CN110789200A - Water-blocking flame-retardant composite film for lithium battery packaging and preparation method thereof - Google Patents

Water-blocking flame-retardant composite film for lithium battery packaging and preparation method thereof Download PDF

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Publication number
CN110789200A
CN110789200A CN201911035402.4A CN201911035402A CN110789200A CN 110789200 A CN110789200 A CN 110789200A CN 201911035402 A CN201911035402 A CN 201911035402A CN 110789200 A CN110789200 A CN 110789200A
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layer
flame
retardant
aluminum foil
thermoplastic resin
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徐雄剑
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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
    • 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
    • B32B15/085—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 polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B15/082—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 vinyl resins; comprising acrylic resins
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2427/00—Characterised by the use of 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; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
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Abstract

The invention provides a water-blocking flame-retardant composite film for lithium battery packaging, which comprises a modified aluminum foil base layer and flame-retardant layers arranged on the upper surface and the lower surface of the modified aluminum foil base layer, wherein a thermoplastic resin layer is arranged on the outer side of the flame-retardant layer, and the flame-retardant layer is formed by uniformly dispersing a flame retardant in an adhesive; the surface of the modified aluminum foil basic layer is passivated, and then surface modification is carried out twice by using an organic silicon oil waterproof agent; the thermoplastic resin layer is bonded on the aluminum foil base layer through the flame-retardant layer and then is pressed into the aluminum-plastic film. The invention provides a water-blocking flame-retardant composite film for lithium battery packaging and a preparation method thereof.

Description

Water-blocking flame-retardant composite film for lithium battery packaging and preparation method thereof
Technical Field
The invention relates to the field of packaging materials, in particular to a water-blocking flame-retardant composite film for lithium battery packaging and a preparation method thereof.
Background
Because the aluminum-plastic film has low manufacturing cost and forms an indispensable important component of the liquid flexible package lithium ion battery, the aluminum-plastic composite film is taken as the shell of the battery at present and replaces the steel or aluminum shell of the common lithium ion battery, and the aluminum-plastic composite film can be roughly divided into three layers: the inner layer is a bonding layer, and is made of polyethylene or polypropylene materials mostly to play a role in sealing and bonding; the middle layer is made of aluminum foil, so that the permeation of water vapor outside the battery can be prevented, and the permeation of electrolyte inside the battery can be prevented; the outer layer is a protective layer, and is made of polyester or nylon materials with high melting point, so that the battery has strong mechanical performance, prevents external force from damaging the battery, and plays a role in protecting the battery.
The aluminum plastic film of the commercial soft package lithium ion battery at present has no flame retardant effect, and the safety can not be ensured when the aluminum plastic film is used for a high-capacity battery with the capacity of more than 200 Ah. For example, the charging voltage is high, and most electrolytes are organic inflammable substances, and if the electrolytes are not used properly, the battery is dangerous and even explodes. In order to improve the flame retardancy of the aluminum plastic film, the stability of the electrolyte is improved by adding some solvents with high boiling point, high flash point and non-flammability into the electrolyte, and the solvents mainly comprise organic phosphide, organic fluoro-compound and halogenated alkyl phosphate. However, these solvents increase the viscosity and impedance of the electrolyte solution, and affect the performance of the battery. In addition, the flame retardant is directly added into the electrolyte, so that the internal resistance of the battery is increased, the constant current ratio and the voltage platform are deteriorated, and the passing of all safety tests cannot be guaranteed. The aluminum plastic film is generally formed by compounding three-layer film materials, and is sequentially provided with a protective layer, an aluminum foil layer and a corrosion-resistant heat sealing layer from outside to inside, wherein the protective layer is a biaxially oriented nylon film (BOPA film), the aluminum foil layer is subjected to single-sided or double-sided passivation treatment, and the corrosion-resistant layer is a cast polypropylene film (CPP film). The outer nylon membrane, because itself easily absorbs water, and it is relatively poor to hinder water nature, higher to service environment requirement, the retention period is short for nylon membrane and intermediate layer aluminium foil bonding gluing agent also easily cause the adhesion stress to reduce scheduling problem because of hydrolysising, and nylon membrane itself fire resistance is also not good, under the condition that causes the fire such as battery short circuit, receives the extrusion, can not effectual assurance safety.
Disclosure of Invention
The invention provides a water-blocking flame-retardant composite film for lithium battery packaging and a preparation method thereof.
A waterproof and flame-retardant composite film for lithium battery packaging comprises a modified aluminum foil base layer and flame-retardant layers arranged on the upper surface and the lower surface of the modified aluminum foil base layer, wherein a thermoplastic resin layer is arranged on the outer side of the flame-retardant layer, and the flame-retardant layer is formed by uniformly dispersing a flame retardant in an adhesive; the surface of the modified aluminum foil basic layer is passivated, and then surface modification is carried out twice by using an organic silicon oil waterproof agent; the thermoplastic resin layer is bonded on the aluminum foil base layer through the flame-retardant layer and then is pressed into the aluminum-plastic film.
Further, after the aluminum foil is subjected to the etching and cleaning treatment process, the aluminum foil is immersed in an aqueous solution of phosphoric acid, and then subjected to cleaning with pure water and heat treatment. Further, the concentration of the aqueous solution of phosphoric acid is 2-5%, the dipping time is 60-90s, and the heat treatment temperature is 250-300 ℃.
Further, the surface modification step of the organic silicon oil waterproof agent comprises the steps of dipping the aluminum foil base layer into the oily organic silicon waterproof agent for 30-90s, and performing heat treatment at the temperature of 140-160 ℃ for 30-60s, and repeating once.
Further, the adhesive is one of epoxy resin, acrylic resin, silicone resin, or organic fluorine resin.
Further, the flame retardant is at least one of melamine and melamine phosphate.
Further, the mass ratio of the adhesive to the flame retardant in the flame-retardant layer is 1: (0.4-0.8).
Further, the thermoplastic resin layer comprises 50-60 parts by mass of homopolymerized polypropylene, 10-20 parts by mass of polyvinylidene fluoride, 10-20 parts by mass of styrene and 1-2 parts by mass of antioxidant.
Further, the thickness of the thermoplastic resin layer is 20-30 μm, the thickness of the flame retardant layer is 2-4 μm, and the thickness of the aluminum foil base layer is 40 μm.
Further, the organic silicone oil waterproofing agent is a low molecular polysiloxane waterproofing agent.
A production process of the composite film for lithium battery packaging comprises the following steps:
(1) the base layer aluminum foil layer adopts annealed soft aluminum with the thickness of 40 mu m, the two sides of the aluminum foil are subjected to surface passivation treatment, then organic silicone oil waterproof agent is carried out for surface modification, and then a flame-retardant layer is coated on the base layer aluminum foil layer;
(2) melt-extruding a thermoplastic resin into a thermoplastic resin layer of a predetermined thickness;
(3) and (3) bonding the thermoplastic resin layer obtained in the step (2) on the aluminum foil base layer through the flame-retardant layer, and then pressing to synthesize the aluminum-plastic film.
The invention carries out surface passivation treatment on the two sides of the aluminum foil to form a compact oxide protective layer on the surface of the aluminum foil, improves the water resistance, and then carries out organic silicone oil waterproofing agent treatment on the surface of the oxide, when the silicone emulsion is heated to above 140 ℃, the polysiloxane is directionally arranged on the fabric, the hydrophobic group-CH 3 faces outwards, and silicon atoms and oxygen atoms of the silicone emulsion and certain atoms on the fiber form coordinate bonds and hydrogen bonds, so that water vapor and air can pass through the fabric, but water drops can not penetrate. The organic silicon oil waterproof agent has two properties of permeability and film-forming property, the film-forming property is generally macromolecular silicone oil containing hydrogen-terminated silicone oil, the permeability is low molecular weight silicone oil, the low molecular weight silicone oil is preferred in the invention, because the film formed by macromolecular silicone oil can affect the bonding strength. And through twice repeated treatment, a waterproof layer can be formed more uniformly. The flame-retardant layer is added with the melamine flame retardant, so that the flame-retardant layer can effectively resist flame, and the melamine has good compatibility. The polymer composition formed by adding polyvinylidene fluoride into the thermoplastic resin layer has stronger sealing property and waterproofness and can improve the heat sealing effect.
The invention has the beneficial technical effects that:
according to the invention, surface passivation treatment is carried out on the two sides of the aluminum foil, surface waterproof treatment is carried out on the organic silicon oil waterproof agent, the waterproof agent is preferably low-molecular organic polysiloxane, a melamine flame retardant is added into the flame retardant layer, and meanwhile, a certain amount of polyvinylidene fluoride is added into the thermoplastic resin layer, so that high water resistance and flame retardancy of the aluminum plastic film are realized, other performances of the aluminum plastic film reach the standard, and the aluminum plastic film is suitable for flexible packaging of lithium batteries.
Detailed Description
The present invention is further illustrated by the following specific examples.
The organic silicon waterproof agent is purchased from macromolecular organic polysiloxane RJ-202 and low molecular polysiloxane waterproof agent RJ-WP03E of Hangzhou Ruizjiang New Material technology Co.
Example 1
A production process of the composite film for lithium battery packaging comprises the following steps:
(1) the base layer aluminum foil layer is made of annealed soft aluminum with the thickness of 40 mu m, the aluminum foil is subjected to corrosion and cleaning treatment, then is soaked in 3% phosphoric acid water solution for 75s, then is subjected to pure water cleaning and heat treatment, the heat treatment temperature is 280 ℃, the two sides of the aluminum foil are subjected to surface passivation treatment, the aluminum foil base layer is soaked in a low molecular polysiloxane waterproof agent RJ-WP03E for 60s, the heat treatment is carried out at 150 ℃ for 40s, the process is repeated once, and then a flame-retardant layer is coated on the base layer aluminum foil layer, wherein the flame-retardant layer comprises an adhesive epoxy resin and a flame retardant melamine, the mass ratio of the adhesive epoxy resin to the flame retardant melamine is: 0.6;
(2) the thermoplastic resin layer comprises 55 parts by mass of homopolymerized polypropylene, 15 parts by mass of polyvinylidene fluoride, 15 parts by mass of styrene and 2151.5 parts by mass of antioxidant B, and the thermoplastic resin is melted and extruded into a thermoplastic resin layer with a preset thickness;
(3) and (3) bonding the thermoplastic resin layer obtained in the step (2) on the aluminum foil base layer through the flame-retardant layer, and then pressing to synthesize the aluminum-plastic film.
The parameters were adjusted to control the thickness of the thermoplastic resin layer to 25 μm, the thickness of the flame retardant layer to 3 μm, and the thickness of the aluminum foil base layer to 40 μm.
Example 2
A production process of the composite film for lithium battery packaging comprises the following steps:
(1) the base layer aluminum foil layer is made of annealed soft aluminum with the thickness of 40 mu m, the aluminum foil is subjected to corrosion and cleaning treatment, then is soaked in a 5% phosphoric acid aqueous solution for 60s, then is subjected to pure water cleaning and heat treatment at the temperature of 300 ℃ to carry out surface passivation treatment on the two sides of the aluminum foil, the base layer of the aluminum foil is soaked in a low molecular polysiloxane waterproof agent RJ-WP03E for 30s, is subjected to heat treatment at the temperature of 140 ℃ and 160 ℃ for 60s, is repeated once, and then is coated with a flame-retardant layer, wherein the flame-retardant layer comprises an adhesive, namely epoxy resin and a flame retardant, namely melamine, the mass ratio of 1: 0.4;
(2) the thermoplastic resin layer comprises 60 parts by mass of homopolymerized polypropylene, 10 parts by mass of polyvinylidene fluoride, 20 parts by mass of styrene and 2151 parts by mass of antioxidant B, and the thermoplastic resin is melted and extruded into a thermoplastic resin layer with a preset thickness;
(3) and (3) bonding the thermoplastic resin layer obtained in the step (2) on the aluminum foil base layer through the flame-retardant layer, and then pressing to synthesize the aluminum-plastic film.
The thickness of the thermoplastic resin layer was controlled to 30 μm, the thickness of the flame retardant layer was controlled to 2 μm, and the thickness of the aluminum foil base layer was controlled to 40 μm by adjusting the parameters.
Example 3
A production process of the composite film for lithium battery packaging comprises the following steps:
(1) the base layer aluminum foil layer is made of annealed soft aluminum with the thickness of 40 mu m, the aluminum foil is subjected to corrosion and cleaning treatment, then is soaked in 2% phosphoric acid water solution for 90s, then is subjected to pure water cleaning and heat treatment, the heat treatment temperature is 250 ℃, the two sides of the aluminum foil are subjected to surface passivation treatment, the aluminum foil base layer is soaked in a low molecular polysiloxane waterproof agent RJ-WP03E for 90s, is subjected to heat treatment at 140 ℃ for 60s, is repeated once, and then is coated with a flame-retardant layer, wherein the flame-retardant layer comprises an adhesive epoxy resin and a flame retardant melamine, and the mass ratio of the adhesive epoxy resin to the flame retardant melamine is 1: 0.8;
(2) the thermoplastic resin layer comprises 50 parts by mass of homopolymerized polypropylene, 20 parts by mass of polyvinylidene fluoride, 10 parts by mass of styrene and 2152 parts by mass of antioxidant B, and the thermoplastic resin is melted and extruded into a thermoplastic resin layer with a preset thickness;
(3) and (3) bonding the thermoplastic resin layer obtained in the step (2) on the aluminum foil base layer through the flame-retardant layer, and then pressing to synthesize the aluminum-plastic film.
The parameters were adjusted to control the thickness of the thermoplastic resin layer to 20 μm, the thickness of the flame retardant layer to 4 μm, and the thickness of the aluminum foil base layer to 40 μm.
Comparative example 1
The same as example 1 except that the aluminum foil was not surface-passivated on both sides.
Comparative example 2
The same as example 1 except that both sides of the aluminum foil were not surface-treated with the silicone oil water repellent agent.
Comparative example 3
The same as example 1 except that the silicone oil waterproofing agent of both sides of the aluminum foil is macromolecular organopolysiloxane RJ-202.
Comparative example 4
Same as example 1 except that the flame retardant layer did not contain melamine flame retardant.
Comparative example 5
Same as example 1 except that polyvinylidene fluoride was not added to the thermoplastic resin layer.
The aluminum-plastic films prepared in the above embodiments and comparative examples are respectively made into 200Ah lithium ion batteries, and then the safety of the lithium ion batteries is detected according to the standard GB/T18287-2013 of the industry. The results are shown in Table 1. The water permeation through the prepared aluminum plastic film within 24h was tested using a water permeability tester according to the GB 1037 standard. The results are shown in Table 1.
TABLE 1 results of the Performance test of examples and comparative examples
Figure DEST_PATH_IMAGE001
The invention realizes the high water resistance and flame retardance of the aluminum-plastic film by performing surface passivation treatment on the two sides of the aluminum foil and performing surface waterproof treatment on an organic silicon oil waterproof agent, wherein the waterproof agent is preferably low-molecular organopolysiloxane, a melamine flame retardant is added into a flame retardant layer, and a certain amount of polyvinylidene fluoride is added into a thermoplastic resin layer, so that other properties of the aluminum-plastic film reach the standard, and the aluminum-plastic film is suitable for the flexible package of a lithium battery.

Claims (1)

1. A waterproof and flame-retardant composite film for lithium battery packaging comprises a modified aluminum foil base layer and flame-retardant layers arranged on the upper surface and the lower surface of the modified aluminum foil base layer, wherein a thermoplastic resin layer is arranged on the outer side of the flame-retardant layer, and the flame-retardant layer is formed by uniformly dispersing a flame retardant in an adhesive; the surface of the modified aluminum foil basic layer is passivated, and then surface modification is carried out twice by using an organic silicon oil waterproof agent; the thermoplastic resin layer is bonded on the aluminum foil base layer through the flame-retardant layer and then is pressed into an aluminum-plastic film; the passivation treatment is that the aluminum foil is immersed in a phosphoric acid water solution after being subjected to corrosion and cleaning treatment processes, and then is subjected to pure water cleaning and heat treatment; the surface modification step of the organic silicon oil waterproof agent comprises the steps of dipping the aluminum foil base layer into the oily organic silicon waterproof agent for 30-90s, carrying out heat treatment at the temperature of 140-160 ℃ for 30-60s, and repeating once; the organic silicon oil waterproof agent is a low-molecular polysiloxane waterproof agent RJ-WP 03E; the thermoplastic resin layer comprises 50-60 parts by mass of homopolymerized polypropylene, 10-20 parts by mass of polyvinylidene fluoride, 10-20 parts by mass of styrene and 1-2 parts by mass of antioxidant;
the concentration of the aqueous solution of phosphoric acid is 2-5%, the dipping time is 60-90s, and the heat treatment temperature is 250-300 ℃;
the adhesive is one of epoxy resin, acrylic resin, organic silicon resin or organic fluororesin;
the flame retardant is at least one of melamine and melamine phosphate;
the mass ratio of the adhesive to the flame retardant in the flame-retardant layer is 1: (0.4-0.8);
the thickness of the thermoplastic resin layer is 20-30 μm, the thickness of the flame retardant layer is 2-4 μm, and the thickness of the aluminum foil base layer is 40 μm.
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