CN115366507B - Nylon film for lithium ion battery packaging and preparation method thereof - Google Patents
Nylon film for lithium ion battery packaging and preparation method thereof Download PDFInfo
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- CN115366507B CN115366507B CN202210968470.1A CN202210968470A CN115366507B CN 115366507 B CN115366507 B CN 115366507B CN 202210968470 A CN202210968470 A CN 202210968470A CN 115366507 B CN115366507 B CN 115366507B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 42
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 40
- 229920006284 nylon film Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 172
- 229920005989 resin Polymers 0.000 claims abstract description 100
- 239000011347 resin Substances 0.000 claims abstract description 100
- 239000011787 zinc oxide Substances 0.000 claims abstract description 86
- 239000004677 Nylon Substances 0.000 claims abstract description 84
- 229920001778 nylon Polymers 0.000 claims abstract description 84
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 67
- 239000000654 additive Substances 0.000 claims abstract description 66
- 230000000996 additive effect Effects 0.000 claims abstract description 66
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 66
- 239000002344 surface layer Substances 0.000 claims abstract description 61
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 47
- 239000012792 core layer Substances 0.000 claims abstract description 38
- 239000012528 membrane Substances 0.000 claims abstract description 25
- 229920006020 amorphous polyamide Polymers 0.000 claims abstract description 16
- 239000010410 layer Substances 0.000 claims description 40
- 229920002292 Nylon 6 Polymers 0.000 claims description 38
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229920000577 Nylon 6/66 Polymers 0.000 claims description 10
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 8
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 8
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 8
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 8
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 6
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 6
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000571 Nylon 11 Polymers 0.000 claims description 3
- 229920000299 Nylon 12 Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 39
- 239000004952 Polyamide Substances 0.000 description 10
- 229920002647 polyamide Polymers 0.000 description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 8
- 239000000155 melt Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000004080 punching Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229920006233 biaxially oriented polyamide Polymers 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 238000009459 flexible packaging Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 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
- 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
- B32B5/22—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—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 the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/105—Pouches or flexible bags
-
- 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
- B32B2262/0261—Polyamide fibres
-
- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a nylon membrane film for packaging a lithium ion battery and a preparation method thereof, wherein the nylon membrane film for packaging the lithium ion battery comprises an upper surface layer, a core layer and a lower surface layer, and the components of the upper surface layer comprise nylon resin, anti-sticking master batch and a combined additive; the components of the core layer comprise nylon resin and combined additive; the components of the lower surface layer comprise nylon resin, anti-sticking master batch and a combined additive; the combined additive is prepared from nylon resin, amorphous polyamide resin and rare earth doped zinc oxide according to the mass ratio of 75-93: 5-15: 2-10. The nylon film for packaging the lithium ion battery still has excellent performance after being treated under high-temperature and high-humidity conditions, so that the problem that the nylon film cracks in the use process of downstream customers is solved.
Description
Technical Field
The invention relates to the application field of film flexible packaging technology, in particular to a nylon film for packaging a lithium ion battery and a preparation method thereof.
Background
Biaxially oriented nylon film (BOPA) has the characteristics of high tensile strength, excellent puncture resistance, excellent gas barrier property, pinhole resistance, transparency, printability and the like. BOPA films are rarely used alone in practical applications, and are typically combined with other films by glue. In the field of flexible packaging and medicine packaging of lithium batteries, a composite film with a PA// AL// CPP structure is generally adopted, and the composite film is endowed with a deeper pit depth by utilizing the excellent flexibility characteristic of BOPA.
A biaxially oriented polyamide film as disclosed in patent document publication No. CN114132035a (2022, 03, 04), comprising at least three layers of a first polyamide skin layer, a polyamide core layer, a second polyamide skin layer in this order from top to bottom; the first polyamide layer and the second polyamide surface layer comprise the following components in percentage by mass: 73-86.2% of high-viscosity polyamide 6, 10-15% of copolyamide, 3-8% of polyamide elastomer, 0.5-1% of nano particles and 0.3-3% of other auxiliary agents; the polyamide core layer comprises the following components in percentage by mass: 73-86.5% of high-viscosity polyamide 6, 10-15% of copolyamide, 3-8% of polyamide elastomer and 0.5-1% of nano particles; the viscosity of the high-viscosity polyamide 6 is 3.5-3.8 Pa.s. The film has excellent impact resistance, and is particularly suitable for the packaging field of aluminum-plastic composite films of lithium batteries.
However, since the lithium ion battery has a high-temperature and high-humidity application scene in daily use, in order to ensure the use safety of the lithium ion battery, downstream manufacturers generally simulate the use condition of the lithium ion battery soft package material under the high-temperature and high-humidity condition in a laboratory, and researches find that the performance of the common nylon film for packaging the lithium ion battery is obviously reduced after the nylon film is boiled in water at 60 ℃ for one week. Therefore, how to ensure the excellent performance of the nylon film for lithium ion battery packaging under high temperature and high humidity conditions is still a requirement of the industry.
Disclosure of Invention
In order to solve the problem of performance degradation under high temperature and high humidity conditions in the nylon film for lithium ion battery packaging in the prior art, the invention provides a nylon film for lithium ion battery packaging, which comprises an upper surface layer, a core layer and a lower surface layer,
the components of the upper surface layer comprise nylon resin, anti-sticking master batch and a combined additive;
the components of the core layer comprise nylon resin and combined additive;
the components of the lower surface layer comprise nylon resin, anti-sticking master batch and a combined additive;
the composite additive is prepared from nylon resin, amorphous polyamide resin and rare earth doped zinc oxide according to the mass ratio of 75-93: 5-15: 2-10.
The nylon resin of the present invention is a crystalline non-copolymer polymer, and the amorphous polyamide is a non-crystalline polyamide, and is generally copolymerized from a plurality of polyamides, and has excellent toughness, transparency, etc., and can enhance toughness of the nylon resin and pit punching performance.
In one embodiment, the preparation method of the rare earth doped zinc oxide comprises the following steps: adding nano zinc oxide into deionized water for ultrasonic treatment, adding lanthanum chloride, stirring at a constant temperature of 70-90 ℃ to volatilize a solvent, finally, placing a solid substance obtained after the solvent is volatilized into a drying oven to be dried for 3-5 hours at a temperature of 100-125 ℃, placing the solid substance into a muffle furnace to be calcined for 2-3 hours at a temperature of 680-720 ℃, and grinding to obtain the rare earth doped zinc oxide.
In one embodiment, the rare earth doped zinc oxide has a mass ratio n (La 3+ )：n(ZnO)＝1:12～1：18。
In one embodiment, the rare earth doped zinc oxide is further treated with a silane coupling agent to increase the compatibility of the rare earth doped zinc oxide with the nylon resin matrix. The specific mode is that rare earth doped zinc oxide and a silane coupling agent are mixed and stirred in a mixer for at least 3min, and the dosage of the silane coupling agent is 0.1-0.4% of the mass of the rare earth doped zinc oxide.
In one embodiment, the silane coupling agent is at least one of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, vinyltriethoxysilane, and vinyltris (beta-methoxyethoxy) silane.
In one embodiment, the total thickness of the film is 15-30 μm, wherein the thickness of the upper surface layer and the lower surface layer is 1-3 μm.
In one embodiment, the anti-sticking master batch is composed of 80-96 parts of nylon resin, 2-10 parts of anti-sticking agent and 2-8 parts of slipping agent.
In one embodiment, the anti-caking agent is one or more of talcum powder, silicon dioxide, calcium carbonate and crosslinked polystyrene, and the median size of the particle distribution is 0.5-5 um; the slipping agent is one or a combination of more of silicone, ethylene bis stearamide, oleamide, polyethylene waxes and organic silicone oil.
In one embodiment, the nylon resin is at least one of nylon 6, nylon 66, nylon 612, nylon 510, nylon 610, nylon 612, nylon 1010, nylon 11, nylon 12, nylon 1212, nylon 6/66, nylon MXD-6, PA9T, PA T.
In one embodiment, the upper surface layer comprises 1 to 10 parts by weight of anti-sticking master batch, 3 to 10 parts by weight of combined additive and 75 to 96 parts by weight of nylon resin;
the core layer comprises 85-95 parts of nylon resin and 5-15 parts of combined additive;
the lower surface layer comprises 75-96 parts of nylon resin, 1-10 parts of anti-sticking master batch and 3-10 parts of combined additive.
The invention also provides a preparation method of the nylon membrane film for lithium ion battery packaging, which comprises the following steps:
respectively melting and co-extruding all the layers to obtain an unstretched cast sheet;
biaxially stretching the unstretched cast sheet to obtain a nylon film for packaging the lithium ion battery;
the nylon film for packaging the lithium ion battery at least comprises an upper surface layer, a core layer and a lower surface layer,
the components of the upper surface layer comprise nylon resin, anti-sticking master batch and a combined additive;
the components of the core layer comprise nylon resin and combined additive;
the components of the lower surface layer comprise nylon resin, anti-sticking master batch and a combined additive;
the composite additive is prepared from nylon resin, amorphous polyamide resin and rare earth doped zinc oxide according to the mass ratio of 75-93: 5-15: 2-10.
The nylon film for packaging the lithium ion battery still has excellent performance after being treated under high-temperature and high-humidity conditions, so that the problem that the nylon film cracks in the use process of downstream customers is solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it will be obvious that the drawings in the following description are some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
Fig. 1 is a schematic structural diagram of a nylon membrane film for packaging a lithium ion battery according to an embodiment of the invention.
Reference numerals:
100 upper skin 200 core 300 lower skin
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The individual components of the invention will be explained in more detail below.
Referring to fig. 1, the nylon film for packaging a lithium ion battery includes at least three layers, an upper surface layer 100, a core layer 200 and a lower surface layer 300;
the components of the upper surface layer 100 include nylon resin, anti-sticking master batch and combination additive;
the components of the core layer 200 include nylon resin and a combination additive;
the components of the lower surface layer 300 include nylon resin, anti-sticking master batch and combination additive;
the composite additive is prepared from nylon resin, amorphous polyamide resin and rare earth doped zinc oxide according to the mass ratio of 75-93: 5-15: 2-10.
In some preferred embodiments, the rare earth doped zinc oxide is prepared by: adding nano zinc oxide into deionized water for ultrasonic treatment, adding lanthanum chloride, stirring at a constant temperature of 70-90 ℃ to volatilize a solvent, finally, placing a solid substance obtained after the solvent is volatilized into a drying oven to be dried for 3-5 hours at a temperature of 100-125 ℃, placing the solid substance into a muffle furnace to be calcined for 2-3 hours at a temperature of 680-720 ℃, and grinding to obtain the rare earth doped zinc oxide.
In some preferred embodiments, the rare earth doped zinc oxide has a mass ratio n (La 3+ )：n(ZnO)＝1:12～1:18。
In some preferred embodiments, the rare earth doped zinc oxide is further treated with a silane coupling agent to increase the compatibility of the rare earth doped zinc oxide with the nylon resin matrix. The specific mode is that rare earth doped zinc oxide and a silane coupling agent are mixed and stirred in a mixer for at least 3min, and the dosage of the silane coupling agent is 0.1-0.4% of the mass of the rare earth doped zinc oxide.
The silane coupling agent is at least one of gamma-aminopropyl triethoxysilane, gamma-glycidol ether oxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, vinyl triethoxysilane and vinyl tri (beta-methoxyethoxy) silane.
In some preferred embodiments, the total film thickness is 15 to 30 μm, wherein the upper and lower skin layers each have a thickness of 1 to 3 μm.
In some preferred embodiments, the anti-sticking master batch is composed of 80 to 96 parts of nylon resin, 2 to 10 parts of anti-sticking agent, and 2 to 8 parts of slipping agent.
In some preferred embodiments, the anti-binder is one or more of talc, silica, calcium carbonate, and crosslinked polystyrene, and has a median particle size in the range of 0.5 to 5um; the slipping agent is one or a combination of more of silicone, ethylene bis stearamide, oleamide, polyethylene waxes and organic silicone oil.
In some preferred embodiments, the nylon resin is at least one of nylon 6, nylon 66, nylon 612, nylon 510, nylon 610, nylon 612, nylon 1010, nylon 11, nylon 12, nylon 1212, nylon 6/66, nylon MXD-6, PA9T, PA T.
In some preferred embodiments, the upper surface layer comprises, in parts by weight, 1 to 10 parts of an anti-sticking masterbatch, 3 to 10 parts of a combination additive, and 75 to 96 parts of a nylon resin;
the core layer comprises 85-95 parts of nylon resin and 5-15 parts of combined additive;
the lower surface layer comprises 75-96 parts of nylon resin, 1-10 parts of anti-sticking master batch and 3-10 parts of combined additive.
The embodiment of the invention also provides a preparation method of the nylon membrane film for packaging the lithium ion battery, which comprises the following steps:
respectively melting and co-extruding all the layers to obtain an unstretched cast sheet;
biaxially stretching the unstretched cast sheet to obtain a nylon film for packaging the lithium ion battery;
the nylon film for packaging the lithium ion battery at least comprises an upper surface layer, a core layer and a lower surface layer,
the components of the upper surface layer comprise nylon resin, anti-sticking master batch and a combined additive;
the components of the core layer comprise nylon resin and combined additive;
the components of the lower surface layer comprise nylon resin, anti-sticking master batch and a combined additive;
the composite additive is prepared from nylon resin, amorphous polyamide resin and rare earth doped zinc oxide according to the mass ratio of 75-93: 5-15: 2-10.
Specifically, another embodiment of the present invention provides a method for preparing a nylon membrane film for packaging a lithium ion battery, comprising the following steps:
step a, respectively mixing the raw materials of the upper surface layer, the core layer and the lower surface layer according to the formula proportion, respectively adopting an extruder to shear and plasticize the raw materials into a melt, filtering the melt by a filter screen, and then co-extruding the melt into a sheet through a T-shaped port;
step b, attaching the sheet to a chilled roll quenching cast sheet with the surface temperature of 15-40 ℃ through a low-pressure air knife;
and c, carrying out humidity regulation treatment on the cast sheet in a water tank at the temperature of between 25 and 70 ℃, drying residual moisture on the surface of the humidified cast sheet by an air knife, and carrying out horizontal and longitudinal synchronous stretching, wherein the stretching temperature is between 120 and 195 ℃ and the stretching multiplying power is between 2.6X2.6 and 3.4X3.4.
And d, carrying out heat setting treatment on the stretched film at 200-215 ℃, carrying out corona treatment on at least one surface layer of the film, rolling, and cutting into finished products.
For a better understanding of the present invention, the present invention will be described in detail below with reference to specific examples and comparative examples, without limiting the present invention in any way.
Example 1
Referring to fig. 1, the nylon film for lithium ion battery packaging provided in this embodiment includes at least three layers, which are an upper surface layer 100, a core layer 200, and a lower surface layer 300, respectively.
The upper surface layer 100 comprises 96 parts by weight of nylon 6 resin, 1 part by weight of anti-sticking master batch and 3 parts by weight of combined additive;
core layer 200 comprises 90 parts nylon 6 resin and 10 parts combination additive;
the lower skin 300 includes 92 parts nylon 6 resin, 3 parts anti-sticking master batch, and 5 parts combination additive.
The anti-sticking master batch of the embodiment consists of 96 parts of nylon 6 resin, 2 parts of silicon dioxide and 2 parts of ethylene bis stearamide;
the combined additive of this example consisted of 90 parts nylon 6 resin, 5 parts amorphous polyamide resin and 5 parts rare earth doped zinc oxide.
The preparation method of the rare earth doped zinc oxide comprises the following steps: adding proper amount of nano zinc oxide into deionized water, ultrasonic treating for 1.5h, adding lanthanum chloride, stirring at constant temperature of 85 ℃ to volatilize the solvent, finally, placing the solid matters volatilized by the solvent into a drying box, drying at 115 ℃ for 4.5h, placing the solid matters into a muffle furnace, calcining at 700 ℃ for 2.5h, and grinding to obtain rare earth doped zinc oxide, wherein the rare earth doped zinc oxide is prepared according to the mass ratio n (La 3+ )：n(ZnO)＝1:15。
And the rare earth doped zinc oxide is treated by adopting silane coupling agent gamma-aminopropyl triethoxysilane, the rare earth doped zinc oxide is mixed with the silane coupling agent, and the mixture is stirred for 3min in a mixer, wherein the dosage of the silane coupling agent is 0.2 percent of the weight of the rare earth doped zinc oxide.
The total film thickness of this example was 15 μm, wherein the upper and lower skin layers were each 1.5 μm thick.
The preparation method of the nylon membrane for lithium ion battery packaging in the embodiment comprises the following specific steps:
step a, respectively mixing the raw materials of the upper surface layer, the core layer and the lower surface layer according to the formula proportion, respectively adopting an extruder to shear and plasticize the raw materials into a melt, filtering the melt by a filter screen, and then co-extruding the melt into a sheet through a T-shaped port;
step b, attaching the sheet to a chilled roll quenching cast sheet with the surface temperature of 15-40 ℃ through a low-pressure air knife;
and c, carrying out humidity regulation treatment on the cast sheet in a water tank at the temperature of between 25 and 70 ℃, drying residual moisture on the surface of the humidified cast sheet by an air knife, and carrying out horizontal and longitudinal synchronous stretching, wherein the stretching temperature is between 120 and 195 ℃ and the stretching multiplying power is between 2.6X2.6 and 3.4X3.4.
And d, carrying out heat setting treatment on the stretched film at 200-215 ℃, carrying out corona treatment on at least one surface layer of the film, rolling, and cutting into finished products.
Example 2
Referring to fig. 1, the nylon film for lithium ion battery packaging provided in this embodiment includes at least three layers, which are an upper surface layer 100, a core layer 200, and a lower surface layer 300, respectively.
The upper surface layer comprises 80 parts of nylon 6 resin, 10 parts of anti-sticking master batch and 10 parts of combined additive in parts by weight;
the core layer comprises 70 parts of nylon 66 resin, 15 parts of nylon 6/66 and 15 parts of combined additive;
the lower skin layer included 86 parts nylon 6/66 resin, 6 parts anti-sticking masterbatch and 8 parts combination additive.
The release master batch of this example consisted of 91 parts nylon 6 resin, 4 parts crosslinked polystyrene, 1 part silica and 4 parts oleamide.
The combined additive of this example consisted of 65 parts nylon 6 resin, 15 parts nylon 66, 10 parts amorphous polyamide resin and 10 parts rare earth doped zinc oxide.
The preparation method of the rare earth doped zinc oxide comprises the following steps: adding proper amount of nano zinc oxide into deionized water, ultrasonic treating for 1.5h, adding lanthanum chloride, stirring at constant temperature of 85 ℃ to volatilize the solvent, finally, placing the solid matters volatilized by the solvent into a drying box, drying at 115 ℃ for 4.5h, placing the solid matters into a muffle furnace, calcining at 700 ℃ for 2.5h, and grinding to obtain rare earth doped zinc oxide, wherein the rare earth doped zinc oxide is prepared according to the mass ratio n (La 3+ )：n(ZnO)＝1:12。
And the rare earth doped zinc oxide is treated by adopting silane coupling agent gamma-aminopropyl triethoxysilane, the rare earth doped zinc oxide is mixed with the silane coupling agent, and the mixture is stirred for 3min in a mixer, wherein the dosage of the silane coupling agent is 0.2 percent of the weight of the rare earth doped zinc oxide.
The total thickness of the film of this example was 25 μm; wherein the thickness of the upper surface layer and the lower surface layer is 2.5 μm.
The preparation method of the nylon membrane for lithium ion battery packaging of this example is the same as that of example 1.
Example 3
Referring to fig. 1, the nylon film for lithium ion battery packaging provided in this embodiment includes at least three layers, which are an upper surface layer 100, a core layer 200, and a lower surface layer 300, respectively.
The upper surface layer comprises 77 parts of nylon 6 resin, 8 parts of anti-sticking master batch and 5 parts of combined additive in parts by weight;
the core layer comprises 75 parts of nylon 6 resin, 20 parts of nylon 610 and 5 parts of combined additive;
the lower skin layer included 84 parts nylon 6/66 resin, 6 parts anti-sticking masterbatch and 10 parts combination additive.
The anti-sticking master batch of this example consisted of 90 parts nylon 6 resin, 5 parts crosslinked polystyrene, 1 part silica and 5 parts oleamide.
The combined additive of this example consisted of 80 parts nylon 6 resin, 10 parts amorphous polyamide resin and 10 parts rare earth doped zinc oxide.
The preparation method of the rare earth doped zinc oxide comprises the following steps: adding proper amount of nano zinc oxide into deionized water, ultrasonic treating for 1.5h, adding lanthanum chloride, stirring at constant temperature of 85 ℃ to volatilize the solvent, finally, placing the solid matter after solvent volatilization into a drying oven to dry for 4.5h at 115 ℃, placing the solid matter into a muffle furnace to calcine for 2.5h at 700 ℃, and grinding to obtain rare earth doped zinc oxide, wherein n (La 3+ )：n(ZnO)＝1:18。
And the rare earth doped zinc oxide is treated by adopting silane coupling agent gamma-aminopropyl triethoxysilane, the rare earth doped zinc oxide is mixed with the silane coupling agent, and the mixture is stirred for 3min in a mixer, wherein the dosage of the silane coupling agent is 0.2 percent of the weight of the rare earth doped zinc oxide.
The total thickness of the film of this example was 30. Mu.m, wherein the thickness of both the upper and lower skin layers was 3. Mu.m.
The preparation method of the nylon membrane for lithium ion battery packaging of this example is the same as that of example 1.
Comparative example 1
A common commercial nylon film for packaging a lithium ion battery with a thickness of 25 mu m.
Comparative example 2
Referring to fig. 1, the nylon membrane provided in this comparative example includes at least three layers of structures, an upper skin layer 100, a core layer 200, and a lower skin layer 300, respectively.
The upper surface layer 100 comprises 99 parts of nylon 6 resin and 1 part of anti-sticking master batch in parts by weight;
the core layer 200 includes 100 parts of nylon 6 resin;
the lower skin 300 comprises 98 parts nylon 6 resin, 2 parts anti-sticking master batch.
The anti-sticking master batch of the comparative example consists of 96 parts of nylon 6 resin, 2 parts of silicon dioxide and 2 parts of ethylene bis stearamide;
the total thickness of the film of this comparative example was 15. Mu.m, wherein the thickness of both the upper and lower skin layers was 1.5. Mu.m.
The nylon membrane of this comparative example was prepared in the same manner as in example 1.
Comparative example 3
Referring to fig. 1, the nylon membrane provided in this comparative example includes at least three layers of structures, an upper skin layer 100, a core layer 200, and a lower skin layer 300, respectively.
The upper surface layer comprises 80 parts of nylon 6 resin, 10 parts of anti-sticking master batch and 10 parts of combined additive in parts by weight;
the core layer comprises 70 parts of nylon 66 resin, 15 parts of nylon 6/66 and 15 parts of combined additive;
the lower skin layer included 86 parts nylon 6/66 resin, 6 parts anti-sticking masterbatch and 8 parts combination additive.
The anti-sticking master batch of this comparative example consisted of 91 parts of nylon 6 resin, 4 parts of crosslinked polystyrene, 1 part of silica and 4 parts of oleamide.
The combined additive of this comparative example consisted of 65 parts of nylon 6 resin, 15 parts of nylon 66, 10 parts of amorphous polyamide resin and 10 parts of zinc oxide.
The total thickness of the films of this comparative example was 25 μm; wherein the thickness of the upper surface layer and the lower surface layer is 2.5 μm.
The nylon membrane of this comparative example was prepared in the same manner as in example 1.
Comparative example 4
Referring to fig. 1, the nylon membrane provided in this comparative example includes at least three layers of structures, an upper skin layer 100, a core layer 200, and a lower skin layer 300, respectively.
The upper surface layer comprises 77 parts of nylon 6 resin, 8 parts of anti-sticking master batch and 5 parts of combined additive in parts by weight;
the core layer comprises 75 parts of nylon 6 resin, 20 parts of nylon 610 and 5 parts of combined additive;
the lower skin layer included 84 parts nylon 6/66 resin, 6 parts anti-sticking masterbatch and 10 parts combination additive.
The anti-sticking master batch of this comparative example consisted of 90 parts of nylon 6 resin, 5 parts of crosslinked polystyrene, 1 part of silica and 5 parts of oleamide.
The combined additive of this comparative example consisted of 80 parts nylon 6 resin, 10 parts amorphous polyamide resin and 10 parts rare earth doped zinc oxide.
The preparation method of the rare earth doped zinc oxide of the comparative example comprises the following steps: adding proper amount of nano zinc oxide into deionized water, ultrasonic treating for 1.5h, adding lanthanum chloride, stirring at constant temperature of 85 ℃ to volatilize the solvent, finally, placing the solid matter after solvent volatilization into a drying oven to dry for 4.5h at 115 ℃, placing the solid matter into a muffle furnace to calcine for 2.5h at 700 ℃, and grinding to obtain rare earth doped zinc oxide, wherein n (La 3+ )：n(ZnO)＝1:8。
And the rare earth doped zinc oxide is treated by adopting silane coupling agent gamma-aminopropyl triethoxysilane, the rare earth doped zinc oxide is mixed with the silane coupling agent, and the mixture is stirred for 3min in a mixer, wherein the dosage of the silane coupling agent is 0.2 percent of the weight of the rare earth doped zinc oxide.
The total thickness of the film of this comparative example was 30. Mu.m, wherein the thickness of both the upper and lower skin layers was 3. Mu.m.
The nylon membrane of this comparative example was prepared in the same manner as in example 1.
Comparative example 5
Referring to fig. 1, the nylon membrane provided in this comparative example includes at least three layers of structures, an upper skin layer 100, a core layer 200, and a lower skin layer 300, respectively.
The upper surface layer comprises 77 parts of nylon 6 resin, 8 parts of anti-sticking master batch and 5 parts of combined additive in parts by weight;
the core layer comprises 75 parts of nylon 6 resin, 20 parts of nylon 610 and 5 parts of combined additive;
the lower skin layer included 84 parts nylon 6/66 resin, 6 parts anti-sticking masterbatch and 10 parts combination additive.
The anti-sticking master batch of this comparative example consisted of 90 parts of nylon 6 resin, 5 parts of crosslinked polystyrene, 1 part of silica and 5 parts of oleamide.
The combined additive of this comparative example consisted of 80 parts nylon 6 resin, 10 parts amorphous polyamide resin and 10 parts rare earth doped zinc oxide.
The preparation method of the rare earth doped zinc oxide of the comparative example comprises the following steps: adding proper amount of nano zinc oxide into deionized water, ultrasonic treating for 1.5h, adding lanthanum chloride, stirring at constant temperature of 85 ℃ to volatilize the solvent, finally, placing the solid matter after solvent volatilization into a drying oven to dry for 4.5h at 115 ℃, placing the solid matter into a muffle furnace to calcine for 2.5h at 700 ℃, and grinding to obtain rare earth doped zinc oxide, wherein n (La 3+ )：n(ZnO)＝1:22。
And the rare earth doped zinc oxide is treated by adopting silane coupling agent gamma-aminopropyl triethoxysilane, the rare earth doped zinc oxide is mixed with the silane coupling agent, and the mixture is stirred for 3min in a mixer, wherein the dosage of the silane coupling agent is 0.2 percent of the weight of the rare earth doped zinc oxide.
The total thickness of the film of this comparative example was 15. Mu.m, wherein the thickness of both the upper and lower skin layers was 2. Mu.m.
The nylon membrane of this comparative example was prepared in the same manner as in example 1.
Comparative example 6
Referring to fig. 1, the nylon membrane of the comparative example includes at least three layers of structures, an upper skin layer 100, a core layer 200, and a lower skin layer 300, respectively.
The upper surface layer 100 comprises 96 parts by weight of nylon 6 resin, 1 part by weight of anti-sticking master batch and 3 parts by weight of combined additive;
core layer 200 comprises 90 parts nylon 6 resin and 10 parts combination additive;
the lower skin 300 includes 92 parts nylon 6 resin, 3 parts anti-sticking master batch, and 5 parts combination additive.
The anti-sticking master batch of the comparative example consists of 96 parts of nylon 6 resin, 2 parts of silicon dioxide and 2 parts of ethylene bis stearamide;
the combined additive of this comparative example consisted of 90 parts nylon 6 resin, 5 parts amorphous polyamide resin and 5 parts rare earth doped zinc oxide.
The preparation method of the rare earth doped zinc oxide of the comparative example comprises the following steps: adding proper amount of nano zinc oxide into deionized water, ultrasonic treating for 1.5h, adding neodymium chloride, stirring at constant temperature of 85 ℃ to volatilize the solvent, finally, placing the solid matters volatilized by the solvent into a drying box, drying at 115 ℃ for 4.5h, placing the solid matters into a muffle furnace, calcining at 700 ℃ for 2.5h, and grinding to obtain rare earth doped zinc oxide, wherein the rare earth doped zinc oxide is prepared according to the mass ratio n (Nd 3+ )：n(ZnO)＝1:15。
And the rare earth doped zinc oxide is treated by adopting silane coupling agent gamma-aminopropyl triethoxysilane, the rare earth doped zinc oxide is mixed with the silane coupling agent, and the mixture is stirred for 3min in a mixer, wherein the dosage of the silane coupling agent is 0.2 percent of the weight of the rare earth doped zinc oxide.
The total thickness of the film of this comparative example was 15. Mu.m, wherein the thickness of both the upper and lower skin layers was 1.5. Mu.m.
The nylon membrane of this comparative example was prepared in the same manner as in example 1.
It should be noted that the specific parameters or some common reagents in the above embodiments are specific embodiments or preferred embodiments under the concept of the present invention, and are not limited thereto; the skilled artisan can adapt to the present invention within the spirit and scope thereof, and the raw materials employed may be commercially available products or prepared by methods conventional in the art unless otherwise specified.
The nylon film for lithium ion battery packaging prepared in the above examples and comparative examples are subjected to related item tests, and the test method is as follows:
(1) Tensile properties: testing the high temperature and high humidity before and after treatment according to the GBT 1040.3-2006 standard; the high-temperature high-humidity treatment method is that the film is boiled in water at 60 ℃ for 5 days.
(1) Cracking conditions during molding: the polyamide films of the examples and the comparative examples are prepared into PA/AL/CPP composite films, the PA/AL/CPP composite films are clamped by using a pit punching die used by a lithium ion battery aluminum plastic packaging film factory, the pit punching depth is 5.5mm, and the fracture condition during molding is observed. If no crack was observed, it was recorded as o; cracks were observed as delta.
Fracture state after high temperature and high humidity treatment: and (3) placing the PA/AL/CPP composite film after pit punching molding in water at 60 ℃ for one week, and observing the cracking condition of the PA film in the composite film. If the PA film in the composite film has no cracks, the record is that the PA film is in a V shape; the occurrence of cracks in the PA film in the composite film was recorded as x.
The test results are shown in table 1,
TABLE 1 evaluation Table for film Performance test
TABLE 2 comparative film Performance test evaluation Table
As can be seen from Table 1, the nylon films for packaging lithium ion batteries in examples 1-3 still have excellent performance after high-temperature and high-humidity treatment, and meanwhile, after the films are compounded with aluminum foil and CPP, the films have better pit punching performance, and after the high-temperature and high-humidity treatment, the composite films do not crack, so that the nylon films are particularly suitable for flexible packaging of aluminum-plastic composite films. In the comparative example in Table 2, it was found that the physical properties were remarkably reduced in the comparative example in which the additive combination was not added, and the films were broken after molding and high-temperature and high-humidity treatment, and the films were broken after high-temperature and high-humidity treatment when the element ratio of the rare earth-doped zinc oxide was out of the range of the present invention, and the films were broken similarly to the rare earth elements other than lanthanum.
Although terms such as upper skin layer, core layer, lower skin layer, etc. are more used herein, the possibility of using other terms is not precluded. These terms are used merely for convenience in describing and explaining the nature of the invention; they are to be interpreted as any additional limitation that is not inconsistent with the spirit of the present invention.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (7)
1. A nylon membrane film for lithium ion battery packaging is characterized in that: comprises an upper surface layer, a core layer and a lower surface layer,
the components of the upper surface layer comprise nylon resin, anti-sticking master batch and a combined additive;
the components of the core layer comprise nylon resin and combined additive;
the components of the lower surface layer comprise nylon resin, anti-sticking master batch and a combined additive;
the composite additive is prepared from nylon resin, amorphous polyamide resin and rare earth doped zinc oxide according to the mass ratio of 75-93: 5-15: 2-10 parts;
the preparation method of the rare earth doped zinc oxide comprises the following steps: adding nano zinc oxide into deionized water for ultrasonic treatment, adding lanthanum chloride, stirring at a constant temperature of 70-90 ℃ to volatilize a solvent, finally, placing a solid substance obtained after the solvent is volatilized into a drying oven to be dried for 3-5 hours at a temperature of 100-125 ℃, placing the solid substance into a muffle furnace to be calcined for 2-3 hours at a temperature of 680-720 ℃, and grinding to obtain rare earth doped zinc oxide; the rare earth doped zinc oxide has a mass ratio of n (La 3 + ): n (ZnO) =1:12 to 1:18; the rare earth isThe doped zinc oxide is further treated by a silane coupling agent in a specific mode that the rare earth doped zinc oxide is mixed with the silane coupling agent and stirred in a mixer for at least 3min, wherein the dosage of the silane coupling agent is 0.1-0.4% of the mass of the rare earth doped zinc oxide.
2. The nylon membrane film for lithium ion battery packaging according to claim 1, wherein: the upper surface layer comprises 1-10 parts of anti-sticking master batch, 3-10 parts of combined additive and 75-96 parts of nylon resin according to parts by weight;
the core layer comprises 85-95 parts of nylon resin and 5-15 parts of combined additive;
the lower surface layer comprises 75-96 parts of nylon resin, 1-10 parts of anti-sticking master batch and 3-10 parts of combined additive.
3. The nylon membrane film for lithium ion battery packaging according to claim 1, wherein: the anti-sticking master batch consists of 80-96 parts of nylon resin, 2-10 parts of anti-sticking agent and 2-8 parts of slipping agent.
4. The nylon membrane film for lithium ion battery packaging according to claim 3, wherein: the anti-caking agent is one or a combination of more of talcum powder, silicon dioxide, calcium carbonate and crosslinked polystyrene, and the median size of the particle distribution is 0.5-5 um.
5. The nylon membrane film for lithium ion battery packaging according to claim 3, wherein: the slipping agent is one or a combination of more of silicone, ethylene bis stearamide, oleamide, polyethylene waxes and organic silicone oil.
6. The nylon membrane film for lithium ion battery packaging according to claim 1, wherein: the nylon resin is at least one of nylon 6, nylon 66, nylon 612, nylon 510, nylon 610, nylon 612, nylon 1010, nylon 11, nylon 12, nylon 1212, nylon 6/66, nylon MXD-6 and PA9T, PA T.
7. A nylon film for lithium ion battery packaging according to any one of claims 1 to 6, characterized by comprising the steps of:
respectively melting and co-extruding all the layers to obtain an unstretched cast sheet;
biaxially stretching the unstretched cast sheet to obtain a nylon film for packaging the lithium ion battery;
the nylon film for packaging the lithium ion battery at least comprises an upper surface layer, a core layer and a lower surface layer,
the components of the upper surface layer comprise nylon resin, anti-sticking master batch and a combined additive;
the components of the core layer comprise nylon resin and combined additive;
the components of the lower surface layer comprise nylon resin, anti-sticking master batch and a combined additive;
the composite additive is prepared from nylon resin, amorphous polyamide resin and rare earth doped zinc oxide according to the mass ratio of 75-93: 5-15: 2-10.
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| CN109279642A (en) * | 2018-10-23 | 2019-01-29 | 绍兴文理学院 | A kind of preparation method of rare earth doping zinc oxide |
| CN110524992A (en) * | 2019-09-20 | 2019-12-03 | 厦门长塑实业有限公司 | A kind of compound nylon film and preparation method thereof of lithium battery aluminum-plastic film |
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