CN117800335A - Preparation process of composite material of artificial graphite and carbon-coated natural graphite - Google Patents
Preparation process of composite material of artificial graphite and carbon-coated natural graphite Download PDFInfo
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- CN117800335A CN117800335A CN202410224118.6A CN202410224118A CN117800335A CN 117800335 A CN117800335 A CN 117800335A CN 202410224118 A CN202410224118 A CN 202410224118A CN 117800335 A CN117800335 A CN 117800335A
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- 229910021382 natural graphite Inorganic materials 0.000 title claims abstract description 122
- 229910021383 artificial graphite Inorganic materials 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 38
- 230000004048 modification Effects 0.000 claims abstract description 22
- 238000012986 modification Methods 0.000 claims abstract description 22
- 239000010426 asphalt Substances 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000006258 conductive agent Substances 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000000498 ball milling Methods 0.000 claims description 23
- 239000011230 binding agent Substances 0.000 claims description 20
- 238000003763 carbonization Methods 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 239000013543 active substance Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical group [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 229920005546 furfural resin Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims 1
- 239000011300 coal pitch Substances 0.000 claims 1
- 239000011302 mesophase pitch Substances 0.000 claims 1
- 239000011301 petroleum pitch Substances 0.000 claims 1
- 239000011295 pitch Substances 0.000 claims 1
- 238000007599 discharging Methods 0.000 description 26
- 239000002904 solvent Substances 0.000 description 24
- 239000000853 adhesive Substances 0.000 description 18
- 230000001070 adhesive effect Effects 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 18
- 239000007774 positive electrode material Substances 0.000 description 17
- 238000001816 cooling Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000003292 glue Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000005056 compaction Methods 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 12
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 11
- 238000005096 rolling process Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of new energy materials. More particularly, relates to a preparation process of a composite material of artificial graphite and carbon-coated natural graphite. The preparation method comprises the following steps: carrying out electromagnetic microwave modification on the artificial graphite under the protection of inert gas to obtain modified artificial graphite; the electromagnetic microwave modification is that under the condition that the microwave power is 800-1000W, electromagnetic microwave treatment is carried out for 40-60s; uniformly blending spherical natural graphite and a coating material, and carbonizing in an inert atmosphere to obtain modified natural graphite; the spherical natural graphite is selected from natural graphite with sphericity of 0.8-0.85, D50 of 8-15 μm and carbon content of not less than 95%; the coating material is selected from any one of asphalt or organic resin; and uniformly blending the modified artificial graphite and the modified natural graphite according to the mass ratio of 1:1-1:1.5 to obtain the composite material.
Description
Technical Field
The invention belongs to the technical field of new energy materials. More particularly, it relates to a process for preparing a composite material of artificial graphite and carbon-coated natural graphite.
Background
The lithium battery cathode material mainly comprises two major types of carbon-based and non-carbon-based materials, wherein the carbon-based materials comprise natural graphite, artificial graphite, MCMB, soft carbon, hard carbon and the like, and the natural graphite and the artificial graphite are mainstream in market application because of the characteristics of stable structure, low oxidation-reduction potential, low manufacturing cost and easy modification. The artificial graphite is formed by crushing and graphitizing the coke raw material at a high temperature after structural design, and has excellent cycle and multiplying power performance. The natural graphite is prepared by purifying, spheroidizing and surface treating the multi-purpose flake graphite, and has excellent energy density.
With the diversification of the index requirements of the battery cell products, the composite graphite product blended by natural graphite and artificial graphite is becoming one of the solutions. However, how to combine the two organically and fully exert the advantages of the two, is one of the technical problems of the current public relations of the person skilled in the art.
Disclosure of Invention
The invention aims to solve the technical problem that the scheme of mixing artificial graphite and natural graphite is difficult to realize the organic combination of the artificial graphite and the natural graphite, and the defect of fully playing a synergistic effect is overcome, and provides a preparation process of a composite material of the artificial graphite and the carbon-coated natural graphite, a lithium battery negative electrode plate and a lithium battery.
The invention aims at providing a preparation process of a composite material of artificial graphite and carbon-coated natural graphite.
The above object of the present invention is achieved by the following technical scheme:
the preparation process of the composite material of the artificial graphite and the carbon-coated natural graphite comprises the following specific preparation steps:
electromagnetic modification treatment of artificial graphite:
carrying out electromagnetic microwave modification on the artificial graphite under the protection of inert gas to obtain modified artificial graphite;
the electromagnetic microwave modification is that under the condition that the microwave power is 800-1000W, electromagnetic microwave treatment is carried out for 40-60s;
carbon coating of natural graphite:
uniformly blending spherical natural graphite and a coating material, and then performing heat treatment in an inert atmosphere to obtain pretreated natural graphite;
adding the modified artificial graphite with the mass of 8-15% of that of the pretreated natural graphite into the pretreated natural graphite, uniformly mixing, and carbonizing in inert atmosphere to obtain modified natural graphite;
wherein the heat treatment comprises: heat preservation and heat treatment are carried out for 2-4h at the temperature of 400-450 ℃;
the spherical natural graphite is selected from natural graphite with sphericity of 0.8-0.85, D50 of 8-15 μm and carbon content of not less than 95%;
the coating material is selected from any one of asphalt or organic resin;
preparation of the composite material:
and uniformly blending the modified artificial graphite and the modified natural graphite according to the mass ratio of 1:1-1:1.5 to obtain the composite material.
According to the technical scheme, electromagnetic microwave modification treatment is carried out on the artificial graphite, in the process, the action of microwaves is based on the interaction of materials and electromagnetic radiation, so that the artificial graphite can strongly absorb microwaves to generate rapid high heat, holes are formed in the artificial graphite sheet, the interlayer spacing of the artificial graphite sheet is widened, and the diffusion impedance of lithium ions is reduced; however, considering that lithium ions are rapidly intercalated and deintercalated from the interlayer of graphite during rapid charge and discharge, the inventor avoids excessive damage to the physical structure of the artificial graphite by adjusting the power and time of microwave treatment, thereby affecting the stability of the physical structure of the product and ensuring that the performance of the product can be maintained during long-term charge and discharge;
in addition, the resistance when lithium ions diffuse from the surface of the natural graphite to the inside is reduced by carbon coating the natural graphite, and the regulated ion diffusion resistance, especially at the interface of the natural graphite and the artificial graphite, can be improved by selecting spherical natural graphite with specified specification; in addition, the performance is fully balanced by matching with the regulation and control of the mass ratio of the two;
according to the technical scheme, a small amount of modified artificial graphite is further mixed in the modification process of the natural graphite, and the natural graphite and the coating material are subjected to heat treatment before the artificial graphite is added, so that a continuous transition interface is formed between the natural graphite and the carbon coating layer and between the natural graphite and the artificial graphite in the further subsequent high-temperature carbonization process, the lithium ion diffusion resistance between the modified natural graphite and the modified artificial graphite is further improved, and the lithium ion diffusion capacity of each of the modified natural graphite particles and the modified artificial graphite particles is balanced, so that the overall performance of the product can be effectively exerted;
in the preparation of the composite material, if the modified natural graphite used in the blending is selected from the materials doped with the modified artificial graphite, the mass ratio of the modified artificial graphite to the modified natural graphite actually means the mass of the modified natural graphite including the modified artificial graphite doped in the modification of the modified natural graphite.
Further, the carbonization treatment is as follows: heating to 800-1500 ℃ at the heating rate of 1-5 ℃/min, and preserving heat and carbonizing for 4-10h.
Further, the asphalt is selected from any one of coal asphalt, petroleum asphalt, mesophase asphalt and coal tar.
Further, the organic resin is selected from any one of phenolic resin, epoxy resin, urea resin, furfural resin, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, polyvinylidene fluoride, polyacrylic resin and polyvinyl chloride.
Further, the carbon coating of the natural graphite further comprises the steps of:
wherein the coating material accounts for 3-12% of the mass of the spherical natural graphite;
mixing spherical natural graphite and coating material, stirring and mixing for 20-60min under the condition of stirring rotation speed of 100-300r/min, and continuing stirring and coating for 30-120min under the condition of 1200-1500 r/min.
Further, the uniformly mixing includes:
adding the modified artificial graphite with the mass of 8-15% of that of the pretreated natural graphite into the pretreated natural graphite, wherein the mass ratio of the ball material is 20:1-30:1, ball milling rotation speed is 300-350r/min, ball milling revolution speed is 400-450r/min, and ball milling mixing is carried out for 3-5h under the condition.
According to the scheme, the pretreated natural graphite and the modified artificial graphite are subjected to ball milling and mixing, and in the process, the natural graphite and the artificial graphite can form physical adsorption, so that organic combination is formed in the subsequent high-temperature carbonization process.
Further, the electromagnetic modification treatment of the artificial graphite further comprises:
and (3) carrying out electromagnetic microwave modification on the artificial graphite with the D50 of 16-30 mu m under the protection of inert gas to obtain the modified artificial graphite.
The particle size of the artificial graphite is regulated and controlled to be larger than that of the natural graphite, so that the dispersion state of the artificial graphite and the natural graphite can be regulated and controlled, and the natural graphite with smaller particle size can obtain a relatively shorter ion diffusion path, so that the difference of ion diffusion capacity between the artificial graphite and the natural graphite is further reduced, the product performance is further balanced, and the product performance is fully exerted.
Another object of the present invention is to provide a negative electrode tab for a lithium battery.
The above object of the present invention is achieved by the following technical scheme:
the negative pole piece of the lithium battery comprises a negative pole current collector and a negative pole membrane coated on the surface of the negative pole current collector, wherein the negative pole membrane comprises a composite material prepared by the preparation process, a conductive agent and a binder.
Another object of the present invention is to provide a lithium battery.
The above object of the present invention is achieved by the following technical scheme:
a lithium battery comprises the negative electrode plate, a positive electrode plate and a diaphragm; the positive electrode plate comprises a positive electrode current collector and a positive electrode membrane coated on the surface of the positive electrode current collector, wherein the positive electrode membrane comprises a ternary positive electrode active substance, and the ternary positive electrode active substance is nickel cobalt lithium manganate.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
Electromagnetic modification treatment of artificial graphite:
pouring artificial graphite with the D50 of 16 mu m into a ceramic crucible, then carrying out electromagnetic microwave treatment for 40 seconds under the condition of 800W of microwave power in an argon atmosphere, naturally cooling to room temperature, and discharging to obtain modified artificial graphite;
carbon coating of natural graphite:
mixing spherical natural graphite and a coating material with the mass of 3% of that of the spherical natural graphite, pouring the mixture into a mixer, stirring and mixing for 20min under the condition of the stirring speed of 100r/min, continuing stirring and coating for 30min under the condition of 1200r/min, and discharging to obtain a premix;
transferring the premix into a carbonization furnace, heating to 400 ℃ at a speed of 3 ℃/min in an argon protective atmosphere, carrying out heat preservation and heat treatment for 2 hours, cooling to room temperature along with the furnace, and discharging to obtain pretreated natural graphite;
pouring the pretreated natural graphite and the modified artificial graphite accounting for 8% of the mass of the pretreated natural graphite into a ball mill tank, wherein the ball material mass ratio is 20:1, ball milling rotation speed is 300r/min, ball milling revolution speed is 400r/min, and ball milling and mixing are carried out for 3 hours under the condition to obtain ball grinding materials;
transferring the ball-milling material into a carbonization furnace, heating to 800 ℃ at a heating rate of 1 ℃/min, carrying out heat preservation and carbonization treatment for 4 hours, cooling to room temperature along with the furnace, and discharging to obtain modified natural graphite;
the spherical natural graphite is natural graphite with sphericity of 0.8, D50 of 8 mu m and carbon content of 95 percent;
the coating material is selected from asphalt; the asphalt is selected from coal asphalt;
preparation of the composite material:
and mixing the modified artificial graphite and the modified natural graphite according to the mass ratio of 1:1, pouring the mixture into a mixer, stirring and mixing for 3 hours at the stirring rotation speed of 800r/min, and discharging to obtain the composite material.
Preparing a negative electrode plate:
the obtained composite material, the conductive agent and the adhesive are mixed according to the mass ratio of 97:2:1, wherein the adhesive is firstly dispersed with the solvent to prepare the glue solution, then is uniformly mixed with the composite material and the conductive agent, then is extruded and coated on the surface of the negative electrode current collector, and is dried and then is rolled to the compaction density of 1.7g/cm 3 Slitting, die cutting and rolling to obtain a negative electrode plate;
wherein, the conductive agent selects super P, the binder selects CMC, and the negative current collector selects copper foil with the thickness of 6 mu m;
preparing a positive electrode plate:
selecting a 5-series ternary positive electrode material, ni: co: the molar ratio of Mn is 5:3:2, the mass ratio of the positive electrode material, the conductive agent and the binder is 97:1.5:1.5, wherein the adhesive is firstly dispersed with the solvent to prepare a glue solution, then uniformly mixed with the positive electrode material and the conductive agent, then extruded and coated on the surface of the positive electrode current collector, dried and rolled to a compaction density of 3.65g/cm 3 Slitting, die cutting and rolling to obtain a positive electrode plate;
wherein, the conductive agent is acetylene black, the binder is PVDF, and the positive current collector is aluminum foil with the thickness of 12 mu m;
the diaphragm selection base film is 7 mu m PP,2 mu m single-sided ceramic and 1 mu m double-sided rubberized (PVDF) diaphragm;
the electrolyte is prepared from ethylene carbonate and methyl ethyl carbonate according to the mass ratio of 2:3 mixing to form a solvent, adding lithium hexafluorophosphate serving as lithium salt into the solvent to form electrolyte with the concentration of 1 mol/L;
after the positive pole piece, the negative pole piece and the diaphragm are assembled to form a single battery, electrolyte is injected with the injection coefficient of 1.38; after the liquid injection is completed, standing and forming for 8 hours at the temperature of 45 ℃ to obtain the lithium battery product.
Example 2
Electromagnetic modification treatment of artificial graphite:
pouring artificial graphite with D50 of 22 mu m into a ceramic crucible, then carrying out electromagnetic microwave treatment for 50s under the condition of 900W of microwave power in an argon atmosphere, naturally cooling to room temperature, and discharging to obtain modified artificial graphite;
carbon coating of natural graphite:
mixing spherical natural graphite and a coating material with the mass of 8% of that of the spherical natural graphite, pouring the mixture into a mixer, stirring and mixing for 40min under the condition of 200r/min, continuing stirring and coating for 60min under the condition of 1300r/min, and discharging to obtain a premix;
transferring the premix into a carbonization furnace, heating to 420 ℃ at a speed of 4 ℃/min in an argon protective atmosphere, carrying out heat preservation and heat treatment for 3 hours, cooling to room temperature along with the furnace, and discharging to obtain pretreated natural graphite;
pouring the pretreated natural graphite and the modified artificial graphite with the mass of 12% of that of the pretreated natural graphite into a ball mill tank, wherein the ball material mass ratio is 25:1, ball milling rotation speed is 320r/min, ball milling revolution speed is 420r/min, and ball milling and mixing are carried out for 4 hours under the condition to obtain ball grinding materials;
transferring the ball-milling material into a carbonization furnace, heating to 1200 ℃ at a heating rate of 3 ℃/min, carrying out heat preservation carbonization treatment for 8 hours, cooling to room temperature along with the furnace, and discharging to obtain modified natural graphite;
the spherical natural graphite is natural graphite with sphericity of 0.82, D50 of 12 mu m and carbon content of 95.5 percent;
the coating material is selected from organic resins; the organic resin is selected from phenolic resins;
preparation of the composite material:
and mixing the modified artificial graphite and the modified natural graphite according to the mass ratio of 1:1.5, pouring the mixture into a mixer, stirring and mixing for 4 hours at the stirring rotation speed of 900r/min, and discharging to obtain the composite material.
Preparing a negative electrode plate:
the obtained composite material, the conductive agent and the adhesive are mixed according to the mass ratio of 97:2:1, wherein the adhesive is firstly dispersed with the solvent to prepare the glue solution, then is uniformly mixed with the composite material and the conductive agent, then is extruded and coated on the surface of the negative electrode current collector, and is dried and then is rolled to the compaction density of 1.7g/cm 3 Slitting, die cutting and rolling to obtain a negative electrode plate;
wherein, the conductive agent selects super P, the binder selects CMC, and the negative current collector selects copper foil with the thickness of 6 mu m;
preparing a positive electrode plate:
selecting a 5-series ternary positive electrode material, ni: co: the molar ratio of Mn is 5:3:2, the mass ratio of the positive electrode material, the conductive agent and the binder is 97:1.5:1.5, wherein the adhesive is firstly dispersed with the solvent to prepare a glue solution, then uniformly mixed with the positive electrode material and the conductive agent, then extruded and coated on the surface of the positive electrode current collector, dried and rolled to a compaction density of 3.65g/cm 3 Slitting, die cutting and rolling to obtain a positive electrode plate;
wherein, the conductive agent is acetylene black, the binder is PVDF, and the positive current collector is aluminum foil with the thickness of 12 mu m;
the diaphragm selection base film is 7 mu m PP,2 mu m single-sided ceramic and 1 mu m double-sided rubberized (PVDF) diaphragm;
the electrolyte is prepared from ethylene carbonate and methyl ethyl carbonate according to the mass ratio of 2:3 mixing to form a solvent, adding lithium hexafluorophosphate serving as lithium salt into the solvent to form electrolyte with the concentration of 1 mol/L;
after the positive pole piece, the negative pole piece and the diaphragm are assembled to form a single battery, electrolyte is injected with the injection coefficient of 1.38; after the liquid injection is completed, standing and forming for 8 hours at the temperature of 45 ℃ to obtain the lithium battery product.
Example 3
Electromagnetic modification treatment of artificial graphite:
pouring artificial graphite with the D50 of 30 mu m into a ceramic crucible, then carrying out electromagnetic microwave treatment for 60 seconds under the condition of 1000W of microwave power in an argon atmosphere, naturally cooling to room temperature, and discharging to obtain modified artificial graphite;
carbon coating of natural graphite:
mixing spherical natural graphite and a coating material with the mass of 12% of that of the spherical natural graphite, pouring the mixture into a mixer, stirring and mixing for 60min under the condition of the stirring rotation speed of 300r/min, continuing stirring and coating for 120min under the condition of 1500r/min, and discharging to obtain a premix;
transferring the premix into a carbonization furnace, heating to 450 ℃ at a speed of 5 ℃/min in an argon protective atmosphere, carrying out heat preservation and heat treatment for 4 hours, cooling to room temperature along with the furnace, and discharging to obtain pretreated natural graphite;
pouring the pretreated natural graphite and the modified artificial graphite with the mass of 15% of that of the pretreated natural graphite into a ball mill tank, wherein the ball material mass ratio is 30:1, ball milling rotation speed is 350r/min, ball milling revolution speed is 450r/min, and ball milling and mixing are carried out for 5 hours under the condition to obtain ball grinding materials;
transferring the ball-milling material into a carbonization furnace, heating to 1500 ℃ at a heating rate of 5 ℃/min, carrying out heat preservation carbonization treatment for 10 hours, cooling to room temperature along with the furnace, and discharging to obtain modified natural graphite;
the spherical natural graphite is natural graphite with sphericity of 0.85, D50 of 15 mu m and carbon content of 96 percent;
the coating material is selected from organic resins; the organic resin is selected from polyvinyl alcohol;
preparation of the composite material:
and mixing the modified artificial graphite and the modified natural graphite according to the mass ratio of 1:1.2, pouring the mixture into a mixer, stirring and mixing for 5 hours at the stirring speed of 1000r/min, and discharging to obtain the composite material.
Preparing a negative electrode plate:
the obtained composite material, the conductive agent and the adhesive are mixed according to the mass ratio of 97:2:1, wherein the adhesive is firstly dispersed with the solvent to prepare the glue solution, then is uniformly mixed with the composite material and the conductive agent, then is extruded and coated on the surface of the negative electrode current collector, and is dried and then is rolled to the compaction density of 1.7g/cm 3 Slitting, die cutting and rolling to obtain a negative electrode plate;
wherein, the conductive agent selects super P, the binder selects CMC, and the negative current collector selects copper foil with the thickness of 6 mu m;
preparing a positive electrode plate:
selecting a 5-series ternary positive electrode material, ni: co: the molar ratio of Mn is 5:3:2, the mass ratio of the positive electrode material, the conductive agent and the binder is 97:1.5:1.5, wherein the adhesive is firstly dispersed with the solvent to prepare a glue solution, then uniformly mixed with the positive electrode material and the conductive agent, then extruded and coated on the surface of the positive electrode current collector, dried and rolled to a compaction density of 3.65g/cm 3 Slitting, die cutting and rolling to obtain a positive electrode plate;
wherein, the conductive agent is acetylene black, the binder is PVDF, and the positive current collector is aluminum foil with the thickness of 12 mu m;
the diaphragm selection base film is 7 mu m PP,2 mu m single-sided ceramic and 1 mu m double-sided rubberized (PVDF) diaphragm;
the electrolyte is prepared from ethylene carbonate and methyl ethyl carbonate according to the mass ratio of 2:3 mixing to form a solvent, adding lithium hexafluorophosphate serving as lithium salt into the solvent to form electrolyte with the concentration of 1 mol/L;
after the positive pole piece, the negative pole piece and the diaphragm are assembled to form a single battery, electrolyte is injected with the injection coefficient of 1.38; after the liquid injection is completed, standing and forming for 8 hours at the temperature of 45 ℃ to obtain the lithium battery product.
Example 4
The difference between this embodiment and embodiment 1 is that: the D50 of the artificial graphite was 8. Mu.m, and the remaining conditions were kept unchanged.
Comparative example 1
Selecting artificial graphite with D50 of 16 mu m;
carbon coating of natural graphite:
mixing spherical natural graphite and a coating material with the mass of 3% of that of the spherical natural graphite, pouring the mixture into a mixer, stirring and mixing for 20min under the condition of the stirring speed of 100r/min, continuing stirring and coating for 30min under the condition of 1200r/min, and discharging to obtain a premix;
transferring the premix into a carbonization furnace, heating to 400 ℃ at a speed of 3 ℃/min in an argon protective atmosphere, carrying out heat preservation and heat treatment for 2 hours, cooling to room temperature along with the furnace, and discharging to obtain pretreated natural graphite;
pouring the pretreated natural graphite and the artificial graphite accounting for 8% of the mass of the pretreated natural graphite into a ball mill tank, wherein the ball material mass ratio is 20:1, ball milling rotation speed is 300r/min, ball milling revolution speed is 400r/min, and ball milling and mixing are carried out for 3 hours under the condition to obtain ball grinding materials;
transferring the ball-milling material into a carbonization furnace, heating to 800 ℃ at a heating rate of 1 ℃/min, carrying out heat preservation and carbonization treatment for 4 hours, cooling to room temperature along with the furnace, and discharging to obtain modified natural graphite;
the spherical natural graphite is natural graphite with sphericity of 0.8, D50 of 8 mu m and carbon content of 95 percent;
the coating material is selected from asphalt; the asphalt is selected from coal asphalt;
preparation of the composite material:
and mixing the artificial graphite and the modified natural graphite according to the mass ratio of 1:1, pouring the mixture into a mixer, stirring and mixing for 3 hours at the stirring rotation speed of 800r/min, and discharging to obtain the composite material.
Preparing a negative electrode plate:
the obtained composite material, the conductive agent and the adhesive are mixed according to the mass ratio of 97:2:1, wherein the adhesive is firstly dispersed with the solvent to prepare the glue solution, then is uniformly mixed with the composite material and the conductive agent, then is extruded and coated on the surface of the negative electrode current collector, and is dried and then is rolled to the compaction density of 1.7g/cm 3 Slitting, die cutting and rolling to obtain a negative electrode plate;
wherein, the conductive agent selects super P, the binder selects CMC, and the negative current collector selects copper foil with the thickness of 6 mu m;
preparing a positive electrode plate:
selecting a 5-series ternary positive electrode material, ni: co: the molar ratio of Mn is 5:3:2, the mass ratio of the positive electrode material, the conductive agent and the binder is 97:1.5:1.5, wherein the adhesive is dispersed with the solvent to prepare a glue solution, and then is mixed with the glue solutionThe anode material and the conductive agent are uniformly mixed, then the mixture is extruded and coated on the surface of the anode current collector, and after being dried, the mixture is rolled to a compaction density of 3.65g/cm 3 Slitting, die cutting and rolling to obtain a positive electrode plate;
wherein, the conductive agent is acetylene black, the binder is PVDF, and the positive current collector is aluminum foil with the thickness of 12 mu m;
the diaphragm selection base film is 7 mu m PP,2 mu m single-sided ceramic and 1 mu m double-sided rubberized (PVDF) diaphragm;
the electrolyte is prepared from ethylene carbonate and methyl ethyl carbonate according to the mass ratio of 2:3 mixing to form a solvent, adding lithium hexafluorophosphate serving as lithium salt into the solvent to form electrolyte with the concentration of 1 mol/L;
after the positive pole piece, the negative pole piece and the diaphragm are assembled to form a single battery, electrolyte is injected with the injection coefficient of 1.38; after the liquid injection is completed, standing and forming for 8 hours at the temperature of 45 ℃ to obtain the lithium battery product.
Comparative example 2
Electromagnetic modification treatment of artificial graphite:
pouring artificial graphite with the D50 of 16 mu m into a ceramic crucible, then carrying out electromagnetic microwave treatment for 40 seconds under the condition of 800W of microwave power in an argon atmosphere, naturally cooling to room temperature, and discharging to obtain modified artificial graphite;
spherical natural graphite with sphericity of 0.8, D50 of 8 mu m and carbon content of 95 percent is selected;
preparation of the composite material:
and mixing the modified artificial graphite and the spherical natural graphite according to the mass ratio of 1:1, pouring the mixture into a mixer, stirring and mixing for 3 hours at the stirring rotation speed of 800r/min, and discharging to obtain the composite material.
Preparing a negative electrode plate:
the obtained composite material, the conductive agent and the adhesive are mixed according to the mass ratio of 97:2:1, wherein the adhesive is firstly dispersed with the solvent to prepare the glue solution, then is uniformly mixed with the composite material and the conductive agent, then is extruded and coated on the surface of the negative electrode current collector, and is dried and then is rolled to the compaction density of 1.7g/cm 3 Slitting, die cutting and winding to obtain a negative electrodeA pole piece;
wherein, the conductive agent selects super P, the binder selects CMC, and the negative current collector selects copper foil with the thickness of 6 mu m;
preparing a positive electrode plate:
selecting a 5-series ternary positive electrode material, ni: co: the molar ratio of Mn is 5:3:2, the mass ratio of the positive electrode material, the conductive agent and the binder is 97:1.5:1.5, wherein the adhesive is firstly dispersed with the solvent to prepare a glue solution, then uniformly mixed with the positive electrode material and the conductive agent, then extruded and coated on the surface of the positive electrode current collector, dried and rolled to a compaction density of 3.65g/cm 3 Slitting, die cutting and rolling to obtain a positive electrode plate;
wherein, the conductive agent is acetylene black, the binder is PVDF, and the positive current collector is aluminum foil with the thickness of 12 mu m;
the diaphragm selection base film is 7 mu m PP,2 mu m single-sided ceramic and 1 mu m double-sided rubberized (PVDF) diaphragm;
the electrolyte is prepared from ethylene carbonate and methyl ethyl carbonate according to the mass ratio of 2:3 mixing to form a solvent, adding lithium hexafluorophosphate serving as lithium salt into the solvent to form electrolyte with the concentration of 1 mol/L;
after the positive pole piece, the negative pole piece and the diaphragm are assembled to form a single battery, electrolyte is injected with the injection coefficient of 1.38; after the liquid injection is completed, standing and forming for 8 hours at the temperature of 45 ℃ to obtain the lithium battery product.
Comparative example 3
Electromagnetic modification treatment of artificial graphite:
pouring artificial graphite with the D50 of 16 mu m into a ceramic crucible, then carrying out electromagnetic microwave treatment for 40 seconds under the condition of 800W of microwave power in an argon atmosphere, naturally cooling to room temperature, and discharging to obtain modified artificial graphite;
carbon coating of natural graphite:
mixing spherical natural graphite and a coating material with the mass of 3% of that of the spherical natural graphite, pouring the mixture into a mixer, stirring and mixing for 20min under the condition of the stirring speed of 100r/min, continuing stirring and coating for 30min under the condition of 1200r/min, and discharging to obtain a premix;
transferring the obtained premix into a carbonization furnace, heating to 800 ℃ at a heating rate of 1 ℃/min, carrying out heat preservation carbonization treatment for 4 hours, cooling to room temperature along with the furnace, and discharging to obtain modified natural graphite;
the spherical natural graphite is natural graphite with sphericity of 0.8, D50 of 8 mu m and carbon content of 95 percent;
the coating material is selected from asphalt; the asphalt is selected from coal asphalt;
preparation of the composite material:
and mixing the modified artificial graphite and the modified natural graphite according to the mass ratio of 1:1, pouring the mixture into a mixer, stirring and mixing for 3 hours at the stirring rotation speed of 800r/min, and discharging to obtain the composite material.
Preparing a negative electrode plate:
the obtained composite material, the conductive agent and the adhesive are mixed according to the mass ratio of 97:2:1, wherein the adhesive is firstly dispersed with the solvent to prepare the glue solution, then is uniformly mixed with the composite material and the conductive agent, then is extruded and coated on the surface of the negative electrode current collector, and is dried and then is rolled to the compaction density of 1.7g/cm 3 Slitting, die cutting and rolling to obtain a negative electrode plate;
wherein, the conductive agent selects super P, the binder selects CMC, and the negative current collector selects copper foil with the thickness of 6 mu m;
preparing a positive electrode plate:
selecting a 5-series ternary positive electrode material, ni: co: the molar ratio of Mn is 5:3:2, the mass ratio of the positive electrode material, the conductive agent and the binder is 97:1.5:1.5, wherein the adhesive is firstly dispersed with the solvent to prepare a glue solution, then uniformly mixed with the positive electrode material and the conductive agent, then extruded and coated on the surface of the positive electrode current collector, dried and rolled to a compaction density of 3.65g/cm 3 Slitting, die cutting and rolling to obtain a positive electrode plate;
wherein, the conductive agent is acetylene black, the binder is PVDF, and the positive current collector is aluminum foil with the thickness of 12 mu m;
the diaphragm selection base film is 7 mu m PP,2 mu m single-sided ceramic and 1 mu m double-sided rubberized (PVDF) diaphragm;
the electrolyte is prepared from ethylene carbonate and methyl ethyl carbonate according to the mass ratio of 2:3 mixing to form a solvent, adding lithium hexafluorophosphate serving as lithium salt into the solvent to form electrolyte with the concentration of 1 mol/L;
after the positive pole piece, the negative pole piece and the diaphragm are assembled to form a single battery, electrolyte is injected with the injection coefficient of 1.38; after the liquid injection is completed, standing and forming for 8 hours at the temperature of 45 ℃ to obtain the lithium battery product.
The products obtained in examples 1 to 4 and comparative examples 1 to 3 were subjected to performance tests, and specific test methods and test results are as follows:
and (3) testing the cycle performance:
after the constant volume of the battery is carried out at 25 ℃, the battery is charged at 0.33C multiplying power, and is discharged at 0.5C multiplying power, and full-charge discharge cycle test is carried out until the capacity of the battery is attenuated to 80% of the initial capacity, the charging and discharging are stopped, and the cycle number of the battery is recorded; the specific test results are shown in Table 1;
in the full charge process, constant-current charge is carried out at a charging multiplying power of 0.33C, and after the constant-voltage charge is carried out until the current is lower than 0.025C, the constant-voltage charge is continuously carried out until the current is lower than the cut-off voltage (4.25V), and the full charge is regarded as full charge; in the full discharge process, the discharge was performed at a discharge rate of 0.5C to a cut-off voltage of 2.8V, and then the mixture was left standing for 30min.
Table 1: product performance test results
From the test results, the product obtained by the invention has more excellent cycle performance. The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. The preparation process of the composite material of the artificial graphite and the carbon-coated natural graphite is characterized by comprising the following specific preparation steps:
electromagnetic modification treatment of artificial graphite:
carrying out electromagnetic microwave modification on the artificial graphite under the protection of inert gas to obtain modified artificial graphite;
the electromagnetic microwave modification is that under the condition that the microwave power is 800-1000W, electromagnetic microwave treatment is carried out for 40-60s;
carbon coating of natural graphite:
uniformly blending spherical natural graphite and a coating material, and then performing heat treatment in an inert atmosphere to obtain pretreated natural graphite;
adding the modified artificial graphite with the mass of 8-15% of that of the pretreated natural graphite into the pretreated natural graphite, uniformly mixing, and carbonizing in inert atmosphere to obtain modified natural graphite;
wherein the heat treatment comprises: heat preservation and heat treatment are carried out for 2-4h at the temperature of 400-450 ℃;
the spherical natural graphite is selected from natural graphite with sphericity of 0.8-0.85, D50 of 8-15 μm and carbon content of not less than 95%;
the coating material is selected from any one of asphalt or organic resin;
preparation of the composite material:
and uniformly blending the modified artificial graphite and the modified natural graphite according to the mass ratio of 1:1-1:1.5 to obtain the composite material.
2. The process for preparing a composite material of artificial graphite and carbon-coated natural graphite according to claim 1, wherein the carbonization treatment is as follows: heating to 800-1500 ℃ at the heating rate of 1-5 ℃/min, and preserving heat and carbonizing for 4-10h.
3. The process for preparing a composite material of artificial graphite and carbon-coated natural graphite according to claim 1, wherein the pitch is any one selected from coal pitch, petroleum pitch, mesophase pitch and coal tar.
4. The process for preparing the composite material of the artificial graphite and the carbon-coated natural graphite according to claim 1, wherein the organic resin is selected from any one of phenolic resin, epoxy resin, urea-formaldehyde resin, furfural resin, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, polyvinylidene fluoride, polyacrylic resin and polyvinyl chloride.
5. The process for preparing a composite material of artificial graphite and carbon-coated natural graphite according to claim 1, wherein the carbon coating of the natural graphite further comprises the steps of:
wherein the coating material accounts for 3-12% of the mass of the spherical natural graphite;
mixing spherical natural graphite and coating material, stirring and mixing for 20-60min under the condition of stirring rotation speed of 100-300r/min, and continuing stirring and coating for 30-120min under the condition of 1200-1500 r/min.
6. The process for preparing a composite material of artificial graphite and carbon-coated natural graphite according to claim 1, wherein the uniformly mixing comprises:
adding the modified artificial graphite with the mass of 8-15% of that of the pretreated natural graphite into the pretreated natural graphite, wherein the mass ratio of the ball material is 20:1-30:1, ball milling rotation speed is 300-350r/min, ball milling revolution speed is 400-450r/min, and ball milling mixing is carried out for 3-5h under the condition.
7. The process for preparing a composite material of artificial graphite and carbon-coated natural graphite according to claim 1, wherein the electromagnetic modification treatment of artificial graphite further comprises:
and (3) carrying out electromagnetic microwave modification on the artificial graphite with the D50 of 16-30 mu m under the protection of inert gas to obtain the modified artificial graphite.
8. A lithium battery negative electrode plate, which is characterized by comprising a negative electrode current collector and a negative electrode membrane coated on the surface of the negative electrode current collector, wherein the negative electrode membrane comprises a composite material prepared by the preparation process of any one of claims 1-7, a conductive agent and a binder.
9. A lithium battery comprising the negative electrode sheet, the positive electrode sheet and the separator according to claim 8; the positive electrode plate comprises a positive electrode current collector and a positive electrode membrane coated on the surface of the positive electrode current collector, wherein the positive electrode membrane comprises a ternary positive electrode active substance, and the ternary positive electrode active substance is nickel cobalt lithium manganate.
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| CN111646466A (en) * | 2020-03-23 | 2020-09-11 | 万向一二三股份公司 | High-capacity high-compaction fast-charging composite graphite negative electrode material and preparation method thereof |
| CN114044513A (en) * | 2021-11-11 | 2022-02-15 | 博尔特新材料(银川)有限公司 | Preparation method of coal-based graphite/carbon composite negative electrode material for power type lithium ion battery |
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| CN1702894A (en) * | 2005-04-20 | 2005-11-30 | 深圳市贝特瑞电子材料有限公司 | Cathode material of lithium ion cell and preparation method thereof |
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| CN105680022A (en) * | 2016-03-29 | 2016-06-15 | 大连宏光锂业股份有限公司 | Production method of composite graphitic negative-electrode material containing natural oil coke |
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