CN112751075B - Lithium ion battery and preparation method thereof - Google Patents
Lithium ion battery and preparation method thereof Download PDFInfo
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- CN112751075B CN112751075B CN201911055661.3A CN201911055661A CN112751075B CN 112751075 B CN112751075 B CN 112751075B CN 201911055661 A CN201911055661 A CN 201911055661A CN 112751075 B CN112751075 B CN 112751075B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 92
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000011248 coating agent Substances 0.000 claims abstract description 82
- 238000000576 coating method Methods 0.000 claims abstract description 82
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 67
- 239000011230 binding agent Substances 0.000 claims abstract description 44
- 239000006258 conductive agent Substances 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000011267 electrode slurry Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000007773 negative electrode material Substances 0.000 claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 238000005096 rolling process Methods 0.000 claims abstract description 14
- 239000006183 anode active material Substances 0.000 claims abstract description 7
- 239000006256 anode slurry Substances 0.000 claims abstract description 6
- 239000004698 Polyethylene Substances 0.000 claims description 38
- -1 polyethylene Polymers 0.000 claims description 38
- 229920000573 polyethylene Polymers 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000005229 chemical vapour deposition Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000011889 copper foil Substances 0.000 claims description 14
- 239000011888 foil Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001289 polyvinyl ether Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 4
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of batteries, in particular to a lithium ion battery and a preparation method thereof. The preparation method of the lithium ion battery comprises the steps of mixing an anode active material, a conductive agent, a binder, modified aluminum powder and a solvent to prepare anode slurry, coating the anode slurry on an anode current collector with a carbon-containing conductive coating on the surface, and drying, rolling and slitting to obtain an anode plate; mixing a negative electrode active material, a conductive agent, a binder and a solvent to prepare a negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector with a carbon-containing conductive coating on the surface, and drying, rolling and slitting to obtain a negative electrode plate; and assembling the positive electrode plate, the negative electrode plate, the diaphragm and the electrolyte into a lithium ion battery. According to the invention, the modified aluminum powder is added into the positive electrode slurry to be matched with the positive electrode active material, the conductive agent and the binder, so that the charge and discharge efficiency and the cycle service life of the lithium ion battery can be improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a lithium ion battery and a preparation method thereof.
Background
Along with the continuous development of electronic and energy technologies, people are paying more attention to CO 2 and automobile exhaust emission, and electric automobiles become a future development trend. As one of the core components of electric automobiles, research and application of lithium ion batteries have been attracting attention.
The existing lithium ion battery generally adopts lithium cobaltate, lithium manganate, lithium nickel manganate and the like as positive electrode active materials, and adopts artificial graphite, natural graphite and the like as negative electrode active materials, and the battery can be seriously influenced in charge and discharge efficiency and cycle service life due to poor conductivity of the active materials and large internal resistance of the electrode. In order to solve the above problems, the prior art is mainly improved by the following ways: (1) modifying an anode and cathode active material; (2) improving the conductive agent; (3) improving the electrolyte and separator; (4) improving the battery manufacturing process; (5) improvements to the current collector. Wherein the improvement effect on the current collector and the positive and negative electrode active materials is most remarkable. However, in the prior art, modification of the battery anode active material has poor effects of improving the charge and discharge efficiency and prolonging the cycle life of the battery.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, the battery active material is modified, and the charge and discharge efficiency and the cycle service life of a battery cannot be remarkably improved, and further provides a lithium ion battery and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a lithium ion battery comprises the following steps:
1) Mixing an anode active material, a conductive agent, a binder, modified aluminum powder and a solvent to prepare anode slurry, coating the anode slurry on an anode current collector with a carbon-containing conductive coating on the surface, and drying, rolling and slitting to obtain an anode sheet; the mass ratio of the positive electrode active material to the conductive agent to the adhesive to the modified aluminum powder is 96-99 percent: 0.6-2.0%:0.6-2.0%:0.3-1.0%;
2) Mixing a negative electrode active material, a conductive agent, a binder and a solvent to prepare a negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector with a carbon-containing conductive coating on the surface, and drying, rolling and slitting to obtain a negative electrode plate; the mass ratio of the anode active material to the conductive agent to the binder is 92-96%:0.6-2.0%:0.6-2.0%;
3) And assembling the positive electrode plate, the negative electrode plate, the diaphragm and the electrolyte into a lithium ion battery.
The means for assembling the positive electrode plate, the negative electrode plate, the diaphragm and the electrolyte into the lithium ion battery in the invention is conventional in the art, and specifically comprises the means of assembling, liquid injection, formation, clamp baking and capacity division.
Preferably, in step 1), the preparation method of the modified aluminum powder comprises the following steps: mixing aluminum powder, polyethylene wax and toluene at 120-130 ℃, drying after mixing to obtain a solid mixed material of the aluminum powder and the polyethylene wax, and crushing the solid mixed material of the aluminum powder and the polyethylene wax to obtain the modified aluminum powder.
Preferably, the mass ratio of the aluminum powder to the polyethylene wax is 100:5-17.
Preferably, the mass ratio of the aluminum powder to the polyethylene wax is 100:11.
Preferably, the particle size of the modified aluminum powder is 30-50nm.
Preferably, the material in the carbon-containing conductive coating is graphene;
In the step 1), the graphene forms the carbon-containing conductive coating on the surface of the positive electrode current collector through a chemical vapor deposition method to obtain the positive electrode current collector with the carbon-containing conductive coating on the surface;
in the step 2), the graphene forms the carbon-containing conductive coating on the surface of the negative electrode current collector through a chemical vapor deposition method, so as to obtain the negative electrode current collector with the carbon-containing conductive coating on the surface.
In the present invention, the chemical vapor deposition method is a conventional preparation method in the art. The step of forming the carbon-containing conductive coating on the surface of the negative electrode current collector through a chemical vapor deposition method comprises the following steps of: and (3) placing the negative electrode current collector into a reaction chamber for chemical vapor deposition, when the temperature in the reaction chamber reaches 810 ℃, introducing Ar/C 2H2 mixed gas with the C 2H2 content of 9%, and preserving the heat for 0.8h to obtain the negative electrode current collector with the carbon-containing conductive coating on the surface after the heat preservation is finished.
The step of forming the carbon-containing conductive coating on the surface of the anode current collector by a chemical vapor deposition method comprises the following steps: and (3) placing the anode current collector into a reaction chamber for chemical vapor deposition, when the temperature in the reaction chamber reaches 800 ℃, introducing Ar/C 2H2 mixed gas with 10% of C 2H2, and preserving the temperature for 0.8h to obtain the anode current collector with the carbon-containing conductive coating on the surface after the heat preservation is finished.
Preferably, the binder is selected from one or more of polyvinylidene fluoride, styrene-acrylate copolymer, polyacrylonitrile, polyacrylate, sodium carboxymethyl cellulose, polyvinylpyrrolidone and polyvinyl ether;
the conductive agent is selected from one or more of conductive carbon black, lamellar graphite, carbon fiber and carbon nano tube;
the solvent is water or N-methyl pyrrolidone.
Preferably, the positive electrode active material is selected from one or more of lithium cobaltate, lithium manganate, lithium nickel cobalt manganate, lithium iron phosphate, lithium nickel cobalt aluminate, lithium nickel cobaltate and lithium nickelate;
the negative electrode active material is selected from one or more of artificial graphite, natural graphite and silicon carbide.
Preferably, the positive electrode current collector is aluminum foil, and the negative electrode current collector is copper foil.
The invention also provides a lithium ion battery which is prepared by the preparation method.
The invention has the beneficial effects that:
1) According to the preparation method of the lithium ion battery, the modified aluminum powder is added into the positive slurry, and the positive electrode plate obtained by the method is assembled with the negative electrode plate, the diaphragm and the electrolyte obtained by the specific method by mutually matching with the positive electrode active substance, the conductive agent and the binder by utilizing the excellent conductive performance and stability of the modified aluminum powder, so that the lithium ion battery is obtained, and the charging and discharging efficiency and the cycle service life of the lithium ion battery are obviously improved through tests. Meanwhile, the carbon-containing conductive coating arranged on the surface of the anode and cathode current collector can also effectively reduce the resistance, enhance the binding force of the current collector and the active material, and further improve the charge and discharge efficiency and the cycle service life of the battery.
2) The preparation method of the lithium ion battery provided by the invention further comprises the following steps of: mixing aluminum powder, polyethylene wax and toluene at 120-130 ℃, drying after mixing to obtain a solid mixed material of the aluminum powder and the polyethylene wax, and crushing the solid mixed material of the aluminum powder and the polyethylene wax to obtain the modified aluminum powder. According to the invention, through the specific method, the polyethylene wax is utilized to modify the aluminum powder, and the obtained modified aluminum powder is tested to be beneficial to improving the charge and discharge efficiency and the cycle service life of the battery, and meanwhile, the exothermic phenomenon of the lithium ion battery in the discharge process can be improved.
3) According to the preparation method of the lithium ion battery, further, the mass ratio of the aluminum powder to the polyethylene wax is 100:5-17. According to the invention, the mass ratio of the aluminum powder to the polyethylene wax is controlled to be 100:5-17, and under the specific ratio, a part of aluminum powder is only partially coated by the polyethylene wax, so that the high conductivity of the aluminum powder is not affected, and the modified aluminum powder obtained by the ratio can further improve the charge and discharge efficiency and the cycle service life of the battery.
4) According to the preparation method of the lithium ion battery, further, the material in the carbon-containing conductive coating is graphene; in the step 1), the graphene forms the carbon-containing conductive coating on the surface of the positive electrode current collector through a chemical vapor deposition method to obtain the positive electrode current collector with the carbon-containing conductive coating on the surface; in the step 2), the graphene forms the carbon-containing conductive coating on the surface of the negative electrode current collector through a chemical vapor deposition method, so as to obtain the negative electrode current collector with the carbon-containing conductive coating on the surface. Compared with the existing wet coating technology, the method has the advantages of simple operation, short preparation period and uniform prepared carbon-containing conductive coating.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of a lithium ion battery, which comprises the following steps:
1) Mixing and stirring the positive electrode active material, the conductive agent, the binder, the modified aluminum powder and the solvent at the stirring speed of 40rpm for 3 hours to prepare positive electrode slurry, passing the obtained positive electrode slurry through a 150-mesh screen, coating the positive electrode slurry on aluminum foil with a carbon-containing conductive coating on the surface, and then drying, rolling and cutting to obtain a positive electrode plate; wherein the positive electrode active material is LiNi 0.5Co0.2Mn0.3O2, the conductive agent is conductive carbon black, the binder is polyvinylidene fluoride, the solvent is N-methyl pyrrolidone, and the mass ratio of the positive electrode active material to the conductive agent to the binder to the modified aluminum powder is 96%:2.0%:0.6%:1.0%; the addition amount of the solvent is 20 times of the mass of the binder; the carbon-containing conductive coating is made of graphene, the carbon-containing conductive coating is formed on the surface of the aluminum foil through a chemical vapor deposition method, and the aluminum foil with the carbon-containing conductive coating on the surface is obtained, wherein the thickness of the carbon-containing conductive coating is 22nm;
The preparation method of the modified aluminum powder comprises the following steps: mixing aluminum powder, polyethylene wax and toluene at 120 ℃, drying after mixing to obtain a solid mixed material of the aluminum powder and the polyethylene wax, and crushing the solid mixed material of the aluminum powder and the polyethylene wax to obtain the modified aluminum powder; the mass ratio of the aluminum powder to the polyethylene wax is 100:5; the particle size of the modified aluminum powder obtained after crushing is 30nm;
2) Mixing a negative electrode active material, a conductive agent, a binder and a solvent, stirring at 40rpm for 3 hours to prepare a negative electrode slurry, sieving the obtained negative electrode slurry with a 150-mesh screen, coating the negative electrode slurry on a copper foil with a carbon-containing conductive coating on the surface, and then drying, rolling and slitting to obtain a negative electrode plate; wherein the negative electrode active material is artificial graphite, the conductive agent is conductive carbon black, the binder is sodium carboxymethyl cellulose, the solvent is water, and the mass ratio of the negative electrode active material to the conductive agent to the binder is 92%:2.0%:0.6%; the addition amount of the solvent is 80 times of the mass of the binder; the carbon-containing conductive coating is made of graphene, the carbon-containing conductive coating is formed on the surface of the copper foil through a chemical vapor deposition method, and the copper foil with the carbon-containing conductive coating on the surface is obtained, wherein the thickness of the carbon-containing conductive coating is 23nm;
3) And assembling the positive pole piece, the negative pole piece, a diaphragm (the diaphragm is made of polyethylene surface coated ceramic, average porosity is 47%) and electrolyte (the solvent of the electrolyte is binary mixed solvent of ethylene carbonate and ethyl acetate), lithium salt is LiPF6, and auxiliary agents are ethylene carbonate and fluoroethylene carbonate) into the lithium ion battery.
Example 2
The embodiment provides a preparation method of a lithium ion battery, which comprises the following steps:
1) Mixing and stirring the positive electrode active material, the conductive agent, the binder, the modified aluminum powder and the solvent at the stirring speed of 40rpm for 3 hours to prepare positive electrode slurry, passing the obtained positive electrode slurry through a 150-mesh screen, coating the positive electrode slurry on aluminum foil with a carbon-containing conductive coating on the surface, and then drying, rolling and cutting to obtain a positive electrode plate; wherein the positive electrode active material is LiNi 0.5Co0.2Mn0.3O2, the conductive agent is lamellar graphite, the binder is polyvinylidene fluoride, the solvent is N-methylpyrrolidone, and the mass ratio of the positive electrode active material to the conductive agent to the binder to the modified aluminum powder is 99%:0.6%:2.0%:0.3%; the addition amount of the solvent is 20 times of the mass of the binder; the carbon-containing conductive coating is made of graphene, the carbon-containing conductive coating is formed on the surface of the aluminum foil through a chemical vapor deposition method, and the aluminum foil with the carbon-containing conductive coating on the surface is obtained, wherein the thickness of the carbon-containing conductive coating is 22nm;
the preparation method of the modified aluminum powder comprises the following steps: mixing aluminum powder, polyethylene wax and toluene at 130 ℃, drying after mixing to obtain a solid mixed material of the aluminum powder and the polyethylene wax, and crushing the solid mixed material of the aluminum powder and the polyethylene wax to obtain the modified aluminum powder; the mass ratio of the aluminum powder to the polyethylene wax is 100:17; the particle size of the modified aluminum powder obtained after crushing is 50nm;
2) Mixing a negative electrode active material, a conductive agent, a binder and a solvent, stirring at 40rpm for 3 hours to prepare a negative electrode slurry, sieving the obtained negative electrode slurry with a 150-mesh screen, coating the negative electrode slurry on a copper foil with a carbon-containing conductive coating on the surface, and then drying, rolling and slitting to obtain a negative electrode plate; wherein the negative electrode active material is artificial graphite, the conductive agent is conductive carbon black, the binder is sodium carboxymethyl cellulose, the solvent is water, and the mass ratio of the negative electrode active material to the conductive agent to the binder is 96%:0.6%:2.0%; the addition amount of the solvent is 80 times of the mass of the binder; the carbon-containing conductive coating is made of graphene, the carbon-containing conductive coating is formed on the surface of the copper foil through a chemical vapor deposition method, and the copper foil with the carbon-containing conductive coating on the surface is obtained, wherein the thickness of the carbon-containing conductive coating is 23nm;
3) And assembling the positive pole piece, the negative pole piece, a diaphragm (the diaphragm is made of polyethylene surface coated ceramic, average porosity is 47%) and electrolyte (the solvent of the electrolyte is binary mixed solvent of ethylene carbonate and ethyl acetate), lithium salt is LiPF6, and auxiliary agents are ethylene carbonate and fluoroethylene carbonate) into the lithium ion battery.
Example 3
The embodiment provides a preparation method of a lithium ion battery, which comprises the following steps:
1) Mixing and stirring the positive electrode active material, the conductive agent, the binder, the modified aluminum powder and the solvent at the stirring speed of 40rpm for 3 hours to prepare positive electrode slurry, passing the obtained positive electrode slurry through a 150-mesh screen, coating the positive electrode slurry on aluminum foil with a carbon-containing conductive coating on the surface, and then drying, rolling and cutting to obtain a positive electrode plate; wherein the positive electrode active material is LiNi 0.5Co0.2Mn0.3O2, the conductive agent is conductive carbon black, the binder is polyvinylidene fluoride, the solvent is N-methyl pyrrolidone, and the mass ratio of the positive electrode active material to the conductive agent to the binder to the modified aluminum powder is 98 percent: 0.8%:1.0%:0.6%; the addition amount of the solvent is 20 times of the mass of the binder; the carbon-containing conductive coating is made of graphene, the carbon-containing conductive coating is formed on the surface of the aluminum foil through a chemical vapor deposition method, and the aluminum foil with the carbon-containing conductive coating on the surface is obtained, wherein the thickness of the carbon-containing conductive coating is 22nm;
the preparation method of the modified aluminum powder comprises the following steps: mixing aluminum powder, polyethylene wax and toluene at 120 ℃, drying after mixing to obtain a solid mixed material of the aluminum powder and the polyethylene wax, and crushing the solid mixed material of the aluminum powder and the polyethylene wax to obtain the modified aluminum powder; the mass ratio of the aluminum powder to the polyethylene wax is 100:11; the particle size of the modified aluminum powder obtained after crushing is 40nm;
2) Mixing a negative electrode active material, a conductive agent, a binder and a solvent, stirring at 40rpm for 3 hours to prepare a negative electrode slurry, sieving the obtained negative electrode slurry with a 150-mesh screen, coating the negative electrode slurry on a copper foil with a carbon-containing conductive coating on the surface, and then drying, rolling and slitting to obtain a negative electrode plate; wherein the negative electrode active material is artificial graphite, the conductive agent is conductive carbon black, the binder is sodium carboxymethyl cellulose, the solvent is water, and the mass ratio of the negative electrode active material to the conductive agent to the binder is 95%:0.8%:1.2%; the addition amount of the solvent is 80 times of the mass of the binder; the carbon-containing conductive coating is made of graphene, the carbon-containing conductive coating is formed on the surface of the copper foil through a chemical vapor deposition method, and the copper foil with the carbon-containing conductive coating on the surface is obtained, wherein the thickness of the carbon-containing conductive coating is 23nm;
3) And assembling the positive pole piece, the negative pole piece, a diaphragm (the diaphragm is made of polyethylene surface coated ceramic, average porosity is 47%) and electrolyte (the solvent of the electrolyte is binary mixed solvent of ethylene carbonate and ethyl acetate), lithium salt is LiPF6, and auxiliary agents are ethylene carbonate and fluoroethylene carbonate) into the lithium ion battery.
Example 4
The embodiment provides a preparation method of a lithium ion battery, which comprises the following steps:
1) Mixing and stirring the positive electrode active material, the conductive agent, the binder, the modified aluminum powder and the solvent at the stirring speed of 40rpm for 3 hours to prepare positive electrode slurry, passing the obtained positive electrode slurry through a 150-mesh screen, coating the positive electrode slurry on aluminum foil with a carbon-containing conductive coating on the surface, and then drying, rolling and cutting to obtain a positive electrode plate; wherein the positive electrode active material is LiNi 0.5Co0.2Mn0.3O2, the conductive agent is conductive carbon black, the binder is polyvinylidene fluoride, the solvent is N-methyl pyrrolidone, and the mass ratio of the positive electrode active material to the conductive agent to the binder to the modified aluminum powder is 97%:0.9%:0.8%:0.6%; the addition amount of the solvent is 20 times of the mass of the binder; the carbon-containing conductive coating is made of graphene, the carbon-containing conductive coating is formed on the surface of the aluminum foil through a chemical vapor deposition method, and the aluminum foil with the carbon-containing conductive coating on the surface is obtained, wherein the thickness of the carbon-containing conductive coating is 22nm;
The preparation method of the modified aluminum powder comprises the following steps: mixing aluminum powder, polyethylene wax and toluene at 125 ℃, drying after mixing to obtain a solid mixed material of the aluminum powder and the polyethylene wax, and crushing the solid mixed material of the aluminum powder and the polyethylene wax to obtain the modified aluminum powder; the mass ratio of the aluminum powder to the polyethylene wax is 100:9; the particle size of the modified aluminum powder obtained after crushing is 40nm;
2) Mixing a negative electrode active material, a conductive agent, a binder and a solvent, stirring at 40rpm for 3 hours to prepare a negative electrode slurry, sieving the obtained negative electrode slurry with a 150-mesh screen, coating the negative electrode slurry on a copper foil with a carbon-containing conductive coating on the surface, and then drying, rolling and slitting to obtain a negative electrode plate; wherein the negative electrode active material is artificial graphite, the conductive agent is conductive carbon black, the binder is sodium carboxymethyl cellulose, the solvent is water, and the mass ratio of the negative electrode active material to the conductive agent to the binder is 94%:0.9%:1.2%; the addition amount of the solvent is 80 times of the mass of the binder; the carbon-containing conductive coating is made of graphene, the carbon-containing conductive coating is formed on the surface of the copper foil through a chemical vapor deposition method, and the copper foil with the carbon-containing conductive coating on the surface is obtained, wherein the thickness of the carbon-containing conductive coating is 23nm;
3) And assembling the positive pole piece, the negative pole piece, a diaphragm (the diaphragm is made of polyethylene surface coated ceramic, average porosity is 47%) and electrolyte (the solvent of the electrolyte is binary mixed solvent of ethylene carbonate and ethyl acetate), lithium salt is LiPF6, and auxiliary agents are ethylene carbonate and fluoroethylene carbonate) into the lithium ion battery.
Comparative example 1
The comparative example provides a method for manufacturing a lithium ion battery, which is different from example 3 in that no modified aluminum powder is added in the process of manufacturing the positive electrode sheet.
Comparative example 2
The comparative example provides a method for manufacturing a lithium ion battery, which is different from example 3 in that in the step of manufacturing the modified aluminum powder, the mass ratio of the aluminum powder to the polyethylene wax is 1:2.
Performance test:
Performance tests were performed on the lithium ion batteries obtained in the above examples and comparative examples, in which charge and discharge efficiency=0.5C discharge/0.5C charge by 100%; in the recycling performance test, the recycling times when the battery capacity is reduced to 80% under the 5C discharge rate are respectively measured; the temperature of the cell surface at 10C discharge rate was also measured and the results are shown in table 1.
Table 1 lithium ion battery performance test
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (8)
1. The preparation method of the lithium ion battery is characterized by comprising the following steps:
1) Mixing an anode active material, a conductive agent, a binder, modified aluminum powder and a solvent to prepare anode slurry, coating the anode slurry on an anode current collector with a carbon-containing conductive coating on the surface, and drying, rolling and slitting to obtain an anode sheet; the mass ratio of the positive electrode active material to the conductive agent to the adhesive to the modified aluminum powder is 96-99 percent: 0.6-2.0%:0.6-2.0%:0.3-1.0%;
2) Mixing a negative electrode active material, a conductive agent, a binder and a solvent to prepare a negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector with a carbon-containing conductive coating on the surface, and drying, rolling and slitting to obtain a negative electrode plate; the mass ratio of the anode active material to the conductive agent to the binder is 92-96%:0.6-2.0%:0.6-2.0%;
3) Assembling the positive electrode plate, the negative electrode plate, the diaphragm and the electrolyte into a lithium ion battery;
In the step 1), the preparation method of the modified aluminum powder comprises the following steps: mixing aluminum powder, polyethylene wax and toluene at 120-130 ℃, drying after mixing to obtain a solid mixed material of the aluminum powder and the polyethylene wax, and crushing the solid mixed material of the aluminum powder and the polyethylene wax to obtain the modified aluminum powder;
The mass ratio of the aluminum powder to the polyethylene wax is 100:5-17;
the material in the carbon-containing conductive coating is graphene;
the conductive agent is selected from one or more of conductive carbon black, lamellar graphite, carbon fiber and carbon nano tube.
2. The preparation method according to claim 1, wherein the mass ratio of the aluminum powder to the polyethylene wax is 100:11.
3. The method of claim 1, wherein the modified aluminum powder has a particle size of 30-50nm.
4. The preparation method of claim 1, wherein in step 1), the graphene forms the carbon-containing conductive coating on the surface of the positive electrode current collector by a chemical vapor deposition method to obtain the positive electrode current collector with the carbon-containing conductive coating on the surface;
in the step 2), the graphene forms the carbon-containing conductive coating on the surface of the negative electrode current collector through a chemical vapor deposition method, so as to obtain the negative electrode current collector with the carbon-containing conductive coating on the surface.
5. The preparation method according to claim 1, wherein the binder is one or more selected from polyvinylidene fluoride, styrene-acrylate copolymer, polyacrylonitrile, polyacrylate, sodium carboxymethyl cellulose, polyvinylpyrrolidone, and polyvinyl ether;
the solvent is water or N-methyl pyrrolidone.
6. The method according to claim 1, wherein the positive electrode active material is one or more selected from the group consisting of lithium cobaltate, lithium manganate, lithium nickel cobalt manganate, lithium iron phosphate, lithium nickel cobalt aluminate, lithium nickel cobaltate, and lithium nickelate;
the negative electrode active material is selected from one or more of artificial graphite, natural graphite and silicon carbide.
7. The method of manufacturing according to claim 1, wherein the positive electrode current collector is an aluminum foil and the negative electrode current collector is a copper foil.
8. A lithium ion battery prepared by the preparation method of any one of claims 1-7.
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| CN113381057A (en) * | 2021-06-07 | 2021-09-10 | 芜湖天弋能源科技有限公司 | High-safety lithium ion battery and preparation method thereof |
| CN113964288B (en) * | 2021-10-26 | 2022-06-07 | 深圳市杰曼科技股份有限公司 | Preparation method of fiber membrane and pole piece |
| CN114420891B (en) * | 2021-11-25 | 2023-12-19 | 西安交通大学 | High-voltage lithium ion battery current collector, preparation method and application |
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