite negative electrode composite material, a product thereof and application of the conductive polymer coated prelithiation graphite negative electrode composite material in a lithium ion battery.
Background
Graphite is the anode material with the widest application of the current commercial lithium ion battery, and has the advantages of low charge-discharge voltage platform, high specific capacity and the like; the increasing market demand places higher demands on the lithium storage properties of graphite anode materials. The natural graphite anode material is generally required to have the advantages of high initial efficiency, high capacity, high circulation and the like; however, the natural graphite has more pores and defects in the particles, so that the volume expansion and shrinkage of a graphite layer can occur in the process of lithium ion intercalation and deintercalation in the charge and discharge process, and the graphite structure is damaged; in the circulation process, the electrolyte reacts with lithium ions in electrolyte, a layer of solid electrolyte membrane (SEI) capable of allowing the lithium ions to continuously pass through is formed on the surface of graphite, and the SEI membrane is continuously damaged and repaired along with the charge and discharge, so that the consumption of the lithium ions is lost, and further the lithium battery is low in initial efficiency, low in capacity and poor in cycle life; therefore, the natural graphite needs to be subjected to a series of special treatments, so that internal defects are reduced, and the first effect, capacity and cycle life are improved.
The Chinese patent document with publication number CN 113571684A discloses an aluminum-carbon double-coated natural graphite negative electrode material for a lithium ion battery, which is prepared by (1) dissolving tannic acid in deionized water, then adding aluminum sol, and uniformly stirring by ultrasonic wave to form a solution A; (2) Adding natural graphite into the solution A, and stirring ultrasonically for 2 hours; (3) drying the mixed solution in the step (2); (4) Mixing the materials collected in the step (3) with asphalt, and carrying out high-temperature carbonization to obtain an aluminum-carbon double-coated natural graphite anode material; the technical scheme states that the prepared aluminum-carbon double-coated natural graphite anode material has higher initial charge specific capacity and better cycle performance, but in fact, the initial effect, capacity and cycle life of the material are still to be improved.
Wan et al (Spherical natural graphite coated by a thick layer of carbonaceous mesophase for use as an anode material in lithium ion batteries, journal of Applied Electrochemistry, (2009) 39:1081-1086) discloses a method of coating spherical natural graphite as an anode of a lithium ion battery with a thick carbonaceous mesophase; preparing a carbonaceous intermediate phase layer by adopting a heat treatment method of a mixture of coal natural gas and coal tar pitch; the thickness of the carbonaceous mesophase coated on the surface of the spherical natural graphite is about 2.5 mu m, the specific surface area of the spherical natural graphite is greatly reduced by the coated carbonaceous mesophase layer, the structural stability of the natural graphite is improved, and the first effect and the cycle performance of the spherical natural graphite material are correspondingly improved. However, the method needs to separate toluene which is an organic solvent, has high risk, is not suitable for industrial production, needs high-temperature graphitization, has high energy consumption, and in fact, has the first effect, capacity and cycle life to be improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a preparation method of a conductive polymer coated pre-lithiated graphite negative electrode composite material, which solves the problems of uneven coating on the surface of natural graphite, large specific surface area and low tap density after a series of coating and pre-lithiation treatments.
The specific technical scheme is as follows:
the preparation method of the conductive polymer coated pre-lithiated graphite negative electrode composite material comprises the following steps:
(1) Mixing natural graphite, conductive polymer monomer, oxidant and dispersant with solvent, and obtaining conductive polymer coated natural graphite material through polymerization reaction;
(2) Uniformly mixing the natural graphite material coated by the conductive polymer, soft carbon and a pre-lithiation reagent to obtain a composite material precursor;
(3) And carbonizing the precursor, cooling and then performing post-treatment to obtain the conductive polymer coated pre-lithiated graphite negative electrode composite material.
According to the preparation method disclosed by the invention, firstly, conducting polymer is coated on the surface of natural graphite by in-situ polymerization, then the conducting polymer is blended with soft carbon and a pre-lithiation reagent to obtain a precursor, and finally carbonization treatment is carried out to obtain the conducting polymer coated pre-lithiated graphite negative electrode composite material.
The conductive polymer has good electron transmission performance, the impedance among material particles can be reduced, the capacity of the lithium ion battery can be improved theoretically by coating the natural graphite with the conductive polymer, but experiments find that the first effect and the cycle performance of the lithium ion battery finally assembled by only coating and re-carbonizing the natural graphite with the conductive polymer are not ideal. Further experiments show that the capacity, the first effect and the cycle performance of the finally assembled lithium ion battery are improved well when the natural graphite after the coating treatment is firstly mixed with soft carbon and a pre-lithiation reagent and then carbonized. It has also been found in experiments that the final assembled lithium ion battery is not satisfactory in capacity, initial efficiency and cycle if it is blended with only soft carbon, or only a pre-lithiating agent.
In addition, the process of in-situ polymerization coating the conductive polymer and the pre-lithiation agent blending process in the preparation method cannot be changed in sequence, otherwise, the electrochemical performance of the finally assembled lithium ion battery is reduced.
Experiments show that the process conditions of carbonization treatment are also critical, and when three-stage heating carbonization is adopted, the heating rate and the temperature node of each stage of carbonization are precisely controlled, so that the finally assembled lithium ion battery has high initial efficiency, high capacity and excellent cycle stability.
Preferably, in step (1):
the natural graphite is subjected to isostatic compaction treatment, the median particle diameter of the treated natural graphite is 11-18 mu m, and the tap density is 0.9-1 g/cm 3 A specific surface area of 6 to 8m 2 /g。
The conductive polymer monomer is selected from one or more of aniline, thiophene, pyrrole, dopamine and acrylonitrile; preferably, the conductive polymer monomer is selected from aniline, pyrrole, dopaOne or more of the amines. Experiments show that the lithium ion battery finally assembled by adopting the optimized conductive polymer monomer to realize in-situ coating has higher first discharge efficiency and capacity retention rate. The reason for this is probably because the above preferred conductive polymer monomer contains an amino group or imino group, and N in the amino/imino group contains a lone electron and is capable of binding with Li + Forming coordination, providing more ion transmission paths and further improving first effect; meanwhile, the amino and imino groups can make the coating effect between the natural graphite, the polymer and the soft carbon better through intermolecular forces.
Further preferably, the conductive polymer monomer is selected from aniline and/or dopamine.
Preferably, the mass ratio of the natural graphite to the conductive polymer monomer is 1: (0.005-0.05).
The oxidant is selected from one or more of ferric chloride, hydrogen peroxide, ammonium persulfate and potassium dichromate;
preferably, the molar ratio of conductive polymer monomer to oxidant is 1: (1-2); further preferably 1: 1.2-2.
The dispersing agent is selected from hydroxymethyl cellulose and/or sodium dodecyl benzene sulfonate;
the solvent is selected from deionized water and/or ethanol;
preferably, the mass ratio of the natural graphite, the dispersing agent and the solvent is 500: (0.5-2): (1000-1500).
Preferably, the polymerization reaction is carried out at a temperature of 0-30 ℃ for 5-8 hours.
Preferably, in step (2):
the soft carbon is selected from one or more of asphalt, coal tar, needle coke, polyester resin and epoxy resin;
preferably, the soft carbon is selected from pitch, and further preferably pitch having a self softening point of 230 to 250 ℃.
The pre-lithiation reagent is one or more selected from lithium hydroxide, lithium chloride, lithium carbonate, lithium nitrate and lithium oxalate;
the mass ratio of the conductive polymer coated natural graphite material to the soft carbon is 1: (0.01-0.05).
The ratio of the mass of the pre-lithiation reagent to the total mass of the raw materials in step (2) is (0.05-0.2) based on the mass of Li in the pre-lithiation reagent: 100.
the total mass of the raw materials in the step (2) is the sum of the mass of the natural graphite material coated by the conductive polymer, the soft carbon and the pre-lithiation agent.
Preferably, the ratio of the mass of the prelithiation reagent to the total mass of the raw materials in step (2) is (0.08-0.2): 100.
in the step (3):
the carbonization treatment is carried out in three stages under inert atmosphere, and the temperature is raised to 200-350 ℃ at the temperature rising rate of 5-15 ℃/min in the first stage; the second stage is to raise the temperature to 800-1000 ℃ at a heating rate of 3-5 ℃/min; in the third stage, the temperature is raised to 1150-1250 ℃ at a heating rate of 1-3 ℃/min; the temperature rising rate of the first stage is higher than that of the second stage, and the temperature rising rate of the second stage is higher than that of the third stage;
the temperature is reduced to 450-700 ℃ at a temperature reduction rate of 3-8 ℃/min, and then the temperature is reduced to room temperature by natural cooling;
experiments show that if one-time heating carbonization is adopted, or two-stage heating carbonization is adopted, or three-stage heating carbonization is adopted, but the temperature nodes and the heating rate adopted in each stage are unsuitable, the electrochemical performance of the finally assembled lithium ion battery is reduced.
Preferably, the temperature is reduced to 450-550 ℃ at a cooling rate of 3-8 ℃/min, and then naturally cooled to room temperature. Experiments show that the electrochemical performance of the finally assembled lithium ion battery can be further improved by adopting the preferable cooling condition.
The inert atmosphere is selected from conventional types such as nitrogen, argon, helium and the like.
The post-treatment includes crushing and sieving.
The invention also discloses a conductive polymer coated pre-lithiated graphite negative electrode composite material prepared by the method and application thereof in lithium ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a conductive polymer coated pre-lithiated graphite negative electrode composite material, which has simple and controllable process and is easy for industrial production; the prepared natural graphite negative electrode composite material has good electron transmission performance, and a stable SEI film is formed on the surface, so that the problem that an inorganic SEI film naturally generated in the battery charging and discharging process is unstable is avoided; the specific surface area is small, the tap density is high, active sites are reduced, and the structural stability of the material is improved; the lithium ion battery assembled by the graphite cathode composite material has the advantages of high initial efficiency, high capacity, high circulation and the like.
Drawings
Fig. 1 is an SEM image of the conductive polymer coated pre-lithiated graphite negative electrode composite material prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings, in order to make the objects, technical solutions and effects of the present invention more clear and clarified. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
(1) Adding 1g of sodium dodecyl benzene sulfonate into 1000mL of deionized water, and stirring to completely dissolve the sodium dodecyl benzene sulfonate; 500g of spherical natural graphite powder (median diameter D50=14 μm, specific surface area 7.13 m) after isostatic compaction treatment (working pressure 85MPa, treatment time 2 h) 2 Per gram, tap density of 0.93g/cm 3 ) Adding 10g (0.11 mol) of aniline monomer and 18.3g (0.16 mol) of hydrogen peroxide (30 wt%) into the solution, and performing oxidative polymerization for 8h at 20 ℃; after the reaction is finished, filtering the solution, washing the solution for a plurality of times by deionized water and ethanol, then vacuum drying at 80 ℃, crushing, and sieving by a 325-mesh sieve to obtain a natural graphite material coated by the conductive polymer;
(2) Mixing 500g of a conductive polymer-coated natural graphite material, 10g of asphalt (softening point 250 ℃) and 1.75g (0.07 mol) of lithium hydroxide by using a vc high-speed mixer, wherein the feeding time is 300s, and the feeding rotating speed is 30rpm; fusion time is 1800s, and fusion rotating speed is 700rpm; the discharging time is 90s, and the discharging rotating speed is 200rpm; finally, a composite material precursor is obtained;
(3) Carbonizing the obtained composite material precursor under the protection of nitrogen, wherein the temperature is raised to 200 ℃ from room temperature in the first stage at the temperature rise rate of 10 ℃/min, the temperature is raised to 1000 ℃ in the second stage at the temperature rise rate of 5 ℃/min, the temperature is raised to 1250 ℃ in the third stage at the temperature rise rate of 1 ℃/min, the temperature is kept for 6 hours, then the temperature is lowered to 500 ℃ at the temperature rise rate of 5 ℃/min, and then the temperature is naturally cooled; and after cooling to room temperature, crushing the carbonized composite material precursor, and sieving with a 325-mesh sieve to obtain the conductive polymer coated pre-lithiated graphite negative electrode composite material.
Fig. 1 is an SEM image of the conductive polymer coated pre-lithiated graphite negative electrode composite material prepared in this example, and it is known from the observation that the graphite surface is smooth, and there is no obvious delamination phenomenon, which indicates that the polymer coating and the pre-lithiation process are relatively uniform in coating the graphite.
The D50, tap density and specific surface area of the conductive polymer-coated pre-lithiated graphite negative electrode composite material prepared in this example are listed in table 1 below.
Example 2
The preparation process was essentially the same as in example 1, except that:
in the step (2), the asphalt having a softening point of 250 ℃ is replaced with an equal mass of asphalt having a softening point of 60 ℃.
The D50, tap density and specific surface area of the conductive polymer-coated pre-lithiated graphite negative electrode composite material prepared in this example are listed in table 1 below.
Example 3
The preparation process was essentially the same as in example 1, except that:
in the step (1), the monomer was replaced with thiophene of equal mass, and the mass of hydrogen peroxide (30 wt%) was replaced with 19.8g.
The D50, tap density and specific surface area of the conductive polymer-coated pre-lithiated graphite negative electrode composite material prepared in this example are listed in table 1 below.
Example 4
The preparation process was essentially the same as in example 1, except that:
in the step (1), the monomer was replaced with acrylonitrile of equal mass, and the mass of hydrogen peroxide (30 wt%) was replaced with 31.3g.
The D50, tap density and specific surface area of the conductive polymer-coated pre-lithiated graphite negative electrode composite material prepared in this example are listed in table 1 below.
Example 5
The preparation process was essentially the same as in example 1, except that:
in the step (1), the spherical natural graphite powder after isostatic compaction treatment (working pressure is 85MPa, treatment time is 2 h), the median particle diameter D50=11 μm and the specific surface area is 7.68m 2 Per gram, tap density of 0.91g/cm 3 The monomer was replaced with equal mass of dopamine and the oxidant with 21.7g ammonium persulfate.
The D50, tap density and specific surface area of the conductive polymer-coated pre-lithiated graphite negative electrode composite material prepared in this example are listed in table 1 below.
Example 6
The preparation process was essentially the same as in example 1, except that:
in the step (1), the median diameter D50=17 μm and the specific surface area of the spherical natural graphite powder after isostatic compaction treatment (working pressure is 85MPa, treatment time is 2 h) are 6.89m 2 Per gram, tap density of 0.95g/cm 3 The monomer was replaced with an equal mass of pyrrole and the oxidant was replaced with 49.5g of ammonium persulfate.
The D50, tap density and specific surface area of the conductive polymer-coated pre-lithiated graphite negative electrode composite material prepared in this example are listed in table 1 below.
Example 7
The preparation process was essentially the same as in example 1, except that:
in the step (1), the dispersant is replaced by 0.5g of sodium dodecyl benzene sulfonate, the mass of aniline monomer is replaced by 25g, the oxidant is replaced by 52.3g of ferric chloride, the polymerization reaction condition is replaced by 15 ℃, and the reaction is carried out for 6 hours;
in the step (2), the mass of the asphalt is replaced by 25g, and the pre-lithiation reagent is replaced by 3.65g of lithium hydroxide;
in the step (3), the temperature is raised from room temperature to 250 ℃ in the first stage, the temperature raising rate is 15 ℃/min, the temperature is raised to 1000 ℃ in the second stage, the temperature raising rate is 4 ℃/min, the temperature is raised to 1250 ℃ in the third stage, the temperature raising rate is 2 ℃/min, the temperature is kept for 5 hours, then the temperature is lowered to 550 ℃ at the rate of 8 ℃/min, and then the temperature is naturally lowered.
The D50, tap density and specific surface area of the conductive polymer-coated pre-lithiated graphite negative electrode composite material prepared in this example are listed in table 1 below.
Example 8
The preparation process was essentially the same as in example 1, except that:
in the step (1), the solvent is replaced by 1500mL of ethanol, the mass of the aniline monomer is replaced by 2.5g, the oxidant is replaced by 15.81g of potassium dichromate, and the polymerization reaction condition is 30 ℃ for 6 hours;
in the step (2), soft carbon is replaced by 5g of epoxy resin, and the pre-lithiation reagent is replaced by 1.40g of lithium hydroxide;
in the step (3), the temperature is raised from room temperature to 350 ℃ at a temperature raising rate of 6 ℃/min, the temperature is raised to 900 ℃ at a temperature raising rate of 3 ℃/min in the first stage, the temperature is raised to 1150 ℃ at a temperature raising rate of 1 ℃/min, the temperature is kept for 6 hours, then the temperature is lowered to 450 ℃ at a temperature of 3 ℃/min, and then the temperature is naturally lowered.
The D50, tap density and specific surface area of the conductive polymer-coated pre-lithiated graphite negative electrode composite material prepared in this example are listed in table 1 below.
Example 9
The preparation process was essentially the same as in example 1, except that:
in the step (2), soft carbon is replaced by 15g of coal tar, and the pre-lithiation reagent is replaced by 0.9g of lithium hydroxide;
in the step (3), the temperature is raised from room temperature to 300 ℃ at a temperature raising rate of 13 ℃/min, the temperature is raised to 800 ℃ at a temperature raising rate of 2 ℃/min in the first stage, the temperature is raised to 1150 ℃ at a temperature raising rate of 1 ℃/min in the third stage, the temperature is kept for 7 hours, then the temperature is lowered to 450 ℃ at a temperature of 8 ℃/min, and then the temperature is naturally lowered.
The D50, tap density and specific surface area of the conductive polymer-coated pre-lithiated graphite negative electrode composite material prepared in this example are listed in table 1 below.
Example 10
The preparation process was essentially the same as in example 1, except that:
in the step (3), after heat preservation for 6 hours, the temperature is reduced to 700 ℃ at a temperature reduction rate of 5 ℃/min, and then free temperature reduction is carried out.
The D50, tap density and specific surface area of the conductive polymer-coated pre-lithiated graphite negative electrode composite material prepared in this example are listed in table 1 below.
Comparative example 1
(1) 500g of spherical natural graphite material (median diameter D50=14 μm, specific surface area 7.13 m) after isostatic compaction treatment (working pressure is 85MPa, treatment time is 2 h) 2 Per gram, tap density of 0.93g/cm 3 ) 10g of bitumen (softening point 250 ℃) and 1.75g (0.07 mol) of lithium hydroxide are mixed by means of a vc high-speed mixer, the charging time being 300s and the charging speed being 30rpm; fusion time is 1800s, and fusion rotating speed is 700rpm; the discharging time is 90s, and the discharging rotating speed is 200rpm; obtaining a composite material precursor;
(2) Carbonizing the obtained composite material precursor under the protection of nitrogen, wherein the temperature is raised to 200 ℃ from room temperature in the first stage at the temperature rise rate of 10 ℃/min, the temperature is raised to 1000 ℃ in the second stage at the temperature rise rate of 5 ℃/min, the temperature is raised to 1250 ℃ in the third stage at the temperature rise rate of 1 ℃/min, the temperature is kept for 6 hours, then the temperature is lowered to 500 ℃ at the temperature rise rate of 5 ℃/min, and then the temperature is naturally cooled; and after cooling to room temperature, crushing the carbonized composite material precursor, and sieving with a 325-mesh sieve to obtain the conductive polymer coated pre-lithiated graphite negative electrode composite material.
The D50, tap density and specific surface area of the natural graphite anode material prepared in this comparative example are shown in table 1 below.
Comparative example 2
The preparation process was substantially the same as in example 1, except that 10g of asphalt was not added in step (2).
The D50, tap density and specific surface area of the natural graphite anode material prepared in this comparative example are shown in table 1 below.
Comparative example 3
The preparation process was substantially the same as in example 1, except that 1.75g of lithium hydroxide was not added in step (2).
The D50, tap density and specific surface area of the natural graphite anode material prepared in this comparative example are shown in table 1 below.
Comparative example 4
(1) 500g of spherical natural graphite material (median diameter D50=14 μm, specific surface area 7.13 m) after isostatic compaction treatment (working pressure 85MPa, treatment time 2 h) 2 Per gram, tap density of 0.93g/cm 3 ) 10g of bitumen (softening point 250 ℃) and 1.75g of lithium hydroxide were mixed with a vc high-speed mixer, with a feed time of 300s and a feed speed of 30rpm; fusion time is 1800s, and fusion rotating speed is 700rpm; the discharging time is 90s, and the discharging rotating speed is 200rpm; obtaining a mixed material;
(2) Adding 1g of sodium dodecyl benzene sulfonate into 1000mL of deionized water, and stirring to completely dissolve the sodium dodecyl benzene sulfonate; adding the mixed material obtained in the step (1) into the solution, sequentially adding 10g of aniline monomer and 18.3g of hydrogen peroxide (30 wt%) and performing oxidative polymerization for 8h at 20 ℃; after the reaction is finished, filtering the solution, washing the solution for a plurality of times by deionized water and ethanol, then vacuum drying at 80 ℃, crushing, and sieving by a 325-mesh sieve to obtain a composite material precursor;
step (3) is identical to example 1.
The D50, tap density and specific surface area of the natural graphite anode material prepared in this comparative example are shown in table 1 below.
Comparative example 5
The preparation process is basically the same as that of the embodiment 1, except that in the step (3), the obtained composite material precursor is carbonized under the protection of nitrogen, the temperature is raised from room temperature to 200 ℃ in the first stage, the temperature raising rate is 20 ℃/min, the temperature is raised to 1000 ℃ in the second stage, the temperature raising rate is 10 ℃/min, the temperature is raised to 1250 ℃ in the third stage, the temperature raising rate is 5 ℃/min, the temperature is kept for 6 hours, then the temperature is lowered to 500 ℃ at the rate of 10 ℃/min, and then the temperature is freely lowered; and after cooling to room temperature, crushing the carbonized composite material precursor, and sieving with a 325-mesh sieve to obtain the conductive polymer coated pre-lithiated graphite negative electrode composite material.
Comparative example 6
The preparation process is essentially the same as in example 1, except that in step (3), the temperature is directly raised to 1250℃at a constant temperature rise rate of 10℃per minute, and the temperature is maintained for 6 hours.
Comparative example 7
The preparation process was substantially the same as in example 1 except that in step (2), the addition amount of soft carbon was replaced with 30g.
The D50, tap density and specific surface area of the natural graphite anode material prepared in this comparative example are shown in table 1 below.
Comparative example 8
The preparation process was substantially the same as in example 1, except that in step (2), the soft carbon was added in an amount of 3g.
The D50, tap density and specific surface area of the natural graphite anode material prepared in this comparative example are shown in table 1 below.
Performance testing
1. The natural graphite materials prepared in each example and each comparative example are used as negative electrode materials to prepare the button cell with the molding number 2032 respectively, and the specific steps are as follows:
mixing a natural graphite material, a conductive agent SP, a dispersing agent CMC and a binder AONE according to the mass ratio of 96:1:0.5:2.5, and preparing negative electrode slurry by taking water as a solvent; and coating the cathode slurry on a copper foil, and preparing the button cell by taking a lithium sheet as a counter electrode and taking a Celgard 2400 microporous polypropylene film as a diaphragm.
And (3) carrying out charge and discharge circulation on the prepared button battery, wherein the charge and discharge conditions are as follows:
the charge-discharge cut-off voltage is 0.01-1.5V, the discharge multiplying power is that the voltage is firstly 0.1C to 0.005V, then 0.2C to 0.005V, so that the voltage is fully discharged, the charge multiplying power is that the voltage is 0.5C to 1.5V, and the reversible capacity and the first discharge efficiency of the button cell are detected; five button cells were prepared for each set of experimental samples and the average was taken and the results are given in table 1 below.
2. The natural graphite materials prepared in each example and each comparative example are used as negative electrode materials to prepare small soft package batteries respectively, and the specific steps are as follows:
natural graphite material was mixed with commercial synthetic graphite (sandisk in yunnan) at a rate of 8.1:91.9 mass ratio is mixed into active material with 390mAh/g capacity, the active material, binder lithium polyacrylate and conductive agent Super P are dispersed and pulped according to the mass ratio of 95.5:4:0.5, and the battery core preparation procedures of coating, rolling, cutting and the like are carried out, and the battery core preparation procedures are matched with NCM811 positive electrode to prepare a small soft package battery.
And (3) testing the cycle performance: at 25 ℃, the battery subjected to chemical composition is charged to 4.2V at constant current and constant voltage of 0.5C, the cut-off current is 0.02C, the battery is placed for 5min, then the battery is discharged to 2.5V at constant current of 1C, and the battery is placed for 5min. According to the cycle, the 500 th cycle capacity retention rate is calculated after 500 charge/discharge cycles, and the calculation formula is as follows:
500 th cycle capacity retention (%) = (500 th cycle reversible capacity/1 st cycle reversible capacity) ×100%.
Five small pouch batteries were prepared for each experimental sample, and finally, the average value was taken, and the 500 th cycle capacity retention rate data of the small pouch batteries obtained by respectively assembling each example and each comparative example at normal temperature are shown in table 1 below.
TABLE 1
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical solution of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The preparation method of the conductive polymer coated pre-lithiated graphite negative electrode composite material is characterized by comprising the following steps:
(1) Mixing natural graphite, conductive polymer monomer, oxidant and dispersant with solvent, and obtaining conductive polymer coated natural graphite material through polymerization reaction;
(2) Uniformly mixing the natural graphite material coated by the conductive polymer, soft carbon and a pre-lithiation reagent to obtain a composite material precursor;
(3) And carbonizing the precursor, cooling and then performing post-treatment to obtain the conductive polymer coated pre-lithiated graphite negative electrode composite material.
2. The method of preparing a conductive polymer coated prelithiated graphite anode composite of claim 1, wherein in step (1):
the natural graphite is subjected to isostatic compaction treatment, the median particle diameter is 11-18 mu m, and the tap density is 0.9-1 g/cm 3 A specific surface area of 6 to 8m 2 /g；
The conductive polymer monomer is selected from one or more of aniline, thiophene, pyrrole, dopamine and acrylonitrile;
the oxidant is selected from one or more of ferric chloride, hydrogen peroxide, ammonium persulfate and potassium dichromate;
the dispersing agent is selected from hydroxymethyl cellulose and/or sodium dodecyl benzene sulfonate;
the solvent is selected from deionized water and/or ethanol.
3. The method for preparing the conductive polymer coated prelithiation graphite negative electrode composite material according to claim 2, wherein the method comprises the following steps:
the mass ratio of the natural graphite to the conductive polymer monomer is 1: (0.005-0.05);
the molar ratio of the conductive polymer monomer to the oxidant is 1: (1-2);
the mass ratio of the natural graphite to the dispersant to the solvent is 500: (0.5-2): (1000-1500);
the polymerization reaction is carried out at the temperature of 0-30 ℃ for 5-8 h.
4. The method of preparing a conductive polymer coated prelithiated graphite anode composite of claim 1, wherein in step (2):
the soft carbon is selected from one or more of asphalt, coal tar, needle coke, polyester resin and epoxy resin;
the pre-lithiation reagent is one or more selected from lithium hydroxide, lithium chloride, lithium carbonate, lithium nitrate and lithium oxalate;
the mass ratio of the conductive polymer coated natural graphite material to the soft carbon is 1: (0.01-0.05);
the ratio of the mass of the pre-lithiation reagent to the total mass of the raw materials in step (2) is (0.05-0.2) based on the mass of Li in the pre-lithiation reagent: 100.
5. the method of preparing a conductive polymer coated prelithiated graphite anode composite of claim 1, wherein in step (3):
the carbonization treatment is carried out in three stages under inert atmosphere, and the temperature is raised to 200-350 ℃ at the temperature rising rate of 5-15 ℃/min in the first stage; the second stage is to raise the temperature to 800-1000 ℃ at a heating rate of 3-5 ℃/min; in the third stage, the temperature is raised to 1150-1250 ℃ at a heating rate of 1-3 ℃/min; the temperature rising rate of the first stage is higher than that of the second stage, and the temperature rising rate of the second stage is higher than that of the third stage;
the temperature is reduced to 450-700 ℃ at a temperature reduction rate of 3-8 ℃/min, and then the temperature is reduced to room temperature by natural cooling;
the post-treatment includes crushing and sieving.
6. The method for preparing a conductive polymer coated prelithiated graphite anode composite material according to any one of claims 1 to 5, wherein in step (1):
the conductive polymer monomer is selected from one or more of aniline, pyrrole and dopamine.
7. The method of preparing a conductive polymer coated prelithiated graphite anode composite of claim 6, wherein in step (2):
the soft carbon is selected from asphalt with a softening point of 230-250 ℃.
8. The method of preparing a conductive polymer coated prelithiated graphite anode composite of claim 7, wherein in step (3):
firstly, cooling to 450-550 ℃ at a cooling rate of 3-8 ℃/min, and then naturally cooling to room temperature.
9. A conductive polymer coated pre-lithiated graphite negative electrode composite material prepared according to the method of any one of claims 1-8.
10. Use of the conductive polymer coated pre-lithiated graphite negative electrode composite material of claim 9 in a lithium ion battery.
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