WO2024119738A1 - 一种耐腐蚀的铝塑复合膜及其制备方法 - Google Patents

一种耐腐蚀的铝塑复合膜及其制备方法 Download PDF

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WO2024119738A1
WO2024119738A1 PCT/CN2023/097291 CN2023097291W WO2024119738A1 WO 2024119738 A1 WO2024119738 A1 WO 2024119738A1 CN 2023097291 W CN2023097291 W CN 2023097291W WO 2024119738 A1 WO2024119738 A1 WO 2024119738A1
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corrosion
plastic composite
composite film
layer
aluminum
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PCT/CN2023/097291
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English (en)
French (fr)
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杨慧慧
戴平翔
袁功道
徐秋春
戴晓兵
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江西省盛纬材料有限公司
珠海市赛纬电子材料股份有限公司
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Publication of WO2024119738A1 publication Critical patent/WO2024119738A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/02—Layered products comprising a layer of synthetic resin in the form of fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
    • 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
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H01M50/136—Flexibility or foldability
    • 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
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H01M50/145—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against corrosion
    • 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

Definitions

  • the present application relates to the technical field of aluminum-plastic composite films, and more specifically to a corrosion-resistant aluminum-plastic composite film and a preparation method thereof.
  • Lithium-ion batteries are widely used in new energy systems in digital, transportation, military and energy storage.
  • the main soft packaging film for lithium-ion batteries is aluminum-plastic composite film, which is composed of an outer nylon protective layer, an aluminum foil in the middle and an inner CPP (polypropylene) layer.
  • the aluminum-plastic film inevitably contacts the electrolyte during the battery production process, which corrodes the outer surface of the aluminum-plastic film and affects the appearance of the battery.
  • the traditional way is to compound a layer of polyethylene terephthalate film or polybutylene terephthalate film on the outer surface of the aluminum-plastic film to achieve the effect of surface corrosion resistance.
  • the price of the corrosion-resistant film of polyethylene terephthalate film or polybutylene terephthalate film is relatively high, which leads to high production cost of aluminum-plastic film; on the other hand, the thickness of this film is relatively thin, making the composite process difficult.
  • the purpose of the present application is to provide a corrosion-resistant aluminum-plastic composite film and a preparation method thereof.
  • the outermost layer of the aluminum-plastic composite film has excellent corrosion resistance. In the battery production process, it can effectively protect the appearance of the aluminum-plastic film and improve the smoothness and punching ability of the aluminum-plastic composite film.
  • the present application discloses a corrosion-resistant aluminum-plastic composite film, comprising a heat-sealing layer, an aluminum foil layer arranged on the surface of the heat-sealing layer, a nylon layer arranged on the surface of the aluminum foil layer, and a protective layer arranged on the surface of the nylon layer.
  • the raw materials for preparing the protective layer, by weight include 100 parts of a soluble
  • the invention relates to a soluble fluororesin, 25-40 parts of an isocyanate curing agent, and 267-290 parts of a lubricant diluent, wherein the soluble fluororesin contains a hydroxyl functional group.
  • the corrosion-resistant aluminum-plastic composite film of the present application has excellent corrosion resistance of the outermost layer by setting a protective layer on the outer surface of the nylon layer, wherein the protective layer is compounded with a soluble fluororesin containing a hydroxyl functional group, an isocyanate curing agent, and a lubricant diluent, which can not only achieve good corrosion resistance of the aluminum-plastic composite film, effectively protect the appearance of the aluminum-plastic film in the battery production process, but also improve the lubricity and punching ability of the aluminum-plastic composite film.
  • the content of isocyanate curing agent can be but not limited to 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, and 40 parts by weight;
  • the content of lubricant diluent can be but not limited to 267 parts, 275 parts, 280 parts, 285 parts, and 290 parts.
  • the lubricant diluent is prepared by dissolving a lubricant in a solvent, and the lubricant is selected from at least one of stearic acid amide, ethylene bis stearic acid amide, silicone oil, and erucic acid amide.
  • the content of the lubricant in the lubricant diluent is 0.25%-1.0% by mass.
  • the content of the lubricant in the lubricant diluent may be, but is not limited to, 0.25%, 0.50%, 0.75%, or 1.0%.
  • the solvent is selected from aromatic solvents.
  • the aromatic solvent is selected from at least one of xylene and ethylbenzene.
  • the present application provides a method for preparing a corrosion-resistant aluminum-plastic composite film, comprising the steps of:
  • a protective layer coating liquid is applied to the surface of the nylon layer and baked to form a protective layer on the surface of the nylon layer.
  • the protective layer is applied to the surface of the nylon layer and baked to form a protective layer on the surface of the nylon layer.
  • the baking temperature is at least 180°C.
  • the baking temperature may be but is not limited to 180°C, 185°C, 190°C, 195°C, 200°C, etc. If the temperature is low, short-term drying will cause the protective layer to fail to form a solid coating on the surface of the nylon layer, resulting in poor corrosion resistance. In addition, due to the loose structure of the surface, the corrosion-resistant layer fails to form a good film. If a longer drying time is used, the production efficiency is reduced.
  • the coating amount of the protective layer coating liquid is 3-5 g/m 2 .
  • the coating amount of the protective layer coating liquid may be, but is not limited to, 3 g/m 2 , 3.5 g/m 2 , 4 g/m 2 , 4.5 g/m 2 , or 5 g/m 2 .
  • a lower coating amount may result in poor corrosion resistance, deep punching performance, and slip performance.
  • the baking time is greater than 30 seconds.
  • the baking time may be, but is not limited to, 30 seconds, 35 seconds, 40 seconds, 45 seconds, or 50 seconds.
  • a method for preparing a corrosion-resistant aluminum-plastic composite film comprises the following steps:
  • the passivation solution is prepared by mixing chromium nitrate, water-based epoxy resin, sodium fluoride and water in a mass ratio of 2:5:1:92, and then adjusting the pH to 3-4 with phosphoric acid.
  • the passivation solution is used to passivate the aluminum foil on both sides, and then dried at 150°C for standby use.
  • the protective layer coating solution is prepared as follows:
  • a method for preparing a corrosion-resistant aluminum-plastic composite film comprises the following steps:
  • the passivation solution is prepared by containing chromium nitrate, water-based epoxy resin, sodium fluoride and phosphoric acid, wherein chromium nitrate, water-based epoxy resin, sodium fluoride and water are mixed in a mass ratio of 2:5:1:92, and then the pH is adjusted to 3-4 with phosphoric acid, and the passivation solution is used to passivate the double-sided aluminum foil, and then dried at 150°C for standby use;
  • the protective layer coating solution is prepared as follows:
  • Example 3 is basically the same as Example 1, except that the lubricant in Example 3 is silicone oil, while the lubricant in Example 1 is ethylene bis stearamide. The rest is the same as Example 1 and will not be elaborated here.
  • the preparation method of the aluminum-plastic composite film comprises the steps of:
  • the passivation solution is prepared by containing chromium nitrate, water-based epoxy resin, sodium fluoride and phosphoric acid, wherein chromium nitrate, water-based epoxy resin, sodium fluoride and water are mixed in a mass ratio of 2:5:1:92, and then the pH is adjusted to 3-4 with phosphoric acid, and the passivation solution is used to passivate the double-sided aluminum foil, and then dried at 150°C for standby use;
  • the matte surface of the aluminum foil is dry-compounded with a long plastic 25 ⁇ m nylon membrane and cured at 60° C. for 3 days to obtain the product.
  • This comparative example is basically the same as Example 1, except that the coating amount of the protective layer coating liquid in Comparative Example 2 is 2 g/m 2 , while the coating amount of the protective layer coating liquid in Example 1 is 3 g/m 2 . The rest is the same as Example 1 and will not be elaborated here.
  • This comparative example is basically the same as Example 1, except that the baking temperature in Comparative Example 3 is 150° C., while the baking temperature in Example 1 is 180° C. The rest is the same as Example 1 and will not be elaborated here.
  • This comparative example is basically the same as Example 1, except that in Comparative Example 4, the protective layer coating liquid is prepared as follows:
  • Nylon membrane corrosion resistance test method Use 1 mol/L lithium hexafluorophosphate electrolyte, add 0.1% water and stir evenly, then draw a few drops on the surface of the nylon membrane, let it stand for 2 hours, wipe off the surface electrolyte, and observe the changes on the nylon membrane surface;
  • Nylon film friction coefficient test method nylon film against nylon film, test in accordance with GB 10006 method.
  • Punching depth Cut the aluminum-plastic film into 120*150mm samples, punch them with a punching machine, the pit size is 55*60mm, set the punching depth to Xmm, punch 40 shells continuously, use a strong flashlight in a dark box to observe whether there is light transmission at the pit to determine whether it is damaged. If it is not damaged, increase the depth by 0.2mm on the basis of X. If it is damaged with probability of Xmm, reduce the depth by 0.2mm on the basis of X, and continue punching and observing the damage according to the above method. The punching depth H will eventually not break at a certain depth, and at the same time increase 0.2mm to have a probability of damage, and the unbroken value at this time will be taken as the result of the punching depth.
  • the product in comparative example 1 has no protective layer, has poor corrosion resistance, has a large friction coefficient, and has poor lubrication effect.
  • the product of comparative example 3 has poor corrosion resistance, a large friction coefficient, and poor slippery effect.
  • the reason is that the protective layer of the present application is made of a two-component system of isocyanate curing agent and soluble fluororesin containing hydroxyl functional groups, which requires a rapid curing reaction at high temperature.
  • the reaction temperature in comparative example 3 is not enough, resulting in the protective layer failing to form a firm coating on the nylon membrane surface, failing to achieve the effect of electrolyte resistance.
  • the corrosion-resistant layer fails to form a good film, and the punching depth and friction coefficient are not as expected.
  • Comparative Example 4 due to the high content of lubricant, the friction coefficient and punching performance of the nylon membrane surface are not ideal. It may be that the lubricant has a poor solubility in the solvent due to its high concentration and cannot be evenly distributed on the nylon membrane surface.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

一种耐腐蚀的铝塑复合膜，包括热封层，设于所述热封层表面的铝箔层、设于所述铝箔层表面的尼龙层，设于所述尼龙层表面的保护层，所述保护层的制备原料，按重量份数计，包括100份的可溶性氟树脂、25-40份的异氰酸酯固化剂、267-290份的爽滑剂稀释液，其中，所述可溶性氟树脂含羟基官能团。本申请通过在尼龙层外表面设置保护层，有效地提高其抗腐蚀性能，在电池生产工序中，可以有效防护铝塑膜的外观，且能提高铝塑复合膜的爽滑效果和冲深能力。本申请还提供一种耐腐蚀的铝塑复合膜的制备方法。

Description

一种耐腐蚀的铝塑复合膜及其制备方法 技术领域
本申请涉及铝塑复合膜技术领域，更具体地涉及一种耐腐蚀的铝塑复合膜及其制备方法。
背景技术
锂离子电池广泛应用于数码、交通工具、军事以及储能方面的新能源系统，目前锂离子电池软包装膜主要应用的是铝塑复合膜，铝铝塑复合膜(也简称铝塑膜)由外层的尼龙保护层、中间的铝箔以及内层的CPP(聚丙烯)层组成。铝塑膜作为电池的外包装壳，铝塑膜在电池生产工序中，不可避免的接触到电解液，进而腐蚀铝塑膜外表面，影响电池外观。为解决这一问题，传统方式是在铝塑膜外表面复合一层聚对苯二甲酸乙二酯薄膜或聚对苯二甲酸丁二酯薄膜，以达到表面耐腐蚀的效果。一方面，聚对苯二甲酸乙二酯薄膜或聚对苯二甲酸丁二酯薄膜的耐腐蚀薄膜的价格比较高，从而导致铝塑膜的生产成本高；另一方面，这种薄膜的厚度比较薄，使得复合工艺难度大。
申请内容
为了克服现有技术的缺陷，本申请的目的是提供一种耐腐蚀的铝塑复合膜及其制备方法，该铝塑复合膜最外层耐腐蚀性能优良，在电池生产工序中，可以有效防护铝塑膜的外观，且能提高该铝塑复合膜的爽滑效果和冲深能力。
为了实现上述目的，本申请公开了一种耐腐蚀的铝塑复合膜，包括热封层，设于所述热封层表面的铝箔层、设于所述铝箔层表面的尼龙层，设于所述尼龙层表面的保护层，所述保护层的制备原料，按重量份数计，包括100份的可溶 性氟树脂、25-40份的异氰酸酯固化剂、267-290份的爽滑剂稀释液，其中，所述可溶性氟树脂含羟基官能团。
与现有技术相比，本申请的耐腐蚀的铝塑复合膜，通过在尼龙层的外表面设置保护层，使得最外层耐腐蚀性能优良，其中，保护层采用含羟基官能团的可溶性氟树脂、异氰酸酯固化剂、爽滑剂稀释液复配，既可以实现铝塑复合膜良好的耐腐蚀效果，在电池生产工序中，能有效防护铝塑膜的外观，还能提高该铝塑复合膜的爽滑效果和冲深能力。
其中，按重量份数计，异氰酸酯固化剂的含量可为但不限于25份、26份、27份、28份、29份、30份、31份、32份、33份、34份、35份、36份、37份、38份、39份、40份；爽滑剂稀释液的含量可为但不限于267份、275份、280份、285份、290份。
较佳地，所述爽滑剂稀释液通过爽滑剂溶解在溶剂中制得，所述爽滑剂选自硬脂酸酰胺、乙撑双硬脂酸酰胺、硅油、芥酸酰胺中的至少一种。
较佳地，按质量百分数计，所述爽滑剂稀释液中所述爽滑剂的含量为0.25％-1.0％。作为示例地，爽滑剂稀释液中含有有效成分爽滑剂含量可为但不限于0.25％、0.50％、0.75％、1.0％。
较佳地，所述溶剂选自芳香族溶剂。进一步地，所述芳香族溶剂选自二甲苯、乙苯中的至少一种。
相应地，本申请提供一种耐腐蚀的铝塑复合膜的制备方法，包括步骤：
(1)制备保护层涂布液：
(a)将爽滑剂加入溶剂中加热搅拌，得到混合物A；
(b)将可溶性氟树脂、异氰酸酯固化剂和混合物A搅拌均匀，得到保护层涂布液。
(2)提供铝箔并双面钝化处理，在铝箔的哑面复合尼龙层；
(3)在铝箔的亮面复合热封层；
(4)在尼龙层的表面涂覆保护层涂布液，烘烤固化，在尼龙层的表面形成 保护层。
较佳地，步骤(4)中，烘烤温度至少为180℃，作为示例地，烘烤温度可为但不限于180℃、185℃、190℃、195℃、200℃等等，若温度较低，短时间烘干会造成保护层未能在尼龙层表面形成牢固的涂层，耐腐蚀效果不佳，且由于表面的疏松结构，耐腐蚀层未能很好的成膜；若采用较长时间烘干，则生产效率降低。
较佳地，步骤(4)中，保护层涂布液的涂布量为3-5g/m2，作为示例地，保护层涂布液的涂布量可为但不限于3g/m2、3.5g/m2、4g/m2、4.5g/m2、5g/m2，涂布量偏低会导致耐腐蚀性能、冲深性能及爽滑性能不佳。
较佳地，步骤(4)中，烘烤时间大于30s，作为示例地，烘烤时间可为但不限于30s、35s、40s、45s、50s。
具体实施方式
为详细说明本申请的技术内容、构造特征、所实现目的及效果，以下结合实施方式详予说明。
实施例1
一种耐腐蚀的铝塑复合膜的制备方法，包括步骤：
(1)提供河南明泰40μm的铝箔，对铝箔的哑面和亮面均进行钝化处理，
其中，钝化液采用含硝酸铬、水性环氧树脂、氟化钠、磷酸配制。其中，硝酸铬、水性环氧树脂、氟化钠和水，按照2：5：1：92质量比混合后，再用磷酸调节pH至3-4，采用该钝化液对铝箔进行双面钝化，然后在150℃烘干待用；
(2)将钝化处理后的铝箔亮面与40μm聚丙烯膜采用热法复合；
(3)将铝箔哑面与长塑25μm尼龙膜干式复合，60℃固化3天，得到半成品；
(4)在尼龙层的表面涂覆保护层涂布液，涂布量为3g/m2，涂布后烘烤30s， 温度为180℃，实现固化，尼龙层表面形成保护层，得到产品，
其中，保护层涂布液制备如下：
(a)将乙撑双硬脂酸酰胺加入二甲苯中加热搅拌，得到混合物A，其中，乙撑双硬脂酸酰胺与二甲苯质量配比为0.25：99.75；
(b)将100份的可溶性氟树脂(LFX485F)、25份的异氰酸酯固化剂(K75)和267份的混合物A搅拌均匀，得到保护层涂布液。
实施例2
一种耐腐蚀的铝塑复合膜的制备方法，包括步骤：
(1)提供河南明泰40μm的铝箔，对铝箔的哑面和亮面均进行钝化处理，
其中，钝化液采用含硝酸铬、水性环氧树脂、氟化钠、磷酸配制，其中，硝酸铬、水性环氧树脂、氟化钠和水，按照2：5：1：92质量比混合后，再用磷酸调节pH至3-4，采用该钝化液对铝箔进行双面钝化，然后在150℃烘干待用；
(2)将钝化处理后的铝箔亮面与40μm聚丙烯膜采用热法复合；
(3)将铝箔哑面与长塑25μm尼龙膜干式复合，60℃固化3天，得到半成品；
(4)在尼龙层的表面涂覆保护层涂布液，涂布量为5g/m2，涂布后烘烤30s，温度为190℃，实现固化，尼龙层表面形成保护层，得到产品，
其中，保护层涂布液制备如下：
(a)将乙撑双硬脂酸酰胺加入二甲苯中加热搅拌，再加入芥酸酰胺，得到混合物A，其中，乙撑双硬脂酸酰胺与二甲苯质量配比为0.25：99.75；
(b)将100份的可溶性氟树脂(LFX485F)、40份的异氰酸酯固化剂(K75)和290份的混合物A搅拌均匀，得到保护层涂布液。
实施例3
实施例3与实施例1基本相同，不同在于，实施例3中爽滑剂为硅油，实施例1中爽滑剂为乙撑双硬脂酸酰胺，其余与实施例1相同，在此不再阐述。
对比例1
对比例1中无保护层，其铝塑复合膜的制备方法，包括步骤：
(1)提供河南明泰40μm的铝箔，对铝箔的哑面和亮面均进行钝化处理，
其中，钝化液采用含硝酸铬、水性环氧树脂、氟化钠、磷酸配制，其中，硝酸铬、水性环氧树脂、氟化钠和水，按照2：5：1：92质量比混合后，再用磷酸调节pH至3-4，采用该钝化液对铝箔进行双面钝化，然后在150℃烘干待用；
(2)将钝化处理后的铝箔亮面与40μm聚丙烯膜采用热法复合；
(3)将铝箔哑面与长塑25μm尼龙膜干式复合，60℃固化3天，得到产品。
对比例2
本对比例与实施例1基本相同，不同在于：对比例2中保护层涂布液的涂布量为2g/m2，而实施例1中保护层涂布液的涂布量为3g/m2，其余与实施例1相同，在此不再阐述。
对比例3
本对比例与实施例1基本相同，不同在于：对比例3中烘烤温度为150℃，而实施例1中烘烤温度为180℃，其余与实施例1相同，在此不再阐述。
对比例4
本对比例与实施例1基本相同，不同在于：对比例4中，保护层涂布液制备如下：
(a)将乙撑双硬脂酸酰胺加入二甲苯中加热搅拌，得到混合物A，其中， 乙撑双硬脂酸酰胺、二甲苯的质量配比为2:98；
(b)将100份的可溶性氟树脂(LFX485F)、25份的异氰酸酯固化剂(K75)和267份的混合物A搅拌均匀，得到保护层涂布液。
其余与实施例1相同，在此不再阐述。
将实施例1-3和对比例1-4制得铝塑复合膜进行性能检测：
尼龙膜耐腐蚀性检测方法：用六氟磷酸锂含量1mol/L电解液，加入0.1％水搅拌均匀后，吸取数滴滴在尼龙膜表面，静置2h后，擦去表面电解液，观察尼龙膜表面变化；
尼龙膜摩擦系数检测方法，尼龙膜贴尼龙膜，按照GB 10006方法检测。
冲深深度：将铝塑膜裁切120*150mm大小的样片，用冲壳机进行冲深，坑位尺寸55*60mm，设定冲壳深度Xmm，连续冲壳40个，在暗箱中用强光电筒对着坑位观察有无透光判定是否破损，如未破损则在X基础上增加0.2mm深度，如Xmm概率性破损，则在X基础上降低0.2mm深度，按上述方法继续冲深及观察破损情况。冲深深度H最终以某个深度不破，同时增加0.2mm出现概率性破损，以此时的不破值作为冲深深度的结果。
表1性能测试结果

由表1的数据可知，本申请方法实施例1-3得到的产品具有优良的耐腐蚀性能、爽滑效果和冲深能力。
对比例1中的产品没有保护层，耐腐蚀性能较差，且摩擦系数较大，爽滑效果不佳。
对比例2中的产品虽然有保护层，但因保护层涂布量较低，耐腐蚀性能较弱，爽滑效果仍不理想。
对比例3的产品耐腐蚀性能较差，且摩擦系数较大，爽滑效果不佳。原因是本申请的保护层采用异氰酸酯固化剂与含羟基官能团可溶性氟树脂双组份体系制成，需要在高温下快速固化反应，对比例3中反应温度不够，造成保护层未能在尼龙膜面形成牢固的涂层，未达到耐电解液的效果，同时由于表面的疏松结构，耐腐蚀层未能很好的成膜，冲深和摩擦系数也未达预期。
对比例4中因爽滑剂含量较高，导致尼龙膜面摩擦系数及冲深性能均不见得理想，可能是爽滑剂因浓度高使得在溶剂中溶解效果差涂布在尼龙膜面未能均匀分布。
以上所揭露的仅为本申请的优选实施例而已，当然不能以此来限定本申请之权利范围，因此依本申请专利范围所作的等同变化，仍属本申请所涵盖的范围。

Claims (9)

  1. 一种耐腐蚀的铝塑复合膜，其特征在于，包括热封层，设于所述热封层表面的铝箔层、设于所述铝箔层表面的尼龙层，设于所述尼龙层表面的保护层，所述保护层的制备原料，按重量份数计，包括100份的可溶性氟树脂、25-40份的异氰酸酯固化剂、267-290份的爽滑剂稀释液，所述可溶性氟树脂含羟基官能团。
  2. 如权利要求1所述的耐腐蚀的铝塑复合膜，其特征在于，所述爽滑剂稀释液通过爽滑剂溶解在溶剂中制得，所述爽滑剂选自硬脂酸酰胺、乙撑双硬脂酸酰胺、硅油、芥酸酰胺中的至少一种。
  3. 如权利要求2所述的耐腐蚀的铝塑复合膜，其特征在于，所述爽滑剂稀释液中所述爽滑剂的含量为0.25％-1.0％。
  4. 如权利要求2所述的耐腐蚀的铝塑复合膜，其特征在于，所述溶剂选自芳香族溶剂。
  5. 如权利要求4所述的耐腐蚀的铝塑复合膜，其特征在于，所述芳香族溶剂选自二甲苯、乙苯中的至少一种。
  6. 一种如权利要求1-5任一项所述的耐腐蚀的铝塑复合膜的制备方法，其特征在于，包括步骤：
    (1)制备保护层涂布液：
    (a)将爽滑剂加入溶剂中加热搅拌，得到爽滑剂稀释液；
    (b)将可溶性氟树脂、异氰酸酯固化剂和爽滑剂稀释液搅拌均匀，得到保 护层涂布液。
    (2)提供铝箔并进行双面钝化处理，在铝箔的哑面复合尼龙层；
    (3)在铝箔的亮面复合热封层；
    (4)在尼龙层的表面涂覆保护层涂布液，烘烤固化，在尼龙层的表面形成保护层。
  7. 如权利要求6所述的耐腐蚀的铝塑复合膜的制备方法，其特征在于，步骤(4)中，烘烤温度至少为180℃。
  8. 如权利要求6所述的耐腐蚀的铝塑复合膜的制备方法，其特征在于，步骤(4)中，保护层涂布液的涂布量为3-5g/m2。
  9. 如权利要求6所述的耐腐蚀的铝塑复合膜的制备方法，其特征在于，步骤(4)中，烘烤时间大于30s。
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