CN106450046B - Water-resistant anti-flatulence aluminum plastic film for lithium battery packaging and preparation method thereof - Google Patents

Water-resistant anti-flatulence aluminum plastic film for lithium battery packaging and preparation method thereof Download PDF

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CN106450046B
CN106450046B CN201610754827.0A CN201610754827A CN106450046B CN 106450046 B CN106450046 B CN 106450046B CN 201610754827 A CN201610754827 A CN 201610754827A CN 106450046 B CN106450046 B CN 106450046B
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layer
parts
temperature
resistant
aluminum
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CN106450046A (en
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丘晓琳
吴宇涛
傅苗苗
普布曲珍
陈臻杰
富坚定
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WUXI HUAJING NEW MATERIAL CO LTD
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Jiangsu Hua Gu New Materials Co ltd
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    • 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
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • 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
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance 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
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Sealing Battery Cases Or Jackets (AREA)
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Abstract

The invention discloses a water-resistant anti-flatulence aluminum plastic film for lithium battery packaging and a preparation method thereof. The scratch-resistant aluminum foil is characterized in that the scratch-resistant aluminum foil is sequentially provided with a scratch-resistant layer, an aluminum foil layer, a chemical protection layer, an absorption layer and a blocking layer from outside to inside, viscose layers are respectively arranged between the scratch-resistant layer and the aluminum foil layer, between the chemical protection layer and the absorption layer and between the absorption layer and the blocking layer, and the aluminum foil layer and the chemical protection layer are formed together. The method comprises the steps of firstly preparing a scratch-resistant layer, forming a chemical protection layer on the surface of an aluminum foil, forming an absorption layer consisting of a gas absorption layer and a water absorption layer, a mechanical support layer, a low-temperature heat sealing layer and a barrier layer, then coating adhesive layers on the adjacent surfaces of the scratch-resistant layer and an aluminum foil layer, the adjacent surfaces of the chemical protection layer and the absorption layer, and the adjacent surfaces of the absorption layer and the barrier layer, and compounding the scratch-resistant layer, the aluminum foil layer and the chemical protection layer, the absorption layer and the barrier layer together through a roller press. The invention has the functions of water resistance and flatulence prevention. By adopting the invention, the safety and the service life of the lithium battery can be improved.

Description

Water-resistant anti-flatulence aluminum plastic film for lithium battery packaging and preparation method thereof
Technical Field
The invention relates to a lithium battery packaging material. In particular to an aluminum-plastic composite film for the flexible package of polymer lithium ion batteries.
Background
The polymer lithium ion battery is the most advanced secondary battery in the world nowadays, has high specific energy and high charging and discharging speed, gradually replaces the lithium ion battery, and is applied to digital products such as mobile phones, notebook computers, MP3, PDAs, DVs and the like.
The swelling phenomenon of the lithium battery is a major factor affecting the safety of the battery, and it causes the performance of the battery to be degraded. The electrolyte of the polymer lithium ion battery is mostly composed of an organic solvent with strong corrosion and permeability and lithium salt which is easy to hydrolyze, and in the storage process, the electrolyte is easy to oxidize and delaminate the inner layer membrane of the lithium ion battery, so that the package loses the integrity. Therefore, the barrier property of the aluminum-plastic composite film and the corrosion resistance of the aluminum foil become factors to be solved. Because the traditional polymer lithium ion battery adopts the composite aluminum-plastic film as the outer packaging material, the traditional polymer lithium ion battery is difficult to bear larger internal gas pressure. Therefore, the ballooning phenomenon becomes a necessary solution.
Because most of the electrolyte of the polymer lithium ion battery is composed of an organic solvent with strong corrosion and permeability and lithium salt which is very easy to hydrolyze, when external moisture and air permeate, CO in the battery is caused 2 At significant increases, a considerable amount of O will be present 2 And N 2 And the water vapor can cause the problems of chemical oxidation, swelling and the like of the electrolyte, the phenomenon of gas expansion can occur, and the service life of the battery can be reduced.
The flexible package aluminum-plastic film barrier layer disclosed in the prior art uses a single-layer polyamide barrier layer, has good barrier property, but has poor tearing strength and insufficient toughness, and is easy to tear in battery processing technologies such as folding and stamping, so that the package integrity is damaged.
In addition, the flexible package aluminum-plastic film barrier layer disclosed in the prior art is a single-layer modified polypropylene barrier layer, has good tensile strength and tensile strength, good corrosion resistance and insulation property, but has poor barrier property, and gas and moisture can enter the package in the storage process, so that the use safety and the service life of the lithium ion battery are influenced.
Disclosure of Invention
The invention aims to provide a waterproof and anti-flatulence aluminum-plastic film for lithium battery packaging. The invention has the functions of water resistance and flatulence prevention. By adopting the invention, the safety and the service life of the lithium battery can be improved.
The invention aims to solve another problem of providing a method for preparing a waterproof anti-flatulence aluminum-plastic film for lithium battery packaging.
The above problems to be solved by the present invention are realized by the following technical solutions:
the waterproof and anti-flatulence aluminum-plastic film for packaging the lithium battery is characterized by sequentially comprising a scratch-resistant layer, an aluminum foil layer, a chemical protection layer, an absorption layer and a blocking layer from outside to inside, wherein viscose layers are arranged between the scratch-resistant layer and the aluminum foil layer, between the chemical protection layer and the absorption layer and between the absorption layer and the blocking layer, and the aluminum foil layer and the chemical protection layer are formed together.
Wherein:
the scratch-resistant layer comprises the following raw materials in parts by mass:
90 to 95 parts of polyethylene terephthalate;
5 to 10 portions of benzoyl peroxide;
1 to 3 parts of acrylonitrile.
The aluminum foil layer is an aluminum foil with the thickness of 30-50 micrometers.
The chemical protective layer is inorganic-organic siloxane passivation solution.
The absorption layer comprises a gas absorption layer and a water absorption layer.
The gas absorption layer comprises the following raw materials in parts by mass:
90 to 95 parts of polyethylene terephthalate;
10 to 15 parts of hydroxyl-terminated polybutadiene/maleic anhydride esterified oxygen absorbent or 1, 4-butylene glycol/maleic anhydride esterified substance or 1, 4-butylene glycol/methyltetrahydrophthalic anhydride esterified absorbent;
0.05 to 0.1 portion of cobalt acetate catalyst;
0.5 to 3 parts of metal-organic framework Materials (MOFs) pumice imidazolyl framework materials.
The water absorbing layer comprises the following raw materials in parts by mass:
40 to 90 parts of nano silica gel;
10 to 15 parts of nano-grade alumina;
0 to 15 parts of nano calcium oxide.
The barrier layer comprises a mechanical support layer and a low-temperature heat sealing layer.
The mechanical support layer comprises the following raw materials in parts by mass:
80-90 parts of random copolymerization polypropylene;
0 to 0.3 portion of nano silicon dioxide;
1 to 3 parts of polyvinyl chloride;
15-18 parts of polyolefin elastomer;
0.1 to 1 part of dehydroabietic acid;
0.05 to 0.075 portion of calcium stearate.
The low-temperature heat sealing layer comprises the following raw materials in parts by mass:
80-90 parts of random copolymerization polypropylene;
0 to 0.3 part of nano silicon dioxide;
15-18 parts of polyolefin elastomer.
The adhesive layer is acid modified polyolefin adhesive.
The method for preparing the waterproof and flatulence-preventing aluminum plastic film for lithium battery packaging is characterized by sequentially comprising the following steps of:
(1) Firstly, blow molding polyethylene glycol terephthalate to form a film, uniformly coating benzoyl peroxide on the surface of the film, and then placing the film coated with benzoyl peroxide in acrylonitrile steam for graft polymerization reaction to obtain a scratch-resistant layer;
(2) Firstly, uniformly coating inorganic-organic siloxane passivation solution on the surface of an aluminum foil, then putting the aluminum foil coated with the inorganic-organic siloxane passivation solution on the surface into an oven at the temperature of 95-105 ℃ for drying for 58-62 minutes, and forming a chemical protective layer on the surface of the aluminum foil;
(3) Putting polyethylene glycol terephthalate into a vacuum drying oven at the temperature of 115-125 ℃ for drying for 23-25 hours, then fully mixing hydroxyl-terminated polybutadiene/maleic anhydride esterified oxygen absorbent, 1, 4-butylene glycol/maleic anhydride esterified substance, or 1, 4-butylene glycol/methyltetrahydrophthalic anhydride esterified absorbent and a cobalt acetate catalyst, putting the mixture, metal-organic framework Materials (MOFs) pumice imidazolyl framework materials and dried polyethylene glycol terephthalate into a high-speed stirring pot, and uniformly mixing to obtain a mixture; then, extruding and drying the mixture by using a double-screw extruder with a runner temperature of 255-275 ℃, a film opening temperature of 255-265 ℃ and a vacuum degree of 0.08Mpa to obtain a first layer material; then, the first layer material is put into an extruder and co-extruded into a sheet at the temperature of 270-290 ℃; then, carrying out biaxial tension at the temperature of 100-120 ℃ to obtain a gas absorption layer;
then, putting the nanoscale silica gel, the nanoscale aluminum oxide and the nanoscale calcium oxide into a high-speed stirring pot together, and uniformly mixing to obtain nanoscale silica gel particles;
then, spraying a layer of the nano silica gel particles on the surface of the gas absorption layer, forming a water absorption layer on the surface of the gas absorption layer, and forming the absorption layer by the gas absorption layer and the water absorption layer;
(4) Firstly, putting random copolymerization polypropylene, nano silicon dioxide, polyvinyl chloride, polyolefin elastomer, dehydroabietic acid and calcium stearate into a high-speed stirring pot, and uniformly mixing to obtain a mixture; then, extruding the mixture by using a double-screw extruder at a runner temperature of 215-225 ℃ and a film opening temperature of 195-205 ℃, rapidly cooling to normal temperature, and drying by using an oven at a temperature of 120-130 ℃ for 50-60 minutes to obtain a raw material for the mechanical support layer;
(5) Firstly, putting the random copolymerization polypropylene, the nano silicon dioxide and the polyolefin elastomer into a high-speed stirring pot, and uniformly mixing to obtain a mixture; then, extruding the mixture by using a double-screw extruder at a runner temperature of 205-215 ℃ and a film opening temperature of 195-205 ℃, rapidly cooling to normal temperature, and drying by using an oven at a temperature of 120-130 ℃ for 25-35 minutes to obtain a raw material for the low-temperature heat-sealing layer;
(6) Respectively extruding a raw material of a mechanical supporting layer and a raw material of a low-temperature heat sealing layer by using two double-screw extruders with the runner temperatures of 205-215 ℃ and 178-182 ℃ and the film mouth temperature of 210-220 ℃, and then co-extruding the materials by using a co-extruder to form a film, so as to obtain a barrier layer consisting of the mechanical supporting layer and the low-temperature heat sealing layer;
(7) All scribble the viscose layer on resistant layer and the adjacent face of aluminium foil layer, chemical inoxidizing coating and absorbed layer and barrier layer, will be resistant through the roll squeezer and scrape layer, aluminium foil layer and chemical inoxidizing coating, absorbed layer and barrier layer complex together, obtain lithium cell packing with waterproof flatulence plastic-aluminum membrane of preventing.
According to the scheme, the aluminum-plastic composite film for the polymer lithium ion package sequentially comprises a scratch-resistant layer, an aluminum foil layer, a chemical protective layer, an absorption layer and a blocking layer from outside to inside, wherein the scratch-resistant layer and the aluminum foil layer, the chemical protective layer and the absorption layer are laminated together through a glue-melting layer in a cold pressing mode.
Because the invention adopts polyethylene glycol terephthalate/acrylonitrile graft copolymerization modification, the oxygen-blocking and water-blocking performance of the scratch-resistant layer is effectively improved.
Because the surface of the aluminum foil layer is passivated by adopting inorganic-organic siloxane, the aluminum foil is effectively prevented from corrosion and rust, and the siloxane has hydrophobicity and more effectively prevents the corrosion of the internal electrolyte to the aluminum foil.
Because the absorption layer comprises oxygen, carbon dioxide absorption layer and water absorption layer, through the absorption to oxygen, carbon dioxide in the packing, the effectual quality problem of preventing the battery because the gassing produces. The nano particle water absorption layer on the spraying layer absorbs moisture in the package, can effectively prevent water vapor from entering the electrolyte to generate corrosive acid such as hydrofluoric acid and other gases, and improves the comprehensive barrier property of the aluminum plastic film.
The barrier layer is composed of a mechanical support layer and a low-temperature heat sealing layer. Through the modification of the structural design and the formula of the barrier layer, the corrosion resistance and the insulativity of the barrier layer are improved, the electrolyte resistance of the composite film is enhanced, the heat-sealing temperature is reduced, and the heat-sealing process is optimized, so that the service life of the aluminum-plastic composite film for the flexible package of the lithium ion battery is prolonged. The crystallization degree of the mechanical supporting layer is optimized through the synergistic effect of dehydroabietic acid and calcium stearate, and the barrier film with high toughness and low haze is obtained. The aluminum foil layer is subjected to chromium plating, so that the interlayer strength is improved, the tensile strength and the elongation at break of the aluminum-plastic composite film for the flexible package of the lithium ion battery are improved, and the composite film can be formed by punching.
Drawings
Fig. 1 is a schematic structural diagram of a water-resistant anti-flatulence aluminum-plastic film for packaging a lithium battery.
Detailed Description
Example one
The invention is explained in more detail below with reference to the drawings and examples
As shown in fig. 1, the waterproof and anti-flatulence aluminum-plastic film for packaging a lithium battery of the invention sequentially comprises a scratch-resistant layer, an aluminum foil layer, a chemical protection layer, an absorption layer and a barrier layer from outside to inside, wherein viscose layers are respectively arranged between the scratch-resistant layer and the aluminum foil layer, between the chemical protection layer and the absorption layer and between the absorption layer and the barrier layer, and the aluminum foil layer and the chemical protection layer are formed together. Wherein:
the scratch-resistant layer comprises the following raw materials in parts by mass:
90 parts of polyethylene terephthalate;
7 parts of benzoyl peroxide;
3 parts of acrylonitrile.
The aluminum foil layer is an aluminum foil with the thickness of 30 micrometers.
The chemical protective layer is inorganic-organic siloxane passivation solution.
The absorption layer comprises a gas absorption layer and a water absorption layer.
The gas absorption layer comprises the following raw materials in parts by mass:
92 parts of polyethylene terephthalate;
15 parts of hydroxyl-terminated polybutadiene/maleic anhydride esterified oxygen absorbent, 1, 4-butylene glycol/maleic anhydride esterified compound or 1, 4-butylene glycol/methyltetrahydrophthalic anhydride esterified absorbent;
0.05 part of cobalt acetate catalyst;
3 parts of metal-organic framework Materials (MOFs) pumice imidazolyl framework materials.
The water absorbing layer comprises the following raw materials in parts by mass:
40 parts of nano silica gel;
10 parts of nano-alumina;
12 parts of nano calcium oxide.
The barrier layer comprises a mechanical support layer and a low-temperature heat sealing layer.
The mechanical support layer comprises the following raw materials in parts by mass:
90 parts of random copolymerization polypropylene;
2 parts of polyvinyl chloride;
15 parts of polyolefin elastomer;
0.6 part of dehydroabietic acid;
0.075 part of calcium stearate.
The low-temperature heat sealing layer comprises the following raw materials in parts by mass:
80 parts of random copolymer polypropylene;
0.15 part of nano silicon dioxide;
and 18 parts of polyolefin elastomer.
The adhesive layer is acid modified polyolefin adhesive.
The method for preparing the waterproof and anti-flatulence aluminum-plastic film for lithium battery packaging sequentially comprises the following steps of:
(1) Firstly, blow molding polyethylene glycol terephthalate to form a film, and then uniformly coating benzoyl peroxide on the surface of the film. Then, placing the film coated with the benzoyl peroxide in acrylonitrile steam for graft polymerization reaction to obtain a scratch-resistant layer;
(2) Firstly, uniformly coating inorganic-organic siloxane passivation solution on the surface of an aluminum foil, and then putting the aluminum foil coated with the inorganic-organic siloxane passivation solution on the surface into a drying oven at the temperature of 95 ℃ for drying for 62 minutes to form a chemical protective layer on the surface of the aluminum foil;
(3) Firstly putting polyethylene glycol terephthalate into a vacuum drying oven at the temperature of 115 ℃ for drying for 23 hours, then fully mixing hydroxyl-terminated polybutadiene/maleic anhydride esterified oxygen absorbent, 1, 4-butylene glycol/maleic anhydride esterified substance, or 1, 4-butylene glycol/methyl tetrahydrophthalic anhydride esterified absorbent with a cobalt acetate catalyst, putting the mixture, metal-organic framework (MOFs) pumice imidazolyl framework material and dried polyethylene glycol terephthalate into a high-speed stirring pot, and uniformly mixing to obtain a mixture. Then, extruding and drying the mixture by using a double-screw extruder with the flow channel temperature of 275 ℃, the membrane opening temperature of 275 ℃ and the vacuum degree of 0.07Mpa to obtain a first layer material; the first layer was then fed into an extruder and co-extruded into sheets at a temperature of 270 ℃. Then, carrying out biaxial stretching at the temperature of 110 ℃ to obtain a gas absorption layer;
then, putting the nanoscale silica gel, the nanoscale alumina and the nanoscale calcium oxide into a high-speed stirring pot together, and uniformly mixing to obtain nanoscale silica gel particles;
then, spraying a layer of the nano silica gel particles on the surface of the gas absorption layer to form a water absorption layer on the surface of the gas absorption layer, wherein the gas absorption layer and the water absorption layer form the absorption layer;
(4) Firstly, random copolymerization polypropylene, nano silicon dioxide, polyvinyl chloride, polyolefin elastomer, dehydroabietic acid and calcium stearate are put into a high-speed stirring pot and uniformly mixed to obtain a mixture. Then, extruding the mixture by using a double-screw extruder at a runner temperature of 225 ℃ and a film opening temperature of 205 ℃, rapidly cooling to normal temperature, and drying for 60 minutes by using an oven at a temperature of 120 ℃ to obtain a raw material for the mechanical support layer;
(5) Firstly, putting the random copolymerization polypropylene, the nano silicon dioxide and the polyolefin elastomer into a high-speed stirring pot, and uniformly mixing to obtain a mixture. Then, extruding the mixture by using a double-screw extruder at a runner temperature of 205 ℃ and a film opening temperature of 200 ℃, rapidly cooling to normal temperature, and drying for 35 minutes by using an oven at a temperature of 120 ℃ to obtain a raw material for a low-temperature heat-sealing layer;
(6) Extruding the raw materials of the mechanical supporting layer and the low-temperature heat-sealing layer by two double-screw extruders with the flow channel temperatures of 215 ℃ and 178 ℃ and the film opening temperature of 220 ℃ respectively, and then co-extruding the raw materials of the mechanical supporting layer and the low-temperature heat-sealing layer by using the co-extruder to form a film so as to obtain a barrier layer consisting of the mechanical supporting layer and the low-temperature heat-sealing layer;
(7) All scribble the viscose layer on resistant layer and the adjacent face of aluminium foil layer, chemical inoxidizing coating and absorbed layer and barrier layer, will be resistant through the roll squeezer and scrape layer, aluminium foil layer and chemical inoxidizing coating, absorbed layer and barrier layer complex together, obtain lithium cell packing with waterproof flatulence plastic-aluminum membrane of preventing.
Example two
As shown in fig. 1, the waterproof and anti-flatulence aluminum-plastic film for packaging a lithium battery of the invention sequentially comprises a scratch-resistant layer, an aluminum foil layer, a chemical protection layer, an absorption layer and a barrier layer from outside to inside, wherein viscose layers are respectively arranged between the scratch-resistant layer and the aluminum foil layer, between the chemical protection layer and the absorption layer and between the absorption layer and the barrier layer, and the aluminum foil layer and the chemical protection layer are formed together. Wherein:
the scratch-resistant layer comprises the following raw materials in parts by mass:
93 parts of polyethylene terephthalate;
10 parts of benzoyl peroxide;
1 part of acrylonitrile.
The aluminum foil layer is an aluminum foil with a thickness of 40 microns.
The chemical protective layer is inorganic-organic siloxane passivation solution.
The absorption layer comprises a gas absorption layer and a water absorption layer.
The gas absorption layer comprises the following raw materials in parts by mass:
95 parts of polyethylene terephthalate;
10 parts of hydroxyl-terminated polybutadiene/maleic anhydride esterified oxygen absorbent, 1, 4-butylene glycol/maleic anhydride esterified compound or 1, 4-butylene glycol/methyltetrahydrophthalic anhydride esterified absorbent;
0.07 part of cobalt acetate catalyst;
1.5 parts of metal-organic framework Materials (MOFs) pumice imidazolyl framework materials.
The water absorbing layer comprises the following raw materials in parts by mass:
65 parts of nano silica gel;
13 parts of nano-alumina;
and 15 parts of nano calcium oxide.
The barrier layer comprises a mechanical support layer and a low-temperature heat sealing layer.
The mechanical support layer comprises the following raw materials in parts by mass:
80 parts of random copolymer polypropylene;
0.15 part of nano silicon dioxide;
3 parts of polyvinyl chloride;
15 parts of polyolefin elastomer;
1 part of dehydroabietic acid;
0.06 part of calcium stearate.
The low-temperature heat sealing layer comprises the following raw materials in parts by mass:
85 parts of random copolymer polypropylene;
16 parts of polyolefin elastomer.
The adhesive layer is acid modified polyolefin adhesive.
The method for preparing the waterproof and flatulence-preventing aluminum plastic film for lithium battery packaging sequentially comprises the following steps of:
(1) Firstly, blow molding polyethylene glycol terephthalate to form a film, and then uniformly coating benzoyl peroxide on the surface of the film. Then, placing the film coated with the benzoyl peroxide in acrylonitrile steam for graft polymerization reaction to obtain a scratch-resistant layer;
(2) Firstly, uniformly coating inorganic-organic siloxane passivation solution on the surface of an aluminum foil, and then putting the aluminum foil coated with the inorganic-organic siloxane passivation solution on the surface into a drying oven at the temperature of 100 ℃ for drying for 60 minutes to form a chemical protective layer on the surface of the aluminum foil;
(3) Firstly putting polyethylene glycol terephthalate into a vacuum drying oven at the temperature of 120 ℃ for drying for 24 hours, then fully mixing hydroxyl-terminated polybutadiene/maleic anhydride esterified oxygen absorbent, 1, 4-butylene glycol/maleic anhydride esterified substance, or 1, 4-butylene glycol/methyl tetrahydrophthalic anhydride esterified absorbent with a cobalt acetate catalyst, putting the mixture, metal-organic framework Materials (MOFs) pumice imidazolyl framework materials and dried polyethylene glycol terephthalate into a high-speed stirring pot, and uniformly mixing to obtain a mixture. Then, extruding and drying the mixture by using a double-screw extruder with the flow channel temperature of 255 ℃, the membrane opening temperature of 255 ℃ and the vacuum degree of 0.08Mpa to obtain a first layer material; then, the first layer material is put into an extruder and co-extruded into a sheet at a temperature of 280 ℃. Then, carrying out biaxial stretching at the temperature of 120 ℃ to obtain a gas absorption layer;
then, putting the nanoscale silica gel, the nanoscale aluminum oxide and the nanoscale calcium oxide into a high-speed stirring pot together, and uniformly mixing to obtain nanoscale silica gel particles;
then, spraying a layer of the nano silica gel particles on the surface of the gas absorption layer to form a water absorption layer on the surface of the gas absorption layer, wherein the gas absorption layer and the water absorption layer form the absorption layer;
(4) Firstly, random copolymerization polypropylene, nano silicon dioxide, polyvinyl chloride, polyolefin elastomer, dehydroabietic acid and calcium stearate are put into a high-speed stirring pot and mixed uniformly to obtain a mixture. Then, extruding the mixture by using a double-screw extruder at a runner temperature of 220 ℃ and a film opening temperature of 200 ℃, rapidly cooling to normal temperature, and drying for 55 minutes by using an oven at a temperature of 125 ℃ to obtain a raw material for the mechanical support layer;
(5) Firstly, putting the random copolymerization polypropylene, the nano silicon dioxide and the polyolefin elastomer into a high-speed stirring pot, and uniformly mixing to obtain a mixture. Then, extruding the mixture by using a double-screw extruder at a runner temperature of 210 ℃ and a film opening temperature of 205 ℃, rapidly cooling to normal temperature, and drying for 30 minutes by using an oven at a temperature of 125 ℃ to obtain a raw material for the low-temperature heat-sealing layer;
(6) Extruding the raw materials of the mechanical supporting layer and the low-temperature heat-sealing layer by two double-screw extruders with the flow channel temperatures of 210 ℃ and 180 ℃ and the film opening temperature of 215 ℃ respectively, and then co-extruding the raw materials of the mechanical supporting layer and the low-temperature heat-sealing layer by using a co-extruder to form a film so as to obtain a barrier layer consisting of the mechanical supporting layer and the low-temperature heat-sealing layer;
(7) All scribble the viscose layer on resistant layer and the adjacent face of aluminium foil layer, chemical inoxidizing coating and absorbed layer and barrier layer, will be resistant through the roll squeezer and scrape layer, aluminium foil layer and chemical inoxidizing coating, absorbed layer and barrier layer complex together, obtain lithium cell packing with waterproof flatulence plastic-aluminum membrane of preventing.
EXAMPLE III
As shown in fig. 1, the waterproof and anti-flatulence aluminum-plastic film for packaging a lithium battery of the invention sequentially comprises a scratch-resistant layer, an aluminum foil layer, a chemical protection layer, an absorption layer and a barrier layer from outside to inside, wherein viscose layers are respectively arranged between the scratch-resistant layer and the aluminum foil layer, between the chemical protection layer and the absorption layer and between the absorption layer and the barrier layer, and the aluminum foil layer and the chemical protection layer are formed together. Wherein:
the scratch-resistant layer comprises the following raw materials in parts by mass:
95 parts of polyethylene terephthalate;
5 parts of benzoyl peroxide;
2 parts of acrylonitrile.
The aluminum foil layer is an aluminum foil with a thickness of 50 microns.
The chemical protective layer is inorganic-organic siloxane passivation solution.
The absorption layer comprises a gas absorption layer and a water absorption layer.
The gas absorption layer comprises the following raw materials in parts by mass:
90 parts of polyethylene terephthalate;
13 parts of hydroxyl-terminated polybutadiene/maleic anhydride esterified oxygen absorbent, 1, 4-butylene glycol/maleic anhydride esterified compound or 1, 4-butylene glycol/methyltetrahydrophthalic anhydride esterified absorbent;
0.1 part of cobalt acetate catalyst;
0.5 part of metal-organic framework Materials (MOFs) pumice imidazolyl framework materials.
The water absorbing layer comprises the following raw materials in parts by mass:
90 parts of nano silica gel;
15 parts of nano-alumina.
The barrier layer comprises a mechanical support layer and a low-temperature heat sealing layer.
The mechanical support layer comprises the following raw materials in parts by mass:
85 parts of random copolymer polypropylene;
0.3 part of nano silicon dioxide;
1 part of polyvinyl chloride;
18 parts of polyolefin elastomer;
0.1 part of dehydroabietic acid;
0.05 part of calcium stearate.
The low-temperature heat-sealing layer comprises the following raw materials in parts by mass:
90 parts of random copolymerization polypropylene;
0.3 part of nano silicon dioxide;
15 parts of polyolefin elastomer.
The adhesive layer is acid modified polyolefin adhesive.
The method for preparing the waterproof and flatulence-preventing aluminum plastic film for lithium battery packaging sequentially comprises the following steps of:
(1) Firstly, blow molding polyethylene glycol terephthalate to form a film, and then uniformly coating benzoyl peroxide on the surface of the film. Then, placing the film coated with the benzoyl peroxide in acrylonitrile steam for graft polymerization reaction to obtain a scratch-resistant layer;
(2) Firstly, uniformly coating inorganic-organic siloxane passivation solution on the surface of an aluminum foil, then putting the aluminum foil coated with the inorganic-organic siloxane passivation solution on the surface into a drying oven with the temperature of 105 ℃ for drying for 58 minutes, and forming a chemical protective layer on the surface of the aluminum foil;
(3) Firstly putting polyethylene glycol terephthalate into a vacuum drying oven at the temperature of 125 ℃ for drying for 25 hours, then fully mixing hydroxyl-terminated polybutadiene/maleic anhydride esterified oxygen absorbent, 1, 4-butylene glycol/maleic anhydride esterified substance, or 1, 4-butylene glycol/methyl tetrahydrophthalic anhydride esterified absorbent with a cobalt acetate catalyst, putting the mixture, metal-organic framework Materials (MOFs) pumice imidazolyl framework materials and dried polyethylene glycol terephthalate into a high-speed stirring pot, and uniformly mixing to obtain a mixture. Then, extruding and drying the mixture by using a double-screw extruder with the runner temperature of 265 ℃, the film opening temperature of 265 ℃ and the vacuum degree of 0.075Mpa to obtain a first layer material; then, the first layer was fed into an extruder and co-extruded into sheets at a temperature of 290 ℃. Then, carrying out biaxial stretching at the temperature of 100 ℃ to obtain a gas absorption layer;
then, putting the nanoscale silica gel, the nanoscale aluminum oxide and the nanoscale calcium oxide into a high-speed stirring pot together, and uniformly mixing to obtain nanoscale silica gel particles;
then, spraying a layer of the nano silica gel particles on the surface of the gas absorption layer to form a water absorption layer on the surface of the gas absorption layer, wherein the gas absorption layer and the water absorption layer form the absorption layer;
(4) Firstly, random copolymerization polypropylene, nano silicon dioxide, polyvinyl chloride, polyolefin elastomer, dehydroabietic acid and calcium stearate are put into a high-speed stirring pot and uniformly mixed to obtain a mixture. Then, extruding the mixture by using a double-screw extruder at a runner temperature of 215 ℃ and a film opening temperature of 195 ℃, rapidly cooling to normal temperature, and drying for 50 minutes by using an oven at a temperature of 130 ℃ to obtain a raw material for the mechanical support layer;
(5) Firstly, putting the random copolymerization polypropylene, the nano silicon dioxide and the polyolefin elastomer into a high-speed stirring pot, and uniformly mixing to obtain a mixture. Then, extruding the mixture by using a double-screw extruder at a runner temperature of 215 ℃ and a film opening temperature of 195 ℃, rapidly cooling the mixture to normal temperature, and drying the mixture for 35 minutes by using an oven at a temperature of 130 ℃ to obtain a raw material for a low-temperature heat-sealing layer;
(6) Extruding the raw materials of the mechanical supporting layer and the low-temperature heat-sealing layer by two double-screw extruders with the flow channel temperatures of 205 ℃ and 180 ℃ and the film opening temperature of 210 ℃ respectively, and then co-extruding the raw materials into a film by using a co-extruder to obtain a barrier layer consisting of the mechanical supporting layer and the low-temperature heat-sealing layer;
(7) When all coating the viscose layer on resistant layer and aluminium foil layer, chemical protection layer and absorbed layer and the adjacent face of barrier layer, will be able to bear or endure to scrape layer, aluminium foil layer and chemical protection layer, absorbed layer and barrier layer complex together through the roll squeezer, obtain lithium cell packing and use water-fast flatulence plastic-aluminum membrane of preventing.

Claims (11)

1. The method for preparing the waterproof anti-flatulence aluminum-plastic film for the lithium battery packaging comprises a scratch-resistant layer, an aluminum foil layer, a chemical protection layer, an absorption layer and a blocking layer which are sequentially arranged from outside to inside, wherein viscose layers are respectively arranged between the scratch-resistant layer and the aluminum foil layer, between the chemical protection layer and the absorption layer and between the absorption layer and the blocking layer, and the aluminum foil layer and the chemical protection layer are formed together; the method is characterized by sequentially comprising the following steps:
(1) Firstly, blow-molding polyethylene glycol terephthalate to form a film, uniformly coating benzoyl peroxide on the surface of the film, and then placing the film coated with benzoyl peroxide in acrylonitrile steam for graft polymerization reaction to obtain a scratch-resistant layer;
(2) Firstly, uniformly coating inorganic-organic siloxane passivation solution on the surface of an aluminum foil, then putting the aluminum foil coated with the inorganic-organic siloxane passivation solution on the surface into an oven at the temperature of 95-105 ℃ for drying for 58-62 minutes, and forming a chemical protective layer on the surface of the aluminum foil;
(3) Putting polyethylene glycol terephthalate into a vacuum drying oven at the temperature of 115-125 ℃ for drying for 23-25 hours, then fully mixing hydroxyl-terminated polybutadiene/maleic anhydride esterified substance oxygen absorbent, 1, 4-butylene glycol/maleic anhydride esterified substance, or 1, 4-butylene glycol/methyltetrahydrophthalic anhydride esterified absorbent with a cobalt acetate catalyst, putting the mixture, metal-organic framework Materials (MOFs) pumice imidazolyl framework materials and dried polyethylene glycol terephthalate into a high-speed stirring pot, and uniformly mixing to obtain a mixture; then, extruding and drying the mixture by using a double-screw extruder with the runner temperature of 255-275 ℃, the membrane opening temperature of 255-265 ℃ and the vacuum degree of 0.08Mpa to obtain a first layer material; then, the first layer material is put into an extruder and co-extruded into a sheet at the temperature of 270-290 ℃; then, carrying out biaxial tension at the temperature of 100-120 ℃ to obtain a gas absorption layer;
then, putting the nanoscale silica gel, the nanoscale aluminum oxide and the nanoscale calcium oxide into a high-speed stirring pot together, and uniformly mixing to obtain nanoscale silica gel particles;
then, spraying a layer of the nano silica gel particles on the surface of the gas absorption layer to form a water absorption layer on the surface of the gas absorption layer, wherein the gas absorption layer and the water absorption layer form the absorption layer;
(4) Firstly, putting random copolymerization polypropylene, nano silicon dioxide, polyvinyl chloride, polyolefin elastomer, dehydroabietic acid and calcium stearate into a high-speed stirring pot, and uniformly mixing to obtain a mixture; then, extruding the mixture by using a double-screw extruder at a runner temperature of 215-225 ℃ and a film opening temperature of 195-205 ℃, rapidly cooling to normal temperature, and drying by using an oven at a temperature of 120-130 ℃ for 50-60 minutes to obtain a raw material for the mechanical support layer;
(5) Firstly, putting the random copolymerization polypropylene, the nano silicon dioxide and the polyolefin elastomer into a high-speed stirring pot, and uniformly mixing to obtain a mixture; then, extruding the mixture by using a double-screw extruder at a runner temperature of 205-215 ℃ and a film opening temperature of 195-205 ℃, rapidly cooling to normal temperature, and drying by using an oven at a temperature of 120-130 ℃ for 25-35 minutes to obtain a raw material for the low-temperature heat-sealing layer;
(6) Extruding a raw material of a mechanical supporting layer and a raw material of a low-temperature heat sealing layer by two double-screw extruders with the runner temperature of 205-215 ℃ and the film mouth temperature of 178-182 ℃ respectively, and the film mouth temperature of 210-220 ℃ respectively, and then co-extruding the raw materials by a co-extruder to form a film, so as to obtain a barrier layer consisting of the mechanical supporting layer and the low-temperature heat sealing layer;
(7) When all coating the viscose layer on resistant layer and aluminium foil layer, chemical protection layer and absorbed layer and the adjacent face of barrier layer, will be able to bear or endure to scrape layer, aluminium foil layer and chemical protection layer, absorbed layer and barrier layer complex together through the roll squeezer, obtain lithium cell packing and use water-fast flatulence plastic-aluminum membrane of preventing.
2. The method for preparing the water-resistant anti-swelling aluminum plastic film for lithium battery packaging according to claim 1, wherein the scratch-resistant layer comprises the following raw materials in parts by mass:
90 to 95 parts of polyethylene terephthalate;
5 to 10 portions of benzoyl peroxide;
1 to 3 parts of acrylonitrile.
3. The method for preparing the water-resistant anti-ballooning aluminum plastic film for lithium battery packaging as claimed in claim 1, wherein the aluminum foil layer is an aluminum foil with a thickness of 30 to 50 micrometers.
4. The method for preparing a water-resistant anti-swelling aluminum plastic film for lithium battery packaging according to claim 1, wherein the chemical protective layer is an inorganic-organic siloxane passivation solution.
5. The method for preparing a water-resistant and anti-swelling aluminum plastic film for lithium battery packaging according to claim 1, wherein the absorption layer comprises a gas absorption layer and a water absorption layer.
6. The method for preparing the water-resistant anti-flatulence aluminum plastic film for lithium battery packaging according to claim 5, wherein the gas absorption layer comprises the following raw materials in parts by mass:
90 to 95 parts of polyethylene terephthalate;
10 to 15 parts of hydroxyl-terminated polybutadiene/maleic anhydride esterified oxygen absorbent or 1, 4-butylene glycol/maleic anhydride esterified substance or 1, 4-butylene glycol/methyltetrahydrophthalic anhydride esterified absorbent;
0.05 to 0.1 part of cobalt acetate catalyst;
0.5 to 3 parts of metal-organic framework Materials (MOFs) pumice imidazolyl framework materials.
7. The method for preparing the water-resistant anti-flatulence aluminum-plastic film for the lithium battery packaging as recited in claim 5, wherein the water absorption layer comprises the following raw materials in parts by mass:
40 to 90 parts of nano silica gel;
10 to 15 parts of nano-grade alumina;
0 to 15 parts of nano calcium oxide.
8. The method for preparing a water-resistant and flatulence-preventing aluminum plastic film for lithium battery packaging according to claim 1, wherein the barrier layer comprises a mechanical support layer and a low-temperature heat sealing layer.
9. The method for preparing the water-resistant anti-swelling aluminum plastic film for lithium battery packaging according to claim 8, wherein the mechanical support layer comprises the following raw materials in parts by mass:
80-90 parts of random copolymer polypropylene;
0 to 0.3 part of nano silicon dioxide;
1 to 3 parts of polyvinyl chloride;
15-18 parts of polyolefin elastomer;
0.1 to 1 part of dehydroabietic acid;
0.05 to 0.075 portion of calcium stearate.
10. The method for preparing the water-resistant and flatulence-proof aluminum-plastic film for lithium battery packaging according to claim 8, wherein the low-temperature heat-sealing layer comprises the following raw materials in parts by mass:
80-90 parts of random copolymerization polypropylene;
0 to 0.3 portion of nano silicon dioxide;
15-18 parts of polyolefin elastomer.
11. The method for preparing a water-resistant anti-swelling aluminum plastic film for lithium battery packaging as claimed in claim 1, wherein the adhesive layer is an acid-modified polyolefin adhesive.
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