CN115366507A - Nylon film for packaging lithium ion battery and preparation method thereof - Google Patents
Nylon film for packaging lithium ion battery and preparation method thereof Download PDFInfo
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- CN115366507A CN115366507A CN202210968470.1A CN202210968470A CN115366507A CN 115366507 A CN115366507 A CN 115366507A CN 202210968470 A CN202210968470 A CN 202210968470A CN 115366507 A CN115366507 A CN 115366507A
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- nylon
- parts
- resin
- lithium ion
- ion battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 46
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920006284 nylon film Polymers 0.000 title claims description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 178
- 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 89
- 239000004677 Nylon Substances 0.000 claims abstract description 87
- 229920001778 nylon Polymers 0.000 claims abstract description 87
- 239000002344 surface layer Substances 0.000 claims abstract description 72
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 70
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 69
- 239000000654 additive Substances 0.000 claims abstract description 66
- 230000000996 additive effect Effects 0.000 claims abstract description 46
- 239000012792 core layer Substances 0.000 claims abstract description 37
- 239000012528 membrane Substances 0.000 claims abstract description 31
- 229920006020 amorphous polyamide Polymers 0.000 claims abstract description 16
- 229920002292 Nylon 6 Polymers 0.000 claims description 38
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 33
- 239000010410 layer Substances 0.000 claims description 30
- 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
- 239000002904 solvent Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 238000005538 encapsulation Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 238000003756 stirring Methods 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
- 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
- 238000009210 therapy by ultrasound Methods 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
- 238000005266 casting Methods 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
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 238000001354 calcination Methods 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
- 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 3
- 238000009826 distribution Methods 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
- 229920006111 poly(hexamethylene terephthalamide) Polymers 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
- 239000001993 wax Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 38
- 239000002131 composite material Substances 0.000 description 11
- 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
- 238000004080 punching Methods 0.000 description 6
- 229920006233 biaxially oriented polyamide Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000009459 flexible packaging Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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
- 239000002105 nanoparticle Substances 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
- 238000010008 shearing Methods 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000000181 anti-adherent effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 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
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
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
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- 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 batches and a combined additive; the components of the core layer comprise nylon resin and combined additives; the lower surface layer comprises nylon resin, anti-sticking master batches and combined additives; 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 to 15:2 to 10. The nylon membrane film for packaging the lithium ion battery provided by the invention has excellent performance after being treated under high-temperature and high-humidity conditions, so that the problem that the nylon membrane cracks in the use process of downstream customers is solved.
Description
Technical Field
The invention relates to the field of application of a film flexible packaging technology, in particular to a nylon film for packaging a lithium ion battery and a preparation method thereof.
Background
The biaxially oriented nylon film (BOPA) has the characteristics of high tensile strength, excellent puncture resistance, excellent gas barrier property, pinhole resistance, transparency, printing property and the like. BOPA films are rarely used alone in practice and are often combined with other films by glue. In the field of lithium battery flexible packaging and medicine packaging, a composite film with a PA// AL// CPP structure is generally adopted, and the composite film is endowed with deeper 'pit punching depth' by utilizing the excellent flexibility characteristic of BOPA.
For example, patent document CN114132035A (03/04/2022) discloses a biaxially oriented polyamide film, comprising at least three layers of a first polyamide surface layer, a polyamide core layer, and a second polyamide surface layer in sequence from top to bottom; the first polyamide layer and the second polyamide surface layer comprise the following components in percentage by mass: 73 to 86.2 percent of high-viscosity polyamide 6, 10 to 15 percent of copolyamide, 3 to 8 percent of polyamide elastomer, 0.5 to 1 percent of nano particles and 0.3 to 3 percent of other auxiliary agents; the polyamide core layer comprises the following components in percentage by mass: 73 to 86.5 percent of high-viscosity polyamide 6, 10 to 15 percent of copolyamide, 3 to 8 percent of polyamide elastomer and 0.5 to 1 percent 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 field of lithium battery aluminum-plastic composite film packaging.
However, since the lithium ion battery has a high-temperature 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 soft packaging material of the lithium ion battery under the high-temperature high-humidity condition in a laboratory, and researches show 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 membrane film for lithium ion battery encapsulation under the high-temperature and high-humidity condition is still a demand of the industry.
Disclosure of Invention
In order to solve the problem that the performance of the nylon membrane film for packaging the lithium ion battery is reduced under the high-temperature and high-humidity condition in the prior art, the invention provides the nylon membrane film for packaging the lithium ion battery, 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 batches and combined additives;
the components of the core layer comprise nylon resin and combined additives;
the lower surface layer comprises nylon resin, anti-sticking master batches and combined additives;
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 to 15:2 to 10.
The nylon resin of the present invention is a crystalline non-copolymerized polymer, and the amorphous polyamide is an amorphous polyamide, and is generally copolymerized from a plurality of polyamides, and has good toughness, transparency, and the like, and can enhance the toughness and the crater punching performance of the nylon resin.
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, then adding lanthanum chloride, stirring at a constant temperature of 70-90 ℃ to volatilize the solvent, finally placing the solid matter obtained after the solvent is volatilized into a drying oven, drying at 100-125 ℃ for 3-5 h, calcining in a muffle furnace at 680-720 ℃ for 2-3 h, and grinding to obtain the rare earth doped zinc oxide.
In one embodiment, the rare earth doped zinc oxide is doped with n (La) according to the mass ratio of the rare earth doped zinc oxide 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 preparation method specifically comprises the steps of mixing the rare earth doped zinc oxide with a silane coupling agent and stirring 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.
In one embodiment, the silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, 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 consists 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 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, and PA 6T.
In one embodiment, the upper surface layer comprises 1-10 parts by weight of anti-sticking master batch, 3-10 parts by weight of combined additive and 75-96 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 packaging the lithium ion battery, which comprises the following steps:
respectively melting and co-extruding each layer of components to obtain an unstretched cast sheet;
biaxially stretching the unstretched casting sheet to obtain a nylon membrane film for packaging the lithium ion battery;
the nylon membrane 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 batches and combined additives;
the components of the core layer comprise nylon resin and a combined additive;
the lower surface layer comprises nylon resin, anti-sticking master batches and combined additives;
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 to 15:2 to 10.
The nylon membrane film for packaging the lithium ion battery provided by the invention has excellent performance after being treated under high-temperature and high-humidity conditions, so that the problem that the nylon membrane 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 in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a nylon film for packaging a lithium ion battery according to an embodiment of the present invention.
Reference numerals:
100 upper skin 200 core 300 lower skin
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The individual components of the present invention will be explained in more detail below.
An embodiment of the present invention provides a nylon membrane film for lithium ion battery packaging, please refer to fig. 1, wherein the nylon membrane film for lithium ion battery packaging comprises at least three layers, which are an upper layer 100, a core layer 200 and a lower layer 300;
the components of the upper surface layer 100 comprise nylon resin, anti-sticking master batches and combined additives;
the components of the core layer 200 include nylon resin and a combination additive;
the lower surface layer 300 comprises nylon resin, anti-sticking master batches and combined additives;
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 to 15:2 to 10.
In some preferred embodiments, the preparation method of the rare earth doped zinc oxide comprises the following steps: adding nano zinc oxide into deionized water for ultrasonic treatment, then adding lanthanum chloride, stirring at a constant temperature of 70-90 ℃ to volatilize the solvent, finally placing the solid matter obtained after the solvent is volatilized into a drying oven for drying at 100-125 ℃ for 3-5 h, placing the solid matter into a muffle furnace for calcining at 680-720 ℃ for 2-3 h, and then grinding to obtain the rare earth doped zinc oxide.
In some preferred embodiments, the rare earth doped zinc oxide is present in the rare earth doped zinc oxide in a mass ration(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 preparation method specifically comprises the steps of mixing the rare earth doped zinc oxide with a silane coupling agent and stirring 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.
The silane coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane and vinyltris (beta-methoxyethoxy) silane.
In some preferred embodiments, the total thickness of the film is 15 to 30 μm, wherein the thickness of each of the upper and lower surface layers is 1 to 3 μm.
In some preferred embodiments, the release masterbatch is composed of 80 to 96 parts of nylon resin, 2 to 10 parts of an anti-adhesive agent, and 2 to 8 parts of a slipping agent.
In some preferred embodiments, 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 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 6T.
In some preferred embodiments, the upper surface layer comprises 1 to 10 parts by weight of the anti-sticking master batch, 3 to 10 parts by weight of the combined additive and 75 to 96 parts by weight of the 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.
An embodiment of the present invention further provides a method for preparing a nylon membrane film for lithium ion battery encapsulation, including the following steps:
respectively melting and co-extruding the components of each layer to obtain an unstretched cast sheet;
biaxially stretching the unstretched casting sheet to obtain a nylon membrane film for packaging the lithium ion battery;
the nylon membrane 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 batches and combined additives;
the components of the core layer comprise nylon resin and combined additives;
the lower surface layer comprises nylon resin, anti-sticking master batches and combined additives;
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 to 15:2 to 10.
Specifically, another embodiment of the present invention provides a method for preparing a nylon film for lithium ion battery encapsulation, including the following steps:
step a, mixing the raw materials of the upper surface layer, the core layer and the lower surface layer according to a formula ratio, shearing and plasticizing the raw materials into melt in an extruder, filtering the melt by a filter screen, and co-extruding the melt into a sheet through a T-shaped opening;
b, attaching the slice to a chilled roller quenching cast slice with the surface temperature of 15-40 ℃ by a low-pressure air knife;
c, humidifying the casting sheet in a water tank at the temperature of 25-70 ℃, drying the residual moisture on the surface of the humidified casting sheet by using an air knife, and stretching the casting sheet transversely and longitudinally synchronously, wherein the stretching temperature is 120-195 ℃ and the stretching magnification is 2.6 multiplied by 2.6-3.4 multiplied by 3.4.
And d, performing heat setting treatment on the stretched film at the temperature of 200-215 ℃, performing corona treatment on at least one surface layer of the film, then rolling and cutting into finished products.
For a better understanding of the invention, the invention is described in detail below with reference to specific examples and to the scale, without restricting the invention in any way.
Example 1
Referring to fig. 1, the nylon film for packaging a lithium ion battery provided in this embodiment includes at least three layers, namely, an upper layer 100, a core layer 200, and a lower layer 300.
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;
The anti-sticking master batch of the embodiment is composed of 96 parts of nylon 6 resin, 2 parts of silicon dioxide and 2 parts of ethylene bis stearamide;
the additive package 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 of the embodiment comprises the following steps: adding a proper amount of nano zinc oxide into deionized water, carrying out ultrasonic treatment for 1.5h, then adding lanthanum chloride, stirring at constant temperature of 85 ℃ to volatilize the solvent, finally, placing the solid substance after the solvent volatilization into a drying oven to be dried for 4.5h at 115 ℃, placing the solid substance into a muffle furnace to be calcined for 2.5h at 700 ℃, and then carrying out grinding treatment to obtain rare earth doped zinc oxide, wherein the rare earth doped zinc oxide contains n (La) according to the mass ratio of the substance 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 and the silane coupling agent are mixed and stirred in a mixer for 3min, and 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 15 μm, wherein the thickness of each of the upper and lower skin layers was 1.5. Mu.m.
The preparation method of the nylon membrane for packaging the lithium ion battery comprises the following specific steps:
step a, mixing the raw materials of the upper surface layer, the core layer and the lower surface layer according to a formula ratio, shearing and plasticizing the raw materials into melt in an extruder, filtering the melt by a filter screen, and co-extruding the melt into a sheet through a T-shaped opening;
b, attaching the slice to a chilled roller quenching cast slice with the surface temperature of 15-40 ℃ by a low-pressure air knife;
and c, humidifying the cast piece in a water tank at 25-70 ℃, drying the residual moisture on the surface of the humidified cast piece by using an air knife, and stretching the surface of the humidified cast piece synchronously in the transverse direction and the longitudinal direction, wherein the stretching temperature is 120-195 ℃, and the stretching magnification is 2.6 multiplied by 2.6-3.4 multiplied by 3.4.
And d, performing heat setting treatment on the stretched film at the temperature of 200-215 ℃, performing corona treatment on at least one surface layer of the film, then rolling and cutting into finished products.
Example 2
Referring to fig. 1, the nylon film for packaging a lithium ion battery provided in this embodiment includes at least three layers, which are an upper layer 100, a core layer 200, and a lower layer 300.
The upper surface layer comprises 80 parts by weight of nylon 6 resin, 10 parts by weight of anti-sticking master batch and 10 parts by weight of combined additive;
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 release masterbatch and 8 parts combination additive.
The release masterbatch of this example consisted of 91 parts nylon 6 resin, 4 parts cross-linked polystyrene, 1 part silica, and 4 parts oleamide.
The additive package 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 of the embodiment comprises the following steps: adding proper amount of nano zinc oxide into deionized water to obtain the invented productPerforming sound treatment for 1.5h, adding lanthanum chloride, stirring at constant temperature of 85 ℃ to volatilize the solvent, finally, placing the solid substance after the solvent volatilization in a drying oven for drying at 115 ℃ for 4.5h, placing the dried solid substance in a muffle furnace for calcining at 700 ℃ for 2.5h, and then grinding to obtain the rare earth doped zinc oxide, wherein the rare earth doped zinc oxide contains n (La) according to the mass ratio of the substance 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 and the silane coupling agent are mixed and stirred in a mixer for 3min, and 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 film for lithium ion battery encapsulation of the present example is the same as that of example 1.
Example 3
Referring to fig. 1, the nylon film for packaging a lithium ion battery provided in this embodiment includes at least three layers, namely, an upper layer 100, a core layer 200, and a lower layer 300.
The upper surface layer comprises 77 parts by weight of nylon 6 resin, 8 parts by weight of anti-sticking master batch and 5 parts by weight of combined additive;
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 comprised 84 parts nylon 6/66 resin, 6 parts release masterbatch and 10 parts combination additive.
The release masterbatch of this example consisted of 90 parts nylon 6 resin, 5 parts cross-linked polystyrene, 1 part silica and 5 parts oleamide.
The additive package 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 of the embodiment comprises the following steps: adding appropriate amount of nanometer zinc oxide into deionized water, performing ultrasonic treatment for 1.5h, adding lanthanum chloride, stirring at constant temperature of 85 deg.C to volatilize solvent, and dissolvingDrying the solid substance volatilized by the agent in a drying oven at 115 ℃ for 4.5h, calcining the dried solid substance in a muffle furnace at 700 ℃ for 2.5h, and grinding to obtain the rare earth doped zinc oxide, wherein n (La) is 3+ )：n(ZnO)＝1:18。
And the rare earth doped zinc oxide is treated by adopting silane coupling agent gamma-aminopropyltriethoxysilane, the rare earth doped zinc oxide is mixed with the silane coupling agent, the mixture is stirred for 3min in a mixer, and 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 μm, wherein the thickness of the upper and lower surface layers was 3 μm.
The preparation method of the nylon film for lithium ion battery encapsulation of the present example is the same as that of example 1.
Comparative example 1
A nylon membrane for encapsulating a common commercial 25-micron-thick lithium ion battery is provided.
Comparative example 2
Referring to fig. 1, the comparative example provides a nylon film including at least three layers of an upper surface layer 100, a core layer 200 and a lower surface 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 lower surface layer 300 comprises 98 parts of nylon 6 resin and 2 parts of 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 μm, wherein the thickness of each of the upper and lower skin layers was 1.5 μm.
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 comparative example provides a nylon film including at least three layers of a structure of an upper surface layer 100, a core layer 200, and a lower surface layer 300, respectively.
The upper surface layer comprises 80 parts by weight of nylon 6 resin, 10 parts by weight of anti-sticking master batch and 10 parts by weight of combined additive;
the core layer comprises 70 parts of nylon 66 resin, 15 parts of nylon 6/66 and 15 parts of combined additive;
the lower surface layer comprises 86 parts of nylon 6/66 resin, 6 parts of anti-sticking master batch and 8 parts of combined additive.
The anti-sticking master batch of this comparative example was composed of 91 parts of nylon 6 resin, 4 parts of crosslinked polystyrene, 1 part of silica, and 4 parts of oleamide.
The additive package 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 film 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 comparative example provides a nylon film including at least three layers of an upper surface layer 100, a core layer 200 and a lower surface layer 300, respectively.
The upper surface layer comprises 77 parts by weight of nylon 6 resin, 8 parts by weight of anti-sticking master batch and 5 parts by weight of combined additive;
the core layer comprises 75 parts of nylon 6 resin, 20 parts of nylon 610 and 5 parts of combined additive;
the lower surface layer comprises 84 parts of nylon 6/66 resin, 6 parts of anti-sticking master batch and 10 parts of combined additive.
The anti-sticking master batch of this comparative example was composed of 90 parts of nylon 6 resin, 5 parts of crosslinked polystyrene, 1 part of silica, and 5 parts of oleamide.
The additive package 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 appropriate amount of nanometer zinc oxide into deionized water, performing ultrasonic treatment for 1.5h, adding lanthanum chloride, stirring at constant temperature of 85 deg.C to volatilize solvent, drying the solid material volatilized from solvent in a drying oven at 115 deg.C for 4.5h, and placing into horseCalcining the mixture for 2.5 hours at 700 ℃ in a muffle furnace, and grinding the calcined mixture 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 and the silane coupling agent are mixed and stirred in a mixer for 3min, and 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 μm, wherein the thickness of each of the upper and lower skin layers was 3 μm.
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 comparative example provides a nylon film including at least three layers of an upper surface layer 100, a core layer 200 and a lower surface layer 300, respectively.
The upper surface layer comprises 77 parts by weight of nylon 6 resin, 8 parts by weight of anti-sticking master batch and 5 parts by weight of combined additive;
the core layer comprises 75 parts of nylon 6 resin, 20 parts of nylon 610 and 5 parts of combined additive;
the lower surface layer comprises 84 parts of nylon 6/66 resin, 6 parts of anti-sticking master batch and 10 parts of combined additive.
The anti-sticking master batch of this comparative example was composed of 90 parts of nylon 6 resin, 5 parts of crosslinked polystyrene, 1 part of silica, and 5 parts of oleamide.
The additive package 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 a proper amount of nano zinc oxide into deionized water, carrying out ultrasonic treatment for 1.5h, then adding lanthanum chloride, stirring at constant temperature of 85 ℃ to volatilize the solvent, finally, placing the solid substance after the solvent volatilization into a drying oven to be dried for 4.5h at 115 ℃, placing the solid substance into a muffle furnace to be calcined for 2.5h at 700 ℃, and then carrying out grinding treatment to obtain the rare earth doped zinc oxide, wherein n (La) is used as the rare earth doped zinc oxide 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 and the silane coupling agent are mixed and stirred in a mixer for 3min, and the dosage of the silane coupling agent is 0.2 percent of the weight of the rare earth doped zinc oxide.
The film of this comparative example had a total thickness of 15 μm, wherein the upper and lower surface layers each had a thickness of 2 μm.
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 film of this comparative example includes at least three layers of 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;
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 additive package 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 a proper amount of nano zinc oxide into deionized water, carrying out ultrasonic treatment for 1.5h, then adding neodymium chloride, stirring at constant temperature of 85 ℃ to volatilize the solvent, finally, placing the solid substance after the solvent volatilization into a drying oven to dry for 4.5h at 115 ℃, placing the solid substance into a muffle furnace to calcine for 2.5h at 700 ℃, and then carrying out grinding treatment to obtain the rare earth doped zinc oxide, wherein the rare earth doped zinc oxide contains n (Nd) according to the mass ratio 3+ )：n(ZnO)＝1:15。
And the rare earth doped zinc oxide is treated by adopting silane coupling agent gamma-aminopropyltriethoxysilane, the rare earth doped zinc oxide is mixed with the silane coupling agent, the mixture is stirred for 3min in a mixer, and 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 μm, wherein the thickness of each of the upper and lower skin layers was 1.5 μm.
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 examples or preferred embodiments under the concept of the present invention, and are not limited thereto; those skilled in the art can adapt the method within the spirit and scope of the present invention, and the raw materials used may be commercially available products or prepared by methods conventional in the art unless otherwise specified.
The nylon film for packaging the lithium ion battery prepared in the above examples and comparative examples was subjected to the following tests:
(1) Tensile property: testing before and after high-temperature and high-humidity treatment according to GBT 1040.3-2006 standard; the high-temperature high-humidity treatment method is to place the film in water at 60 ℃ for 5 days.
(1) And (3) fracture condition during molding: the PA/AL/CPP composite film is prepared by using the polyamide films of the examples and the comparative examples, a pit punching mold used in a lithium ion battery aluminum-plastic packaging film factory is used for clamping the PA/AL/CPP composite film, the pit punching depth is 5.5mm, and the cracking condition during molding is observed. If no cracks were observed, it was recorded as ∘; cracks were observed and recorded as Δ.
Fracture status after high-temperature high-humidity treatment: and (3) boiling the PA/AL/CPP composite membrane subjected to pit punching forming in water at 60 ℃ for one week, and observing the cracking condition of the PA membrane in the composite membrane. If no cracks appear in the PA film in the composite film, recording the cracks as √; the appearance of cracks in the PA film in the composite film was recorded as X.
The results of the tests are shown in table 1,
table 1 evaluation table of film property test of examples
TABLE 2 evaluation table for film property test of comparative example
As can be seen from table 1, the nylon films for packaging lithium ion batteries in embodiments 1 to 3 of the present invention still have excellent performance after high temperature and high humidity treatment, and simultaneously have good pit punching performance after the films are combined with aluminum foil and CPP, and the composite films after high temperature and high humidity treatment do not crack BOPA films, and are particularly suitable for flexible packaging of aluminum-plastic composite films. In the comparative example shown in Table 2, it can be seen that the comparative example without the additive package is remarkably deteriorated in physical properties and cracked after molding and high temperature and high humidity treatment, and when the element ratio of the rare earth-doped zinc oxide is out of the range of the present invention, the film is cracked after high temperature and high humidity treatment, and similarly, the film is cracked by rare earth elements other than lanthanum element.
Although terms such as upper skin, core, lower skin, etc. are used more herein, the possibility of using other terms is not excluded. These terms are used merely to more conveniently describe and explain the nature of the present invention; they are to be construed as being without limitation to any additional limitations that may be imposed by the spirit of the present invention.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A kind of lithium ion battery encapsulates and uses the nylon membrane film, characterized by 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 batches and combined additives;
the components of the core layer comprise nylon resin and combined additives;
the lower surface layer comprises nylon resin, anti-sticking master batches and combined additives;
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 to 15:2 to 10.
2. The nylon film for lithium ion battery encapsulation according to claim 1, characterized in that: the preparation method of the rare earth doped zinc oxide comprises the following steps: adding nano zinc oxide into deionized water for ultrasonic treatment, then adding lanthanum chloride, stirring at a constant temperature of 70-90 ℃ to volatilize the solvent, finally placing the solid matter obtained after the solvent is volatilized into a drying oven, drying at 100-125 ℃ for 3-5 h, calcining in a muffle furnace at 680-720 ℃ for 2-3 h, and grinding to obtain the rare earth doped zinc oxide.
3. The nylon film for lithium ion battery encapsulation according to claim 2, wherein: the rare earth doped zinc oxide contains n (La) according to the mass ratio of the substances 3+ )：n(ZnO)＝1:12～1：18。
4. The nylon film for lithium ion battery encapsulation according to claim 1, wherein: the rare earth doped zinc oxide is further treated by a silane coupling agent, the specific mode is that the rare earth doped zinc oxide and the 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.
5. The nylon film for lithium ion battery encapsulation 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 in 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.
6. The nylon film for lithium ion battery encapsulation according to claim 1, characterized in that: 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.
7. The nylon film for lithium ion battery encapsulation according to claim 6, wherein: the anti-caking agent is one or a combination of talcum powder, silicon dioxide, calcium carbonate and crosslinked polystyrene, and the median size of the particle distribution is 0.5-5 um.
8. The nylon film for lithium ion battery encapsulation according to claim 6, wherein: the slipping agent is one or a combination of silicone, ethylene bis stearamide, oleamide, polyethylene waxes and organic silicone oil.
9. The nylon film for lithium ion battery encapsulation 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, PA9T and PA 6T.
10. The nylon film for lithium ion battery encapsulation according to any one of claims 1 to 9, comprising the steps of:
respectively melting and co-extruding each layer of components to obtain an unstretched cast sheet;
biaxially stretching the unstretched casting sheet to obtain a nylon membrane film for packaging the lithium ion battery;
the nylon membrane 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 batches and combined additives;
the components of the core layer comprise nylon resin and combined additives;
the lower surface layer comprises nylon resin, anti-sticking master batches and combined additives;
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 to 15:2 to 10.
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