CN116477615B - High-magnification graphite negative electrode material and preparation method thereof - Google Patents
High-magnification graphite negative electrode material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 99
- 239000010439 graphite Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 61
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 36
- 239000010426 asphalt Substances 0.000 claims abstract description 52
- 239000010405 anode material Substances 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 238000010000 carbonizing Methods 0.000 claims abstract description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 45
- 239000000843 powder Substances 0.000 claims description 38
- 229920001568 phenolic resin Polymers 0.000 claims description 24
- 239000005011 phenolic resin Substances 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 20
- 229920001169 thermoplastic Polymers 0.000 claims description 18
- 239000004416 thermosoftening plastic Substances 0.000 claims description 18
- 239000002023 wood Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims description 16
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011300 coal pitch Substances 0.000 claims description 14
- 239000011295 pitch Substances 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 239000010875 treated wood Substances 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000002070 nanowire Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229940083037 simethicone Drugs 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 230000002829 reductive effect Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910021383 artificial graphite Inorganic materials 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
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- 238000000197 pyrolysis Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
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- 230000009471 action Effects 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910021384 soft carbon Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 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
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
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- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 239000011888 foil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 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
- 238000004898 kneading Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
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- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to the field of lithium ion battery negative electrode materials, and particularly discloses a high-rate graphite negative electrode material and a preparation method thereof. The preparation method of the high-rate graphite anode material comprises the following steps: spheroidizing: spheroidizing natural crystalline flake graphite to prepare spherical graphite with the granularity d50=5-10 mu m; granulating: mixing and stirring the spherical graphite and a carbon source, and coating the surface to obtain a coating; carbonizing: heating the coating to 1200-1350 ℃, and carbonizing for 5.5-6h to obtain a negative electrode material; the mass ratio of the carbon source to the spherical graphite is 0.1-0.15:1, and the carbon source is a mixture of asphalt and hard carbon resin or modified asphalt. The high-rate graphite negative electrode material disclosed by the application has the advantages that a carbon source is uniformly coated on graphite, the rate of the negative electrode material is high, and the discharge capacity and the cycle performance are excellent.
Description
Technical Field
The application relates to the technical field of lithium ion battery negative electrode materials, in particular to a high-rate graphite negative electrode material and a preparation method thereof.
Background
Lithium ion batteries are batteries that rely on movement of lithium ions between a positive electrode and a negative electrode to operate, and have numerous advantages such as high energy density, long cycle life, small self-discharge, no memory effect, and environmental friendliness, and have been widely used in consumer electronics and vehicle power batteries as well as in energy storage. The lithium ion battery mainly comprises an anode, a cathode, electrolyte, a diaphragm and the like, wherein the capacity, the multiplying power charge-discharge capacity, the service life and the like of the lithium ion battery are closely related to the cathode material.
The negative electrode material comprises natural graphite, artificial graphite, soft carbon and hard carbon, and the former two graphite negative electrode materials are widely applied in lithium ion battery production, and are used as main negative electrode materials of 3C type electronic products and widely applied due to the advantages of high capacity, good lithium intercalation/deintercalation reversibility, low point location platform, excellent cycle performance and the like of the graphite negative electrode materials.
However, the anisotropic structure of the artificial graphite limits the free diffusion of lithium ions in the graphite structure, restricts the exertion of the electrochemical capacity of the graphite negative electrode, and particularly influences the rate capability of the graphite negative electrode material. In order to improve the defect of the charging rate performance of the artificial graphite, the current mainstream technology improves the conductivity of the surface of the artificial graphite by a surface coating mode.
Chinese patent CN201510793882.6 discloses a graphite negative electrode material of lithium ion battery with high discharge rate and its preparation method, wherein a layer of asphalt is coated on the surface of the graphite negative electrode material, which is used for improving the conductivity of the surface of artificial graphite and improving the low temperature performance. However, the anode material prepared by the method cannot ensure the coating uniformity of the asphalt material, so that the capacity is general, and the rate capability of the anode material is not obviously improved compared with that of an uncoated product.
Disclosure of Invention
In order to enable asphalt to be uniformly coated on graphite and improve the multiplying power of a negative electrode material, the application provides a high-multiplying power graphite negative electrode material and a preparation method thereof.
In a first aspect, the application provides a preparation method of a high-rate graphite anode material, which adopts the following technical scheme:
the preparation method of the high-rate graphite anode material comprises the following steps:
spheroidizing: spheroidizing natural crystalline flake graphite to prepare spherical graphite with the granularity d50=5-10 mu m;
granulating: mixing and stirring the spherical graphite and a carbon source, and coating the surface to obtain a coating;
carbonizing: heating the coating to 1200-1350 ℃, and carbonizing for 5.5-6h to obtain a negative electrode material;
the mass ratio of the carbon source to the spherical graphite is 0.1-0.15:1, and the carbon source is a mixture of asphalt and hard carbon resin or modified asphalt.
Through adopting above-mentioned technical scheme, after spheroidizing natural crystalline flake graphite, obtain spherical graphite that the particle diameter is even, mix spherical graphite, carbon source, carry out cladding, granulation, obtain solid structure's graphite negative pole material, the carbon source quantity is few, can the cladding even when carbonizing to guarantee the intensity of granule, also can guarantee energy density when improving the multiplying power performance by a wide margin, optionally, the preparation method of modified asphalt includes the following steps:
crushing medium-temperature coal pitch, sieving to prepare pitch powder;
mixing 0.05-0.1 part of sodium dodecyl benzene sulfonate and 0.1-0.15 part of simethicone by weight, heating to 280-290 ℃, uniformly stirring, adding 1-3 parts of asphalt powder, preserving heat, stirring for 4-5h, adding 0.3-0.5 part of nano silicon particles, cooling to 70-80 ℃, stirring at constant temperature for 4-5h, vacuum drying at 90-100 ℃ for 12-14h, heating to 900-1000 ℃ by taking nitrogen as protective gas, and preserving heat for 3-3.5h.
According to the technical scheme, the medium-temperature coal tar pitch is used as a main raw material of the modified pitch, the hot melting temperature is low, coating and granulating are facilitated, the medium-temperature coal pitch is made of sodium dodecyl benzene sulfonate as an emulsifier, dimethyl silicone oil as a dispersion medium and a heat conducting agent, asphalt powder is gradually softened after heating, and then the asphalt powder and the dimethyl silicone oil form low-viscosity liquid colloid, so that the medium-temperature coal pitch forms emulsified pitch, the dilution of the pitch is improved, the viscosity of the pitch is reduced, the modified pitch can be uniformly coated on spherical graphite, the asphalt with larger viscosity cannot be uniformly coated on the spherical graphite, and agglomeration phenomenon of nano silicon particles in the emulsified pitch can be prevented, quinoline insoluble matters in the heat treatment process of the medium-temperature coal pitch can prevent formation of an intermediate phase, so that the coal pitch is of a compact structure, the surface is relatively flat, the nano silicon particles are coated in the emulsified pitch after heat treatment, and the silicon volume expansion is prevented; in the coating and granulating process, the nano silicon particles can be uniformly inserted into the graphite sheet layer through pyrolysis and mechanical acting force, so that the volume expansion effect of the nano silicon particles is relieved, the conductivity of the composite material is improved, the structural stability of the composite material is improved, the attenuation degree of the nano silicon particles in the circulating process is higher than that of coal pitch, the energy density of the anode material can be greatly improved, the coal pitch graphite carbon and the nano silicon particles are better compounded, namely, the nano silicon is embedded into the coal pitch graphite carbon layer, the conductivity can be increased, the diffusion of lithium ions is facilitated, and the circulating stability of the anode material is further improved.
Optionally, the mass ratio of the hard carbon resin to the asphalt is 1:0.3-0.5, and the hard carbon resin is modified phenolic resin.
By adopting the technical scheme, the hard carbon resin coated spherical graphite can effectively reduce the first irreversible capacity of the graphite, so that the surface coating of the spherical graphite is complete and the thickness of the coating layer is uniform.
Optionally, the modified phenolic resin comprises thermoplastic phenolic resin, silicon carbide nanowires and wood powder in a mass ratio of 1:0.3-0.5:0.1-0.3.
According to the technical scheme, after the modified phenolic resin is subjected to hot melting, liquid is formed, under the action of surface tension, the modified phenolic resin is tightly coated on the surface of spherical graphite, and after carbonization, a pyrolytic carbon layer is formed to be coated on the surface of the graphite, so that the electrochemical performance of the graphite is improved, the irreversible capacity is reduced, the structural stability and the cyclic stability of the graphite are improved, and after the wood powder contained in the thermoplastic phenolic resin is subjected to severe decomposition, volatile substances are continuously removed, carbon residues are left, and a hexagonal annular structure which is relatively stable to heat is formed by mutual condensation, dehydrogenation and aromatic cyclization, so that amorphous carbon with a microcrystalline structure similar to a graphite layer sheet shape is obtained, the tap density of a cathode material is reduced, and the multiplying power is improved; the silicon carbide nanowire has the characteristics of large specific surface area, good activity and the like, is added into thermoplastic phenolic resin, and can be used for embedding lithium ions after the phenolic resin is coated on spherical graphite, so that the capacity and the cycle performance of the anode material can be improved.
Optionally, the preparation method of the modified phenolic resin comprises the following steps:
soaking wood powder in 8-10wt% alkali liquor, cleaning, and drying to obtain alkali treated wood powder;
uniformly mixing the silicon carbide nanowires and the alkali-treated wood powder, adding a silane coupling agent with the concentration of 2-4wt%, carrying out dipping treatment for 1-2h, filtering, and drying to prepare a blend;
diluting the thermoplastic phenolic resin, soaking the blend in the diluted thermoplastic phenolic resin for 2-3d at normal temperature, filtering, and air-drying for 20-24h.
By adopting the technical scheme, the wood powder is soaked by alkali liquor, the aliphatic micromolecular compounds and hemicellulose in the wood powder are dissolved, and simultaneously lignin is partially dissolved, important connecting bonds in the cellulose are partially broken, partial hydrogen bonds are destroyed, free radicals are released, and the reactivity of the cellulose is improved; the alkali treatment improves the micropore structure of wood powder, increases the active surface area of wood on cellulose, and is convenient for the penetration and diffusion of phenolic resin; after the wood powder and the silicon carbide nano-fiber are treated by the silane coupling agent, the thermoplastic phenolic resin is conveniently coated, the silicon carbide nano-wire and the wood powder are impregnated by the phenolic resin and then carbonized, so that soft carbon formed by loose porous texture obtained by relatively low-temperature rapid carbonization of the wood powder in the pyrolysis process of the wood powder can be reserved, and the glassy hard carbon with hard texture obtained by high-temperature slow carbonization of the phenolic resin in the pyrolysis process of the injected wood can be increased.
Optionally, the following pretreatment is performed before the coating is carbonized:
mixing the coating with liquid silicon containing metal salt, heating to 1000-1100 ℃ under the protection of argon, and preserving heat for 4-6h.
According to the technical scheme, spherical graphite coated by a carbon source is mixed with liquid silicon, the liquid silicon spontaneously penetrates into a pore canal of a coating due to capillary action, silicon carbide is generated by reacting with the pore canal wall, the surface of the coating is carbonized by phenolic resin, the material of the coating belongs to glassy carbon, and the wetting of the glassy carbon and the liquid silicon belongs to reactive wetting, so that the liquid silicon can spontaneously infiltrate into the coating, metal salt contained in the liquid silicon infiltrates into the coating along with the liquid silicon, metal oxide is generated after carbonization, the metal oxide has larger charge-discharge specific capacity than graphite, and the liquid silicon/metal oxide composite has unique various and rapid axial electron transport and radial ion diffusion characteristics, so that the lithium ion migration path can be shortened, lithium ions can rapidly shuttle in the liquid silicon, and the multiplying power of a lithium ion battery can be improved.
Optionally, in the granulating step, firstly, heat is preserved for 2-3 hours at 500-550 ℃, then the temperature is raised to 650-700 ℃, and the heat is preserved for 4-4.5 hours.
Through adopting above-mentioned technical scheme, when the carbon source carries out the cladding, select suitable heating rate, on the one hand can make the carbon source fully soften and evenly coat on spherical graphite surface to can have abundant time to repair the defect that partial spherical graphite surface exists, on the other hand can prevent the cladding in-process, because of the heating rate too fast and lead to the carbon source to be heated inhomogeneous local softening phenomenon that appears.
Optionally, in the carbonization step, the temperature is raised to 1200-1350 ℃ within 4-4.5h.
In a second aspect, the application provides a high-rate graphite anode material, which adopts the following technical scheme:
a high-magnification graphite negative electrode material is prepared by a preparation method of the high-magnification graphite negative electrode material.
By adopting the technical scheme, the graphite anode material prepared by the method has the advantages of high capacity retention rate and good multiplying power.
In summary, the application has the following beneficial effects:
1. the application adopts the mixed coating of the carbon source and the spherical graphite, and the anode material is prepared after carbonization, so that the carbon source is added little, the coating is uniform, the multiplying power and the capacity of the anode material are high, and the cycle life is good.
2. In the application, the modified asphalt is preferably prepared by adopting medium-temperature coal asphalt, sodium dodecyl benzene sulfonate, dimethyl silicone oil, nano silicon particles and the like, the viscosity of the medium-temperature coal asphalt is reduced by emulsifying the sodium dodecyl benzene sulfonate, the medium-temperature coal asphalt can be uniformly coated on graphite, and the nano silicon particles can be inserted into a graphite sheet layer under the pyrolysis and mechanical action, so that the conductivity is improved, and the prepared modified asphalt is favorable for the diffusion of lithium ions and the electrochemical performance is improved.
3. In the application, hard carbon resin and asphalt are preferably used as carbon sources, and modified phenolic resin is used as the hard carbon resin, wherein the modified phenolic resin contains thermoplastic phenolic resin, silicon carbide nanowires and wood powder, the prepared modified phenolic resin is coated on spherical graphite, loose porous soft carbon and hard carbon with hard texture can be formed, and the silicon carbide nanowires can further improve the multiplying power, capacity and cycle performance of a carbon layer after pyrolysis of the modified phenolic resin.
Detailed Description
Preparation examples 1 to 4 of modified asphalt
Preparation example 1: crushing and sieving medium-temperature coal pitch to prepare pitch powder; mixing 0.1kg of sodium dodecyl benzene sulfonate and 0.15kg of simethicone, heating to 280 ℃, uniformly stirring, adding 3kg of asphalt powder, carrying out heat preservation and stirring for 5h, adding 0.5kg of nano silicon particles, cooling to 70 ℃, carrying out constant temperature and stirring for 5h, then carrying out vacuum drying at 90 ℃ for 14h, heating to 1000 ℃ by taking nitrogen as a protective gas, and carrying out heat preservation for 3.5h.
Preparation example 2: crushing and sieving medium-temperature coal pitch to prepare pitch powder; mixing 0.05kg of sodium dodecyl benzene sulfonate and 0.1kg of simethicone, heating to 290 ℃, uniformly stirring, adding 1kg of asphalt powder, carrying out heat preservation and stirring for 4 hours, adding 0.3kg of nano silicon particles, cooling to 80 ℃, carrying out constant temperature and stirring for 4 hours, then carrying out vacuum drying at 100 ℃ for 12 hours, heating to 900 ℃ by taking nitrogen as a protective gas, and carrying out heat preservation for 3 hours.
Preparation example 3: the difference from preparation example 1 is that no nano-silicon particles were added.
Preparation example 4: crushing and sieving medium-temperature coal pitch to prepare pitch powder; 3kg of asphalt powder and 0.5kg of nano silicon particles are mixed, heated to 90 ℃ and stirred for 5 hours at constant temperature.
Preparation examples 5 to 9 of modified phenolic resin
Preparation example 5: soaking 0.3kg of wood powder in 10wt% alkali solution, washing, and drying to obtain alkali treated wood powder;
uniformly mixing 0.5kg of silicon carbide nanowires and alkali-treated wood powder, adding a silane coupling agent KH550 with the concentration of 4wt%, carrying out dipping treatment for 2 hours, and then filtering and drying to prepare a blend;
1kg of a thermoplastic phenolic resin with the model 2123 is diluted with 0.5 times of ethanol, the blend is immersed in the diluted thermoplastic phenolic resin for 3d at normal temperature, and the mixture is filtered and air-dried for 24h.
Preparation example 6: soaking 0.1kg of wood powder in 8wt% alkali solution, washing, and drying to obtain alkali treated wood powder;
uniformly mixing 0.3kg of silicon carbide nanowires and alkali-treated wood powder, adding a silane coupling agent KH550 with the concentration of 2wt%, carrying out dipping treatment for 1h, filtering, and drying to prepare a blend;
1kg of a thermoplastic phenolic resin with the model 2123 was diluted with 0.5 times of ethanol, the blend was immersed in the diluted thermoplastic phenolic resin at normal temperature for 2d, filtered and air-dried for 20h.
Preparation example 7: mixing 0.5kg of silicon carbide nanowire with 4wt% silane coupling agent KH550, soaking for 2h, filtering, and drying to obtain a blend;
1kg of a thermoplastic phenolic resin with the model 2123 is diluted with 0.5 times of ethanol, the blend is immersed in the diluted thermoplastic phenolic resin for 3d at normal temperature, and the mixture is filtered and air-dried for 24h.
Preparation example 8: soaking 0.3kg of wood powder in 10wt% alkali solution, washing, and drying to obtain alkali treated wood powder;
1kg of thermoplastic phenolic resin with the model 2123 is diluted with 0.5 times of ethanol, and alkali-treated wood powder is immersed in the diluted thermoplastic phenolic resin for 3d at normal temperature, filtered and air-dried for 24h.
Preparation example 9: the difference from preparation example 5 is that the silicon carbide nanowire and the alkali-treated wood flour were not subjected to the impregnation treatment using the silane coupling agent KH 550.
Examples
Example 1: the preparation method of the high-rate graphite anode material comprises the following steps:
s1, spheroidizing: spheroidizing natural crystalline flake graphite to prepare spherical graphite with the granularity d50=10μm;
s2, granulating: mixing and stirring spherical graphite and a carbon source, wherein the stirring frequency is 25Hz, firstly heating to 500 ℃, preserving heat for 2 hours, then heating to 650 ℃, preserving heat for 4 hours, and carrying out surface coating to obtain a coating; the carbon source is modified asphalt, the mass ratio of the modified asphalt to the spherical graphite is 0.1:1, and the modified asphalt is prepared from preparation example 1;
s3, carbonizing: and heating the coating to 1200 ℃ for 4 hours, and carbonizing for 6 hours to obtain the negative electrode material.
Example 2: the preparation method of the high-rate graphite anode material comprises the following steps:
s1, spheroidizing: spheroidizing natural crystalline flake graphite to prepare spherical graphite with the granularity d50=5μm;
s2, granulating: mixing and stirring spherical graphite and a carbon source, wherein the stirring frequency is 25Hz, firstly heating to 550 ℃, preserving heat for 3 hours, then heating to 700 ℃, preserving heat for 4.5 hours, and carrying out surface coating to obtain a coating; the carbon source is modified asphalt, the mass ratio of the modified asphalt to the spherical graphite is 0.1:1, and the modified asphalt is prepared from preparation example 1;
s3, carbonizing: and heating the coating to 1350 ℃ for 4.5 hours, and carbonizing for 5.5 hours to obtain the negative electrode material.
Preparation example 3: a preparation method of a high-rate graphite anode material is different from example 1 in that the mass ratio of modified asphalt to spherical graphite is 0.15:1.
Example 4: a preparation method of a high-rate graphite anode material, which is different from example 1 in that modified asphalt is prepared from preparation example 2.
Example 5: a preparation method of a high-rate graphite anode material is different from example 1 in that modified asphalt is prepared from preparation example 3.
Example 6: a preparation method of a high-rate graphite anode material is different from example 1 in that modified asphalt is prepared from preparation example 4.
Example 7: a preparation method of a high-rate graphite anode material is different from example 1 in that a carbon source comprises hard carbon resin and asphalt in a mass ratio of 1:0.5, wherein the hard carbon resin is modified phenolic resin, the high-rate graphite anode material is prepared from preparation example 5, and the asphalt is No. 70 asphalt.
Example 8: a preparation method of a high-rate graphite anode material is different from example 1 in that a carbon source comprises hard carbon resin and asphalt in a mass ratio of 1:0.3, wherein the hard carbon resin is modified phenolic resin, the high-rate graphite anode material is prepared from preparation example 6, and the asphalt is No. 70 asphalt.
Example 9: a preparation method of a high-rate graphite anode material, which is different from example 7 in that a modified phenolic resin is prepared from preparation example 7.
Example 10: a preparation method of a high-rate graphite anode material, which is different from example 7 in that a modified phenolic resin is prepared from preparation example 8.
Example 11: a method for preparing a high-rate graphite anode material, which is different from example 7 in that a modified phenolic resin is prepared from preparation example 9.
Example 12: the preparation method of the high-rate graphite anode material is different from example 7 in that the following pretreatment is performed before the coating is carbonized:
mixing the coating with liquid silicon containing metal salt, heating to 1100 ℃ under the protection of argon, and preserving heat for 4 hours, wherein the mass ratio of the coating to the liquid silicon to the metal salt is 1:0.3:0.06, and the metal salt is cobalt nitrate.
Comparative example
Comparative example 1: a preparation method of a high-rate graphite anode material is different from example 1 in that the carbon source is coal pitch.
Comparative example 2: the high-rate graphite negative electrode material is different from example 1 in that the carbon source is added in an amount of 30% of the spherical graphite in step S2, and the coating is graphitized at 3000 ℃ for 5 hours.
Comparative example 3: the preparation method of the high-rate graphite anode material comprises the following steps:
mixing 77.91wt% of artificial graphite, 21.91wt% of liquid asphalt, 0.09wt% of carbon black and 0.09wt% of carbon nano tubes to prepare slurry, carrying out spray drying granulation or extrusion kneading granulation on the slurry to obtain particles with the particle size of 25 mu m, placing the particles into a rotary sintering furnace, heating from room temperature to 800 ℃ at the heating rate of 2.5 ℃/min, sintering under inert atmosphere, preserving heat for two hours, and cooling to room temperature to obtain sintered massive materials; dispersing the block material, then immersing the block material in liquid asphalt, repeating sintering and immersing for 2 times, and dispersing until the particle size is 25 mu m; and then graphitizing at 3250 ℃ to obtain the high-magnification graphite anode material.
Performance test
Negative electrode materials were prepared according to the methods in examples and comparative examples, and the properties of the negative electrode materials were measured with reference to the following methods, and the measurement results are recorded in table 1.
1. Tap density: testing the tap density of graphite cathode material by using tap meter TF-100B
2. Specific surface area: testing the specific surface area of the graphite anode material by adopting a specific surface area tester NOVATouch 2000;
3. d50 median particle diameter: testing the D50 median particle size and the particle size distribution range of the graphite anode material by adopting a laser particle size distribution instrument MS 2000;
4. first discharge capacity and first discharge efficiency: according to the cathode material: CMC: SBR: the mass ratio of SP=96.1:1.3:1.8:0.8 is uniformly mixed in an aqueous solution, coated on a copper foil, and then dried and rolled to prepare the pole piece. Positive electrode material: PVDF: the mass ratio of CNTs=98:1:1 is uniformly mixed in NMP solution, coated on aluminum foil, and then dried and rolled to prepare the pole piece. And assembling the positive and negative plates into the 8Ah soft-package battery cell. The electrolyte adopts standard test electrolyte 1mol LiPF6+EC+EMC+DEC, the diaphragm EC coats the rubber diaphragm, and the charging test is carried out by adopting 1C-25C multiplying power, and the charging and discharging voltage ranges from 2.8V to 4.2V.
TABLE 1
As can be seen from the data in table 1, the modified pitch prepared in preparation example 1 was used as a carbon source in examples 1 and 2, the addition amount was small, the fluidity was increased, the tap density of the prepared negative electrode material after coating and carbonization was small, the first discharge capacity was large, and the first discharge efficiency was high.
In example 3, the amounts of the spherical graphite and the modified asphalt were changed, and in example 4, the modified asphalt prepared in preparation example 2 was used, and the electrical properties of the negative electrode materials prepared in example 3 and example 4 were not greatly changed as compared with example 1.
In example 5, the modified asphalt prepared in preparation example 3 was used, in which no nano silicon particles were added, and the first discharge capacity of the negative electrode material prepared in example 5 was decreased, and the first discharge efficiency was decreased, and the rate was decreased, as compared with example 1.
In example 6, the modified asphalt prepared in preparation example 4 was used, and in preparation example 4, the asphalt was not emulsified, and it is shown in table 1 that the anode material prepared in example 6 was large in particle size and poor in initial discharge effect.
Pitch and modified phenolic resin were used as carbon sources in examples 7 and 8, and modified phenolic resins in examples 7 and 8 were prepared from preparation examples 5 and 6, respectively, and the anode materials prepared in examples 7 and 8 were excellent in discharge performance as compared with example 1.
In example 9, the modified phenolic resin prepared in preparation example 7 was used, in which no alkali-treated wood flour was added, and it is shown in table 1 that the first discharge capacity and first discharge efficiency of the negative electrode material prepared in example 9 were reduced, and the rate was decreased.
Example 10 the modified phenolic resin prepared in preparation example 8 was used compared to example 1, wherein no silicon carbide nanowires were added, and the negative electrode material prepared in example 10 was reduced in magnification compared to example 7.
The modified phenolic resin prepared in preparation example 9 was used in example 11, in which the blend of silicon carbide nanofibers and alkali-treated wood flour was not impregnated with the silane coupling agent KH550, and the anode material prepared in example 11 was reduced in magnification and reduced in first discharge capacity.
In example 12, compared with example 7, the coating is pretreated before carbonization, and the multiplying power of the prepared anode material is further improved.
The carbon source of comparative example 1 was coal pitch, the added amount of the carbon source of comparative example 2 was increased, the carbonization temperature was increased, it is shown in table 1 that the first discharge effect of the anode materials prepared in comparative example 1 and comparative example 2 was reduced, and the detection result of comparative example 2 was worse than that of example 1.
Comparative example 3 is a negative electrode material prepared in the prior art, in which a mixed slurry is prepared from artificial graphite, asphalt, etc., and is granulated by spray drying or extrusion, and then sintered and graphitized, and the initial discharge capacity and discharge efficiency of the prepared graphite negative electrode material are inferior to those of example 1.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (6)
1. The preparation method of the high-magnification graphite anode material is characterized by comprising the following steps of:
spheroidizing: spheroidizing natural crystalline flake graphite to prepare spherical graphite with the granularity d50=5-10 mu m;
granulating: mixing and stirring the spherical graphite and a carbon source, and coating the surface to obtain a coating;
carbonizing: heating the coating to 1200-1350 ℃, and carbonizing for 5.5-6h to obtain a negative electrode material;
the mass ratio of the carbon source to the spherical graphite is 0.1-0.15:1, and the carbon source is a mixture of asphalt and hard carbon resin or modified asphalt;
the preparation method of the modified asphalt comprises the following steps:
crushing medium-temperature coal pitch, sieving to prepare pitch powder;
mixing 0.05-0.1 part of sodium dodecyl benzene sulfonate and 0.1-0.15 part of simethicone by weight, heating to 280-290 ℃, uniformly stirring, adding 1-3 parts of asphalt powder, preserving heat, stirring for 4-5h, adding 0.3-0.5 part of nano silicon particles, cooling to 70-80 ℃, stirring at constant temperature for 4-5h, vacuum drying at 90-100 ℃ for 12-14h, heating to 900-1000 ℃ by taking nitrogen as protective gas, and preserving heat for 3-3.5h;
the hard carbon resin is modified phenolic resin, the modified phenolic resin comprises thermoplastic phenolic resin, silicon carbide nanowires and wood powder in a mass ratio of 1:0.3-0.5:0.1-0.3, and the preparation method of the modified phenolic resin comprises the following steps:
soaking wood powder in 8-10wt% alkali liquor, cleaning, and drying to obtain alkali treated wood powder;
uniformly mixing the silicon carbide nanowires and the alkali-treated wood powder, adding a silane coupling agent with the concentration of 2-4wt%, carrying out dipping treatment for 1-2h, filtering, and drying to prepare a blend;
diluting the thermoplastic phenolic resin, soaking the blend in the diluted thermoplastic phenolic resin for 2-3d at normal temperature, filtering, and air-drying for 20-24h.
2. The method for preparing a high-magnification graphite anode material according to claim 1, wherein the mass ratio of the hard carbon resin to the asphalt is 1:0.3-0.5.
3. The method for preparing a high-rate graphite negative electrode material according to claim 1, wherein the following pretreatment is performed before the coating is carbonized:
mixing the coating with liquid silicon containing metal salt, heating to 1000-1100 ℃ under the protection of argon, and preserving heat for 4-6h.
4. The method for preparing a high-rate graphite negative electrode material according to claim 1, wherein in the granulating step, the temperature is kept at 500-550 ℃ for 2-3 hours, and then the temperature is raised to 650-700 ℃ and kept for 4-4.5 hours.
5. The method for preparing a high-magnification graphite anode material according to claim 1, wherein in the carbonization step, the temperature is raised to 1200-1350 ℃ within 4-4.5 hours.
6. A high-rate graphite anode material, characterized by being prepared by the method for preparing the high-rate graphite anode material according to any one of claims 1 to 5.
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| CN111454536A (en) * | 2020-05-29 | 2020-07-28 | 郭芳芳 | Modified phenolic resin material and preparation method thereof |
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| WO2023001506A1 (en) * | 2021-07-02 | 2023-01-26 | Nanocore Aps | Carbon nanotube composite comprising mechanical ligands |
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| JP4137350B2 (en) * | 2000-06-16 | 2008-08-20 | 三星エスディアイ株式会社 | Negative electrode material for lithium secondary battery, electrode for lithium secondary battery, lithium secondary battery, and method for producing negative electrode material for lithium secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105924991A (en) * | 2016-07-02 | 2016-09-07 | 刘平 | High-temperature-resistant epoxy asphalt material and preparation method thereof |
| CN109970052A (en) * | 2019-02-27 | 2019-07-05 | 福建翔丰华新能源材料有限公司 | A kind of method of natural graphite granulation and secondary coating modification |
| CN111454536A (en) * | 2020-05-29 | 2020-07-28 | 郭芳芳 | Modified phenolic resin material and preparation method thereof |
| WO2023001506A1 (en) * | 2021-07-02 | 2023-01-26 | Nanocore Aps | Carbon nanotube composite comprising mechanical ligands |
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