CN115466581B - Gummed paper, preparation method of gummed paper and preparation method of lithium ion battery - Google Patents
Gummed paper, preparation method of gummed paper and preparation method of lithium ion battery Download PDFInfo
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- CN115466581B CN115466581B CN202211124310.5A CN202211124310A CN115466581B CN 115466581 B CN115466581 B CN 115466581B CN 202211124310 A CN202211124310 A CN 202211124310A CN 115466581 B CN115466581 B CN 115466581B
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- gummed paper
- pole piece
- mass
- lithium ion
- ion battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 28
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 229920001577 copolymer Polymers 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 239000010410 layer Substances 0.000 claims abstract description 16
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 14
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 4
- 239000012790 adhesive layer Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims description 43
- 239000003292 glue Substances 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 42
- 239000011248 coating agent Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 23
- 229920002125 Sokalan® Polymers 0.000 claims description 22
- 239000004584 polyacrylic acid Substances 0.000 claims description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 238000004804 winding Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 8
- 239000011267 electrode slurry Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002390 adhesive tape Substances 0.000 claims description 3
- 150000003254 radicals Chemical group 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 abstract description 36
- 230000001070 adhesive effect Effects 0.000 abstract description 36
- 239000011888 foil Substances 0.000 abstract description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000004513 sizing Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000013543 active substance Substances 0.000 description 5
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical group CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000283070 Equus zebra Species 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005405 multipole Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The gummed paper comprises: an acrylate copolymer gel layer, and a substrate overlying the acrylate copolymer gel layer; the acrylic copolymer adhesive layer is prepared from the following raw materials: a solvent; an initiator; the monomer is butyl acrylate and vinyl acetate, and the total mass of the monomer accounts for 24-38% of the mass of the solvent. The application aims at the gummed paper for the lithium ion battery pole piece, and uses the specific monomer and the initiator to prepare the pressure-sensitive gummed paper, so that the gummed paper meets the requirements of the adhesive force and the stripping force of the pole piece current collector, and when the gummed paper is used for preparing the pole piece, the gummed paper has good adhesive capacity without damaging the foil, and meanwhile, no residual adhesive is left after stripping, thereby avoiding bad influence on the battery performance.
Description
Technical Field
The application belongs to the technical field of lithium ion batteries, and particularly relates to gummed paper used in a preparation process of a lithium ion battery pole piece, a preparation method of the gummed paper and a preparation method of the lithium ion battery.
Background
The fast charge performance of batteries has become one of the battery performances that consumers are increasingly focusing on. The multipolar ear process is an effective method for reducing the impedance of the battery core and improving the charging speed of the lithium ion battery. Currently, commercial multi-tab lithium ion batteries generally comprise a winding core formed by winding a positive plate, a negative plate and a diaphragm, wherein the positive plate is formed by a current collector and a paste coated on the surface of the current collector, and a plurality of tabs punched by reserved tab areas on the current collector are arranged on the positive plate. After the pole piece is wound into a winding core, a plurality of pole lugs of the positive pole piece are connected, a plurality of pole lugs of the negative pole piece are connected, and the multi-pole lug structure can reduce the internal resistance of the battery and improve the quick charge performance of the battery.
The electrode sheet for the multi-tab structure battery is generally coated with slurry on a current collector by zebra coating, and empty foil areas are reserved at the edges and the middle of the width direction of the current collector for cutting and leading out the tab so as to spot-weld the tab. Due to factors such as uniformity, surface tension and current collector flatness of paste formed by the paste, after coating, the thickness of the edge position of a paste coating area is higher than that of other positions of the paste coating area, so that a thick edge phenomenon is caused, the thick edge can cause the warping degree of a pole piece to be increased in the rolling process, a snake-shaped pole piece is formed, and the pole piece is easily broken.
Aiming at the thick edge phenomenon, the current solution method is to adjust the coating knife pad to thin the edge of the paste coating area so as to ensure that the thickness of the edge position of the paste coating area is consistent with the thickness of other positions of the paste coating area.
The other method is that foaming adhesive paper containing foaming agent is stuck on the welding position of the tab of the current collector, then slurry is coated to prepare a pole piece, the prepared pole piece is heated by a baking oven, and then the foaming adhesive paper is removed by a brush, so as to obtain the pole piece with an empty foil area (tab reserved area) for cutting and leading out the tab. However, the production practice shows that after the foaming adhesive paper is removed, residual adhesive phenomena with different degrees exist on the current collector, the performance of the battery can be influenced, and the foaming adhesive has high process cost and is difficult to be widely applied to the production and preparation of pole pieces.
Disclosure of Invention
The application aims to provide gummed paper for preparing a lithium ion battery pole piece, a preparation method of gummed paper and a preparation method of a lithium ion battery, wherein gummed paper does not have residual gum after being peeled off, and the problem of thinning of the edge of the pole piece can be solved.
In order to achieve the above object, the present application adopts the following technical solutions:
a gummed paper comprising: an acrylate copolymer gel layer, and a substrate overlying the acrylate copolymer gel layer; the acrylic copolymer adhesive layer is prepared from the following raw materials: a solvent; an initiator; the monomer is butyl acrylate and vinyl acetate, and the total mass of the monomer accounts for 24-38% of the mass of the solvent.
The gummed paper as described above, optionally, the monomer further comprises acrylic acid, and the mass of the acrylic acid is 0 to 8% of the total mass of all the monomers.
As described above, the adhesive paper may optionally have a mass of butyl acrylate of 20% to 28% of the mass of the solvent and a mass of vinyl acetate of 4% to 7% of the mass of the solvent.
The adhesive paper is characterized in that the initiator is a free radical initiator, and the amount of the initiator is 0-0.7% of the mass of the solvent.
The adhesive paper is optionally provided with a peeling force of 3-12N/25 mm.
According to the technical scheme, the adhesive paper for the lithium ion battery pole piece is prepared by using the monomer and the initiator with specific types and specific amounts, so that the adhesive paper meets the requirements of adhesive force and stripping force of a pole piece current collector, has the characteristics of easy adhesion and easy tearing, can be adhered to the surface of the current collector by pressing under pressure when being used for preparing the pole piece, has good adhesive capacity, and can not leave residual adhesive after stripping, thereby avoiding bad influence on the battery performance.
The application also provides a preparation method of the gummed paper, which comprises the following steps:
s1, adding a monomer and an initiator into a solvent, stirring, heating to T1 ℃, and preserving heat for Q1;
s2, continuously dropwise adding a monomer into a solvent for Q2, and preserving heat for Q3 at the temperature of T2 ℃ to prepare a mixed solution;
s3, adding a cross-linking agent into the mixed solution, stirring, cooling to obtain polyacrylic acid copolymer glue solution, and preserving for later use; and coating the polyacrylic copolymer glue solution on the surface of an adherend, and covering a substrate on a polyacrylic copolymer glue layer formed by the polyacrylic copolymer glue solution to obtain the gummed paper.
According to the preparation method of the gummed paper, the cross-linking agent is optionally used in an amount of 0-2% of the mass of the mixed solution.
According to the preparation method of the gummed paper, the solid content of the polyacrylic copolymer gum solution is 40% -50% and the viscosity is 400-2000 Pa.s.
In the above-mentioned method for preparing gummed paper, optionally, T1 in step S1 is 80 ℃ and Q1 is 30 minutes; q2 in the step S2 is 3-4 hours, Q3 is 1-2 hours, and T2 is 85 ℃.
According to the technical scheme, the adhesive force (stripping force) of the adhesive paper is adjusted by adopting the specific monomer and the initiator and adjusting the dosage of the monomer and the dosage of the initiator when the adhesive paper is used for preparing the pole piece, so that the adhesive paper has good adhesive capacity and is easy to strip, residual adhesive is not left after stripping, the surface of the current collector is kept clean without cleaning, and the follow-up production is convenient.
The application also provides a preparation method of the lithium ion battery, wherein the lithium ion battery comprises a positive plate, a negative plate and a diaphragm; the preparation method of the gummed paper prepared by the preparation method of the gummed paper in the preparation process of the pole piece comprises the following steps of:
a. preparing a pole piece; coating the polyacrylic acid copolymer glue solution on a pole lug reserved area of a pole piece current collector, and then covering a base material of the glue paper on the polyacrylic acid copolymer glue solution to enable the pole lug reserved area to be stuck with the glue paper; the width of the base material is consistent with the coating width of the polyacrylic copolymer glue solution; respectively coating positive electrode slurry and negative electrode slurry on a pole piece current collector to respectively prepare a positive pole piece and a negative pole piece, wherein the slurry covers part or all of the gummed paper;
b. the positive electrode plate and the negative electrode plate are sent into an oven for baking, then the rolled electrode plate is rolled, and gummed paper is separated from the electrode plate while the rolled electrode plate is rolled;
c. and after the positive plate and the negative plate are respectively cut, sheared and made into tabs, the positive plate, the negative plate and the diaphragm are made into a winding core by adopting a winding process, and then the winding core is packaged, injected with liquid and formed into a volume to prepare the lithium ion battery.
According to the technical scheme, the special pressure-sensitive adhesive paper is applied to the preparation of the pole piece, the adhesive paper is adhered to the reserved area of the pole lug of the current collector when the pole piece is prepared, and then the slurry is coated, so that the problems of thin pole piece edge, small local CB value of the edge of the battery core and poor flatness of the battery core existing in the existing coating process for adjusting the coating knife pad are solved, the conditions of head lithium precipitation and battery core deformation of the battery in the later period of cycle can be avoided, the electrochemical performance of the battery is improved, the coating amount of active substances can be increased to the greatest extent, and the energy density of the lithium ion battery is improved. According to the application, the acrylic ester copolymer glue solution is coated on the reserved area of the tab of the current collector, then the base material is covered, and then the preparation process of the coating slurry is smooth, so that the automatic production can be realized through coating equipment, the method is simple and easy to implement, the coating process capability and the coating productivity are improved, the cost is reduced, and the industrialized popularization is easy to realize.
Drawings
In order to more clearly illustrate the embodiments of the present application, the following description will briefly explain the embodiments or the drawings required for the description of the prior art, it being obvious that the drawings in the following description are only some embodiments of the present application and that other drawings may be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a schematic view of a gummed paper according to an embodiment of the present application;
FIG. 2 is a schematic illustration of an embodiment of the present application with a sticker applied to a current collector;
FIG. 3 is a schematic illustration of an embodiment of the present application with the gummed paper removed from the pole piece;
FIG. 4 is a graph showing the thickness comparison of the pole pieces of example 3 and comparative example of the present application;
fig. 5 is a graph showing the comparison of the edge sizes of the pole pieces of example 3 and comparative example of the present application.
Detailed Description
In describing embodiments of the present application in detail, the drawings showing the structure of the device are not to scale locally for ease of illustration, and the schematic illustrations are merely examples, which should not limit the scope of the application. It should be noted that the drawings are in simplified form and are not to scale precisely, but rather are merely intended to facilitate and clearly illustrate the embodiments of the present application. Meanwhile, in the description of the present application, the terms "first", "second", etc. are used only for distinguishing the description, and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated; the terms "forward," "reverse," "bottom," "upper," "lower," and the like are used for convenience in describing and simplifying the description only, and do not denote or imply that the devices or elements being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the application.
In the description of the present application, it should be noted that, unless explicitly specified and limited otherwise, the terms "connected," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; the two components can be directly connected or indirectly connected through an intermediate medium, or can be communicated inside the two components, or can be connected wirelessly or in a wired way. The specific meaning of the above terms in the present application will be understood in specific cases by those of ordinary skill in the art.
The adhesive paper is pressure sensitive adhesive paper, and the adhesive paper can be adhered to the surface of an adherend by pressurization. The adhesive paper is applied to the preparation of the lithium ion battery pole piece, so that specific requirements on the adhesive force (initial adhesive force and holding adhesive force) and the stripping force of the adhesive paper are met, the current collector (foil) is required to be not damaged, the adhesive paper can be adhered, and meanwhile, residual adhesive is not generated after stripping. Therefore, the application provides the pressure-sensitive gummed paper specially used for preparing the pole piece of the lithium ion battery.
As shown in fig. 1, the gummed paper of the present application comprises a substrate 1 and an acrylate copolymer layer 2, wherein the substrate 1 is covered on the acrylate copolymer layer 2, and the acrylate copolymer layer 2 is formed by coating an acrylate copolymer glue solution on the surface of an adherend. The substrate 1 and the acrylate copolymer layer 2 are equally wide so that the substrate 1 can cover the acrylate copolymer layer 2. The thickness of the gummed paper of the present application may be 12 μm to 50 μm. When in use, the acrylic copolymer layer 2 of the gummed paper is stuck on the surface of a current collector, the current collector can be copper foil or aluminum foil, and the thickness of the copper foil or the aluminum foil is 2-12 mu m.
The substrate 1 of the present application may be any one or more of PP (polypropylene), PET (polyethylene terephthalate), PE (polyethylene) and PU (polyurethane), and PE is preferably used as the substrate.
The polyacrylic copolymer glue solution is prepared from Butyl Acrylate (BA) and vinyl acetate (2-EHA) through polymerization reaction. Preferably, the monomer further comprises Acrylic Acid (AA). In the polyacrylic acid copolymer glue solution, the total mass of all monomers accounts for 24-38% of the mass of the solvent, wherein the mass of butyl acrylate is 20-28% of the mass of the solvent, the mass of vinyl acetate is 4-7% of the mass of the solvent, and the mass of acrylic acid monomers is 0-8% of the total mass of all monomers, preferably 5%.
The preparation method of the polyacrylic acid copolymer glue solution comprises the following steps:
s1, adding a monomer and an initiator into a solvent, stirring, heating to T1 ℃ through free radical polymerization, and preserving heat for Q1; the initiator adopted by the application is a free radical initiator, and the dosage of the initiator is 0-0.7 percent of the mass of the solvent, preferably 0.2 percent; t1 may be 80deg.C and Q1 may be 30min;
s2, continuously dropwise adding a monomer into a solvent for Q2, and preserving heat for Q3 at the temperature of T2 ℃ to prepare a mixed solution; q2 can be 3-4 hours, Q3 can be 1-2 hours, and T2 can be 85 ℃;
s3, adding a cross-linking agent into the mixed solution, stirring, cooling to obtain polyacrylic acid copolymer glue solution, and preserving for later use. The dosage of the cross-linking agent is 0-2% of the mass of the mixed solution. The solid content of the prepared polyacrylic copolymer glue solution can be 40-50%, and the viscosity of the glue solution can be 400-2000 Pa.s. The polyacrylic acid copolymer glue solution is coated on the surface of a current collector (an adherend), and a base material is covered on a polyacrylic acid copolymer glue layer formed by the polyacrylic acid copolymer glue solution to obtain gummed paper, wherein the peeling force of the gummed paper is 3-12N/25 mm. The addition of the cross-linking agent can lead the gummed paper to have no residue on the surface of the current collector after being stripped.
The method for preparing the lithium ion battery by using the gummed paper of the application comprises the following steps:
a. preparing a pole piece; the positive electrode plate is a positive electrode plate and the negative electrode plate, the preparation steps of the positive electrode plate and the negative electrode plate are the same, and the difference is only that the active substances in the slurry are different;
coating the polyacrylic acid copolymer glue solution on a pole lug reserved area of a pole piece current collector, and then covering a base material of glue paper on the polyacrylic acid copolymer glue solution, so that the pole lug reserved area is stuck with the glue paper; the width of the base material is consistent with the coating width of the polyacrylic acid copolymer glue solution, so that the base material is covered on the polyacrylic acid copolymer glue solution, and the glue solution can be prevented from polluting positive sizing agent; the tab reserved area refers to an empty foil area reserved on the current collector and used for cutting and leading out the tab; the current collector covered with gummed paper is shown in fig. 2, and the diagonally filled portions in fig. 2 represent gummed paper; then coating sizing agent on the pole piece current collector, wherein the sizing agent covers part or all of gummed paper; respectively preparing a positive plate and a negative plate by adopting the same method;
b. the positive electrode plate and the negative electrode plate are sent into a baking oven for baking, the baking temperature is 80-150 ℃, the baking is carried out, rolling is carried out, when the rolled electrode plate is rolled, the gummed paper is separated from the electrode plate, the electrode plate after the gummed paper is stripped is shown in a figure 3, and after the gummed paper is removed, the area which is originally covered by the gummed paper is an empty foil area which is not coated with sizing agent;
c. after the positive plate and the negative plate are respectively cut and sheared to manufacture tabs, the positive plate, the negative plate and the diaphragm are manufactured into a winding core with a multi-tab structure by adopting a conventional winding process, and then the lithium ion battery is manufactured after packaging, liquid injection and formation into a volume.
The application is further illustrated by the following examples. The reagents, materials and instruments used in the following description are commercially available as conventional reagents, conventional materials and conventional instruments unless otherwise specified, and the reagents involved can also be synthesized by conventional synthetic methods.
Example 1
The preparation steps of the polyacrylic acid copolymer gum solution of the present example are as follows:
s1, using ethyl acetate (Etac) as a solvent, adding two monomers of butyl acrylate and vinyl acetate and an initiator into the solvent, wherein the dosage of butyl acrylate is 24% of the mass of the solvent, the dosage of vinyl acetate is 5.8% of the mass of the solvent, in the embodiment, an acrylic acid monomer is not used, namely the dosage of the acrylic acid monomer is 0, the initiator is Benzoyl Peroxide (BPO), the dosage of benzoyl peroxide is 0.2% of the mass of the solvent, stirring, heating to 80 ℃ through free radical polymerization under the stirring rotating speed, and preserving heat for 30min;
s2, continuously dropwise adding butyl acrylate and vinyl acetate for 3.5 hours, and preserving heat at 85 ℃ for 1.5 hours to obtain a mixed solution;
s3, adding a cross-linking agent into the mixed solution and stirring, wherein the cross-linking agent is aluminum acetylacetonate, and the use amount of the aluminum acetylacetonate is 0.2% of the mass of the mixed solution; cooling to obtain polyacrylic copolymer glue solution, and storing for later use. The solid content of the polyacrylic copolymer gum solution prepared in the example is 40.8%, and the peel strength of the gum paper to the current collector is 11.1+/-0.41N/25 mm.
The procedure for preparing the lithium ion battery in this example is as follows:
a. preparing a pole piece; coating the prepared polyacrylic acid copolymer glue solution on a reserved area of a tab of a current collector (positive current collector and negative current collector), then covering PE (polyethylene) base materials on the surface of the glue solution, and then coating positive electrode slurry and negative electrode slurry on the positive current collector and the negative current collector respectively, wherein the coating process is the same as that of a conventional coating process, so that a positive electrode plate and a negative electrode plate are prepared; the size and the shape of the gummed paper correspond to those of the prepared battery cell model, and after the sizing agent is coated, the area where the gummed paper is positioned is at least partially or completely covered by the sizing agent;
b. the positive electrode plate and the negative electrode plate coated with the sizing agent are sent into a baking oven to be baked, and are dried at 80-150 ℃; in the process, the adhesiveness of the gummed paper is reduced after being heated, the adhesive force between the gummed paper and the foil (current collector) is reduced, and the stripping force is less than 1g/25mm; rolling and coiling the pole piece after baking, wherein when coiling, the gummed paper is separated from the current collector under the action of a bending acting force and an adhesive tape coiling device (not shown), so that an empty foil area which is not covered by the active material layer is formed on the current collector; operating the other side of the current collector by adopting the same method, wherein symmetrical empty foil areas are formed on the two sides of the current collector;
c. after the positive plate and the negative plate are respectively cut, sheared and made into tabs, the positive plate, the negative plate and the diaphragm are coiled into a coiled core with a multi-tab structure by adopting a conventional coiling process, and then the coiled core is packaged, injected and formed into a volume to prepare the lithium ion battery.
According to the pole piece preparation method, before the coating of the sizing agent, the adhesive paper is stuck to the reserved area of the pole lug, and the adhesive paper is removed after the coating is finished, so that the situation that the thickness of the edge area of the paste coating area is higher than that of other positions of the paste coating area is avoided, the thickness of the edge area of the paste coating area is equivalent to that of other positions of the paste coating area, the problem of pole piece breakage caused by the phenomenon of thick edges can be solved, the problem of head lithium precipitation and the problem of battery core deformation caused by the thinning of the edge thickness of the paste coating area can be avoided, the coating amount of active substances can be increased, the active substances are utilized to the maximum extent, the energy density of the lithium ion battery is improved, and the battery core performance deterioration caused by the problem of the thinning of the edge of the pole piece is avoided.
Example 2
The lithium ion battery of example 2 was prepared in the same manner as in example 1, except that the polyacrylic acid copolymer gum solution was prepared in example 2 and example 1, wherein the monomer used to prepare the polyacrylic acid copolymer gum solution in example 1 did not include an acrylic acid monomer, and wherein an acrylic acid monomer was added in example 2, the polyacrylic acid copolymer gum solution of this example was prepared as follows:
s1, using ethyl acetate as a solvent, adding butyl acrylate, vinyl acetate, acrylic acid and an initiator, wherein the dosage of the butyl acrylate is 24% of the mass of the solvent, the dosage of the vinyl acetate is 5.8% of the mass of the solvent, the dosage of an acrylic acid monomer is 2.2% of the total mass of the monomers, the dosage of benzoyl peroxide as an initiator is 0.2% of the mass of the solvent, stirring, carrying out free radical polymerization at a stirring rotating speed, heating to 80 ℃, and preserving heat for 30min;
s2, continuously dropwise adding butyl acrylate, vinyl acetate and acrylic acid for 3.5 hours, and preserving heat at 85 ℃ for 1.5 hours to obtain a mixed solution;
s3, adding a cross-linking agent into the mixed solution and stirring, wherein the used cross-linking agent is aluminum acetylacetonate, and the consumption of the aluminum acetylacetonate is 0.2% of the mass of the mixed solution; cooling to obtain polyacrylic copolymer glue solution, and storing for later use. The solid content of the polyacrylic copolymer gum solution prepared in the example is 44.3%, and the peel strength of the gum paper to the current collector is 7.96+/-0.33N/25 mm.
By adding the acrylic acid, the stripping strength of the gummed paper to the current collector can be adjusted, so that the gummed paper is suitable for the preparation of the lithium ion battery pole piece, good adhesion of an empty foil area of the current collector can be maintained, separation of the gummed paper and the current collector is facilitated, and no residual adhesive exists after the gummed paper is stripped.
Example 3
The lithium ion battery of example 3 was prepared in the same manner as in example 3 except that the amount of the acrylic acid monomer used in the preparation of the acrylic acid copolymer dope was different, and the amount of the acrylic acid monomer used in this example was 5% of the total mass of the monomers. The solid content of the prepared polyacrylic acid copolymer glue solution is 48.7%, and the peeling strength of the glue paper to a current collector is 5.9+/-0.45N/25 mm. When the amount of acrylic acid is increased, the peeling strength of the gummed paper to the current collector can be reduced.
Comparative example
The comparative example is different from the previous examples in that the pole piece of the present application is prepared by a conventional coating process with a regulated coating blade pad, i.e., no gummed paper is attached to the current collector, and the current collector is coated with the slurry by a conventional zebra coating method. The slurries used were the same as those of the previous examples.
The pole pieces prepared in example 3 and comparative example were subjected to edge dimension detection and energy density testing. As shown in fig. 4, the edge dimension measurement is to measure the thickness of the pole piece from the root of the pole piece to the bottom of the pole piece along the width direction (x-axis direction in fig. 4) of the pole piece using a height gauge. Fig. 5 is a graph comparing thickness data at positions 3mm from the edge of the pole piece, and the height gauge measures the thickness of the region between positions 3mm from the edge of the pole piece in the width direction of the pole piece.
The energy density testing method comprises the following steps: (1) placing the battery for 10min; (2) Constant-current and constant-voltage charging is carried out on the battery for 150min, the voltage limit is 4800mV, and the current is 0.5C and 0.025C; (3) placing the battery for 10min; (4) Constant-current discharge is carried out for 330min, the voltage limit is 3000mV, and the current is 0.2C; (5) placing the battery for 10min. The capacity density (ED) was calculated using the following formula: capacity density = discharge capacity plateau voltage/cell volume, discharge capacity is the measured battery capacity after step 4 discharge.
The results of the edge dimension test and the energy density test are shown in table 1, and the theoretical capacity in table 1 is the actual capacity of the battery, and the measured capacity is the capacity-division discharge capacity of the battery. The CB (cell balance) value is a ratio of the negative electrode capacity and the positive electrode capacity of the battery, i.e., CB value=negative electrode capacity/positive electrode capacity. The negative electrode capacity of the lithium ion battery is greater than the positive electrode capacity.
As can be seen from fig. 4, the pole piece of example 3 has a uniform overall thickness, the pole piece of comparative example has a non-uniform thickness, and the edge on the tab side has a reduced thickness. Meanwhile, as can be seen from fig. 5, the thickness fluctuation of the edge of the pole piece manufactured in example 3 is smaller, while the thickness fluctuation of the edge of the pole piece manufactured in comparative example is larger, and the phenomenon of thinning the edge is caused. The edge thinning phenomenon of the pole piece prepared by the gummed paper of the application is obviously improved, and the thickness of the edge of the pole piece is equivalent to the thickness of other positions of the pole piece, such as the middle of the pole piece.
TABLE 1
| Design capacity | Theoretical capacity | Measured capacity | Measured thinning loss capacity | ED loss | |
| Comparative example | 2095 | 2063 | 2066 | 1.5％ | ↓1.2％ |
| Example 3 | 2095 | 2084 | 2081 | 0.5％ | -- |
As can be seen from the results of table 1, the lithium ion battery of example 3 has an improved capacity of 20mah and an improved ed of about 1.2% over the lithium ion battery of the comparative example. The edge thinning of the pole piece is improved, so that the problems of small local CB value of the edge of the battery cell and poor flatness of the battery cell are solved, the situation that the head is separated out of lithium or the battery cell is deformed in the later period of circulation is avoided, the thickness of the pole piece is uniform, the situation that the edge thickness is thin is avoided, the coating amount of active substances can be increased to the greatest extent, the energy density of the lithium ion battery is improved, and the energy density of the battery is improved.
The above embodiments are only for illustrating the technical aspects of the present application and not for limiting the same, and although the present application has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the specific embodiments of the present application without departing from the spirit and scope of the present application, and any modifications and equivalents are intended to be included in the scope of the present application.
Claims (7)
1. The preparation method of the lithium ion battery comprises a positive plate, a negative plate and a diaphragm; the method is characterized in that: when preparing the pole piece, paste the adhesive tape in the utmost point ear reserve area of current collector, then coating thick liquids, the adhesive tape includes:
an acrylate copolymer gel layer, and a substrate overlying the acrylate copolymer gel layer;
the acrylic copolymer adhesive layer is prepared from the following raw materials:
a solvent;
an initiator;
monomers, wherein the monomers comprise butyl acrylate, vinyl acetate and acrylic acid, the mass of the acrylic acid is 0-8% of the total mass of all monomers, the mass of the butyl acrylate is 20-28% of the mass of the solvent, the mass of the vinyl acetate is 4-7% of the mass of the solvent, the total mass of the monomers accounts for 24-38% of the mass of the solvent, and the amount of the initiator is 0-0.7% of the mass of the solvent;
the stripping force of the gummed paper is 3-12N/25 mm.
2. The method for preparing a lithium ion battery according to claim 1, wherein: the initiator is a free radical initiator.
3. The method for producing a lithium ion battery according to any one of claims 1 to 2, characterized in that: the preparation of the gummed paper comprises the following steps:
s1, adding a monomer and an initiator into a solvent, stirring, heating to T1 ℃, and preserving heat for Q1;
s2, continuously dropwise adding a monomer into a solvent for Q2, and preserving heat for Q3 at the temperature of T2 ℃ to prepare a mixed solution;
s3, adding a cross-linking agent into the mixed solution, stirring, cooling to obtain polyacrylic acid copolymer glue solution, and preserving for later use; and coating the polyacrylic copolymer glue solution on the surface of an adherend, and covering a substrate on a polyacrylic copolymer glue layer formed by the polyacrylic copolymer glue solution to obtain the gummed paper.
4. The method for preparing a lithium ion battery according to claim 3, wherein: the dosage of the cross-linking agent is 0-2% of the mass of the mixed solution.
5. The method for preparing a lithium ion battery according to claim 3, wherein: the solid content of the polyacrylic copolymer glue solution is 40-50%, and the viscosity is 400-2000 Pa.s.
6. The method for preparing a lithium ion battery according to claim 3, wherein: t1 in the step S1 is 80 ℃, and Q1 is 30 minutes; q2 in the step S2 is 3-4 hours, Q3 is 1-2 hours, and T2 is 85 ℃.
7. The method for preparing a lithium ion battery according to claim 3, wherein: the method comprises the following steps:
a. preparing a pole piece; coating the polyacrylic acid copolymer glue solution on a pole lug reserved area of a pole piece current collector, and then covering a base material of the glue paper on the polyacrylic acid copolymer glue solution to enable the pole lug reserved area to be stuck with the glue paper; the width of the base material is consistent with the coating width of the polyacrylic copolymer glue solution; respectively coating positive electrode slurry and negative electrode slurry on a pole piece current collector to respectively prepare a positive pole piece and a negative pole piece, wherein the slurry covers part or all of the gummed paper;
b. the positive electrode plate and the negative electrode plate are sent into an oven for baking, then the rolled electrode plate is rolled, and gummed paper is separated from the electrode plate while the rolled electrode plate is rolled;
c. and after the positive plate and the negative plate are respectively cut, sheared and made into tabs, the positive plate, the negative plate and the diaphragm are made into a winding core by adopting a winding process, and then the winding core is packaged, injected with liquid and formed into a volume to prepare the lithium ion battery.
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| WO2008034295A1 (en) * | 2006-09-19 | 2008-03-27 | Shenzhen Bak Battery Co., Ltd | A lithium ion battery electrode plate,a lithium ion battery electrode core and the preparation method of the same |
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| CN112795321A (en) * | 2020-12-30 | 2021-05-14 | 浙江锂威能源科技有限公司 | Gummed paper for realizing tab slot position, preparation method of pole piece, pole piece and lithium ion battery |
| CN112838189A (en) * | 2019-11-07 | 2021-05-25 | 珠海冠宇电池股份有限公司 | Pole piece for improving heat abuse of high-voltage system of lithium ion battery and preparation method thereof |
| CN115050928A (en) * | 2022-07-01 | 2022-09-13 | 惠州锂威新能源科技有限公司 | Pole piece preparation method, pole piece and battery cell |
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| WO2008034295A1 (en) * | 2006-09-19 | 2008-03-27 | Shenzhen Bak Battery Co., Ltd | A lithium ion battery electrode plate,a lithium ion battery electrode core and the preparation method of the same |
| CN112838189A (en) * | 2019-11-07 | 2021-05-25 | 珠海冠宇电池股份有限公司 | Pole piece for improving heat abuse of high-voltage system of lithium ion battery and preparation method thereof |
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