CN112009057B - Composite aluminum-plastic film for power battery - Google Patents

Composite aluminum-plastic film for power battery Download PDF

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Publication number
CN112009057B
CN112009057B CN202010886686.4A CN202010886686A CN112009057B CN 112009057 B CN112009057 B CN 112009057B CN 202010886686 A CN202010886686 A CN 202010886686A CN 112009057 B CN112009057 B CN 112009057B
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China
Prior art keywords
parts
plastic film
epoxy resin
layer
aluminum
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CN202010886686.4A
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Chinese (zh)
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CN112009057A (en
Inventor
吴安理
陈汉城
王桂彬
吴淑芬
熊泽民
温虹钰
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Guangdong Dexing Polymer Film Material Research Co ltd
Guangdong Andeli New Materials Co ltd
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Guangdong Dexing Polymer Film Material Research Co ltd
Guangdong Andeli New Materials Co ltd
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Priority to CN202010886686.4A priority Critical patent/CN112009057B/en
Publication of CN112009057A publication Critical patent/CN112009057A/en
Priority to KR1020210110321A priority patent/KR102660822B1/en
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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • 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
    • B32B15/088—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
    • B32B15/20—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
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    • 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
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • 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
    • C23C22/24—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 hexavalent chromium compounds
    • C23C22/33—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 hexavalent chromium compounds containing also phosphates
    • 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
    • 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
    • H01M50/1245—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the external coating on the casing
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    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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    • B32B2311/00—Metals, their alloys or their compounds
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2323/10—Polypropylene
    • 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
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    • 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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  • Engineering & Computer Science (AREA)
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Abstract

The invention discloses a composite aluminum-plastic film for a power battery, which is mainly formed by co-extruding and compounding an aluminum foil layer, a polypropylene layer and an external protective layer through a casting process, wherein the aluminum foil layer is bonded with the external protective layer through a first binder, and the aluminum foil layer is bonded with the polypropylene layer through a second binder; the invention provides a composite aluminum-plastic film for a power battery through the overall improvement of various functional layers and a binder, and the composite aluminum-plastic film has excellent electrolyte resistance, good binding power, stamping forming performance, tensile performance and the like.

Description

Composite aluminum-plastic film for power battery
Technical Field
The invention relates to the technical field of power batteries, in particular to a composite aluminum-plastic film for a power battery.
Background
The lithium ion power battery is known as 'green chemical energy' in 21 st century and widely applied to many fields such as 3C consumer electronics, power batteries and energy storage, and the aluminum plastic film is used as a key material of a soft package lithium ion battery and contains high technological content, and the quality of the aluminum plastic film directly determines the quality of the lithium ion battery. The aluminum-plastic film can be roughly divided into three layers: the inner layer is a bonding layer, is mostly made of polypropylene materials and plays a role in sealing and bonding, and the middle layer is an aluminum foil, so that the permeation of water vapor outside the battery can be prevented, and the permeation of internal electrolyte can be prevented; the outer layer is a protective layer, a high-melting-point nylon material is mostly adopted, so that the battery has strong mechanical performance, the damage of external force to the battery is prevented, and the battery is protected.
The research and development of the high-quality aluminum plastic film are the key for the successful research and development of the soft package lithium ion battery, namely a high and new technical product, and the high-quality aluminum plastic film is an indispensable important component part for forming the soft package lithium ion battery as a shell of the soft package lithium ion battery. However, most of the existing improvements to the aluminum plastic film of the lithium ion battery are limited to the improvement of a certain substance or the single improvement of an adhesive playing a connecting role, and the aluminum plastic film material obtained after the improvement still has the phenomenon of poor electrolyte resistance, and the problems that the binding power and the stamping forming performance are limited to a certain extent, and further the service life of the lithium ion battery is short are caused.
Therefore, the problem to be solved by the technical personnel in the art is how to provide a composite aluminum plastic film for a power battery, which has excellent electrolyte resistance and excellent adhesion, stamping forming capability and the like.
Disclosure of Invention
In view of the above, the present invention provides a composite aluminum plastic film for a power battery, which has excellent electrolyte resistance, good adhesion, good press-forming properties, good tensile properties, and the like, through overall improvements of the functional layers and the binder.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composite aluminum-plastic film for a power battery is mainly formed by co-extrusion compounding of an aluminum foil layer, a polypropylene layer and an external protective layer through a tape casting process, wherein the aluminum foil layer is bonded with the external protective layer through a first bonding agent, and the aluminum foil layer is bonded with the polypropylene layer through a second bonding agent;
the external protective layer consists of a nylon film and a protective layer coated on the surface of the nylon film, wherein the protective layer comprises 1-5% of water-soluble novolac epoxy resin, 70-85% of emulsion adhesive and the balance of ethanol;
the first binder comprises the following raw materials in parts by weight: 10-15 parts of polyester polyol, 5-10 parts of polyether polyol, 3-5 parts of carbon nano tube, 0.1-0.5 part of toluene diisocyanate, 2-5 parts of epoxy resin, 0.2-0.5 part of silane coupling agent, 3-5 parts of polyisocyanate and 50-60 parts of solvent;
the second adhesive comprises 25-30 parts of modified acrylate, 10-15 parts of maleic anhydride grafted modified polypropylene, 5-8 parts of tackifying vinyl chloride-vinyl acetate resin, 2-3 parts of organosilicon coupling agent and 50-60 parts of ethyl acetate.
The invention solves the problems that the existing external nylon layer of the aluminum-plastic film is easy to absorb water, so that the overall strength of the aluminum-plastic film is reduced, and the temperature resistance and the bonding capability of the adhesive are poor, so that the aluminum-plastic film is easy to deform by improving the nylon layer and the two layers of the adhesive in the traditional external protective layer-aluminum foil layer-polypropylene layer aluminum-plastic film.
Specifically, the protective layer is coated on the surface of the nylon film, so that the entering of external moisture, oxygen and the like can be effectively prevented, the electrolyte corrosion resistance of the whole aluminum-plastic film is improved, and the protective effect of the nylon layer on the lithium ion power battery is further enhanced; meanwhile, through the improvement of the external protective layer and the aluminum foil layer binder, the mixture of the polyester polyol and the polyether polyol is adopted to provide initial adhesion, bonding strength and acid and alkali resistance, and through the compounding with the carbon nano tube, the heat resistance and electrolyte resistance of the adhesive are further improved; and through the improvement of the adhesive between the aluminum foil layer and the polypropylene layer, the smoothness of the aluminum-plastic film is ensured, the stress balance between the two layers is improved, the whitening phenomenon and the generation of fine cracks are weakened, and the tensile property and the peel strength of the aluminum-plastic film are improved.
Preferably, in the composite aluminum-plastic film for a power battery, the aluminum foil layer is subjected to surface treatment by using a passivation solution, and the passivation solution comprises the following raw materials in parts by weight: 0.3-1 part of chromium solution, 0.5-2 parts of epoxy modified phenolic resin, 2-5 parts of potassium zirconium carbonate, 2-5 parts of disodium succinate, 0.5-2 parts of tributyl phosphate, 40-55 parts of ethanol and 35-40 parts of water.
The beneficial effects of the above technical scheme are: the aluminum foil layer mainly plays a role in framework protection, and the corrosion resistance of an oxide film layer formed by the passivation solution can be improved under the action of the modified phenolic resin and the substances, so that water vapor and oxygen are prevented from entering the passivation solution.
Preferably, in the composite aluminum plastic film for a power battery, the water-soluble novolac epoxy resin is any one of phenol-novolac epoxy resin, o-cresol-novolac epoxy resin and bisphenol a-novolac epoxy resin.
The beneficial effects of the above technical scheme are: the water-soluble novolac epoxy resin can improve the temperature resistance of the nylon membrane, enables the nylon membrane to bear the high temperature of more than 210 ℃, and can be soaked in the electrolyte for 48 hours without being corroded under the synergistic effect of the water-soluble novolac epoxy resin and the emulsion adhesive, so that the corrosion resistance of an external protective layer is effectively improved.
Preferably, in the composite aluminum plastic film for a power battery, the emulsion adhesive is any one of polyvinylidene chloride resin emulsion, polyvinyl acetate emulsion or polyacrylate emulsion.
The beneficial effects of the above technical scheme are: the addition of the emulsion adhesive can effectively enhance the corrosion resistance of the nylon film, block moisture and external gas to a great extent and improve the electrolyte corrosion resistance of the power battery aluminum-plastic film, especially when the emulsion adhesive is polyvinylidene chloride resin emulsion.
Preferably, in the composite aluminum plastic film for a power battery, the polyester polyol and the polyether polyol are both modified by acrylic acid or epoxy resin.
The beneficial effects of the above technical scheme are: the modified polyester polyol or polyether polyol can effectively improve the dispersion performance of the adhesive and improve the electrolyte resistance of the adhesive, so that the nylon and the aluminum foil are combined more firmly.
Preferably, in the composite aluminum plastic film for a power battery, the epoxy resin is prepared by mixing the following components in a mass ratio of 1: (1-2): (0.5-1) bisphenol A type epoxy resin, phenolic aldehyde type epoxy resin and alicyclic epoxy resin.
The beneficial effects of the above technical scheme are: the bisphenol A epoxy resin is directly added into a mixture of polyester polyol and polyether polyol which mainly provide bonding strength, and is cured with the polyisocyanate component to obtain a network polymer of grafted epoxy resin, so that the peel strength of the polyurethane adhesive is effectively improved, and the solvent resistance of the adhesive is enhanced; the phenolic epoxy resin improves the heat resistance of the adhesive material; the alicyclic epoxy resin can improve the processing performance of the adhesive, so that the adhesive is more flat and smooth in coating.
Preferably, in the composite aluminum-plastic film for a power battery, the carbon nanotubes are mixed by mass ratio of 1: (8-9) a mixture of single-walled carbon nanotubes and multi-walled carbon nanotubes.
The beneficial effects of the above technical scheme are: the addition of the carbon nano tube greatly improves the peeling strength, heat resistance, electrolyte resistance and the like of the adhesive.
Preferably, in the composite aluminum plastic film for a power battery, the polyisocyanate is any one of methyl ethyl ketoxime blocked polyisocyanate, diethyl malonate blocked polyisocyanate and acetylacetone blocked polyisocyanate.
The beneficial effects of the above technical scheme are: the sealing agent has higher activity on polyisocyanate, can generate sealing reaction without using a catalyst, has good storage stability and lower deblocking temperature, and further enhances the bonding property of the adhesive.
Preferably, in the composite aluminum-plastic film for the power battery, a pre-coated layer is further included between the aluminum foil layer and the second adhesive, and the pre-coated layer is composed of 5% of polybutadiene primer, 65% of ethanol and 30% of deionized water.
The beneficial effects of the above technical scheme are: the glue of precoating both can guarantee the level and smooth of aluminium foil face, and through the glue of precoating, can guarantee that follow-up adhesive levels the polypropylene rete and adheres together with the aluminium foil face, strengthens the stamping forming performance of compound plastic-aluminum membrane.
Preferably, in the composite aluminum-plastic film for the power battery, the thickness of the aluminum foil layer is 40 μm, the thickness of the polypropylene layer is 78-80 μm, and the thickness of the outer protection layer is 25-30 μm.
According to the technical scheme, compared with the prior art, the composite aluminum-plastic film for the power battery is obtained by modifying the external protective layer, the first adhesive and the second adhesive simultaneously, the aluminum-plastic film which is high in initial peeling strength and still has strong binding power after being soaked for a long time is obtained, the corrosion resistance of the aluminum-plastic film to electrolyte is improved, the three improvements are carried out simultaneously, and the tensile property, the heat sealing strength, the punch forming property and the like of the aluminum-plastic film are improved well.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. 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.
A composite aluminum-plastic film for a power battery is mainly formed by co-extrusion compounding of an aluminum foil layer, a polypropylene layer and an external protective layer through a tape casting process, wherein the aluminum foil layer and the external protective layer are bonded through a first bonding agent, and the aluminum foil layer and the polypropylene layer are bonded through a second bonding agent;
the external protective layer consists of a nylon film and a protective layer coated on the surface of the nylon film, wherein the protective layer comprises 1-5% of water-soluble novolac epoxy resin, 70-85% of emulsion adhesive and the balance of ethanol;
the first binder comprises the following raw materials in parts by weight: 10-15 parts of polyester polyol, 5-10 parts of polyether polyol, 3-5 parts of carbon nano tube, 0.1-0.5 part of toluene diisocyanate, 2-5 parts of epoxy resin, 0.2-0.5 part of silane coupling agent, 3-5 parts of polyisocyanate and 50-60 parts of solvent;
the second adhesive comprises 25-30 parts of modified acrylate, 10-15 parts of maleic anhydride grafted modified polypropylene, 5-8 parts of tackifying vinyl chloride-vinyl acetate resin, 2-3 parts of organosilicon coupling agent and 50-60 parts of ethyl acetate.
In order to further optimize the technical scheme, the aluminum foil layer is subjected to surface treatment through passivation solution, and the passivation solution comprises the following raw materials in parts by weight: 0.3-1 part of chromium solution, 0.5-2 parts of epoxy modified phenolic resin, 2-5 parts of potassium zirconium carbonate, 2-5 parts of disodium succinate, 0.5-2 parts of tributyl phosphate, 40-55 parts of ethanol and 35-40 parts of water.
In order to further optimize the technical scheme, the water-soluble novolac epoxy resin is any one of phenol novolac epoxy resin, o-cresol novolac epoxy resin and bisphenol A novolac epoxy resin.
In order to further optimize the technical scheme, the emulsion adhesive is any one of polyvinylidene chloride resin emulsion, polyvinyl acetate emulsion or polyacrylate emulsion.
In order to further optimize the technical scheme, the polyester polyol and the polyether polyol are modified by acrylic acid or epoxy resin.
In order to further optimize the technical scheme, the epoxy resin is prepared from the following components in a mass ratio of 1: (1-2): (0.5-1) bisphenol A type epoxy resin, phenolic aldehyde type epoxy resin and alicyclic epoxy resin.
In order to further optimize the technical scheme, the mass ratio of the carbon nano tube is 1: (8-9) a mixture of single-walled carbon nanotubes and multi-walled carbon nanotubes.
In order to further optimize the technical scheme, the polyisocyanate is any one of methyl ethyl ketoxime blocked polyisocyanate, diethyl malonate blocked polyisocyanate and acetylacetone blocked polyisocyanate.
In order to further optimize the technical scheme, a pre-coated layer is further arranged between the aluminum foil layer and the second adhesive, and the pre-coated layer is composed of 5% of polybutadiene primer, 65% of ethanol and 30% of deionized water.
Example 1
A composite aluminum-plastic film for a power battery is mainly formed by co-extrusion compounding of an aluminum foil layer, a polypropylene layer and an external protection layer through a casting process, wherein the aluminum foil layer and the external protection layer are bonded through a first bonding agent, and the aluminum foil layer and the polypropylene layer are bonded through a second bonding agent;
the outer protective layer consists of a nylon film and a protective layer coated on the surface of the nylon film, wherein the protective layer comprises 1% of phenol novolac epoxy resin, 70% of polyvinylidene chloride resin emulsion and the balance of ethanol;
the first binder comprises the following raw materials in parts by weight: 10 parts of polyester polyol, 5 parts of polyether polyol, 3 parts of single-walled carbon nanotube, 0.1 part of toluene diisocyanate, 2 parts of bisphenol A epoxy resin, 0.2 part of silane coupling agent, 3 parts of acetylacetone blocked polyisocyanate and 50 parts of ethyl acetate;
the second adhesive comprises 25 parts of modified acrylate, 10 parts of maleic anhydride grafted modified polypropylene, 5 parts of tackifying vinyl chloride-vinyl acetate resin, 2 parts of organosilicon coupling agent and 50 parts of ethyl acetate.
Example 2
A composite aluminum-plastic film for a power battery is mainly formed by co-extrusion compounding of an aluminum foil layer, a polypropylene layer and an external protective layer through a tape casting process, wherein the aluminum foil layer and the external protective layer are bonded through a first bonding agent, and the aluminum foil layer and the polypropylene layer are bonded through a second bonding agent;
the outer protective layer consists of a nylon film and a protective layer coated on the surface of the nylon film, wherein the protective layer comprises 35% of o-cresol novolac epoxy resin, 78% of polyvinyl acetate emulsion and the balance of ethanol;
the first binder comprises the following raw materials in parts by weight: 12 parts of acrylic acid modified polyester polyol, 8 parts of epoxy resin modified polyether polyol, 4 parts of multi-walled carbon nanotube and 0.3 part of toluene diisocyanate, wherein the mass ratio of the components is 1:1:0.5 of 3 parts of epoxy resin consisting of bisphenol A type epoxy resin, phenolic aldehyde type epoxy resin and alicyclic epoxy resin, 0.4 part of silane coupling agent, 4 parts of diethyl malonate blocked polyisocyanate and 55 parts of ethyl acetate;
the second adhesive comprises 28 parts of modified acrylate, 12 parts of maleic anhydride grafted modified polypropylene, 7 parts of tackified vinyl chloride-vinyl acetate copolymer, 2.5 parts of organosilicon coupling agent and 55 parts of ethyl acetate.
Example 3
A composite aluminum-plastic film for a power battery is mainly formed by co-extrusion compounding of an aluminum foil layer, a polypropylene layer and an external protective layer through a tape casting process, wherein the aluminum foil layer and the external protective layer are bonded through a first bonding agent, and the aluminum foil layer and the polypropylene layer are bonded through a second bonding agent;
the outer protective layer consists of a nylon film and a protective layer coated on the surface of the nylon film, wherein the protective layer comprises 5% of bisphenol A type novolac epoxy resin, 85% of polyacrylate emulsion and the balance of ethanol;
the first binder comprises the following raw materials in parts by weight: 10 parts of acrylic acid modified polyester polyol, 10 parts of acrylic acid modified polyether polyol and a weight ratio of 1:8, 5 parts of a mixture of single-walled carbon nanotubes and multi-walled carbon nanotubes, 0.5 part of toluene diisocyanate, and a mixture of the single-walled carbon nanotubes and the multi-walled carbon nanotubes in a mass ratio of 1:2:1, 2-5 parts of epoxy resin consisting of bisphenol A type epoxy resin, phenolic aldehyde type epoxy resin and alicyclic epoxy resin, 0.5 part of silane coupling agent, 5 parts of methyl ethyl ketoxime blocked polyisocyanate and 60 parts of ethyl acetate;
the second adhesive comprises 30 parts of modified acrylate, 15 parts of maleic anhydride grafted modified polypropylene, 8 parts of tackified vinyl chloride-vinyl acetate copolymer, 3 parts of organosilicon coupling agent and 60 parts of ethyl acetate.
Example 4
The composite aluminum-plastic film for power batteries obtained in example 4 is the same as that obtained in example 3, and is different from the composite aluminum-plastic film in only that: the aluminum foil layer is subjected to surface treatment through a passivation solution, and the passivation solution comprises 0.5 part of chromium solution, 1 part of epoxy modified phenolic resin, 4 parts of potassium zirconium carbonate, 3 parts of disodium succinate, 1 part of tributyl phosphate, 50 parts of ethanol and 38 parts of water.
Example 5
The composite aluminum-plastic film for power batteries obtained in example 5 is the same as that obtained in example 4, and is different from the composite aluminum-plastic film in only that: carrying out surface treatment on the aluminum foil layer through a passivation solution, wherein the passivation solution comprises 0.3 part of chromium solution, 0.5 part of epoxy modified phenolic resin, 2 parts of potassium zirconium carbonate, 5 parts of disodium succinate, 2 parts of tributyl phosphate, 40 parts of ethanol and 40 parts of water;
and a pre-glued layer is arranged between the aluminum foil layer and the second adhesive and consists of 5% of polybutadiene primer, 65% of ethanol and 30% of deionized water.
Comparative example 1
Comparative example 1 the resulting composite aluminum plastic film for a power cell is the same as example 5 except that the outer protective layer is a conventional nylon film.
Comparative example 2
The composite aluminum-plastic film for power battery obtained in comparative example 2 is the same as that obtained in example 5, and is different from the composite aluminum-plastic film for power battery only in that: the first binder comprises the following raw materials in parts by weight: 10 parts of polyester polyol, 10 parts of polyether polyol, 0.5 part of toluene diisocyanate, 2-5 parts of phenolic epoxy resin, 0.5 part of silane coupling agent, 5 parts of phenol-blocked polyisocyanate and 60 parts of ethyl acetate.
Comparative example 3
The composite aluminum-plastic film for power battery obtained in comparative example 3 is the same as that obtained in example 5, and is different from the composite aluminum-plastic film for power battery only in that: the second adhesive comprises 45 parts of modified acrylate, 8 parts of tackifying vinyl chloride-vinyl acetate copolymer, 3 parts of organosilicon coupling agent and 60 parts of ethyl acetate.
The composite aluminum-plastic film for the power battery obtained in the examples 1 to 5 and the comparative examples 1 to 3 is subjected to performance test, and the detection results are shown in the following table 1:
TABLE 1 composite aluminum-plastic film Performance test results
Figure BDA0002655782610000091
The above results show that the composite aluminum-plastic film for power batteries obtained by the invention mainly improves the electrolyte resistance by improving the nylon layer, the first adhesive and the second adhesive, and has better improvement on the adhesive force, the tensile property, the stamping forming property and the like, and the pre-coating of the adhesive between the aluminum foil layer and the polypropylene layer and the passivation of the aluminum foil by using the passivation solution can also have excellent effect on the performance of the composite aluminum-plastic film.
In the present specification, the embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the scheme disclosed by the embodiment, the scheme corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (8)

1. The composite aluminum-plastic film for the power battery is characterized by being mainly formed by co-extruding and compounding an aluminum foil layer, a polypropylene layer and an external protective layer through a casting process, wherein the aluminum foil layer is bonded with the external protective layer through a first bonding agent, and the aluminum foil layer is bonded with the polypropylene layer through a second bonding agent;
the outer protective layer consists of a nylon film and a protective layer coated on the surface of the nylon film, wherein the protective layer comprises 1-5% of water-soluble novolac epoxy resin, 70-85% of emulsion adhesive and the balance of ethanol;
the first binder comprises the following raw materials in parts by weight: 10-15 parts of polyester polyol, 5-10 parts of polyether polyol, 3-5 parts of carbon nano tube, 0.1-0.5 part of toluene diisocyanate, 2-5 parts of epoxy resin, 0.2-0.5 part of silane coupling agent, 3-5 parts of polyisocyanate and 50-60 parts of solvent;
the second adhesive comprises 25-30 parts of modified acrylate, 10-15 parts of maleic anhydride grafted modified polypropylene, 5-8 parts of tackifying vinyl chloride-vinyl acetate resin, 2-3 parts of organosilicon coupling agent and 50-60 parts of ethyl acetate;
the aluminum foil layer is subjected to surface treatment through passivation solution, and the passivation solution comprises the following raw materials in parts by weight: 0.3-1 part of chromium solution, 0.5-2 parts of epoxy modified phenolic resin, 2-5 parts of potassium zirconium carbonate, 2-5 parts of disodium succinate, 0.5-2 parts of tributyl phosphate, 40-55 parts of ethanol and 35-40 parts of water;
the epoxy resin is prepared from the following components in percentage by mass of 1: (1-2): (0.5-1) bisphenol A type epoxy resin, phenolic aldehyde type epoxy resin and alicyclic epoxy resin.
2. The composite aluminum-plastic film for the power battery as claimed in claim 1, wherein the water-soluble novolac epoxy resin is any one of phenol-novolac epoxy resin, o-cresol-novolac epoxy resin or bisphenol A-novolac epoxy resin.
3. The composite aluminum-plastic film for the power battery as claimed in claim 1, wherein the emulsion adhesive is any one of polyvinylidene chloride resin emulsion, polyvinyl acetate emulsion or polyacrylate emulsion.
4. The composite aluminum-plastic film for the power battery as recited in claim 1, wherein the polyester polyol and the polyether polyol are both modified by acrylic or epoxy resin.
5. The composite aluminum-plastic film for the power battery as recited in claim 1, wherein the carbon nanotubes are mixed by mass ratio of 1: (8-9) a mixture of single-walled carbon nanotubes and multi-walled carbon nanotubes.
6. The composite aluminum-plastic film for the power battery as recited in claim 1, wherein the polyisocyanate is any one of methyl ethyl ketoxime blocked polyisocyanate, diethyl malonate blocked polyisocyanate or acetylacetone blocked polyisocyanate.
7. The composite aluminum-plastic film for the power battery as claimed in any one of claims 1 to 6, wherein a pre-coated layer is further included between the aluminum foil layer and the second adhesive, and the pre-coated layer consists of 5% polybutadiene primer, 65% ethanol and 30% deionized water.
8. The composite aluminum-plastic film for power batteries according to claim 7, wherein the thickness of the aluminum foil layer is 40 μm, the thickness of the polypropylene layer is 78-80 μm, and the thickness of the outer protective layer is 25-30 μm.
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