CN111572135A - Aluminum-plastic film for lithium battery packaging and preparation method thereof - Google Patents
Aluminum-plastic film for lithium battery packaging and preparation method thereof Download PDFInfo
- Publication number
- CN111572135A CN111572135A CN202010261344.3A CN202010261344A CN111572135A CN 111572135 A CN111572135 A CN 111572135A CN 202010261344 A CN202010261344 A CN 202010261344A CN 111572135 A CN111572135 A CN 111572135A
- Authority
- CN
- China
- Prior art keywords
- aluminum
- plastic film
- layer
- mixture
- antioxidant
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- 239000002985 plastic film Substances 0.000 title claims abstract description 118
- 229920006255 plastic film Polymers 0.000 title claims abstract description 118
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- 238000004806 packaging method and process Methods 0.000 title abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000010410 layer Substances 0.000 claims abstract description 154
- 229920000098 polyolefin Polymers 0.000 claims abstract description 134
- 230000001070 adhesive effect Effects 0.000 claims abstract description 129
- 239000000853 adhesive Substances 0.000 claims abstract description 127
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 119
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 118
- 239000011888 foil Substances 0.000 claims abstract description 96
- -1 polypropylene Polymers 0.000 claims abstract description 85
- 239000003822 epoxy resin Substances 0.000 claims abstract description 83
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 83
- 239000004743 Polypropylene Substances 0.000 claims abstract description 71
- 229920001155 polypropylene Polymers 0.000 claims abstract description 71
- 239000012793 heat-sealing layer Substances 0.000 claims abstract description 66
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 57
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 56
- 229920002635 polyurethane Polymers 0.000 claims abstract description 55
- 239000004814 polyurethane Substances 0.000 claims abstract description 55
- 229920006306 polyurethane fiber Polymers 0.000 claims abstract description 51
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 24
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 14
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 116
- 238000003756 stirring Methods 0.000 claims description 90
- 238000010438 heat treatment Methods 0.000 claims description 66
- 239000012790 adhesive layer Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 27
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 26
- 238000000465 moulding Methods 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 229920000877 Melamine resin Polymers 0.000 claims description 24
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 24
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 21
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910021389 graphene Inorganic materials 0.000 claims description 16
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 claims description 14
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 claims description 13
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 13
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 13
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 12
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 12
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 12
- 229940117955 isoamyl acetate Drugs 0.000 claims description 12
- 239000012188 paraffin wax Substances 0.000 claims description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 12
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 12
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- 238000005538 encapsulation Methods 0.000 claims 9
- 239000012528 membrane Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 21
- 238000005260 corrosion Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 21
- 230000002265 prevention Effects 0.000 abstract description 18
- 230000004888 barrier function Effects 0.000 abstract description 12
- 238000007789 sealing Methods 0.000 abstract description 9
- 239000005022 packaging material Substances 0.000 abstract description 4
- 238000001723 curing Methods 0.000 description 46
- 238000004080 punching Methods 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000013035 low temperature curing Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000005653 Brownian motion process Effects 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0292—Polyurethane fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7246—Water vapor barrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/752—Corrosion inhibitor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the technical field of lithium battery packaging soft packaging materials, in particular to an aluminum plastic film for lithium battery packaging and a preparation method thereof, the aluminum plastic film comprises a polyurethane fiber layer, an aluminum foil layer and a polypropylene heat sealing layer from top to bottom, the aluminum foil layer is attached to the polypropylene heat sealing layer, polyurethane fibers are attached to the aluminum foil layer, the polyurethane fiber layer and the aluminum foil layer are attached through a modified polyolefin adhesive, the aluminum foil layer and the polypropylene heat sealing layer are attached through a polyurethane adhesive, and the modified polyolefin adhesive comprises the following raw materials in parts by weight: 1-5 parts of alpha-methyl styrene dimer, 1-3 parts of dibenzoyl peroxide, 15-25 parts of modified epoxy resin, 20-30 parts of polyolefin, 1-5 parts of curing agent, 0.5-3 parts of antioxidant, 1-3 parts of defoaming agent, 1-5 parts of crosslinking agent and 20-40 parts of solvent. The aluminum-plastic film disclosed by the invention has excellent barrier property, extensibility and corrosion resistance, and also has a good heat-sealing collosol aluminum leakage prevention effect.
Description
Technical Field
The invention relates to the technical field of lithium battery packaging soft packaging materials, in particular to an aluminum plastic film for lithium battery packaging and a preparation method thereof.
Background
In recent years, the application amount of the soft package lithium battery is increased rapidly due to the rapid development of new energy industries. The soft package lithium battery packaged by the aluminum plastic film has the characteristics of flexible shape, good safety performance and high energy density, and greatly improves the flexibility and the applicability of battery design, thereby being capable of matching with the product requirements to be made into batteries with various shapes and capacities and providing higher design flexibility and adaptability for developers on power supply solutions. At present, soft package lithium batteries are mainly used for mainstream digital products and electric vehicles, but a common aluminum plastic film cannot meet the performance requirement of a polymer lithium battery packaging material, and the packaging material of the polymer lithium battery is generally required to have extremely high barrier property, good cold stamping formability, puncture resistance, electrolyte resistance stability, insulating heat sealing performance and the like.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the aluminum-plastic film for lithium battery packaging, which has excellent barrier property, extensibility and corrosion resistance, and also has good heat-sealing sol-phase aluminum leakage prevention effect.
The invention also aims to provide a preparation method of the aluminum-plastic film for lithium battery packaging, which adopts a high-low temperature curing process to make the prepared aluminum-plastic film overcome the problems of poor white line, poor sol property and low peeling force after the aluminum-plastic film is subjected to shell punching and prepared by constant-temperature curing and molding at the low temperature of 40 ℃.
The purpose of the invention is realized by the following technical scheme: an aluminum-plastic film for packaging a lithium battery comprises a polyurethane fiber layer, an aluminum foil layer and a polypropylene heat-sealing layer from top to bottom, wherein the aluminum foil layer is attached to the upper surface of the polypropylene heat-sealing layer, polyurethane fibers are attached to the upper surface of the aluminum foil layer, the polyurethane fiber layer is attached to the aluminum foil layer through a modified polyolefin adhesive, the aluminum foil layer is attached to the polypropylene heat-sealing layer through a polyurethane adhesive, and the polyurethane adhesive is a German Weishi corner-group adhesive COSMOPUR 818C German Weishi polyurethane adhesive; the modified polyolefin adhesive comprises the following raw materials in parts by weight:
the polyolefin is POE 8180 American Dow polyolefin.
The aluminum-plastic film is prepared from a polyurethane fiber layer, an aluminum foil layer and a polypropylene heat-sealing layer which are sequentially laminated from top to bottom, the polyurethane fiber layer and the aluminum foil layer are limited to be laminated through a modified polyolefin adhesive, and the aluminum foil layer and the polypropylene heat-sealing layer are laminated through a polyurethane adhesive, so that the prepared aluminum-plastic film has excellent barrier property, extensibility and corrosion resistance, and simultaneously has good heat-sealing collosol-property aluminum leakage prevention function and white line condition after being placed and stamped. The adopted polyurethane fiber layer can effectively prevent air, particularly oxygen, from permeating, maintain the internal environment of the battery, and simultaneously ensure that the packaging aluminum foil has good deformation capacity; the aluminum foil layer can effectively prevent moisture in the air from permeating, maintain the internal structure of the battery, have certain thickness and strength, and can prevent the electric core from being damaged by external force; the polypropylene heat-sealing layer cannot be dissolved, corroded, swelled and the like by an organic solvent in the battery cell, is the most direct package protection, insulation and effective prevention of the contact between the internal electrolyte and the aluminum foil layer in the internal environment of the battery cell, and avoids the corrosion of the aluminum foil layer. In addition, the alpha-methyl styrene dimer adopted in the modified polyolefin adhesive takes a linear dimer as a molecular chain transfer agent, so that the obtained modified polyolefin adhesive has good adhesion, bubbling resistance, smoothness, surface strength and printability; the dibenzoyl peroxide is used as the initiator of the adhesive, and free radicals generated by electron transfer between an oxidant and a reducing agent are used for initiating polymerization reaction, so that the reaction rate for preparing the modified polyolefin adhesive can be increased, and the energy consumption is reduced; the polyolefin has the characteristics of low surface energy, high crystallinity, weak polarity and poor viscosity, so that the raw materials and the process are required to be modified to improve the adhesive property of the polyolefin.
Preferably, each part of the modified epoxy resin comprises the following raw materials in parts by weight:
the modified epoxy resin is prepared by the following method:
s1, adding epoxy resin, melamine and graphene in parts by weight into a stirring device, heating to 60-80 ℃, and stirring at the speed of 200-300r/min for 30-60min to obtain a mixture A for later use;
s2, adding the polyurethane prepolymer and silicon dioxide into the mixture A obtained in the step S1, heating to 80-120 ℃, stirring for 20-40min, adding N, N-dimethylformamide, continuously stirring for 1-3h at the speed of 300-450r/min, and cooling to obtain the modified epoxy resin.
The modified epoxy resin modified by the raw materials and the process has good wear resistance, scratch resistance and tensile resistance. N, N dimethyl formamide as an organic solvent can well dissolve and disperse silicon dioxide and graphene into epoxy resin together with melamine to carry out filling modification on the epoxy resin; the polyurethane prepolymer can be used as a main component with an adhesive function in the modified epoxy resin, and the adhesive property, the ductility and the barrier property of the modified polyolefin adhesive are improved in an auxiliary manner in the preparation process of the modified polyolefin adhesive; in addition, the stirring speed in the step S1 needs to be strictly controlled to 200-300r/min in the process of preparing the modified epoxy resin, if the stirring speed is too fast, the dispersion effect between the graphene and the epoxy resin and the melamine due to too large centrifugal force is not good, and if the stirring speed is too low, the dispersion between the graphene and the epoxy resin and the melamine is not good, and further the modification of the epoxy resin by the graphene is not good.
Preferably, each part of the curing agent is at least one of p-hydroxybenzene sulfonic acid, n-butyl ester, methyl hexahydrophthalic anhydride and tin laurate; more preferably, the curing agent is a mixture of p-hydroxybenzene sulfonic acid, n-butyl ester, methyl hexahydrophthalic anhydride and tin laurate according to the weight ratio of 0.4-0.8:0.6-1.0:0.1-0.5: 0.8-1.2. Each part of the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 619, antioxidant 703, antioxidant BHT, antioxidant 2112 and antioxidant 703; preferably, the antioxidant is a mixture of 0.4-0.8:0.8-1.2:0.6-1.0:0.1-0.5 by weight of antioxidant 1010, antioxidant 168, antioxidant 2112 and antioxidant 703.
The p-hydroxybenzene sulfonic acid adopted by the curing agent is used for curing the modified polyolefin adhesive and has an emulsifying effect, and the curing effect of the curing agent in the process of preparing the modified polyolefin adhesive is further improved by coordinating the respective advantages of the p-hydroxybenzene sulfonic acid, the n-butyl ester, the methyl hexahydrophthalic anhydride and the tin laurate, so that the prepared modified polyolefin adhesive has a good coating effect. The antioxidant 1010 has excellent oxidation resistance on the modified epoxy resin and the polyolefin, and the antioxidant 1010 can effectively prevent the thermal oxidation degradation of the modified polyolefin adhesive in the long-term aging process, so that the service life of the aluminum-plastic film is prolonged, and in addition, the antioxidant 1010 can be used together with the antioxidant 168 to have a synergistic effect; the antioxidant 168, the antioxidant 2112 and the antioxidant 703 are auxiliary antioxidants of the antioxidant 1010, are compounded with the main antioxidant 1010, have good synergistic effect, can effectively prevent the thermal degradation of the modified epoxy resin and the polyolefin in the basic injection molding, and provide extra long-term protection for the modified polyolefin adhesive.
Preferably, each part of the defoaming agent is at least one of polydimethylsiloxane, tributyl phosphate and paraffin; more preferably, the defoaming agent is a mixture of polydimethylsiloxane, tributyl phosphate and paraffin wax according to the weight ratio of 0.6-1.0:0.8-1.2: 0.1-0.5. Each part of the cross-linking agent is a mixture of melamine, polymethylhydrosiloxane and vinyl triethoxysilane according to the weight ratio of 0.6-1.0:0.1-0.5: 0.8-1.2. Each part of the solvent is at least one of acetone, butyl acetate, ethylene oxide and isoamyl acetate; more preferably, the solvent is a mixture of acetone, butyl acetate, ethylene oxide and isoamyl acetate in a weight ratio of 0.4-0.8:0.6-1.0:0.1-0.5: 0.8-1.2.
The defoaming agent can remove air entrained in the preparation process of the modified polyolefin adhesive to form bubbles or generate bubbles due to reaction, so that the influence on the bonding effect of the modified polyolefin adhesive between the polyurethane fiber layer and the aluminum foil layer is avoided, and the quality of an aluminum-plastic film product is further influenced; the crosslinking agent adopts polymethyl hydrogen siloxane molecules, active hydrogen atoms directly connected with silicon atoms in the polymethyl hydrogen siloxane molecules and vinyl in modified epoxy resin and modified epoxy resin-polyolefin to carry out addition reaction so as to vulcanize raw rubber, and generally, more than 3 Si-H groups are arranged in one molecule, so that the flexibility and the physical and mechanical properties of a vulcanized rubber network structure can be obviously improved; the adopted solvent has good dissolving effect on the raw materials, so that the raw materials are convenient to fuse and diffuse, and the efficiency of preparing the modified polyolefin adhesive can be well improved.
Preferably, the modified polyolefin adhesive is prepared by the following method:
e1, dispersing the modified epoxy resin, the polyolefin and the dibenzoyl peroxide into a solvent according to the parts by weight, adding the solvent into a reaction device, heating to 80-100 ℃, and stirring at 450r/min for 20-40min to obtain a mixture A for later use;
e2, mixing the alpha-methyl styrene dimer, the cross-linking agent and the antioxidant, heating to 40-60 ℃, and uniformly stirring to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2 and the defoaming agent into the mixture A obtained in the step E1, mixing and heating to 80-100 ℃, stirring for 60-90min at the speed of 250-350r/min, adding the curing agent, continuing stirring for 40-60min, cooling to normal temperature, and filtering to obtain a filtrate, namely the modified polyolefin adhesive.
The modified polyolefin adhesive prepared by the method has the characteristics of good adhesion, smoothness, surface strength, solvent resistance and acid resistance, an inner layer modified polyolefin adhesive layer is formed by coating the modified polyolefin adhesive on the surface of a polypropylene heat-sealing layer, and the polypropylene heat-sealing layer with the inner layer modified polyolefin adhesive layer is compounded with an aluminum foil layer in a dry mode, so that the electrolyte resistance of the aluminum plastic film is improved. When the modified polyolefin adhesive is prepared, the heating temperature of the step E1 needs to be strictly controlled to be 80-100 ℃, if the temperature is too high, the initiation effect of dibenzoyl peroxide is limited, the subsequent reaction between the modified epoxy resin and olefin and other auxiliaries is not facilitated, and if the temperature is too low, the Brownian motion of a system is reduced, and the dispersion and the compounding among the raw materials are not facilitated; in addition, the stirring speed in the step E3 needs to be controlled to be 250-350r/min, if the stirring speed is too high, more bubbles are mixed in the system, which is not favorable for subsequent defoaming, and further influences the quality of the prepared modified polyolefin adhesive, and finally influences the quality of the prepared aluminum-plastic film, and if the stirring speed is too low, the diffusion between the defoaming agent and the mixing system is not favorable, and further is not favorable for defoaming the finally prepared modified polyolefin adhesive.
The invention also provides a preparation method of the aluminum-plastic film for lithium battery packaging, which comprises the following steps:
1) taking a polypropylene heat-sealing layer, pasting a polyurethane adhesive layer on the upper surface of the polypropylene heat-sealing layer, and pasting an aluminum foil layer on the polyurethane adhesive layer;
2) pasting a layer of modified polyolefin adhesive on the upper surface of the aluminum foil layer, and pasting a polyurethane fiber layer on the modified polyolefin adhesive layer to obtain an aluminum-plastic film primary product;
3) placing the primary aluminum-plastic film in an oven, heating to 60-70 ℃, and curing and molding for 4.5-5.5 h;
4) then, the temperature of the oven in the step 3) is increased to 80-90 ℃ for high-temperature curing molding for 71-73 h;
5) and then, reducing the temperature of the oven in the step 4) to 60-70 ℃ for low-temperature forming for 64-66h to obtain the finished product of the aluminum-plastic film.
The aluminum-plastic film is prepared by the method, and the aluminum-plastic film prepared by the method has excellent barrier property, heat sealing property, extensibility and corrosion resistance; the method adopts a high-low temperature curing process to make the prepared aluminum-plastic film overcome the problems of poor white line, poor sol property and low peeling force after the shell of the aluminum-plastic film prepared by constant-temperature curing molding at low temperature of 40 ℃ in the prior art is punched; in the method, the heating temperature in the step 3), the step 4) and the step 5) needs to be controlled, so that a high-temperature and low-temperature curing process is formed.
The invention has the beneficial effects that: the aluminum plastic film disclosed by the invention has excellent barrier property, heat sealing property, extensibility and corrosion resistance. The inner layer modified polyolefin adhesive layer is formed by coating the modified polyolefin adhesive on the surface of the polypropylene heat-sealing layer, and then the polypropylene heat-sealing layer with the inner layer modified polyolefin adhesive layer is compounded with the aluminum foil layer in a dry manner, so that the electrolyte resistance of the aluminum plastic film is improved. The adopted polyurethane fiber layer can effectively prevent air, particularly oxygen, from permeating, maintain the internal environment of the battery, and simultaneously ensure that the packaging aluminum foil has good deformation capacity; the aluminum foil layer can effectively prevent moisture in the air from permeating, maintain the internal structure of the battery, have certain thickness and strength, and can prevent the electric core from being damaged by external force; the polypropylene heat-sealing layer cannot be dissolved, corroded, swelled and the like by an organic solvent in the battery cell, is the most direct package protection, insulation and effective prevention of the contact between the internal electrolyte and the aluminum foil layer in the internal environment of the battery cell, and avoids the corrosion of the aluminum foil layer.
The preparation method of the aluminum plastic film for lithium battery packaging is simple and efficient, convenient to operate and control, high in quality of produced products and beneficial to industrial production.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
An aluminum-plastic film for packaging a lithium battery comprises a polyurethane fiber layer, an aluminum foil layer and a polypropylene heat-sealing layer from top to bottom, wherein the aluminum foil layer is attached to the upper surface of the polypropylene heat-sealing layer, polyurethane fibers are attached to the upper surface of the aluminum foil layer, the polyurethane fiber layer is attached to the aluminum foil layer through a modified polyolefin adhesive, the aluminum foil layer is attached to the polypropylene heat-sealing layer through a polyurethane adhesive, and the polyurethane adhesive is a German Weishi corner-group adhesive COSMOPUR 818C German Weishi polyurethane adhesive; the modified polyolefin adhesive comprises the following raw materials in parts by weight:
the polyolefin is POE 8180 American Dow polyolefin.
Each part of the modified epoxy resin comprises the following raw materials in parts by weight:
the polyurethane prepolymer is a polyurethane prepolymer HC-8799AB produced by Shanghai Hecheng Polymer technology Co., Ltd; the type of the epoxy resin is epoxy resin E44.
The modified epoxy resin is prepared by the following method:
s1, adding epoxy resin, melamine and graphene in parts by weight into a stirring device, heating to 60 ℃, and stirring at a speed of 200r/min for 30min to obtain a mixture A for later use;
s2, adding the polyurethane prepolymer and silicon dioxide into the mixture A obtained in the step S1, heating to 80 ℃, stirring for 20min, adding N, N-dimethylformamide, continuously stirring for 1h at the speed of 300r/min, and cooling to obtain the modified epoxy resin.
Each part of the curing agent is a mixture of p-hydroxybenzene sulfonic acid, n-butyl ester, methyl hexahydrophthalic anhydride and tin laurate according to the weight ratio of 0.4:0.6:0.1: 0.8.
Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 in a weight ratio of 0.4:0.8:0.6: 0.1.
Each part of the defoaming agent is a mixture of polydimethylsiloxane, tributyl phosphate and paraffin according to the weight ratio of 0.6:0.8: 0.1.
Each part of the cross-linking agent is a mixture of melamine, polymethylhydrosiloxane and vinyl triethoxysilane according to the weight ratio of 0.6:0.1: 0.8.
Each part of the solvent is a mixture of acetone, butyl acetate, ethylene oxide and isoamyl acetate according to the weight ratio of 0.4:0.6:0.1: 0.8.
The modified polyolefin adhesive is prepared by the following method:
e1, dispersing the modified epoxy resin, the polyolefin and the dibenzoyl peroxide into a solvent according to the parts by weight, adding the solvent into a reaction device, heating to 80 ℃, and stirring at 350r/min for 20min to obtain a mixture A for later use;
e2, mixing the alpha-methyl styrene dimer, the cross-linking agent and the antioxidant, heating to 40 ℃, and uniformly stirring to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2 and a defoaming agent into the mixture A obtained in the step E1, mixing and heating to 80 ℃, stirring at 250r/min for 60min, adding a curing agent, continuing stirring for 40min, cooling to normal temperature, and filtering to obtain a filtrate, namely the modified polyolefin adhesive.
The aluminum-plastic film for lithium battery packaging is prepared by the following steps:
1) taking a polypropylene heat-sealing layer, pasting a polyurethane adhesive layer on the upper surface of the polypropylene heat-sealing layer, and pasting an aluminum foil layer on the polyurethane adhesive layer;
2) pasting a layer of modified polyolefin adhesive on the upper surface of the aluminum foil layer, and pasting a polyurethane fiber layer on the modified polyolefin adhesive layer to obtain an aluminum-plastic film primary product;
3) placing the primary aluminum-plastic film in an oven, heating to 60 ℃, and curing and molding for 4.5 hours;
4) then, the temperature of the oven in the step 3) is increased to 80 ℃ for high-temperature curing molding for 71 h;
5) and then, reducing the temperature of the oven in the step 4) to 60 ℃ for low-temperature forming for 64h to obtain the finished product of the aluminum-plastic film.
Example 2
An aluminum-plastic film for packaging a lithium battery comprises a polyurethane fiber layer, an aluminum foil layer and a polypropylene heat-sealing layer from top to bottom, wherein the aluminum foil layer is attached to the upper surface of the polypropylene heat-sealing layer, polyurethane fibers are attached to the upper surface of the aluminum foil layer, the polyurethane fiber layer is attached to the aluminum foil layer through a modified polyolefin adhesive, the aluminum foil layer is attached to the polypropylene heat-sealing layer through a polyurethane adhesive, and the polyurethane adhesive is a German Weishi corner-group adhesive COSMOPUR 818C German Weishi polyurethane adhesive; the modified polyolefin adhesive comprises the following raw materials in parts by weight:
the polyolefin is POE 8180 American Dow polyolefin.
Each part of the modified epoxy resin comprises the following raw materials in parts by weight:
the polyurethane prepolymer is a polyurethane prepolymer HC-8799AB produced by Shanghai Hecheng Polymer technology Co., Ltd; the type of the epoxy resin is epoxy resin E44.
The modified epoxy resin is prepared by the following method:
s1, adding epoxy resin, melamine and graphene in parts by weight into a stirring device, heating to 65 ℃, and stirring at a speed of 225r/min for 38min to obtain a mixture A for later use;
s2, adding the polyurethane prepolymer and silicon dioxide into the mixture A obtained in the step S1, heating to 90 ℃, stirring for 25min, adding N, N-dimethylformamide, continuously stirring for 1.5h at the speed of 332r/min, and cooling to obtain the modified epoxy resin.
Each part of the curing agent is a mixture of p-hydroxybenzene sulfonic acid, n-butyl ester, methyl hexahydrophthalic anhydride and tin laurate according to the weight ratio of 0.5:0.7:0.2: 0.9.
Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 in a weight ratio of 0.5:0.9:0.7: 0.2.
Each part of the defoaming agent is a mixture of polydimethylsiloxane, tributyl phosphate and paraffin according to the weight ratio of 0.7:0.9: 0.2.
Each part of the cross-linking agent is a mixture of melamine, polymethylhydrosiloxane and vinyl triethoxysilane according to the weight ratio of 0.7:0.2: 0.9.
Each part of the solvent is a mixture of acetone, butyl acetate, ethylene oxide and isoamyl acetate according to the weight ratio of 0.5:0.7:0.2: 0.9.
The modified polyolefin adhesive is prepared by the following method:
e1, dispersing the modified epoxy resin, the polyolefin and the dibenzoyl peroxide into a solvent according to the parts by weight, adding the solvent into a reaction device, heating to 85 ℃, and stirring at 375r/min for 25min to obtain a mixture A for later use;
e2, mixing the alpha-methyl styrene dimer, the cross-linking agent and the antioxidant, heating to 45 ℃, and uniformly stirring to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2 and a defoaming agent into the mixture A obtained in the step E1, mixing and heating to 85 ℃, stirring at 275r/min for 68min, adding a curing agent, continuing stirring for 45min, cooling to normal temperature, and filtering to obtain a filtrate, namely the modified polyolefin adhesive.
The aluminum-plastic film for lithium battery packaging is prepared by the following steps:
1) taking a polypropylene heat-sealing layer, pasting a polyurethane adhesive layer on the upper surface of the polypropylene heat-sealing layer, and pasting an aluminum foil layer on the polyurethane adhesive layer;
2) pasting a layer of modified polyolefin adhesive on the upper surface of the aluminum foil layer, and pasting a polyurethane fiber layer on the modified polyolefin adhesive layer to obtain an aluminum-plastic film primary product;
3) placing the primary aluminum-plastic film in an oven, heating to 63 ℃, and curing and molding for 4.75 hours;
4) then, the temperature of the oven in the step 3) is increased to 83 ℃ for high-temperature curing molding for 71.5 h;
5) and then, reducing the temperature of the oven in the step 4) to 63 ℃ for low-temperature forming for 64.5 hours to obtain the finished product of the aluminum-plastic film.
Example 3
An aluminum-plastic film for packaging a lithium battery comprises a polyurethane fiber layer, an aluminum foil layer and a polypropylene heat-sealing layer from top to bottom, wherein the aluminum foil layer is attached to the upper surface of the polypropylene heat-sealing layer, polyurethane fibers are attached to the upper surface of the aluminum foil layer, the polyurethane fiber layer is attached to the aluminum foil layer through a modified polyolefin adhesive, the aluminum foil layer is attached to the polypropylene heat-sealing layer through a polyurethane adhesive, and the polyurethane adhesive is a German Weishi corner-group adhesive COSMOPUR 818C German Weishi polyurethane adhesive; the modified polyolefin adhesive comprises the following raw materials in parts by weight:
the polyolefin is POE 8180 American Dow polyolefin.
Each part of the modified epoxy resin comprises the following raw materials in parts by weight:
the polyurethane prepolymer is a polyurethane prepolymer HC-8799AB produced by Shanghai Hecheng Polymer technology Co., Ltd; the type of the epoxy resin is epoxy resin E44.
The modified epoxy resin is prepared by the following method:
s1, adding epoxy resin, melamine and graphene in parts by weight into a stirring device, heating to 70 ℃, and stirring at a speed of 250r/min for 45min to obtain a mixture A for later use;
s2, adding the polyurethane prepolymer and silicon dioxide into the mixture A obtained in the step S1, heating to 100 ℃, stirring for 30min, adding N, N-dimethylformamide, continuously stirring for 2h at the speed of 375r/min, and cooling to obtain the modified epoxy resin.
Each part of the curing agent is a mixture of p-hydroxybenzene sulfonic acid, n-butyl ester, methyl hexahydrophthalic anhydride and tin laurate according to the weight ratio of 0.6:0.8:0.3: 1.0.
Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 in a weight ratio of 0.6:1.0:0.8: 0.3.
Each part of the defoaming agent is a mixture of polydimethylsiloxane, tributyl phosphate and paraffin according to the weight ratio of 0.8:1.0: 0.3.
Each part of the cross-linking agent is a mixture of melamine, polymethylhydrosiloxane and vinyl triethoxysilane according to the weight ratio of 0.8:0.3: 1.0.
Each part of the solvent is a mixture of acetone, butyl acetate, ethylene oxide and isoamyl acetate according to the weight ratio of 0.6:0.8:0.3: 1.0.
The modified polyolefin adhesive is prepared by the following method:
e1, dispersing the modified epoxy resin, the polyolefin and the dibenzoyl peroxide into a solvent according to the parts by weight, adding the solvent into a reaction device, heating to 90 ℃, and stirring for 30min at the speed of 400r/min to obtain a mixture A for later use;
e2, mixing the alpha-methyl styrene dimer, the cross-linking agent and the antioxidant, heating to 50 ℃, and uniformly stirring to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2 and a defoaming agent into the mixture A obtained in the step E1, mixing and heating to 90 ℃, stirring at 300r/min for 75min, adding a curing agent, continuing stirring for 50min, cooling to normal temperature, and filtering to obtain a filtrate, namely the modified polyolefin adhesive.
The aluminum-plastic film for lithium battery packaging is prepared by the following steps:
1) taking a polypropylene heat-sealing layer, pasting a polyurethane adhesive layer on the upper surface of the polypropylene heat-sealing layer, and pasting an aluminum foil layer on the polyurethane adhesive layer;
2) pasting a layer of modified polyolefin adhesive on the upper surface of the aluminum foil layer, and pasting a polyurethane fiber layer on the modified polyolefin adhesive layer to obtain an aluminum-plastic film primary product;
3) placing the primary aluminum-plastic film in an oven, heating to 65 ℃, and curing and molding for 5.0 h;
4) then, the temperature of the oven in the step 3) is increased to 85 ℃ for high-temperature curing molding for 72 hours;
5) and then, reducing the temperature of the oven in the step 4) to 65 ℃ for low-temperature molding for 65 hours to obtain the finished product of the aluminum-plastic film.
Example 4
An aluminum-plastic film for packaging a lithium battery comprises a polyurethane fiber layer, an aluminum foil layer and a polypropylene heat-sealing layer from top to bottom, wherein the aluminum foil layer is attached to the upper surface of the polypropylene heat-sealing layer, polyurethane fibers are attached to the upper surface of the aluminum foil layer, the polyurethane fiber layer is attached to the aluminum foil layer through a modified polyolefin adhesive, the aluminum foil layer is attached to the polypropylene heat-sealing layer through a polyurethane adhesive, and the polyurethane adhesive is a German Weishi corner-group adhesive COSMOPUR 818C German Weishi polyurethane adhesive; the modified polyolefin adhesive comprises the following raw materials in parts by weight:
the polyolefin is POE 8180 American Dow polyolefin.
Each part of the modified epoxy resin comprises the following raw materials in parts by weight:
the polyurethane prepolymer is a polyurethane prepolymer HC-8799AB produced by Shanghai Hecheng Polymer technology Co., Ltd; the type of the epoxy resin is epoxy resin E44.
The modified epoxy resin is prepared by the following method:
s1, adding epoxy resin, melamine and graphene in parts by weight into a stirring device, heating to 75 ℃, and stirring at 275r/min for 52min to obtain a mixture A for later use;
s2, adding the polyurethane prepolymer and silicon dioxide into the mixture A obtained in the step S1, heating to 110 ℃, stirring for 35min, adding N, N-dimethylformamide, continuously stirring for 2.5h at the speed of 407r/min, and cooling to obtain the modified epoxy resin.
Each part of the curing agent is a mixture of p-hydroxybenzene sulfonic acid, n-butyl ester, methyl hexahydrophthalic anhydride and tin laurate according to the weight ratio of 0.7:0.9:0.4: 1.1.
Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 in a weight ratio of 0.7:1.1:0.9: 0.4.
Each part of the defoaming agent is a mixture of polydimethylsiloxane, tributyl phosphate and paraffin according to the weight ratio of 0.9:1.1: 0.4.
Each part of the cross-linking agent is a mixture of melamine, polymethylhydrosiloxane and vinyl triethoxysilane according to the weight ratio of 0.9:0.4: 1.1.
Each part of the solvent is a mixture of acetone, butyl acetate, ethylene oxide and isoamyl acetate according to the weight ratio of 0.7:0.9:0.4: 1.1.
The modified polyolefin adhesive is prepared by the following method:
e1, dispersing the modified epoxy resin, the polyolefin and the dibenzoyl peroxide into a solvent according to the parts by weight, adding the solvent into a reaction device, heating to 95 ℃, and stirring at 425r/min for 35min to obtain a mixture A for later use;
e2, mixing the alpha-methyl styrene dimer, the cross-linking agent and the antioxidant, heating to 55 ℃, and uniformly stirring to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2 and a defoaming agent into the mixture A obtained in the step E1, mixing and heating to 95 ℃, stirring at 275r/min for 82min, adding a curing agent, continuing stirring for 55min, cooling to normal temperature, and filtering to obtain a filtrate, namely the modified polyolefin adhesive.
The aluminum-plastic film for lithium battery packaging is prepared by the following steps:
1) taking a polypropylene heat-sealing layer, pasting a polyurethane adhesive layer on the upper surface of the polypropylene heat-sealing layer, and pasting an aluminum foil layer on the polyurethane adhesive layer;
2) pasting a layer of modified polyolefin adhesive on the upper surface of the aluminum foil layer, and pasting a polyurethane fiber layer on the modified polyolefin adhesive layer to obtain an aluminum-plastic film primary product;
3) placing the primary aluminum-plastic film in an oven, heating to 68 ℃, and curing and molding for 5.25 hours;
4) then, the temperature of the oven in the step 3) is increased to 88 ℃ for high-temperature curing molding for 72.5 h;
5) and then, reducing the temperature of the oven in the step 4) to 68 ℃ for low-temperature forming for 65.5 hours to obtain the finished product of the aluminum-plastic film.
Example 5
An aluminum-plastic film for packaging a lithium battery comprises a polyurethane fiber layer, an aluminum foil layer and a polypropylene heat-sealing layer from top to bottom, wherein the aluminum foil layer is attached to the upper surface of the polypropylene heat-sealing layer, polyurethane fibers are attached to the upper surface of the aluminum foil layer, the polyurethane fiber layer is attached to the aluminum foil layer through a modified polyolefin adhesive, the aluminum foil layer is attached to the polypropylene heat-sealing layer through a polyurethane adhesive, and the polyurethane adhesive is a German Weishi corner-group adhesive COSMOPUR 818C German Weishi polyurethane adhesive; the modified polyolefin adhesive comprises the following raw materials in parts by weight:
the polyolefin is POE 8180 American Dow polyolefin.
Each part of the modified epoxy resin comprises the following raw materials in parts by weight:
the polyurethane prepolymer is a polyurethane prepolymer HC-8799AB produced by Shanghai Hecheng Polymer technology Co., Ltd; the type of the epoxy resin is epoxy resin E44.
The modified epoxy resin is prepared by the following method:
s1, adding epoxy resin, melamine and graphene in parts by weight into a stirring device, heating to 80 ℃, and stirring at the speed of 300r/min for 60min to obtain a mixture A for later use;
s2, adding the polyurethane prepolymer and silicon dioxide into the mixture A obtained in the step S1, heating to 120 ℃, stirring for 40min, adding N, N-dimethylformamide, continuously stirring for 3h at the speed of 450r/min, and cooling to obtain the modified epoxy resin.
Each part of the curing agent is a mixture of p-hydroxybenzene sulfonic acid, n-butyl ester, methyl hexahydrophthalic anhydride and tin laurate according to the weight ratio of 0.8:1.0:0.5: 1.2.
Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 in a weight ratio of 0.8:1.2:1.0: 0.5.
Each part of the defoaming agent is a mixture of polydimethylsiloxane, tributyl phosphate and paraffin according to the weight ratio of 1.0:1.2: 0.5.
Each part of the cross-linking agent is a mixture of melamine, polymethylhydrosiloxane and vinyl triethoxysilane according to the weight ratio of 1.0:0.5: 1.2.
Each part of the solvent is a mixture of acetone, butyl acetate, ethylene oxide and isoamyl acetate according to the weight ratio of 0.8:1.0:0.5: 1.2.
The modified polyolefin adhesive is prepared by the following method:
e1, dispersing the modified epoxy resin, the polyolefin and the dibenzoyl peroxide into a solvent according to the parts by weight, adding the solvent into a reaction device, heating to 100 ℃, and stirring at 450r/min for 40min to obtain a mixture A for later use;
e2, mixing the alpha-methyl styrene dimer, the cross-linking agent and the antioxidant, heating to 60 ℃, and uniformly stirring to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2 and a defoaming agent into the mixture A obtained in the step E1, mixing and heating to 100 ℃, stirring at 350r/min for 90min, adding a curing agent, continuing stirring for 60min, cooling to normal temperature, and filtering to obtain a filtrate, namely the modified polyolefin adhesive.
The aluminum-plastic film for lithium battery packaging is prepared by the following steps:
1) taking a polypropylene heat-sealing layer, pasting a polyurethane adhesive layer on the upper surface of the polypropylene heat-sealing layer, and pasting an aluminum foil layer on the polyurethane adhesive layer;
2) pasting a layer of modified polyolefin adhesive on the upper surface of the aluminum foil layer, and pasting a polyurethane fiber layer on the modified polyolefin adhesive layer to obtain an aluminum-plastic film primary product;
3) placing the primary aluminum-plastic film in an oven, heating to 70 ℃, and curing and molding for 5.5 hours;
4) then, the temperature of the oven in the step 3) is increased to 90 ℃ for high-temperature curing molding for 73 h;
5) and then, reducing the temperature of the oven in the step 4) to 70 ℃ for low-temperature forming for 66 hours to obtain the finished product of the aluminum-plastic film.
Comparative example 1
An aluminum-plastic film for packaging a lithium battery comprises a modified polypropylene layer, an aluminum foil layer and a polypropylene heat-sealing layer from top to bottom, wherein the aluminum foil layer is attached to the upper surface of the polypropylene heat-sealing layer, the modified polypropylene layer is attached to the upper surface of the aluminum foil layer, the modified polypropylene layer is attached to the aluminum foil layer through a modified polyolefin adhesive, the aluminum foil layer is attached to the polypropylene heat-sealing layer through a polyurethane adhesive, and the polyurethane adhesive is a German Weishi angle adhesive COSMOPUR 818C German Weishi polyurethane adhesive; the modified polyolefin adhesive comprises the following raw materials in parts by weight:
the polyolefin is POE 8180 American Dow polyolefin.
Each part of the modified epoxy resin comprises the following raw materials in parts by weight:
the polyurethane prepolymer is a polyurethane prepolymer HC-8799AB produced by Shanghai Hecheng Polymer technology Co., Ltd; the type of the epoxy resin is epoxy resin E44.
The modified epoxy resin is prepared by the following method:
s1, adding epoxy resin, melamine and graphene in parts by weight into a stirring device, heating to 60 ℃, and stirring at a speed of 200r/min for 30min to obtain a mixture A for later use;
s2, adding the polyurethane prepolymer and silicon dioxide into the mixture A obtained in the step S1, heating to 80 ℃, stirring for 20min, adding N, N-dimethylformamide, continuously stirring for 1h at the speed of 300r/min, and cooling to obtain the modified epoxy resin.
Each part of the curing agent is a mixture of p-hydroxybenzene sulfonic acid, n-butyl ester, methyl hexahydrophthalic anhydride and tin laurate according to the weight ratio of 0.4:0.6:0.1: 0.8.
Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 in a weight ratio of 0.4:0.8:0.6: 0.1.
Each part of the defoaming agent is a mixture of polydimethylsiloxane, tributyl phosphate and paraffin according to the weight ratio of 0.6:0.8: 0.1.
Each part of the cross-linking agent is a mixture of melamine, polymethylhydrosiloxane and vinyl triethoxysilane according to the weight ratio of 0.6:0.1: 0.8.
Each part of the solvent is a mixture of acetone, butyl acetate, ethylene oxide and isoamyl acetate according to the weight ratio of 0.4:0.6:0.1: 0.8.
The modified polyolefin adhesive is prepared by the following method:
e1, dispersing the modified epoxy resin, the polyolefin and the dibenzoyl peroxide into a solvent according to the parts by weight, adding the solvent into a reaction device, heating to 80 ℃, and stirring at 350r/min for 20min to obtain a mixture A for later use;
e2, mixing the alpha-methyl styrene dimer, the cross-linking agent and the antioxidant, heating to 40 ℃, and uniformly stirring to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2 and a defoaming agent into the mixture A obtained in the step E1, mixing and heating to 80 ℃, stirring at 250r/min for 60min, adding a curing agent, continuing stirring for 40min, cooling to normal temperature, and filtering to obtain a filtrate, namely the modified polyolefin adhesive.
The aluminum-plastic film for lithium battery packaging is prepared by the following steps:
1) taking a polypropylene heat-sealing layer, pasting a polyurethane adhesive layer on the upper surface of the polypropylene heat-sealing layer, and pasting an aluminum foil layer on the polyurethane adhesive layer;
2) pasting a layer of modified polyolefin adhesive on the upper surface of the aluminum foil layer, and then pasting a modified polypropylene layer on the modified polyolefin adhesive layer to obtain an aluminum-plastic film primary product;
3) placing the primary aluminum-plastic film in an oven, heating to 60 ℃, and curing and molding for 4.5 hours;
4) then, the temperature of the oven in the step 3) is increased to 80 ℃ for high-temperature curing molding for 71 h;
5) and then, reducing the temperature of the oven in the step 4) to 60 ℃ for low-temperature forming for 64h to obtain the finished product of the aluminum-plastic film.
Comparative example 2
An aluminum-plastic film for packaging a lithium battery comprises a polyurethane fiber layer, an aluminum foil layer and a polypropylene heat-sealing layer from top to bottom, wherein the aluminum foil layer is attached to the upper surface of the polypropylene heat-sealing layer, polyurethane fibers are attached to the upper surface of the aluminum foil layer, the polyurethane fiber layer is attached to the aluminum foil layer through a modified polyolefin adhesive, the aluminum foil layer is attached to the polypropylene heat-sealing layer through a polyurethane adhesive, and the polyurethane adhesive is a German Weishi corner-group adhesive COSMOPUR 818C German Weishi polyurethane adhesive; the modified polyolefin adhesive comprises the following raw materials in parts by weight:
the polyolefin is POE 8180 American Dow polyolefin.
Each part of the curing agent is a mixture of p-hydroxybenzene sulfonic acid, n-butyl ester, methyl hexahydrophthalic anhydride and tin laurate according to the weight ratio of 0.6:0.8:0.3: 1.0.
Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 in a weight ratio of 0.6:1.0:0.8: 0.3.
Each part of the defoaming agent is a mixture of polydimethylsiloxane, tributyl phosphate and paraffin according to the weight ratio of 0.8:1.0: 0.3.
Each part of the cross-linking agent is a mixture of melamine, polymethylhydrosiloxane and vinyl triethoxysilane according to the weight ratio of 0.8:0.3: 1.0.
Each part of the solvent is a mixture of acetone, butyl acetate, ethylene oxide and isoamyl acetate according to the weight ratio of 0.6:0.8:0.3: 1.0.
The modified polyolefin adhesive is prepared by the following method:
e1, dispersing epoxy resin, polyolefin and dibenzoyl peroxide into a solvent according to parts by weight, adding the mixture into a reaction device, heating to 90 ℃, and stirring for 30min at a speed of 400r/min to obtain a mixture A for later use;
e2, mixing the alpha-methyl styrene dimer, the cross-linking agent and the antioxidant, heating to 50 ℃, and uniformly stirring to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2 and a defoaming agent into the mixture A obtained in the step E1, mixing and heating to 90 ℃, stirring at 300r/min for 75min, adding a curing agent, continuing stirring for 50min, cooling to normal temperature, and filtering to obtain a filtrate, namely the modified polyolefin adhesive.
The aluminum-plastic film for lithium battery packaging is prepared by the following steps:
1) taking a polypropylene heat-sealing layer, pasting a polyurethane adhesive layer on the upper surface of the polypropylene heat-sealing layer, and pasting an aluminum foil layer on the polyurethane adhesive layer;
2) pasting a layer of modified polyolefin adhesive on the upper surface of the aluminum foil layer, and pasting a polyurethane fiber layer on the modified polyolefin adhesive layer to obtain an aluminum-plastic film primary product;
3) placing the primary aluminum-plastic film in an oven, heating to 65 ℃, and curing and molding for 5.0 h;
4) then, the temperature of the oven in the step 3) is increased to 85 ℃ for high-temperature curing molding for 72 hours;
5) and then, reducing the temperature of the oven in the step 4) to 65 ℃ for low-temperature molding for 65 hours to obtain the finished product of the aluminum-plastic film.
Comparative example 3
An aluminum-plastic film for packaging a lithium battery comprises a polyurethane fiber layer, an aluminum foil layer and a polypropylene heat-sealing layer from top to bottom, wherein the aluminum foil layer is attached to the upper surface of the polypropylene heat-sealing layer, polyurethane fibers are attached to the upper surface of the aluminum foil layer, the polyurethane fiber layer is attached to the aluminum foil layer through a modified polyolefin adhesive, the aluminum foil layer is attached to the polypropylene heat-sealing layer through a polyurethane adhesive, and the polyurethane adhesive is a German Weishi corner-group adhesive COSMOPUR 818C German Weishi polyurethane adhesive; the modified polyolefin adhesive comprises the following raw materials in parts by weight:
the polyolefin is POE 8180 American Dow polyolefin.
Each part of the modified epoxy resin comprises the following raw materials in parts by weight:
the polyurethane prepolymer is a polyurethane prepolymer HC-8799AB produced by Shanghai Hecheng Polymer technology Co., Ltd; the type of the epoxy resin is epoxy resin E44.
The modified epoxy resin is prepared by the following method:
s1, adding epoxy resin and melamine into a stirring device according to parts by weight, heating to 80 ℃, and stirring at the speed of 300r/min for 60min to obtain a mixture A for later use;
s2, adding the polyurethane prepolymer and silicon dioxide into the mixture A obtained in the step S1, heating to 120 ℃, stirring for 40min, adding N, N-dimethylformamide, continuously stirring for 3h at the speed of 450r/min, and cooling to obtain the modified epoxy resin.
Each part of the curing agent is a mixture of p-hydroxybenzene sulfonic acid, n-butyl ester, methyl hexahydrophthalic anhydride and tin laurate according to the weight ratio of 0.8:1.0:0.5: 1.2.
Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 in a weight ratio of 0.8:1.2:1.0: 0.5.
Each part of the defoaming agent is a mixture of polydimethylsiloxane, tributyl phosphate and paraffin according to the weight ratio of 1.0:1.2: 0.5.
Each part of the cross-linking agent is a mixture of melamine, polymethylhydrosiloxane and vinyl triethoxysilane according to the weight ratio of 1.0:0.5: 1.2.
Each part of the solvent is a mixture of acetone, butyl acetate, ethylene oxide and isoamyl acetate according to the weight ratio of 0.8:1.0:0.5: 1.2.
The modified polyolefin adhesive is prepared by the following method:
e1, dispersing the modified epoxy resin, the polyolefin and the dibenzoyl peroxide into a solvent according to the parts by weight, adding the solvent into a reaction device, heating to 100 ℃, and stirring at 450r/min for 40min to obtain a mixture A for later use;
e2, mixing the alpha-methyl styrene dimer, the cross-linking agent and the antioxidant, heating to 60 ℃, and uniformly stirring to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2 and a defoaming agent into the mixture A obtained in the step E1, mixing and heating to 100 ℃, stirring at 350r/min for 90min, adding a curing agent, continuing stirring for 60min, cooling to normal temperature, and filtering to obtain a filtrate, namely the modified polyolefin adhesive.
The aluminum-plastic film for lithium battery packaging is prepared by the following steps:
1) taking a polypropylene heat-sealing layer, pasting a polyurethane adhesive layer on the upper surface of the polypropylene heat-sealing layer, and pasting an aluminum foil layer on the polyurethane adhesive layer;
2) pasting a layer of modified polyolefin adhesive on the upper surface of the aluminum foil layer, and pasting a polyurethane fiber layer on the modified polyolefin adhesive layer to obtain an aluminum-plastic film primary product;
3) placing the primary aluminum-plastic film in an oven, heating to 70 ℃, and curing and molding for 5.5 hours;
4) then, the temperature of the oven in the step 3) is increased to 90 ℃ for high-temperature curing molding for 73 h;
5) and then, reducing the temperature of the oven in the step 4) to 70 ℃ for low-temperature forming for 66 hours to obtain the finished product of the aluminum-plastic film.
Comparative example 4
An aluminum-plastic film for packaging a lithium battery comprises a polyurethane fiber layer, an aluminum foil layer and a polypropylene heat-sealing layer from top to bottom, wherein the aluminum foil layer is attached to the upper surface of the polypropylene heat-sealing layer, polyurethane fibers are attached to the upper surface of the aluminum foil layer, the polyurethane fiber layer is attached to the aluminum foil layer through a modified polyolefin adhesive, the aluminum foil layer is attached to the polypropylene heat-sealing layer through a polyurethane adhesive, and the polyurethane adhesive is a German Weishi corner-group adhesive COSMOPUR 818C German Weishi polyurethane adhesive; the modified polyolefin adhesive comprises the following raw materials in parts by weight:
the polyolefin is POE 8180 American Dow polyolefin.
Each part of the modified epoxy resin comprises the following raw materials in parts by weight:
the polyurethane prepolymer is HC-8799AB produced by Shanghai Hecheng polymer technology Co.
The modified epoxy resin is prepared by the following method:
s1, adding epoxy resin, melamine and graphene in parts by weight into a stirring device, heating to 80 ℃, and stirring at the speed of 300r/min for 60min to obtain a mixture A for later use;
s2, adding the polyurethane prepolymer and silicon dioxide into the mixture A obtained in the step S1, heating to 120 ℃, stirring for 40min, adding N, N-dimethylformamide, continuously stirring for 3h at the speed of 450r/min, and cooling to obtain the modified epoxy resin.
Each part of the curing agent is a mixture of p-hydroxybenzene sulfonic acid, n-butyl ester, methyl hexahydrophthalic anhydride and tin laurate according to the weight ratio of 0.8:1.0:0.5: 1.2.
Each part of the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168, an antioxidant 2112 and an antioxidant 703 in a weight ratio of 0.8:1.2:1.0: 0.5.
Each part of the defoaming agent is a mixture of polydimethylsiloxane, tributyl phosphate and paraffin according to the weight ratio of 1.0:1.2: 0.5.
Each part of the cross-linking agent is a mixture of melamine, polymethylhydrosiloxane and vinyl triethoxysilane according to the weight ratio of 1.0:0.5: 1.2.
Each part of the solvent is a mixture of acetone, butyl acetate, ethylene oxide and isoamyl acetate according to the weight ratio of 0.8:1.0:0.5: 1.2.
The modified polyolefin adhesive is prepared by the following method:
e1, dispersing the modified epoxy resin, the polyolefin and the dibenzoyl peroxide into a solvent according to the parts by weight, adding the solvent into a reaction device, heating to 100 ℃, and stirring at 450r/min for 40min to obtain a mixture A for later use;
e2, mixing the alpha-methyl styrene dimer, the cross-linking agent and the antioxidant, heating to 60 ℃, and uniformly stirring to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2 and a defoaming agent into the mixture A obtained in the step E1, mixing and heating to 100 ℃, stirring at 350r/min for 90min, adding a curing agent, continuing stirring for 60min, cooling to normal temperature, and filtering to obtain a filtrate, namely the modified polyolefin adhesive.
The aluminum-plastic film for lithium battery packaging is prepared by the following steps:
1) taking a polypropylene heat-sealing layer, pasting a polyurethane adhesive layer on the upper surface of the polypropylene heat-sealing layer, and pasting an aluminum foil layer on the polyurethane adhesive layer;
2) pasting a layer of modified polyolefin adhesive on the upper surface of the aluminum foil layer, and pasting a polyurethane fiber layer on the modified polyolefin adhesive layer to obtain an aluminum-plastic film primary product;
3) and placing the primary aluminum-plastic film product in an oven, heating to 40 ℃, and curing and molding for 144h to obtain a finished aluminum-plastic film product.
The peeling force (GB/T15254-94), elongation at break (GB/T1701-2001), corrosion resistance efficiency (CGSB 31-GP-0A METH 38.2-1957), white line after punching, and whether the heat sealing sol leaks the aluminum surface or not of the aluminum plastic films prepared in examples 1-5 and comparative examples 1-4 were tested, and the results are shown in the following table:
as can be seen from the above table, the peeling force, the elongation at break, and the corrosion resistance efficiency of the aluminum-plastic film prepared in the embodiments 1 to 5 of the present invention are significantly improved, and meanwhile, whether the white line and the heat-seal sol leak aluminum after the shell punching is significantly improved, so that the prepared aluminum-plastic film has good barrier property, ductility, and internal corrosion, and in addition, the aluminum-plastic film has the advantages of good aluminum leakage prevention effect of the white line and the heat-seal sol after the shell punching, long service life, and low production cost.
Compared with the example 1, in the comparative example 1, the modified polypropylene layer is used for replacing the polyurethane fiber layer in the preparation of the aluminum-plastic film, and various physical property tests are carried out on the aluminum-plastic film prepared by using the raw materials, so that the analysis shows that the peeling force, the elongation at break and the corrosion resistance efficiency of the aluminum-plastic film are relatively reduced, and the white line and the heat-sealing sol leakage prevention effect after shell punching are relatively weakened; the polyurethane fiber layer is used in the preparation of the aluminum-plastic film, so that the prepared aluminum-plastic film has good stripping force, elongation at break and corrosion resistance efficiency, and meanwhile, the white line and heat-seal sol leakage prevention effect after shell punching are obviously improved, so that the prepared aluminum-plastic film has good barrier property, ductility and internal corrosion, and in addition, the polyurethane fiber layer has the advantages of good white line and heat-seal sol leakage prevention effect after shell punching, long service life and low production cost.
Compared with the example 3, in the comparative example 2, the modified epoxy resin is replaced by the epoxy resin when the modified polyolefin adhesive used for preparing the aluminum-plastic film is prepared, and the aluminum-plastic film prepared by using the raw materials is subjected to various physical property tests, and the analysis shows that the peeling force, the elongation at break and the corrosion resistance efficiency of the aluminum-plastic film are remarkably reduced, and the white line and the heat-sealing sol leakage prevention effect after shell punching are relatively weakened; the modified epoxy resin is adopted when the modified polyolefin adhesive used for preparing the aluminum-plastic film is prepared, so that the prepared aluminum-plastic film has good stripping force, elongation at break and corrosion resistance efficiency, and simultaneously, the white line and the heat-seal sol leakage prevention effect after shell punching are obviously improved, so that the prepared aluminum-plastic film has good barrier property, ductility and internal corrosion, and in addition, the modified polyolefin adhesive also has the advantages of good white line and heat-seal sol leakage prevention effect after shell punching, long service life and low production cost.
Compared with the embodiment 5, in the comparative example 3, the graphene is not added when the modified epoxy resin is added into the modified polyolefin adhesive used for preparing the aluminum-plastic film, and various physical property tests are carried out on the aluminum-plastic film prepared by using the raw materials, so that the analysis shows that the peeling force, the elongation at break and the corrosion resistance efficiency of the aluminum-plastic film are relatively reduced, and the white line and the heat-seal sol leakage prevention effect after shell punching are relatively weakened; the graphene is added when the epoxy resin is modified in the modified polyolefin adhesive used for preparing the aluminum-plastic film, so that the prepared aluminum-plastic film has good stripping force, elongation at break and corrosion resistance efficiency, and meanwhile, the white line after shell punching and the heat-seal collosol aluminum leakage prevention effect are obviously improved, so that the prepared aluminum-plastic film has good barrier property, ductility and internal corrosivity, and in addition, the graphene-based aluminum-plastic film has the good white line after shell punching and heat-seal collosol aluminum leakage prevention effect, and has the advantages of long service life and low production cost.
Compared with the embodiment 5, in the comparative example 4, the aluminum-plastic film prepared by the prior art is cured and formed at the constant temperature of 40 ℃ in the process for preparing the aluminum-plastic film, and various physical property tests are carried out on the aluminum-plastic film prepared by the process, and analysis shows that the peeling force, the elongation at break and the corrosion resistance efficiency of the aluminum-plastic film are relatively reduced, and the white line and the heat-seal sol leakage prevention effect are obviously weakened after shell punching; the invention shows that the existing high-low temperature curing molding is adopted in the process for preparing the aluminum-plastic film, so that the prepared aluminum-plastic film has good stripping force, elongation at break and corrosion resistance efficiency, and simultaneously, the white line and the heat-seal collosol aluminum leakage prevention effect after shell punching can be obviously improved, so that the prepared aluminum-plastic film has good barrier property, ductility and internal corrosion, and in addition, the invention also has the advantages of good white line and heat-seal collosol aluminum leakage prevention effect after shell punching, long service life and low production cost.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (10)
1. The utility model provides a lithium cell encapsulation is with plastic-aluminum membrane which characterized in that: the aluminum plastic film comprises a polyurethane fiber layer, an aluminum foil layer and a polypropylene heat sealing layer from top to bottom, wherein the aluminum foil layer is attached to the upper surface of the polypropylene heat sealing layer, polyurethane fibers are attached to the upper surface of the aluminum foil layer, the polyurethane fiber layer is attached to the aluminum foil layer through a modified polyolefin adhesive, the aluminum foil layer is attached to the polypropylene heat sealing layer through a polyurethane adhesive, and the modified polyolefin adhesive comprises the following raw materials in parts by weight:
3. the aluminum-plastic film for lithium battery encapsulation according to claim 2, wherein: the modified epoxy resin is prepared by the following method:
s1, adding epoxy resin, melamine and graphene in parts by weight into a stirring device, heating to 60-80 ℃, and stirring at the speed of 200-300r/min for 30-60min to obtain a mixture A for later use;
s2, adding the polyurethane prepolymer and silicon dioxide into the mixture A obtained in the step S1, heating to 80-120 ℃, stirring for 20-40min, adding N, N-dimethylformamide, continuously stirring for 1-3h at the speed of 300-450r/min, and cooling to obtain the modified epoxy resin.
4. The aluminum-plastic film for lithium battery encapsulation according to claim 1, wherein: each part of the curing agent is at least one of p-hydroxybenzene sulfonic acid, n-butyl ester, methyl hexahydrophthalic anhydride and tin laurate.
5. The aluminum-plastic film for lithium battery encapsulation according to claim 1, wherein: each part of the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 619, antioxidant 703, antioxidant BHT, antioxidant 2112 and antioxidant 703.
6. The aluminum-plastic film for lithium battery encapsulation according to claim 1, wherein: each part of the defoaming agent is at least one of polydimethylsiloxane, tributyl phosphate and paraffin.
7. The aluminum-plastic film for lithium battery encapsulation according to claim 1, wherein: each part of the cross-linking agent is a mixture of melamine, polymethylhydrosiloxane and vinyl triethoxysilane according to the weight ratio of 0.6-1.0:0.1-0.5: 0.8-1.2.
8. The aluminum-plastic film for lithium battery encapsulation according to claim 1, wherein: each part of the solvent is at least one of acetone, butyl acetate, ethylene oxide and isoamyl acetate.
9. The aluminum-plastic film for lithium battery pack according to any one of claims 1 to 8, wherein: the modified polyolefin adhesive is prepared by the following method:
e1, dispersing the modified epoxy resin, the polyolefin and the dibenzoyl peroxide into a solvent according to the parts by weight, adding the solvent into a reaction device, heating to 80-100 ℃, and stirring at 450r/min for 20-40min to obtain a mixture A for later use;
e2, mixing the alpha-methyl styrene dimer, the cross-linking agent and the antioxidant, heating to 40-60 ℃, and uniformly stirring to obtain a mixture B for later use;
e3, adding the mixture B obtained in the step E2 and the defoaming agent into the mixture A obtained in the step E1, mixing and heating to 80-100 ℃, stirring for 60-90min at the speed of 250-350r/min, adding the curing agent, continuing stirring for 40-60min, cooling to normal temperature, and filtering to obtain a filtrate, namely the modified polyolefin adhesive.
10. A method for preparing the aluminum plastic film for lithium battery encapsulation according to any one of claims 1 to 8, wherein: the method comprises the following steps:
1) taking a polypropylene heat-sealing layer, pasting a polyurethane adhesive layer on the upper surface of the polypropylene heat-sealing layer, and pasting an aluminum foil layer on the polyurethane adhesive layer;
2) pasting a layer of modified polyolefin adhesive on the upper surface of the aluminum foil layer, and pasting a polyurethane fiber layer on the modified polyolefin adhesive layer to obtain an aluminum-plastic film primary product;
3) placing the primary aluminum-plastic film in an oven, heating to 60-70 ℃, and curing and molding for 4.5-5.5 h;
4) then, the temperature of the oven in the step 3) is increased to 80-90 ℃ for high-temperature curing molding for 71-73 h;
5) and then, reducing the temperature of the oven in the step 4) to 60-70 ℃ for low-temperature forming for 64-66h to obtain the finished product of the aluminum-plastic film.
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CN115000604A (en) * | 2022-06-24 | 2022-09-02 | 江西永德立新能源有限公司 | Preparation process of aluminum plastic film for lithium battery outer package |
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WO2021196669A1 (en) * | 2020-04-03 | 2021-10-07 | 江西明冠锂膜技术有限公司 | Aluminum plastic film for encapsulating lithium battery and preparation method thereof |
CN115000604A (en) * | 2022-06-24 | 2022-09-02 | 江西永德立新能源有限公司 | Preparation process of aluminum plastic film for lithium battery outer package |
CN115000604B (en) * | 2022-06-24 | 2023-09-15 | 江西永德立新能源有限公司 | Preparation process for lithium battery outer package aluminum plastic film |
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