CN115215962A - Preparation method of binder resin for protecting edge of positive pole piece of lithium battery, binder resin and insulating glue - Google Patents
Preparation method of binder resin for protecting edge of positive pole piece of lithium battery, binder resin and insulating glue Download PDFInfo
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- CN115215962A CN115215962A CN202211119122.3A CN202211119122A CN115215962A CN 115215962 A CN115215962 A CN 115215962A CN 202211119122 A CN202211119122 A CN 202211119122A CN 115215962 A CN115215962 A CN 115215962A
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- Prior art keywords
- mass
- binder resin
- pole piece
- edge
- initiator
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- 239000011230 binding agent Substances 0.000 title claims abstract description 46
- 229920005989 resin Polymers 0.000 title claims abstract description 43
- 239000011347 resin Substances 0.000 title claims abstract description 43
- 239000003292 glue Substances 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 17
- 229910052744 lithium Inorganic materials 0.000 title abstract description 17
- 238000009413 insulation Methods 0.000 claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 14
- 239000004840 adhesive resin Substances 0.000 claims abstract description 5
- 229920006223 adhesive resin Polymers 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000003999 initiator Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 14
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 6
- 230000001502 supplementing effect Effects 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229920000193 polymethacrylate Polymers 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 239000002313 adhesive film Substances 0.000 abstract description 41
- 239000011888 foil Substances 0.000 abstract description 15
- 239000002033 PVDF binder Substances 0.000 abstract description 13
- 239000000428 dust Substances 0.000 abstract description 10
- 238000005520 cutting process Methods 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 7
- 238000005336 cracking Methods 0.000 abstract description 4
- 239000012790 adhesive layer Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 abstract description 3
- 230000001788 irregular Effects 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 description 17
- 239000000853 adhesive Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 229920001897 terpolymer Polymers 0.000 description 10
- 230000014509 gene expression Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- -1 butyl acrylate-acrylonitrile-vinyl acetate Chemical compound 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007761 roller coating Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000004026 adhesive bonding Methods 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- FXBZWPXBAZFWIY-UHFFFAOYSA-N butyl prop-2-enoate;ethenyl acetate Chemical compound CC(=O)OC=C.CCCCOC(=O)C=C FXBZWPXBAZFWIY-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- 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
- C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- 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
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- 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
- C09J133/18—Homopolymers or copolymers of nitriles
- C09J133/20—Homopolymers or copolymers of acrylonitrile
-
- 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the field of lithium ion batteries, in particular to a binder resin for providing insulation protection for the edge of a positive pole piece of a lithium battery, an insulation adhesive film comprising the binder resin and a preparation method of the insulation adhesive film. The adhesive resin and the insulating adhesive film formed by the adhesive resin have good adhesion performance with a positive pole piece, and can avoid the defects of foil burrs generated by the irregular cutting of the edge of the pole piece, dust, flanging and the like generated by the cutting of the edge of the film layer, and the internal short circuit condition of the battery caused by the problems of cracking, peeling and the like of the adhesive layer, thereby influencing the safe use of the lithium battery. Compared with the polyvinylidene fluoride binder in the prior art, the polyvinylidene fluoride binder resin has the advantages of strong binding power, good flexibility and mechanical property, good electrochemical stability, low cost, simple preparation process and popularization value.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a binder resin for providing insulation protection for a lithium battery positive pole piece, an insulation adhesive film comprising the binder resin and a preparation method of the insulation adhesive film.
Background
The lithium ion battery has the advantages of high working voltage, high specific capacity, quick charging, good cycle performance, environmental protection and the like, and is widely applied to various fields. In the production process of the lithium ion battery, a lot of materials need to be cut, and the positive pole piece is one of the materials. In the process of slitting the positive pole piece, the defects of burrs, dust, turned edges and the like are easily generated, and the performance and the safe use of the battery can be seriously influenced. The burrs are thin short wires or sharp and thin metal burrs existing on the cutting edge of the pole piece; the flanging is the phenomenon that the edge of the pole piece is tilted and bent; in the pole piece slitting process, the shearing action can cause powder at the edge of part of the coating to fall off and adhere to the surface of the pole piece, thereby causing pollution; the more defects such as burrs and turnups are generated, the more dust is generated. In addition, the poorer the cohesiveness of the resin in the pole piece, the more dust is generated by slitting; therefore, the adhesion of the coating layer is properly increased, burrs and flanging are reduced, and dust can be reduced. The existence of burrs and dust can break through the diaphragm, so that the self-discharge of the battery is caused, and the qualification rate of the battery is reduced; the burring even causes an internal short circuit of the battery, reducing the safety of the battery. When the battery is used under adverse environmental conditions such as high temperature, the strength of the battery separator is reduced, and burrs and dust are more likely to pierce the separator to cause accidents.
In order to eliminate the pole piece slitting defects and the influence thereof, in addition to a novel slitting technology (such as laser slitting) and field management enhancement (such as addition of a dust removal device), other auxiliary means are also adopted, such as flattening burrs by adopting a roller edge method (CN 101068045A), melting burrs at the edge of a positive pole piece by adopting plasma gas (CN 102694148A), rolling and gluing the edge of the pole piece (JP 2013080629A), coating resin on the free end of the pole piece (JP 2013069527A) and the like. The method is simple and easy to implement by coating the insulating protective adhesive on the edge of the pole piece of the lithium ion battery. Most of the currently used adhesive resins for such insulation protective adhesives are polyvinylidene fluoride (PVDF) binders. PVDF has good thermochemical and electrochemical stability, excellent mechanical properties and excellent processability after being modified. But the adhesive force of PVDF and aluminum foil and other positive current collectors is poor, the problems of cracking, peeling and the like of a coating structure are easy to occur, and certain potential safety hazards exist. PVDF is a crystalline polymer, and the crystallinity is generally about 50%, and this crystallinity causes a large difference in volume shrinkage rate from the current collector, and the active material-containing coating film is easily peeled off from the current collector, causing short circuit and consequently shortening the battery life (CN 108690533A). In addition, the PVDF binder has high cost, and in order to adapt to the rapid development of the lithium battery industry, the development of a substitute product with low cost and excellent comprehensive performance is needed in the field.
Disclosure of Invention
As previously mentioned, there remains a need in the art for an alternative to PVDF binders that are cost effective and have a good balance of properties. The inventor of the invention finds that the butyl acrylate-acrylonitrile-vinyl acetate terpolymer prepared by the method and the monomer ratio has the advantages of butyl acrylate, acrylonitrile and vinyl acetate, and on the basis of the terpolymer, the terpolymer is matched with inorganic filler to be dispersed in an organic solvent, then the inorganic filler is applied to the edge of the surface of the positive pole piece, and an insulating adhesive film is obtained after drying and curing, so that the insulating protection of the edge of the positive pole piece is realized, and the defects of a PVDF (polyvinylidene fluoride) binder are overcome.
Accordingly, in a first aspect, there is provided a method of preparing a binder resin, comprising the steps of:
(1) Under the protection of nitrogen or argon, dissolving 0.02 to 1 part by mass of a dispersing agent in 50 to 55 parts by mass of deionized water in a reaction vessel, and stirring and dispersing for 15 to 30min; wherein the dispersant is selected from sodium polyacrylate or sodium polymethacrylate with a relative molecular mass Mw of 2000 to 20000;
(2) Preparing 30-35 parts by mass of mixed monomer, and adding 1/3-1/2 of mixed monomer into the reaction container; the mixed monomer comprises the following components in percentage by mass (1-4): (1-4): 1 of n-butyl acrylate, acrylonitrile and vinyl acetate;
(3) Dissolving 0.05 to 1.0 mass part of initiator into 10 mass parts of deionized water, and adding 2/5 to 1/2 of initiator into the reaction container; wherein the initiator is selected from potassium persulfate, sodium persulfate or ammonium persulfate;
(4) Heating to 55-70 deg.C, and reacting for 15-45 min;
(5) Adding 0 to 2.0 parts by mass of a cross-linking agent to the remaining mixed monomers, wherein the cross-linking agent is selected from oligomeric polyethylene glycol diacrylate or polyethylene glycol dimethacrylate;
(6) Dropwise adding the rest mixed monomer and the rest initiator into the reaction container within 45-75 min, and carrying out the reaction for 2-5 h;
(7) And (3) supplementing 0 to 1 mass part of initiator, and carrying out the reaction for 30 to 120min.
In a second aspect, there is provided a binder resin prepared by the method of the first aspect.
In a third aspect, there is provided an insulating paste prepared from a dispersion comprising:
-a binder resin prepared by the method of the first aspect;
-an inorganic powder filler selected from silica, titania, alumina, zirconia, or combinations thereof; and
-an organic solvent selected from N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone;
the adhesive resin, the inorganic powder filler and the organic solvent are in a mass ratio of (1-4): (1-3): (4-5).
In a fourth aspect, a method for providing insulation protection for the edge of a positive electrode plate of a lithium ion battery is provided, which comprises coating the insulation adhesive of the third aspect on the edge of the positive electrode plate, and curing at a temperature of 80 ℃ to 150 ℃ to form an insulation adhesive film.
The invention has the advantages that:
(1) The binder resin provided by the invention combines the advantages of the n-butyl acrylate chain segment, the acrylonitrile chain segment and the vinyl acetate chain segment, not only provides good ductility and processability for an insulating adhesive film, but also has enhanced mechanical strength and cohesiveness, and has good electrochemical stability.
(2) The binder resin can be well matched with a coating process of a lithium ion battery positive pole piece for gluing, and the existing pole piece manufacturing process does not need to be adjusted.
(3) The insulating adhesive film prepared from the binder resin has good flexibility and good adhesion performance with a pole piece, and various problems existing in the use of the existing PVDF binder are solved. For example, the problem of degumming with a base material aluminum foil due to poor adhesion can be avoided, and the problem that the safe use of the lithium battery is influenced due to the short circuit condition inside the battery caused by the defects of foil burrs generated by the uneven cutting of the edge of a pole piece, dust, flanging and the like generated by the cutting of the edge of a film layer, the cracking, peeling and the like of the adhesive layer can also be avoided.
(4) The preparation process of the invention is simple, low in cost and environment-friendly. The adhesive is prepared by adopting a dispersion suspension polymerization mode, the dispersing agent adsorbed on the product is less, the product is easy to elute and remove, emulsion breaking is not needed, and the production cost is low. The used raw materials are cheap and easy to obtain, the solvent is deionized water, the process is simple, and the existing production equipment does not need to be modified to a large extent; the produced wastewater can be treated by a method well known in the field, such as a Fenton method, can meet the primary discharge standard of the petrochemical industry, and cannot cause pollution to the environment.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to examples. It is to be understood that the following description is intended to illustrate the invention by way of example only and is not intended to limit the scope of the invention, which is defined by the appended claims. Also, it is understood by those skilled in the art that modifications may be made to the technical aspects of the present invention without departing from the spirit and gist of the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Where numerical ranges are provided, such as concentration ranges, percentage ranges, or ratio ranges, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range is encompassed within the subject matter. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and such embodiments are also encompassed within the subject matter, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the subject matter.
In the context of the present invention, many embodiments use the expressions "comprise", "include" or "consist essentially/essentially of \8230;. The expressions "comprising", "including" or "consisting essentially of/essentially of 8230 \8230; …" in general terms can be understood as open-ended expressions that encompass not only the elements, components, assemblies, method steps, etc. specifically listed after the expression, but also other elements, components, assemblies, method steps. In addition, in this document, the expressions "comprising", "including" or "consisting essentially of/8230 \8230; \8230composition" may in some cases also be understood as a closed expression, meaning that each element, component, assembly, method step specifically listed after the expression is included only, without any other element, component, assembly, method step. At this time, the expression is equivalent to the expression "consisting of 8230 \8230;.
For a better understanding of the present teachings and without limiting the scope of the present teachings, unless otherwise indicated, all numbers expressing quantities, percentages, or proportions, and other numerical values used in the specification and claims are to be understood as being modified in all instances by the term "about. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Accordingly, in a first aspect, there is provided a method of preparing a binder resin, comprising the steps of:
(1) Under the protection of nitrogen or argon, dissolving 0.02 to 1 part by mass of a dispersing agent in 50 to 55 parts by mass of deionized water in a reaction vessel, and stirring and dispersing for 15 to 30min; wherein the dispersant is selected from sodium polyacrylates or sodium polymethacrylates having a relative molecular mass Mw of 2000 to 20000;
(2) Preparing 30-35 parts by mass of mixed monomer, and adding 1/3-1/2 of mixed monomer into the reaction container; the mixed monomer comprises the following components in percentage by mass (1-4): (1-4): 1 of n-butyl acrylate, acrylonitrile and vinyl acetate;
(3) Dissolving 0.05 to 1.0 mass part of initiator into 10 mass parts of deionized water, and adding 2/5 to 1/2 of initiator into the reaction container; wherein the initiator is selected from potassium persulfate, sodium persulfate or ammonium persulfate;
(4) Heating to 55-70 deg.C, and reacting for 15-45 min;
(5) Adding 0 to 2.0 parts by mass of a cross-linking agent to the remaining mixed monomer, wherein the cross-linking agent is selected from oligomeric polyethylene glycol diacrylate or polyethylene glycol dimethacrylate;
(6) Dropwise adding the rest mixed monomer and the rest initiator into the reaction container within 45-75 min, and carrying out the reaction for 2-5 h;
(7) And (3) supplementing 0 to 1 mass part of initiator, and carrying out the reaction for 30 to 120min.
In the context of the present invention, "oligomeric" means polymers composed of a relatively small number of repeating units, for example from 10 to 20 repeating units, and generally having a molecular weight of not more than 1 ten thousand.
In a more specific embodiment, the oligomeric polyethylene glycol diacrylate or polyethylene glycol dimethacrylate may be selected from PEG200DA, PEG400DA, PEG200DMA, or PEG400DMA.
In yet another specific embodiment, the method further comprises filtering, washing and drying at 50 to 80 ℃ for 12 to 36 hours after the reaction is finished to obtain the binder resin in a white powder shape.
In a second aspect, there is provided a binder resin prepared by the method of the first aspect.
The binder resin prepared according to the process of the present invention is an n-butyl acrylate-acrylonitrile-vinyl acetate terpolymer. The invention selects the mass ratio of each monomer of the terpolymer and combines the method of the first aspect to prepare the terpolymer which has the advantages of n-butyl acrylate chain segment, acrylonitrile chain segment and vinyl acetate chain segment. Compared with the polyvinylidene fluoride adhesive commonly used for the electrode pole piece of the lithium battery in the prior art, the adhesive provided by the invention has the advantages of strong adhesive force, good electrochemical stability, good mechanical property, low cost and simple preparation process.
Particularly, in the terpolymer, the n-butyl acrylate chain segment has good flexibility and good adhesive force with a base material aluminum foil, provides good ductility for an adhesive film, enhances the adhesive property between the adhesive film and a pole piece, and avoids the problem that the PVDF adhesive is degummed from the base material aluminum foil due to poor adhesive force. The acrylonitrile chain segment has good electrochemical and thermodynamic stability, excellent mechanical stability and film forming property, provides good processability for the polymer, and can reduce the brittleness and increase the mechanical strength of the polymer by introducing the acrylonitrile structural unit. The vinyl acetate chain segment has good dispersibility with the inorganic filler, provides better adhesive property and mechanical strength for the adhesive film, and increases the adhesive property with the base material aluminum foil. The cross-linking agent is introduced to cross-link the polymer to a certain degree, so that the structural strength of the insulating adhesive film prepared from the binder resin can be further enhanced.
In a third aspect, there is provided an insulating glue prepared from a dispersion comprising:
-a binder resin prepared by the method of the first aspect;
-an inorganic powder filler selected from silica, titania, alumina, zirconia, or combinations thereof; and
-an organic solvent selected from N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone;
wherein the mass ratio of the binder resin to the inorganic powder filler to the organic solvent is (1-4): (1-3): (4-5).
In a specific embodiment, the inorganic powder filler has a particle size of 0.05 μm to 20 μm.
As mentioned above, the butyl acrylate-acrylonitrile-vinyl acetate terpolymer prepared by the method and the monomer ratio of the invention has the advantages of butyl acrylate, acrylonitrile and vinyl acetate, and on the basis of the butyl acrylate-acrylonitrile-vinyl acetate terpolymer, a certain proportion of inorganic filler is matched and dispersed in an organic solvent, and the butyl acrylate-acrylonitrile-vinyl acetate terpolymer is coated on the edge of the surface of the positive pole piece in a brushing, scraping, rolling and other modes, and an insulating adhesive film is obtained after drying and curing, so that the insulating protection of the edge of the positive pole piece is realized.
In a fourth aspect, a method for providing insulation protection for the edge of a positive electrode plate of a lithium ion battery is provided, which comprises coating the insulation adhesive of the third aspect on the edge of the positive electrode plate, and curing at a temperature of 80 ℃ to 150 ℃ to form an insulation adhesive film.
In a specific embodiment, the coating can be performed by means well known to those skilled in the art, such as brushing, knife coating, roller coating, and the like, without limitation.
In yet another specific embodiment, the thickness of the insulating adhesive film is 15 μm to 45 μm.
The insulating adhesive film has good flexibility and good adhesion performance with a pole piece, and can avoid the defects of foil burrs caused by uneven cutting of the edge of the pole piece, dust, flanging and the like caused by cutting of the edge of a film layer, and the influence on the safe use of a lithium battery caused by the short circuit condition in the battery caused by the problems of cracking, peeling and the like of the adhesive layer.
Examples
In the following examples, the preparation method of the insulating adhesive film of the present invention and the characterization of the relevant properties are shown. Unless otherwise specified, the test methods employed therein were all conventional methods, and, unless otherwise specified, the test materials used in the following examples were all purchased from a conventional reagent store. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It should be noted that the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The foregoing summary of the invention, as well as the following detailed description, is intended to be illustrative of the invention only and is not intended to be in any way limiting. The scope of the invention is to be determined by the appended claims without departing from the spirit and scope of the invention.
Example 1
In this embodiment, the preparation process of the insulating adhesive film for providing insulating protection to the edge of the positive electrode plate of the lithium ion battery is as follows:
(1) Preparation of binder resin: under the protection of nitrogen, 1 part by mass of sodium polyacrylate is taken in a reaction vessel and dissolved in 55 parts by mass of deionized water, and stirring and dispersing are carried out for 15 min; preparing 35 parts by mass of mixed monomers (wherein the mass ratio of n-butyl acrylate, acrylonitrile and vinyl acetate is 1; dissolving 1.0 part by mass of potassium persulfate in 10 parts by mass of deionized water to prepare an initiator solution, adding two fifths of the total amount of the initiator solution into a reaction vessel, and heating to 55 ℃ for reaction; after reacting for 45min, respectively dropwise adding the rest mixed monomer and the rest initiator, after finishing dropwise adding within 45min, maintaining the reaction for 5h, and continuing to react for 30min under the condition of not supplementing the initiator; filtering, washing with water for three times, and drying at 50 deg.C for 36 hr to obtain white powder.
(2) Preparing an insulating adhesive film: taking the binder powder obtained in the step (1), and mixing the binder powder with powder silicon oxide and N, N-dimethylformamide according to a ratio of 4:1:5, after being dispersed uniformly in a mass ratio, the coating is coated on an aluminum foil at the edge of the positive pole piece of the lithium battery, and is cured into an insulating adhesive film with the thickness of 45 mu m at the temperature of 80 ℃.
Example 2
In this embodiment, the preparation process of the insulating adhesive film for providing insulating protection to the edge of the positive electrode plate of the lithium ion battery is as follows:
(1) Preparation of binder resin: under the protection of argon, 0.02 part by mass of sodium polymethacrylate is taken in a reaction container and dissolved in 50 parts by mass of deionized water, and the mixture is stirred and dispersed for 30min; preparing 30 parts by mass of mixed monomers (wherein the mass ratio of n-butyl acrylate, acrylonitrile and vinyl acetate is 2: 4); dissolving 0.05 parts by mass of sodium persulfate in 10 parts by mass of deionized water to prepare an initiator solution, adding two fifths of the initiator solution into a reaction vessel, and heating to 70 ℃ for reaction; after reacting for 15min, respectively dropwise adding the rest mixed monomer and the rest initiator, after finishing dropwise adding within 75min, maintaining the reaction for 2h, and then continuing to react for 120min after supplementing 0.5 part by mass of sodium persulfate (which is also dissolved in deionized water); filtering, washing with water for three times, and drying at 80 deg.C for 12 hr to obtain white powder.
(2) Preparing an insulating adhesive film: taking the binder powder obtained in the step (1), powdery titanium oxide and N, N-dimethylacetamide according to the weight ratio of 3:3:4, then blade-coating the mixture on an aluminum foil at the edge of the lithium battery positive pole piece, and curing the mixture into an insulating adhesive film with the thickness of 15 mu m at 150 ℃.
Example 3
In this embodiment, the preparation process of the insulating adhesive film for providing insulating protection to the edge of the positive electrode plate of the lithium ion battery is as follows:
(1) Preparation of binder resin: under the protection of argon, 0.1 part by mass of sodium polyacrylate is taken from a reaction vessel and dissolved in 52 parts by mass of deionized water, and stirring and dispersing are carried out for 20min; preparing 33 parts by mass of mixed monomers (wherein the mass ratio of n-butyl acrylate, acrylonitrile and vinyl acetate is 2.5; dissolving 0.1 part by mass of ammonium persulfate in 10 parts by mass of deionized water to prepare an initiator solution, adding two fifths of the initiator solution into a reaction container, and heating to 60 ℃ for reaction; after reacting for 25min, respectively dropwise adding the rest mixed monomer and the rest initiator, after dropwise adding within 55min, maintaining the reaction for 4h, and then continuing to react for 100min after adding 0.3 mass part of initiator (which is also dissolved in deionized water); filtering, washing with water for three times, and drying at 70 deg.C for 18 hr to obtain white powder;
(2) Preparing an insulating adhesive film: taking the binder powder obtained in the step (1), powdery zirconium oxide and N-methyl pyrrolidone, and mixing the binder powder, the powdery zirconium oxide and the N-methyl pyrrolidone according to the weight ratio of 2:3:5, roller coating the mixture on an aluminum foil at the edge of the positive pole piece of the lithium battery after the mixture is uniformly dispersed in a mass ratio, and curing the mixture at 100 ℃ to form an insulating adhesive film with the thickness of 30 mu m.
Example 4
In this embodiment, the preparation process of the insulating adhesive film for providing insulating protection to the edge of the positive electrode plate of the lithium ion battery is as follows:
(1) Preparation of binder resin: under the protection of nitrogen, 0.5 part by mass of sodium polymethacrylate is taken out from a reaction vessel and dissolved in 54 parts by mass of deionized water, and stirring and dispersing are carried out for 25min; preparing 32 parts by mass of mixed monomers (wherein the mass ratio of n-butyl acrylate, acrylonitrile and vinyl acetate is 4; adding 0.5 part by mass of potassium persulfate into 10 parts by mass of deionized water to prepare an initiator solution, adding two fifths of the initiator solution into a reaction vessel, and heating to 65 ℃ for reaction; after reacting for 30min, respectively dropwise adding the rest mixed monomer and the rest initiator, maintaining the reaction for 3h after the dropwise adding is finished within 70min, and continuously reacting for 50min after 0.7 mass part of potassium persulfate (dissolved in deionized water in the same way) is added; filtering, washing with water for three times, and drying at 60 deg.C for 24 hr to obtain white powder;
(2) Preparing an insulating adhesive film: taking the binder powder obtained in the step (1), alumina powder and N, N-dimethylformamide powder according to the ratio of 3:2:5, roller coating the mixture on an aluminum foil at the edge of the positive pole piece of the lithium battery after the mixture is uniformly dispersed in a mass ratio, and curing the mixture at 120 ℃ to form an insulating adhesive film with the thickness of 25 mu m.
Example 5
In this embodiment, the preparation process of the insulating adhesive film for providing insulating protection to the edge of the positive electrode plate of the lithium ion battery is as follows:
(1) Preparation of binder resin: under the protection of nitrogen, 0.7 part by mass of sodium polyacrylate is taken in a reaction container and dissolved in 53 parts by mass of deionized water, and stirring and dispersing are carried out for 24min; preparing 34 parts by mass of mixed monomers (wherein the mass ratio of n-butyl acrylate, acrylonitrile and vinyl acetate is 2: 3); dissolving 0.3 part by mass of sodium persulfate in 10 parts by mass of deionized water to prepare an initiator solution, adding two fifths of the initiator solution into a reaction vessel, and heating to 50 ℃ for reaction; after reacting for 40min, respectively dropwise adding the rest mixed monomer and the rest initiator, after finishing dropwise adding within 65min, maintaining the reaction for 5h, and then continuing to react for 45min after supplementing 1 part by mass of sodium persulfate (which is also dissolved in deionized water); filtering, washing with water for three times, and drying at 70 deg.C for 16 hr to obtain white powder;
(2) Preparing an insulating adhesive film: taking the binder powder obtained in the step (1), powdery silicon oxide and N, N-dimethylacetamide according to the weight ratio of 4:1:5, then blade-coating the mixture on an aluminum foil at the edge of the positive pole piece of the lithium battery, and curing the mixture at 140 ℃ to form an insulating adhesive film with the thickness of 20 mu m.
Comparative example 1:
the preparation process of the insulating glue for protecting the edge of the positive pole piece of the lithium battery comprises the following steps:
(1) Preparation of binder resin: under the protection of nitrogen, 0.7 part by mass of sodium polyacrylate is taken in a reaction vessel and dissolved in 53 parts of deionized water, and stirring and dispersing are carried out for 24min; preparing 34 parts by mass of mixed monomers (the mass ratio of n-butyl acrylate to vinyl acetate is 1; preparing 0.3 part by mass of aqueous solution of sodium persulfate (in 10 parts by mass of deionized water), adding two fifths of the total amount of the initiator solution into a reaction vessel, and heating to 70 ℃ for reaction; after reacting for 40min, respectively dropwise adding the rest mixed monomer and the rest initiator, finishing dropwise adding within 65min, maintaining the reaction for 5h, adding 1 part by mass of sodium persulfate, and continuing to react for 45min; filtering, washing with water for three times, and drying at 70 deg.C for 16 hr to obtain white powder;
(2) Preparing an insulating adhesive film: taking the resin powder obtained in the step (1) and powdery silicon oxide and N, N-dimethylacetamide according to the weight ratio of 4:1:5, then blade-coating the mixture on an aluminum foil at the edge of the positive pole piece of the lithium battery, and curing the mixture at 140 ℃ to form an adhesive film with the thickness of 25 mu m.
Example 6: characterization of Binder resin and insulating adhesive films
In this example, the binder resin and the insulating adhesive film prepared in examples 1 to 5 and comparative example 1 were subjected to a performance test.
The test method is as follows:
(1) 7% viscosity: polymer (i.e., binder resin) powders were dissolved in the organic solvents in each example, respectively, to prepare polymer solutions having a solid content of 7%, and the viscosity was measured using a rotational viscometer (room temperature, rotation speed 12 rpm, duration 6 min).
(2) 180 ° peel strength: the substrates were aluminum sheets and aluminum foils and tested by a universal material tester (tensile rate 50 mm/min, pre-tensile length 5 mm).
(3) Electrolyte resistance: the electrolyte is a solution which is dissolved in a ternary solvent (the mass ratio of ethylene carbonate, dimethyl carbonate and diethyl carbonate is 1. After the bonding resin is cured into a dry film, the dry film is soaked in the selected electrolyte for 24 hours at 85 ℃, and the swelling degree of the adhesive film is observed.
(4) Anode decomposition voltage: the electrochemical stability of the resin binder was characterized by the anodic decomposition voltage. And (3) carrying out linear potential scanning on the glue film soaked with the electrolyte in the step (3), wherein the scanning speed is 0.2mV/s, scanning is carried out from open circuit voltage to 6V, and the change of current along with the voltage is recorded. The working electrode is a static mercury electrode, and the auxiliary electrode and the reference electrode are metal lithium. The current-voltage curve is plotted and the voltage at the inflection point is taken as the anode split voltage.
(5) Mechanical strength: the mechanical strength of the bonded resin specimen was measured by a servo-controlled tensile tester (tensile rate 100mm/min, the specimen is a dumbbell-shaped specimen prepared from powder resin).
(6) Stability of the dispersion: the dispersion was prepared according to the formulation of the insulating paste of each example. After standing for 24 hours, touching the bottom of the container with a paint mixing knife to pick up the dispersion, and observing the stability of the dispersion with naked eyes.
(7) Volume resistivity: preparing a sample by using the dry film of the insulating adhesive of each embodiment, testing resistance by using a resistivity tester, and then testing the resistance according to a formula
Volume resistivity = resistance of sample x area of electrode ÷ distance between electrodes
The volume resistivity of each sample was calculated.
The test results are shown in Table 1.
Table 1: properties of adhesive and insulating adhesive film prepared in examples 1 to 5 and comparative example 1
As can be seen from table 1, the binder resin and the insulating adhesive film of the present invention exhibit more excellent properties in electrolyte resistance, electrochemical stability, mechanical strength, volume resistivity, and the like, as compared to the binder and the insulating adhesive film formed of n-butyl acrylate-vinyl acetate binary copolymer, which are outside the scope of the present invention.
Claims (8)
1. A method for preparing a binder resin, comprising the steps of:
(1) Under the protection of nitrogen or argon, dissolving 0.02 to 1 part by mass of a dispersing agent in 50 to 55 parts by mass of deionized water in a reaction vessel, and stirring and dispersing for 15 to 30min; wherein the dispersant is selected from sodium polyacrylate or sodium polymethacrylate with a relative molecular mass Mw of 2000 to 20000;
(2) Preparing 30-35 parts by mass of mixed monomer, and adding 1/3-1/2 of mixed monomer into the reaction container; the mixed monomer comprises the following components in percentage by mass (1-4): (1-4): 1 of n-butyl acrylate, acrylonitrile and vinyl acetate;
(3) Dissolving 0.05 to 1.0 mass part of initiator into 10 mass parts of deionized water, and adding 2/5 to 1/2 of initiator into the reaction container; wherein the initiator is selected from potassium persulfate, sodium persulfate or ammonium persulfate;
(4) Heating to 55-70 deg.C, and reacting for 15-45 min;
(5) Adding 0 to 2.0 parts by mass of a cross-linking agent to the remaining mixed monomers, wherein the cross-linking agent is selected from oligomeric polyethylene glycol diacrylate or polyethylene glycol dimethacrylate;
(6) Dropwise adding the rest mixed monomer and the rest initiator into the reaction container within 45-75 min, and carrying out the reaction for 2-5 h;
(7) And (3) supplementing 0 to 1 mass part of initiator, and carrying out the reaction for 30 to 120min.
2. The method of claim 1, further comprising filtering, washing, and drying at 50 ℃ to 80 ℃ for 12h to 36h after the reaction is completed to obtain the binder resin in a white powder form.
3. The method of claim 1 or 2, wherein the cross-linking agent is selected from PEG200DA, PEG400DA, PEG200DMA, or PEG400DMA.
4. A binder resin prepared by the method of any one of claims 1-3.
5. An insulating glue prepared from a dispersion comprising:
-a binder resin prepared by the method of any one of claims 1 to 3;
-an inorganic powder filler selected from silica, titania, alumina, zirconia, or combinations thereof; and
-an organic solvent selected from N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone;
the adhesive resin, the inorganic powder filler and the organic solvent are in a mass ratio of (1-4): (1-3): (4-5).
6. The insulation paste according to claim 5, wherein the inorganic powder filler has a particle size of 0.05 to 20 μm.
7. A method for providing insulation protection for the edge of a positive pole piece of a lithium ion battery, which comprises the steps of coating the insulating glue of claim 5 or 6 on the edge of the positive pole piece, and curing the insulating glue at a temperature of 80-150 ℃ to form an insulating glue film.
8. The method of claim 7, wherein the thickness of the insulating glue film is 15 μm to 45 μm.
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