CN112793253A - Aluminum plastic film for lithium battery flexible package and preparation method thereof - Google Patents

Aluminum plastic film for lithium battery flexible package and preparation method thereof Download PDF

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Publication number
CN112793253A
CN112793253A CN202110076533.8A CN202110076533A CN112793253A CN 112793253 A CN112793253 A CN 112793253A CN 202110076533 A CN202110076533 A CN 202110076533A CN 112793253 A CN112793253 A CN 112793253A
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layer
aluminum
rare earth
aluminum foil
plastic film
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范开成
余小玉
沈丽梅
魏晓东
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Suzhou First Pv Material Co ltd
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Suzhou First Pv Material Co ltd
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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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • 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
    • 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
    • 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
    • B32B9/041—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 metal
    • 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

Abstract

The invention discloses an aluminum plastic film for a lithium battery flexible package and a preparation method thereof, wherein the aluminum plastic film comprises a substrate layer (1), a first bonding layer (2), an aluminum foil layer (3), a second bonding layer (4) and a heat sealing layer (5) which are sequentially laminated; a first rare earth passivation film layer (31) is arranged on one side of the bright surface of the aluminum foil layer (3), and a second rare earth passivation film layer (32) is arranged on the dark surface of the aluminum foil layer (3); the first rare earth passivation film layer and the second rare earth passivation film layer are both prepared by physical vapor deposition of a treating agent and a doping element on the aluminum foil layer; the thickness of the first rare earth passivation film layer and the thickness of the second rare earth passivation film layer are 200-1500 nm. The preparation process of the aluminum plastic film is simple, safe and environment-friendly, can avoid the use of harmful chemical substances in the aluminum foil treatment process, and has excellent corrosion resistance. When the second rare earth passive film is also arranged on the dark side of the aluminum foil, aluminum-plastic films with different colors can be obtained.

Description

Aluminum plastic film for lithium battery flexible package and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery packaging materials, in particular to an aluminum plastic film for lithium battery flexible packaging and a preparation method thereof.
Background
The aluminum plastic film is a material for lithium battery flexible packaging, and generally comprises an outer layer substrate layer, a middle aluminum foil layer and an inner layer heat sealing layer, wherein the layers are bonded through an adhesive in a pressing mode. The inner layer of the aluminum-plastic film must have good corrosion resistance due to direct contact with corrosive and permeable electrolyte. In the prior art, a chromate passivation method is mostly adopted, chromic acid, chromate and the like are used as treating agents, and a layer of chemical passivation film is formed on the surface of an aluminum foil so as to achieve the effect of corrosion protection. However, the method has complex process, the aerosol generated in the process seriously threatens the health of operators, and the discharged industrial wastewater also seriously pollutes the environment. Therefore, the development of new chromium-free passivation techniques has become a necessary trend. Conventionally, as disclosed in application No. CN200880115429.8, a lithium battery packaging material having a multilayer structure including a layer (a) in which 1 to 100 parts by mass of phosphoric acid or a phosphate is blended with 100 parts by mass of a rare earth element-based oxide, and a layer (X) having an anionic polymer and a crosslinking agent for crosslinking the anionic polymer, and a sealing layer are sequentially laminated on one surface of a base material layer, and a lithium battery packaging material having the same, and a method for producing the same are disclosed. The present invention provides a packaging material for lithium batteries, which is excellent in electrolyte resistance, hydrofluoric acid resistance, and water resistance, and which is obtained by using a multilayer coating layer comprising a rare earth element oxide, phosphoric acid or a phosphate, and having an anionic polymer and a crosslinking agent for crosslinking the anionic polymer. However, the coating layer with the multilayer structure is not only long in time consumption and complex in process, but also cannot avoid the use of toxic substances such as phosphoric acid and the like as a dispersion stabilizer.
In summary, it is an urgent need to solve the problem of finding an aluminum plastic film for lithium battery packaging, which has simple and convenient process, safety, environmental protection and excellent corrosion resistance.
Disclosure of Invention
The invention aims to solve the problems and provides the aluminum plastic film for the lithium battery flexible package, which has the advantages of simple preparation process, safety, environmental protection and excellent corrosion resistance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an aluminum plastic film for a lithium battery flexible package comprises a substrate layer, a first bonding layer, an aluminum foil layer, a second bonding layer and a heat sealing layer which are sequentially stacked; a first rare earth passivation film layer is arranged on one side of the bright surface of the aluminum foil layer, and a second rare earth passivation film layer is arranged on the dark surface of the aluminum foil layer; the first rare earth passivation film layer and the second rare earth passivation film layer are prepared by depositing a treating agent and a doping element on the aluminum foil layer through physical vapor deposition; the thickness of the first rare earth passivation film layer and the thickness of the second rare earth passivation film layer are 200-1500 nm.
When the thickness of the first rare earth passivation film layer and the second rare earth passivation film layer is less than 100nm, the aluminum foil layer cannot be completely covered by the rare earth passivation film, the corrosion resistance is poor, when the thickness is more than 1000nm, the surface of the rare earth passivation film becomes loose, and the corrosion resistance is reduced.
The invention adopts a physical vapor deposition method, the treating agent and the doping element are vaporized from solid state into atom, molecule or ion evaporation particles, and then the evaporation particles carrying energy are deposited on the bright surface and the dark surface of the aluminum foil layer to form a film layer with corrosion resistance. The formation of the rare earth passivation film layer can improve the capability of the aluminum plastic film material for resisting the corrosion of the electrolyte; and the aluminum-plastic films with different colors can be obtained by adjusting the types of treating agents used by the second rare earth passivation film layer arranged on the dark surface side of the aluminum foil layer, the types of doping elements and the film thickness. So that the aluminum plastic film has corrosion resistance and various optional appearance colors.
Preferably, the treating agent is one or more of cerium oxide, lanthanum oxide, yttrium oxide, scandium oxide, samarium oxide and erbium oxide.
Preferably, the thickness of the first rare earth passivation film layer is 200-600 nm.
Preferably, the doping element comprises one or more of aluminum, magnesium, iron, platinum, titanium, zirconium, nickel, molybdenum and nitrogen; the content ratio of the doping element to the rare earth element in the treating agent is 3-1.
The introduction of a proper amount of doping elements can reduce the porosity of the passive film and further improve the corrosion resistance of the rare earth passive film. When the content ratio exceeds 3, the content of the rare earth element is too low, and the corrosion resistance of the rare earth element is difficult to embody; when the content ratio is less than 1, the rare earth element is precipitated alone, and the corrosion protection effect on the substrate is also reduced.
The color of the second rare earth passivation film layer can be changed to green, light yellow, golden yellow, red brown, black and the like by adjusting the film thickness, the doping element type and the proportion of the doping element and the rare earth element, and the color aluminum-plastic film can be obtained by depositing on a dark surface.
Preferably, the physical vapor deposition is one or more of vacuum evaporation, magnetron sputtering, plasma coating, pulsed laser deposition or electron beam evaporation.
Preferably, the aluminum foil layer is a soft one-sided smooth aluminum foil subjected to degreasing treatment, and the thickness of the aluminum foil layer is 20-50 μm.
Preferably, the substrate layer is made of one or more materials of polyamide, polyester or polyimide; the adhesive used by the first bonding layer is one or more of polyurethane adhesive, epoxy resin adhesive, acrylic resin adhesive and polyester adhesive; the adhesive used by the second bonding layer is one or more of acrylic resin adhesive, epoxy resin adhesive and acid modified polypropylene resin; the heat sealing layer is made of one or more of polyolefin or cyclic polyolefin.
The invention also aims to provide a preparation method of the aluminum plastic film for the lithium battery flexible package, which comprises the following steps:
s1 modification treatment of the aluminum foil layer: degreasing the aluminum foil layer, and preparing a rare earth passivation film layer on the bright surface and the dark surface of the degreased aluminum foil layer through physical vapor deposition respectively to obtain a modified aluminum foil layer;
s2 preparation of aluminum plastic film: sequentially laminating a second bonding layer and a heat sealing layer on the bright surface side of the modified aluminum foil layer in the step S1, and compounding the second bonding layer and the heat sealing layer through a press roller to obtain a first laminated body; bonding the base material layer and one side of the dark surface of the aluminum foil layer on the laminated body by using a first bonding layer, and then compounding by using a pressing roller to obtain a second laminated body; and curing the second laminated body to obtain the aluminum-plastic film.
The invention has the following beneficial effects:
1. the invention discloses an aluminum-plastic film for a lithium battery flexible package and a preparation method thereof.A bright surface and a dark surface of an aluminum foil layer are respectively provided with a first rare earth passivation film layer which enables the aluminum-plastic film to have electrolyte corrosion resistance and a second rare earth passivation film layer which endows the aluminum-plastic film with multiple colors; so that the aluminum plastic film has good use performance and sensory property.
2. The treating agent for modifying the aluminum foil layer comprises cerium oxide, lanthanum oxide, yttrium oxide, scandium oxide, samarium oxide and erbium oxide, wherein rare earth elements are nontoxic, the production process is relatively safe and environment-friendly, the generated industrial waste liquid can be directly discharged without polluting the environment, the pollution to the environment and the treatment cost of industrial wastewater are reduced, and the production cost is saved; the method adopts a vapor physical deposition method, has simple operation, simple and convenient process, is convenient for production, saves the production period and improves the production efficiency; the second rare earth passivation film layer avoids the performance reduction of the adhesive layer caused by adding the dye filler into the binder.
Drawings
FIG. 1 is a schematic structural diagram of an aluminum plastic film for a lithium battery flexible package;
the heat-sealing film comprises a substrate layer 1, an aluminum foil layer 3, a second adhesive layer 4, a heat-sealing layer 5, a first rare earth passivation film layer 31 and a second rare earth passivation layer 32, wherein the substrate layer 1 is a substrate layer, the first adhesive layer 2 is a first adhesive layer, the aluminum foil layer 3 is an aluminum foil layer, the second adhesive layer 4 is a second adhesive layer, and the second rare.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The structural schematic diagram of the aluminum plastic film for the lithium battery flexible package is shown in fig. 1, and the aluminum plastic film comprises a substrate layer 1, a first bonding layer 2, an aluminum foil layer 3, a second bonding layer 4 and a heat sealing layer 5 which are sequentially stacked; a first rare earth passivation film layer 31 is arranged on one side of the bright surface of the aluminum foil layer 3, and a second rare earth passivation film layer 32 is arranged on the dark surface of the aluminum foil layer 3; the first rare earth passivation film layer 31 and the second rare earth passivation film layer 32 are both prepared by physical vapor deposition of a treating agent and a doping element on the aluminum foil layer 3; the thicknesses of the first rare earth passivation film layer 31 and the second rare earth passivation film layer 32 are 200-1500 nm.
The bright surface is one side of the aluminum foil layer close to the heat sealing layer, and the dark surface is one side of the aluminum foil layer close to the substrate layer.
The treating agent is one or more of cerium oxide, lanthanum oxide, yttrium oxide, scandium oxide, samarium oxide and erbium oxide.
The thickness of the first rare earth passivation film layer 31 is 200-600 nm.
The doping element comprises one or more of aluminum, magnesium, iron, platinum, titanium, zirconium, nickel, molybdenum and nitrogen; the content ratio of the doping element to the rare earth element in the treating agent is 3-1.
The physical vapor deposition is one or more of vacuum evaporation, magnetron sputtering, plasma coating, pulsed laser deposition or electron beam evaporation.
The aluminum foil layer 3 is a soft one-sided smooth aluminum foil subjected to degreasing treatment, and the thickness of the aluminum foil layer 3 is 20-50 microns.
The substrate layer 1 is made of one or more materials of polyamide, polyester or polyimide; the adhesive used by the first bonding layer 2 is one or more of polyurethane adhesive, epoxy resin adhesive, acrylic resin adhesive and polyester adhesive; the adhesive used by the second bonding layer is one or more of acrylic resin adhesive, epoxy resin adhesive and acid modified polypropylene resin; the heat sealing layer 5 is made of one or more of polyolefin or cyclic polyolefin.
A preparation method of an aluminum plastic film for lithium battery flexible packaging comprises the following steps:
s1 modification treatment of the aluminum foil layer: degreasing the aluminum foil layer 3, and preparing rare earth passivation film layers on the bright surface and the dark surface of the degreased aluminum foil layer 3 through physical vapor deposition respectively to obtain a modified aluminum foil layer 3;
s2 preparation of aluminum plastic film: sequentially laminating a second bonding layer 4 and a heat sealing layer 5 on the bright surface side of the modified aluminum foil layer 3 in the step S1, and then compounding the layers through a press roller to obtain a first laminated body; bonding the base material layer 1 and one side of the dark surface of the aluminum foil layer 3 on the laminated body by using a first bonding layer 2, and then compounding by using a pressing roller to obtain a second laminated body; and curing the second laminated body to obtain the aluminum-plastic film.
In the following embodiments of the present invention, the thicknesses of the first rare earth passivation film layer and the second rare earth passivation film layer are achieved by controlling the time of physical vapor deposition. The corrosion resistance evaluation method comprises the steps of soaking the prepared aluminum-plastic film in electrolyte at 85 ℃, and observing whether the aluminum-plastic film is layered or not. If the mixture is not layered after being soaked for 24 hours, marking the mixture by using the V; if the soaking time is 12 hours, marking with O; if delamination occurs within 12h or 12h, it is marked with x.
In the following examples and comparative examples, the passivation films were the first rare earth passivation film layer unless otherwise specified.
Example 1
The aluminum plastic film for the lithium battery flexible package prepared in the embodiment adopts cerium oxide as a treating agent, no co-doping element is added, and the thickness of the passivation film is 200 +/-20 nm.
Example 2
The aluminum plastic film for the lithium battery flexible package prepared by the embodiment adopts cerium oxide as a treating agent, no co-doping element is added, and the thickness of the passivation film is 400 +/-20 nm.
Example 3
The aluminum plastic film for the lithium battery flexible package prepared in the embodiment adopts yttrium oxide as a treating agent, no co-doping element is added, and the thickness of the passivation film is 600 +/-20 nm.
Example 4
The aluminum plastic film for the lithium battery flexible package prepared by the embodiment adopts lanthanum oxide as a treating agent, no co-doping element is added, and the thickness of the passivation film is 800 +/-20 nm.
Example 5
The aluminum plastic film for the lithium battery flexible package prepared by the embodiment adopts cerium oxide as a treating agent, no co-doping element is added, and the thickness of the passivation film is 900 +/-30 nm.
Example 6
The aluminum plastic film for the lithium battery flexible package prepared in the embodiment adopts cerium oxide as a treating agent, no co-doping element is added, and the thickness of the passivation film is 1000 +/-10 nm.
Example 7
The aluminum plastic film for the lithium battery flexible package prepared in the embodiment adopts cerium oxide as a treating agent, no co-doping element is added, and the thickness of the passivation film is 1200 +/-20 nm.
Example 8
According to the aluminum plastic film for the lithium battery flexible package, the adopted treating agent is samarium oxide, no co-doping element is added, and the thickness of the passivation film is 1300 +/-20 nm.
Example 9
The aluminum plastic film for the lithium battery flexible package prepared by the embodiment adopts cerium oxide as a treating agent, no co-doping element is added, and the thickness of the passivation film is 1500 +/-30 nm.
The corrosion resistance of the aluminum plastic film for the lithium battery flexible package prepared in examples 1 to 9 was tested, and the test results are shown in the following table. According to the test result, when no co-doping element is added and rare earth metal oxide is used as a treating agent, and when the thickness of the passivation film is 600-1300 nm, the prepared aluminum-plastic film is soaked in electrolyte at 85 ℃ for 24h without layering, and has high electrolyte corrosion resistance.
Example 10
The aluminum-plastic film for the lithium battery flexible package prepared in the embodiment adopts cerium oxide as a treating agent, aluminum as a co-doping element, the content ratio of the co-doping element to the rare earth element is 3, and the thickness of the passivation film is 400 +/-20 nm.
Example 11
The aluminum plastic film for the lithium battery flexible package prepared in the embodiment adopts cerium oxide as a treating agent, titanium as a co-doping element, the content ratio of the co-doping element to a rare earth element is 2, and the thickness of the passivation film is 400 +/-20 nm.
Example 12
The aluminum-plastic film for the lithium battery flexible package prepared in the embodiment adopts cerium oxide as a treating agent, aluminum as a co-doping element, the content ratio of the co-doping element to the rare earth element is 1, and the thickness of the passivation film is 400 +/-20 nm.
Compared with the embodiment 2, the embodiment 10-12 is different from the embodiment 2 in that a co-doping element is added into the prepared aluminum-plastic film, and the content of the co-doping element and the content of the rare earth element are respectively 3, 2 and 1. The corrosion resistance test results of the aluminum plastic films prepared in examples 10 to 12 are shown in the following table. According to the test result, on the premise that the thickness of the passivation film is the same, the corrosion resistance of the aluminum-plastic film is improved by adding the co-doping element, the prepared aluminum-plastic film is not layered after being soaked in the electrolyte at 85 ℃ for 24 hours, and the aluminum-plastic film has high electrolyte corrosion resistance.
Comparative example 1
The aluminum plastic film for the lithium battery flexible package prepared in the comparative example 1 adopts cerium oxide as a treating agent, no co-doping element is added, and the thickness of the passivation film is 100 +/-20 nm. Although the prepared aluminum plastic film has no harmful chemical substances; however, the corrosion resistance test result shows that delamination occurs after the passivation film is soaked in the electrolyte at 85 ℃ for 12 hours, which indicates that the prepared aluminum-plastic film can not meet the use requirement when the thickness of the passivation film is less than 200 nm.
Comparative example 2
The aluminum-plastic film for the lithium battery flexible package prepared in the comparative example 2 adopts cerium oxide as a treating agent, aluminum as a co-doping element, the contents of the co-doping element and a rare earth element are respectively 2, and the thickness of the passivation film is 100 +/-20 nm. As shown in the following table, although the prepared aluminum plastic film has no harmful chemical substances; however, the corrosion resistance test result shows that delamination occurs after the passivation film is soaked in the electrolyte at 85 ℃ for 12 hours, which indicates that when the thickness of the passivation film is less than 200nm, the prepared aluminum-plastic film can not meet the use requirement even if the co-doping element is added.
Comparative example 3
The aluminum plastic film for the lithium battery flexible package prepared in the comparative example 3 is a chromate passivation film, and the thickness of the passivation film is 400 +/-20. As shown in the following table, although the prepared aluminum-plastic film does not delaminate after being soaked in the electrolyte at 85 ℃ for 24 hours, the aluminum-plastic film has corrosion resistance; however, chromate-based hazardous chemicals are used in the passivation film.
Comparative example 4
The aluminum plastic film for the lithium battery flexible package prepared in the comparative example 4 has a passivation film of chemically treated rare earth, and the thickness of the passivation film is 400 +/-20. As shown in the following table, although the prepared aluminum-plastic film does not delaminate after being soaked in the electrolyte at 85 ℃ for 24 hours, the aluminum-plastic film has corrosion resistance; however, since an acidic solution such as phosphoric acid is used in the passivation film, the use of harmful chemicals causes a great pollution to the environment.
Comparative examples 3 and 4 further illustrate that physical vapor deposited rare earth passivation films can achieve corrosion resistance properties similar to chemically treated rare earth passivation films and chromate passivation films. Toxic substances such as chromate, phosphoric acid and the like can be used for the chromate passivation film, the use of acidic or alkaline solution is difficult to avoid for the chemical treatment passivation film, and the embodiment can completely avoid the use of harmful chemical substances, so that the harm to the environment is obviously reduced.
Figure DEST_PATH_IMAGE002
The above-described preferred embodiments of the present invention are not intended to limit the present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the claims of the present invention.

Claims (9)

1. The utility model provides a lithium cell is plastic-aluminum membrane for flexible package which characterized in that: the aluminum foil comprises a base material layer (1), a first bonding layer (2), an aluminum foil layer (3), a second bonding layer (4) and a heat sealing layer (5) which are sequentially laminated; a first rare earth passivation film layer (31) is arranged on one side of the bright surface of the aluminum foil layer (3), and a second rare earth passivation film layer (32) is arranged on the dark surface of the aluminum foil layer (3); the first rare earth passivation film layer (31) and the second rare earth passivation film layer (32) are both prepared by physical vapor deposition of a treating agent and a doping element on the aluminum foil layer (3).
2. The aluminum-plastic film for the flexible package of the lithium battery as claimed in claim 1, wherein: the thickness of the first rare earth passivation film layer (31) and the thickness of the second rare earth passivation film layer (32) are 200-1500 nm.
3. The aluminum-plastic film for the flexible package of the lithium battery as claimed in claim 1, wherein: the treating agent is one or more of cerium oxide, lanthanum oxide, yttrium oxide, scandium oxide, samarium oxide and erbium oxide.
4. The aluminum-plastic film for the flexible package of the lithium battery as claimed in claim 1, wherein: the thickness of the first rare earth passivation film layer (31) is 200-600 nm.
5. The aluminum-plastic film for the flexible package of the lithium battery as claimed in claim 1, wherein: the doping element comprises one or more of aluminum, magnesium, iron, platinum, titanium, zirconium, nickel, molybdenum and nitrogen; the content ratio of the doping element to the rare earth element in the treating agent is 3-1.
6. The aluminum-plastic film for the flexible package of the lithium battery as claimed in claim 1, wherein: the physical vapor deposition is one or more of vacuum evaporation, magnetron sputtering, plasma coating, pulsed laser deposition or electron beam evaporation.
7. The aluminum-plastic film for the flexible package of the lithium battery as claimed in claim 1, wherein: the aluminum foil layer (3) is a soft one-sided smooth aluminum foil subjected to degreasing treatment, and the thickness of the aluminum foil layer (3) is 20-50 microns.
8. The aluminum-plastic film for the flexible package of the lithium battery as claimed in claim 1, wherein: the substrate layer (1) is made of one or more materials of polyamide, polyester or polyimide; the adhesive used by the first bonding layer (2) is one or more of polyurethane adhesive, epoxy resin adhesive, acrylic resin adhesive and polyester adhesive; the adhesive used by the second bonding layer is one or more of acrylic resin adhesive, epoxy resin adhesive and acid modified polypropylene resin; the heat sealing layer (5) is prepared from one or more of polyolefin or cyclic polyolefin.
9. The method for preparing an aluminum plastic film for a flexible package of a lithium battery as claimed in claim 1, comprising the steps of:
s1 modification treatment of the aluminum foil layer: degreasing the aluminum foil layer (3), and preparing a rare earth passivation film layer on the bright surface and the dark surface of the degreased aluminum foil layer (3) through physical vapor deposition respectively to obtain a modified aluminum foil layer (3);
s2 preparation of aluminum plastic film: sequentially laminating a second bonding layer (4) and a heat sealing layer (5) on the bright surface side of the modified aluminum foil layer (3) in the step S1, and compounding the layers through a press roller to obtain a first laminated body; bonding the base material layer (1) with one side of the dark surface of the aluminum foil layer (3) on the laminated body by using a first bonding layer (2), and then compounding by using a pressing roller to obtain a second laminated body; and curing the second laminated body to obtain the aluminum-plastic film.
CN202110076533.8A 2021-01-20 2021-01-20 Aluminum plastic film for lithium battery flexible package and preparation method thereof Pending CN112793253A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102905495A (en) * 2011-07-29 2013-01-30 鸿富锦精密工业（深圳）有限公司 Shell and producing method thereof
CN103098257A (en) * 2010-09-08 2013-05-08 凸版印刷株式会社 Lithium ion battery outer cover material
CN103155207A (en) * 2010-10-14 2013-06-12 凸版印刷株式会社 Exterior material for lithium ion battery
CN107154471A (en) * 2016-03-04 2017-09-12 谢彦君 Battery packaging material and soft-package battery and battery heat control device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103098257A (en) * 2010-09-08 2013-05-08 凸版印刷株式会社 Lithium ion battery outer cover material
CN103155207A (en) * 2010-10-14 2013-06-12 凸版印刷株式会社 Exterior material for lithium ion battery
CN102905495A (en) * 2011-07-29 2013-01-30 鸿富锦精密工业（深圳）有限公司 Shell and producing method thereof
CN107154471A (en) * 2016-03-04 2017-09-12 谢彦君 Battery packaging material and soft-package battery and battery heat control device

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Application publication date: 20210514