CN108045026A - Fire-retardant lithium battery encapsulation composite membrane of a kind of high water resistant and preparation method thereof - Google Patents

Fire-retardant lithium battery encapsulation composite membrane of a kind of high water resistant and preparation method thereof Download PDF

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Publication number
CN108045026A
CN108045026A CN201711290404.9A CN201711290404A CN108045026A CN 108045026 A CN108045026 A CN 108045026A CN 201711290404 A CN201711290404 A CN 201711290404A CN 108045026 A CN108045026 A CN 108045026A
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layer
composite membrane
thickness
lithium battery
fire
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Inventor
刘平磊
苗鲁滨
汪裕超
吴新星
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Shanghai HIUV New Materials Co Ltd
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Akcome Film & Applied New Materials (suzhou) Co Ltd
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Priority to CN201711290404.9A priority Critical patent/CN108045026A/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
    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
    • B29C66/026—Chemical pre-treatments
    • 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
    • B32B15/04—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
    • B32B15/09—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 polyesters
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
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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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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 of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the 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 of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
    • 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 of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
    • H01M50/1245—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure characterised by the external coating on the casing
    • 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
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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

Abstract

The present invention improves a kind of fire-retardant lithium battery encapsulation composite membrane of high water resistant; including protective layer, adhesive layer, passivation aluminium foil layer and hot sealing layer; wherein described protective layer is the nylon membrane or polyester film of single or double coating; about 1 ~ 5 μm of thickness of coating; the hot sealing layer seals CPP one layers, about 30 80 μm of thickness for bonding for three-decker, and the three-decker includes cementation layer; supporting role layer seals active layer.The present invention also provides a kind of multilayer lamination techniques for preparing the lithium battery encapsulation composite membrane.Composite membrane prepared by the present invention effectively reduces the water suction of nylon, and enhance the anti-hydrolytic performance of the adhesive layer between aluminium foil, and the technique of multi-layer co-extruded lamination, realize the one-pass molding from raw material to finished product composite membrane, the technique individually produced with binding agent fitting of CPP films is eliminated, effectively reduces production cost and equipment investment.

Description

Fire-retardant lithium battery encapsulation composite membrane of a kind of high water resistant and preparation method thereof
Technical field
The present invention relates to encapsulating material fields, relate generally to soft package lithium battery encapsulating material field, and in particular to Yi Zhonggao Lithium battery encapsulation composite membrane for blocking water fire-retardant and preparation method thereof.
Background technology
Lithium ion battery is since its is light-weight, capacity is big, has extended cycle life and the advantages such as memory-less effect, in digital electricity Subdomains extensive use, it is in recent years, even more fast-developing in emerging fields such as new-energy automobile, energy storage.Traditional lithium battery uses The rigid materials such as aluminum hull, box hat packaging, in addition to lightweight problem, there is also pressure to cross the security risks such as huge explosion.For A series of problems existing for lithium battery mental package, a kind of new aluminum-plastic composite membrane packaging material come into being.The packaging material It is generally formed by trilamellar membrane Material cladding, is protective layer, aluminium foil layer, corrosion-resistant hot sealing layer successively from outside to inside, usual protective layer It is the nylon membrane of biaxial tension（BOPA films）, aluminium foil layer using single or double Passivation Treatment, anti-corrosion layer be cast polypropylene Film（CPP films）.The bonding mode of aluminium foil and outer layer nylon membrane is by adhesive dry-lamination process.Aluminium foil and internal layer CPP films Bonding mode there are two types of.One kind is that hot pressing is compound, i.e., binder resin is squeezed out lamination in aluminium foil surface using extruder, then Hot repressing bonds CPP films.Another is aluminium foil surface coating adhesive, then dry out solvent and CPP films progress dry type are compound.
The nylon membrane of outer layer, since itself is hygroscopic, and water preventing ability is poor, more demanding to use environment, and storage life is short, Agent is sticked also easily because cohesive force reduces caused by hydrolysis the problems such as nylon membrane and interlayer aluminium foil adhesive glue, and nylon membrane itself is fire-retardant Property it is also bad, battery short circuit, be squeezed etc. trigger it is on fire in the case of, it is impossible to it is effective to ensure safety.
The CPP films of internal layer are compound with aluminium foil, and no matter hot pressing squeezes out compound CPP films or the compound CPP films of adhesive dry type, all It needs first to buy or prepare CPP films, adds material and process costs.In addition, hot pressing is compound larger there are integral thickness, Ultrathin encapsulating film problem should not be prepared；Dry type is compound to be needed to face the problems such as solvent is handled.
The content of the invention
For the formation problems of block water anti-flammability deficiency problem and the internal layer CPP film hot sealing layers of conventional protection layers nylon membrane, The present invention provides a kind of fire-retardant lithium battery encapsulation composite membrane of high water resistant and preparation method and a kind of multilayer lamination technique, The composite membrane being prepared is fire-retardant with high water resistant, and multilayer lamination technique preparation flow is simple, at low cost.
The first aspect of the present invention provides a kind of fire-retardant lithium battery encapsulation composite membrane of high water resistant, including protective layer, Adhesive layer, passivation aluminium foil layer and hot sealing layer, wherein the protective layer is the nylon membrane or polyester film of single or double coating, plating About 1 ~ 5 μm of layer thickness, the hot sealing layer seal CPP one layers for bonding for three-decker, about 30-80 μm of thickness, described three layers Structure includes cementation layer, and supporting role layer seals active layer.
Further, coating can be metals or the oxides such as aluminium coated, silica, aluminium oxide.
Further, coating forms single-layer or multi-layer coating using being deposited or sputtering mode.
Further, adhesive layer is modified polyester resin, modified polyurethane resin, modified epoxy, modified propylene One of acid resin, organic siliconresin, polyimide resin or organic fluorine.
Further, the three-decker of hot sealing layer includes：（1）Cementation layer is：Maleic anhydride modified polypropylene 20%- 40%th, acrylic acid modified polypropylene 5%-10%, maleic anhydride modified styrene 5%-10%, copolymer polypropylene 50%-60%, antioxidant 1%-2%, 6-15 μm of thickness；（2）Supporting role layer is：Homopolypropylene 50%-70%, copolymer polypropylene 20%-30%, elastomer 10%-20%, antioxidant 1%-2%, 15-50 μm of thickness；（3）Sealing active layer is：Copolymer polypropylene 60%-70%, elastomer 20%- 40%th, antioxidant 1%-2%, slipping agent 1%-3%, 10-20 μm of thickness.
Further, the ratio between the thickness of supporting role layer with sealing active layer is 3:1-1:1
Further, it is passivated aluminium foil layer and carries out surface passivating treatment using soft aluminium of annealing, and to aluminium foil double spread chromate.
The second aspect of the present invention, which provides a kind of multilayer lamination technique, to be included：Three layers of material of hot sealing layer are respectively with three Double screw extruder squeezes out, while connects three chamber co-extruding moulds；The material of each extruder is compound in mould outlet, then is cast to The aluminium foil surface of semi-finished product is stated, cementation layer is bonded with aluminium foil, then compound by multiple roll hot pressing.Wherein each extruder temperature exists 170-200 DEG C or so, mold temperature is at 210-250 DEG C or so, and hot pressing roll temperature is respectively at 80-130 DEG C or so.
The third aspect of the present invention additionally provides a kind of production technology of above-mentioned lithium battery encapsulation composite membrane, including：
（1）Base's aluminium foil layer uses thickness as the soft aluminium of 15-40 μm of annealing, and surface passivation is carried out to aluminium foil double spread chromate Processing；
（2）The materials such as aluminium, silica, aluminium oxide are plated in thin by nylon membrane or polyester film using conventional vapor deposition or sputtering technology Film surface, 1-5 μm of thickness of coating；
（3）In one face coating adhesive of aluminium foil layer of passivation, 3-5 μm of adhesive thickness, then with the nylon membrane of two-sided coating Or polyester film protective layer progress dry type is compound, prepares the semi-finished product of composite membrane, wherein 15-40 μm of the thickness of protective layer；
（4）Lamination hot sealing layer will be squeezed out on the aluminium foil surface of above-mentioned semi-finished product using multilayer lamination technique, hot sealing layer seals to bond CPP one layers, about 30-80 μm of thickness.For heat sealed package during product final application.
Coating forms single-layer or multi-layer coating using being deposited or sputtering mode.The method of vapor deposition is preferably vacuum evaporation, often The flow seen is cleaned including ungrease treatment with acetone or alcohol, and surface treatment includes Corona discharge Treatment, ultraviolet light irradiation Processing etc., bottom-surface coated/cure process（If necessary）, vacuum evaporation process.The method of sputtering can be common sputter coating Method is preferably magnetron sputtering method.Coating material is preferably the metals such as aluminium, silica, aluminium oxide or oxide, wherein considering Water-fast barriering effect and caking property, the convenience of preparation, preferably by the use of aluminium oxide as coating material.Coating can be with individual layer Or multilayer, it is preferably multilayered structure, can be realized by repeating sputtering.The thickness of coating is preferably 1-5 μm, blocked up coating Cause manufacturing cost excessively high, and lower caking property, too small thickness cannot play good barriering effect.
The material of hot sealing layer is three-layer co-extruded composite membrane, including sealing active layer, supporting role layer, cementation layer.It is viscous Knot active layer primarily serves the effect of cohesive aluminium foil and hot sealing layer.As shown in figure 3, the method for conventional adhesive hot sealing layer and aluminium foil layer It is to be connected therebetween by adhesive layer.And the present invention passes through the maleic anhydride modified polypropylene of multilayer lamination technology utilization Based on cementation layer, in one-step shaping technique directly with passivation aluminium foil it is bonding, reduce production craft step, and Cost is reduced, while avoids the bad corrosion resistance of conventional adhesive.
And supporting role layer primarily serves effect made of endothecium structure, can also play barrier electricity jointly with heat-sealing active layer Solve the effect of corrosion.Supporting role composition of layer includes：Homopolypropylene 50%-70%, copolymer polypropylene 20%-30%, elastomer 10%-20%, antioxidant 1%-2%.15-50 μm of thickness；And it seals active layer and includes：Copolymer polypropylene 60%-70%, elastomer 20%- 40%th, antioxidant 1%-2%, slipping agent 1%-3%.10-20 μm of thickness.Supporting role layer is mixed with homopolypropylene and copolymer polypropylene It closes based on object, and seals active layer based on copolymer polypropylene, the physical property performance of the two includes viscosity, mechanical property and solidifying Solid temperature degree is different, it is achieved thereby that different effects.Supporting role layer and heat-sealing active layer collective effect, play completely isolated electricity The effect of liquid, and the overall structure of supporting role layer support aluminum plastic film are solved, improves its mechanical property.In order to preferably realize this hair The ratio between bright effect, thickness of the supporting role layer with sealing active layer is 3:1-1:1, it is preferably 2：1.
The present invention uses multi-layer co-extruded lamination technique, and using all kinds of raw materials, the direct lamination of internal layer CPP hot sealing layers is coated In the aluminium foil surface of passivation, then hot repressing processing one-pass molding similar to conventional hot-press combination process, but uses more raw materials Multilayer extrusion, reduce CPP films individually produces technique, effectively reduces cost.
The advantageous effects of the present invention：
（1）The protective layer that the present invention uses is the nylon membrane or polyester film of single or double coating, and coating can be aluminium coated, two The metals such as silica, aluminium oxide or oxide, using being deposited or sputtering mode forms single-layer or multi-layer coating, thickness of coating about 1 ~ 5 microns are differed, the protective layer of coating film treatment, there is the excellent flame retardant type that blocks water.Using containing coated nylon or polyester film, protection The permeability rate of layer is by 3-5g/m2/ it is reduced to 1g/m for 24 hours2/ following for 24 hours, the water suction of nylon is effectively reduced, and is enhanced and aluminium foil Between adhesive layer anti-hydrolytic performance.
（2）Hot sealing layer uses the technique of multi-layer co-extruded lamination, realizes the one-pass molding from raw material to finished product composite membrane, The technique individually produced with binding agent fitting of CPP films is eliminated, effectively reduces production cost and equipment investment.
Description of the drawings
Fig. 1：The structure diagram of the fire-retardant lithium battery encapsulation composite membrane of high water resistant of the invention.
Fig. 2：The structure diagram of the hot sealing layer of the fire-retardant lithium battery encapsulation composite membrane of high water resistant of the invention.
Fig. 3：Conventional structure of composite membrane schematic diagram.
Specific embodiment
With reference to specific embodiment, the present invention will be further described.
According to the formula of table 1, embodiment 1-5 and comparative example 1-5 are prepared according to the following steps
（1）Base's aluminium foil layer uses thickness as the soft aluminium of 30 μm of annealing, and aluminium foil double spread chromate is carried out at surface passivation Reason；
（2）The materials such as aluminium, silica, aluminium oxide are plated in thin by nylon membrane or polyester film using conventional vapor deposition or sputtering technology Film surface, 1-5 μm of thickness of coating；
（3）In one face coating adhesive modified epoxy of aluminium foil layer of passivation, 3-5 μm of adhesive thickness, then with two-sided Nylon membrane or polyester film protective layer the progress dry type of coating are compound, prepare the semi-finished product of composite membrane；
（4）Three layers of material of hot sealing layer：Maleic anhydride modified polypropylene 30%, acrylic acid modified polypropylene 7.5%, maleic anhydride change Property styrene 7.5%, copolymer polypropylene 53.5%, antioxidant 1.5%；（2）Homopolypropylene 60%, copolymer polypropylene 25%, elastomer 14%th, antioxidant 1%；（3）Copolymer polypropylene 65%, elastomer 35%, antioxidant 2%, slipping agent 3%.It is squeezed respectively with three twin-screws Go out machine extrusion, while connect three chamber co-extruding moulds；The material of each extruder is compound in mould outlet, then is cast to above-mentioned semi-finished product Aluminium foil surface, cementation layer with aluminium foil be bonded, it is then compound by multiple roll hot pressing.Each extruder temperature is at 200 DEG C or so, mould Has temperature at 230 DEG C or so, hot pressing roll temperature is respectively at 90 DEG C or so.
The aluminum plastic film that comparative example 6 is prepared using common preparation method, as shown in Figure 3.
The formula of 1 embodiment of table and comparative example
Aluminum plastic film prepared by above-described embodiment and comparative example is made into 200Ah lithium ion batteries respectively, then according to the industry Standard GB/T18287-2013 detects the security of lithium ion battery.The results are shown in Table 2.
According to 1037 standards of GB, the water penetration tester test permeable amount through the aluminum plastic film prepared interior for 24 hours is used.Knot Fruit is as shown in table 2.
The performance test results of 2 embodiment of table and comparative example
Comparative example finds that coating of the present invention is preferably the aluminium oxide of multilayer.Comparative example finds do not having with comparative example 1 In the case of coated, the permeability rate of the product of preparation is very high, while the flame resistance of the battery prepared declines, right with comparative example 6 Than in the case of finding without three layers of hot sealing layer, permeability rate and catches fire rate further raise, and illustrate that coating and three layers of hot sealing layer rise High performance effect is put forward to collaboration.Comparative example and comparative example 2, find blocked up coating, cannot play instead it is optimal every Water effect, thus it is speculated that be because blocked up coating causes cohesive force decline between layers not tight enough with ply adhesion so as to cause layer It is close, permeability rate is caused to raise.Comparative example and comparative example 3,4,5, it is found that supporting layer is existed simultaneously and protected with hot sealing layer needs It holds in the range of certain proportion in the case of no supporting layer or hot sealing layer, catches fire rate and permeability rate all greatly improve, may It is because that in the case of supporting layer, the mechanical properties decrease of aluminum plastic film does not cause to be easily broken, without the feelings of hot sealing layer Condition is easy to cause electrolyte exosmosis, so as to trigger safety issue.

Claims (10)

1. a kind of fire-retardant lithium battery encapsulation composite membrane of high water resistant, it is characterised in that：Including protective layer, adhesive layer, passivation Aluminium foil layer and hot sealing layer, wherein the protective layer is the nylon membrane or polyester film of single or double coating, about 1 ~ 5 μ of thickness of coating M, the hot sealing layer bond heat-sealing CPP one layers for three-decker, and about 30-80 μm of thickness, the three-decker is including bonding Active layer, supporting role layer seal active layer.
2. the fire-retardant lithium battery encapsulation composite membrane of high water resistant according to claim 1, it is characterised in that：The coating is Silica, metal layer or metal oxide layer.
3. the fire-retardant lithium battery encapsulation composite membrane of high water resistant according to claim 1, it is characterised in that：The coating is adopted Single-layer or multi-layer coating is formed with being deposited or sputtering mode.
4. the fire-retardant lithium battery encapsulation composite membrane of high water resistant according to claim 1, it is characterised in that：The adhesive Layer is modified polyester resin, modified polyurethane resin, modified epoxy, acrylic resin modified, organic siliconresin, polyamides are sub- One of polyimide resin or organic fluorine.
5. the fire-retardant lithium battery encapsulation composite membrane of high water resistant according to claim 1, it is characterised in that：The hot sealing layer Three-decker include：（1）Cementation layer is：Maleic anhydride modified polypropylene 20%-40%, acrylic acid modified polypropylene 5%- 10%th, maleic anhydride modified styrene 5%-10%, copolymer polypropylene 50%-60%, antioxidant 1%-2%, 6-15 μm of thickness；（2）Support Active layer is：Homopolypropylene 50%-70%, copolymer polypropylene 20%-30%, elastomer 10%-20%, antioxidant 1%-2%, thickness 15-50μm；（3）Sealing active layer is：Copolymer polypropylene 60%-70%, elastomer 20%-40%, antioxidant 1%-2%, slipping agent 1%- 3%, 10-20 μm of thickness.
6. the fire-retardant lithium battery encapsulation composite membrane of high water resistant according to claim 5, it is characterised in that：The hot sealing layer In, it is 3 that supporting role layer acts on the ratio between layer thickness with heat-sealing:1-1：1.
7. the fire-retardant lithium battery encapsulation composite membrane of high water resistant according to claim 1, it is characterised in that：The passivation aluminium Layers of foil carries out surface passivating treatment using soft aluminium of annealing, and to aluminium foil double spread chromate.
8. a kind of multilayer lamination work for preparing the fire-retardant lithium battery encapsulation composite membrane of high water resistant according to claim 1 Skill, it is characterised in that：The multilayer lamination technique includes：Three layers of material of hot sealing layer are squeezed respectively with three double screw extruders Go out, while connect three chamber co-extruding moulds；The material of each extruder is compound in mould outlet, then is cast to the aluminium foil of above-mentioned semi-finished product Surface, cementation layer is bonded with aluminium foil, then compound by multiple roll hot pressing.
9. the production technology of the fire-retardant lithium battery encapsulation composite membrane of high water resistant according to claim 8, it is characterised in that： Each extruder temperature is at 170-200 DEG C or so, and mold temperature is at 210-250 DEG C or so, and hot pressing roll temperature is respectively on a 80-130 DEG C of left side It is right.
10. a kind of production technology of the fire-retardant lithium battery encapsulation composite membrane of high water resistant according to claim 1, including：
（1）Base's aluminium foil layer uses thickness as the soft aluminium of 15-40 μm of annealing, and surface passivation is carried out to aluminium foil double spread chromate Processing；
（2）The materials such as aluminium, silica, aluminium oxide are plated in thin by nylon membrane or polyester film using conventional vapor deposition or sputtering technology Film surface, 1-5 μm of thickness of coating；
（3）In one face coating adhesive of aluminium foil layer of passivation, 3-5 μm of adhesive thickness, then with the nylon membrane of two-sided coating Or polyester film protective layer progress dry type is compound, prepares the semi-finished product of composite membrane, wherein 15-40 μm of the thickness of protective layer；
（4）Lamination hot sealing layer will be squeezed out on the aluminium foil surface of above-mentioned semi-finished product using multilayer lamination technique, hot sealing layer seals to bond CPP one layers, about 30-80 μm of thickness；For heat sealed package during product final application.
CN201711290404.9A 2017-12-08 2017-12-08 Fire-retardant lithium battery encapsulation composite membrane of a kind of high water resistant and preparation method thereof Pending CN108045026A (en)

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CN111976175A (en) * 2020-07-30 2020-11-24 江阴苏达汇诚复合材料有限公司 Preparation method of aluminum-plastic film for battery and aluminum-plastic film
CN112009072A (en) * 2020-08-28 2020-12-01 广东安德力新材料有限公司 Thermal compounding process of composite aluminum plastic film for power battery
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