TWI656021B - Stacked film - Google Patents

Abstract

A stacked film layer includes a metal layer, a first resin layer, a second resin layer, and a first protective layer. The metal layer has a first surface and a second surface opposite to each other. The first resin layer is on a first surface of the metal layer. The second resin layer is on the second surface of the metal layer. The first protective layer is located between the metal layer and the first resin layer. The material of the first protective layer includes polysilazane.

Description

Stacked film

The present invention relates to a stacked film layer, and more particularly to a stacked film layer as a packaging material.

Lithium batteries are used as portable devices such as personal computers or mobile phones, and as storage batteries for hybrid or electric vehicles. With the market demand for lithium batteries that can be repeatedly charged and discharged with light weight, high voltage value, and high energy density, the requirements for the service life of lithium batteries are increasing.

Generally speaking, the aluminum-plastic film used for packaging lithium batteries has a laminated structure, and the metal aluminum foil layer used for the aluminum-plastic film is easily corroded by acid substances, causing defects. For example, when using aluminum-plastic film to package lithium batteries, the metal aluminum foil layer in the laminated structure is exposed to the acid produced by the electrolyte due to the acidic substances (such as hydrofluoric acid (HF)) generated by the electrolyte of the lithium battery. The erosion of acid substances leads to delamination defects, which in turn greatly affects the service life of lithium batteries.

Therefore, how to improve the problem that the metal aluminum foil layer is easily corroded by acidic materials to meet the requirements of the current industry is a problem that is urgently sought by those skilled in the art.

The invention provides a stacked film layer, and in particular relates to a corrosion-resistant stacked film layer.

The present invention provides a stacked film layer, wherein the stacked film layer includes a metal layer, a first resin layer, a second resin layer, and a first protective layer. The metal layer has a first surface and a second surface opposite to each other. The first resin layer is on a first surface of the metal layer. The second resin layer is on the second surface of the metal layer. The first protective layer is located between the metal layer and the first resin layer. The material of the first protective layer includes polysilazane (PSZ).

In one embodiment of the present invention, the thickness of the first protective layer is between 0.05 micrometer and 1.2 micrometer.

In one embodiment of the present invention, a surface roughness of the first protective layer is between 0.09 micrometers and 0.30 micrometers.

In one embodiment of the present invention, the thickness of the first resin layer is between 20 micrometers and 80 micrometers.

In one embodiment of the present invention, the thickness of the metal layer is 30 micrometers to 40 micrometers.

In one embodiment of the present invention, the thickness of the second resin layer is 15 μm to 25 μm.

In one embodiment of the present invention, the stacked film layer further includes a first adhesive layer and a second adhesive layer, and the first adhesive layer is located between the first resin layer and the first protective layer, wherein The thickness of the first adhesive layer is 3 micrometers to 15 micrometers, and the second adhesive layer is located between the metal layer and the second resin layer, wherein the thickness of the second adhesive layer is 3 micrometers to 5 microns.

In one embodiment of the present invention, the stacked film layer further includes a second protective layer between the metal layer and the second resin layer, wherein the material of the second protective layer includes polysilazane .

In one embodiment of the present invention, the thickness of the second protective layer is between 0.05 micrometer and 1.2 micrometer.

In one embodiment of the present invention, a surface roughness of the second protective layer is between 0.09 micrometers and 0.30 micrometers.

In one embodiment of the present invention, the stacked film layer further includes a first adhesive layer and a second adhesive layer, and the first adhesive layer is located between the first resin layer and the first protective layer, wherein The thickness of the first adhesive layer is 3 micrometers to 15 micrometers, and the second adhesive layer is located between the metal layer and the second protective layer, wherein the thickness of the second adhesive layer is 3 micrometers to 5 microns.

Based on the above, the surface of the metal layer in the stacked film layer of the present invention has a (first / second) protective layer, which is a hard protective layer with a dense structure, wherein the protective layer of the present invention has the effect of corrosion resistance, so it can be Avoid delamination defects caused by the erosion of the metal layer by the acidic substances generated by the electrolyte, avoid battery leakage, and thereby improve the service life and safety of the stacked film layer.

In order to make the above features and advantages of the present invention more comprehensible, embodiments are hereinafter described in detail with reference to the accompanying drawings.

In this article, a range represented by "one value to another value" is a summary representation that avoids enumerating all the values in the range one by one in the specification. Therefore, the record of a specific numerical range covers any numerical value within the numerical range and a smaller numerical range defined by any numerical value within the numerical range, as if the arbitrary numerical value and the smaller numerical value were explicitly written in the description. Same scope.

FIG. 1 is a schematic cross-sectional view of a stacked film layer according to an embodiment of the present invention. Referring to FIG. 1, the stacked film layer 100 of the present invention includes a first resin layer 110, a first protective layer 130A, a metal layer 140, a second protective layer 130B, and a second resin layer 160. In another embodiment, the stacked film layer of the present invention further includes a first adhesive layer 120 and a second adhesive layer 150. In this embodiment, an aluminum-plastic film with stacked film layers applied to a battery packaging material is taken as an example, and the foregoing film layers will be described in detail below.

Referring to FIG. 1, the metal layer 140 has a first surface S1 and a second surface S2 opposite to each other. In one embodiment, the material of the metal layer 140 includes, for example, aluminum or steel. In this embodiment, the metal layer 140 has a function of preventing water vapor and blocking. In one embodiment, the thickness of the metal layer 140 is, for example, between 30 micrometers and 40 micrometers, and the present invention is not limited thereto.

The first resin layer 110 is an inner layer of the stacked film layer and is located on the first surface S1 of the metal layer 140. In one embodiment, a material of the first resin layer 110 includes, for example, polypropylene (PP), polyethylene (PE), or a combination thereof. In other embodiments, the first resin layer 110 may further include additives such as polyester elastomer, olefin-based elastomer, polyamide-based elastomer, or a combination thereof. The first resin layer 110 is used as an isolation layer to cover the battery core and isolate the metal layer 140 from the battery core. In one embodiment, the thickness of the first resin layer 110 is, for example, between 20 micrometers and 80 micrometers, and the present invention is not limited thereto.

The first protective layer 130A is disposed on the first surface S1 of the metal layer 140 and is located between the metal layer 140 and the first resin layer 110. The first protective layer 130A can be used as a corrosion-resistant layer of the metal layer 140 to prevent the metal layer 140 from being corroded by the acidic substance generated by the electrolyte, which may cause delamination between stacked film layers and battery leakage. In the present invention, the first protective layer 130A is a hard coating layer having a dense structure, and the material thereof includes a polysilazane having a repeating unit represented by the following formula (I): (I), wherein R ₁ , R ₂ , and R ₃ are each independently selected from the group consisting of a hydrogen atom (H) and a methyl group (—CH ₃ ), and the present invention is not limited thereto. In one embodiment, R ₁ , R ₂ , and R ₃ are each independently selected from other functional functional groups, such as an isocyanate group (—NCO) that can promote the reaction. In one embodiment, the ratio of R ₁ to R ₃ in the repeating unit represented by formula (I) is a methyl group is 33% or more. The first protective layer 130A has a moderate hardness and is not easily broken and / or Cracked. In another embodiment, the ratio of R ₁ to R ₃ in the repeating unit represented by formula (I) is a methyl group, and more preferably, it may be, for example, 67% or more.

In one embodiment, the thickness of the first protective layer 130A is, for example, between 0.05 micrometers and 1.2 micrometers, and preferably between 0.1 micrometers and 0.3 micrometers. The present invention is not limited thereto. It is worth mentioning that if the thickness of the first protective layer 130A is too thick (for example, greater than 1.2 micrometers), the first protective layer 130A may be easily broken and / or cracked. However, if the thickness of the first protective layer 130A is too thin (for example, less than 0.05 micrometers), the metal layer 140 cannot be uniformly covered, which results in poor corrosion resistance. In one embodiment, the surface roughness of the first protective layer 130A is, for example, between 0.09 micrometers and 0.30 micrometers, and the present invention is not limited thereto.

The first adhesive layer 120 is disposed on the first surface S1 of the metal layer 140 and is located between the first resin layer 110 and the first protective layer 130A. In one embodiment, the first resin layer 110 is adhered to the first protective layer 130A through the first adhesive layer 120. In one embodiment, the material of the first adhesive layer 120 includes, for example, acid-modified polyolefin (mPO), modified polypropylene (mPP), modified styrene-ethylene / butene Modified styrene-ethylene / butylene block copolymer (mSEBS), modified polyurethane (mPU), or maleic anhydride grafting on polypropylene (MA-g-PP). In other embodiments, the material of the first adhesive layer 120 may further include additives such as polyester elastomer, olefin-based elastomer, polyamide-based elastomer, or a combination thereof, and the present invention is not limited thereto. In one embodiment, the thickness of the first adhesive layer 120 is, for example, between 3 μm and 15 μm, and the present invention is not limited thereto.

The second resin layer 160 is located on the second surface S2 of the metal layer 140. In one embodiment, the material of the second resin layer 160 includes, for example, a heat-resistant resin. For example, the material of the second resin layer 160 includes, for example, nylon, polyethylenimine (PEI), or polyvinyl butyral resin (PVB). Films produced by casting, stretching and other steps. The second resin layer 160 is used as a protective film of the stacked film layer to maintain the high puncture resistance of the aluminum plastic film and the moldability of the battery. In one embodiment, the thickness of the second resin layer 160 is, for example, between 15 micrometers and 25 micrometers, and the present invention is not limited thereto.

The second protective layer 130B is disposed on the second surface S2 of the metal layer 140 and is located between the metal layer 140 and the second resin layer 160. The second protective layer 130B can be used as a corrosion-resistant layer of the metal layer 140 to prevent the metal layer 140 from being corroded by the acidic substance generated by the electrolyte, which may cause delamination between stacked film layers and battery leakage. In the present invention, the second protective layer 130B is a hard coating layer having a dense structure, and the material thereof includes a polysilazane having a repeating unit represented by the following formula (I): (I), wherein R ₁ , R ₂ , and R ₃ are each independently selected from the group consisting of a hydrogen atom (H) and a methyl group (—CH ₃ ), and the present invention is not limited thereto. In one embodiment, each of R ₁ , R ₂ , and R ₃ may be independently selected from other functional functional groups, such as an isocyanate group (—NCO) that can promote the reaction. In one embodiment, the ratio of R ₁ to R ₃ in the repeating unit represented by formula (I) is a methyl group, for example, is greater than or equal to 33%, so that the first protective layer 130A can have a moderate hardness and is not easily broken. And / or cracked. In another embodiment, the ratio of R ₁ to R ₃ in the repeating unit represented by formula (I) is a methyl group, and more preferably, it may be, for example, 67% or more.

In one embodiment, the thickness of the second protective layer 130B is, for example, between 0.05 μm and 1.2 μm, and preferably between 0.1 μm and 0.3 μm. The present invention is not limited thereto. It is worth mentioning that if the thickness of the second protective layer 130B is too thick (for example, greater than 1.2 micrometers), the second protective layer 130B may be easily broken and / or cracked. However, if the thickness of the second protective layer 130B is too thin (for example, less than 0.05 μm), the metal layer 140 cannot be uniformly covered, which may result in poor corrosion resistance. In one embodiment, the surface roughness of the second protective layer 130B is, for example, between 0.09 micrometers and 0.30 micrometers, and the present invention is not limited thereto.

In some embodiments, the first protective layer 130A and the second protective layer 130B may be formed in the same process step, but the present invention is not limited thereto. In some embodiments, the first protective layer 130A and the second protective layer 130B may be formed in different process steps. In some embodiments, the thickness and roughness of the second protective layer 130B and the thickness and roughness of the first protective layer 130A may be substantially the same, but the present invention is not limited thereto. In other embodiments, the thickness and roughness of the second protective layer 130B and the thickness and roughness of the first protective layer 130A may be different.

The second adhesive layer 150 is disposed on the second surface S2 of the metal layer 140 and is located between the second protective layer 130B and the second resin layer 160. The second protective layer 130B and the second resin layer 160 are adhered through the second adhesive layer 150. In one embodiment, the material of the second adhesive layer 150 includes, for example, modified acrylic resin. In one embodiment, the thickness of the second adhesive layer 150 is, for example, between 3 micrometers and 5 micrometers, and the present invention is not limited thereto.

In the present invention, by using polysilazane as a material, a thin film having a dense structure and a corrosion-resistant film formed on the surface of the metal layer 140 as a protective layer (ie, the first protective layer 130A / the second protective layer 130B) can avoid metal. The layer 140 is corroded by an acidic substance generated when the electrolyte is used to cause delamination between stacked film layers and battery leakage. It is worth mentioning that the manufacturing process of the (first / second) protective layer of the present invention does not require the use of a treatment solution containing phosphorus or heavy metals, and there is no doubt about superior nutrition or heavy metal pollution. In contrast, metal surface treatment technologies, such as chromium phosphate treatment, chromium chromate treatment, or zirconium phosphate treatment, use chemical treatment liquids containing phosphorus and / or heavy metals (such as chromium, zirconium, etc.) during the manufacturing process. Environmental hazards (for example: environmental eutrophication or heavy metal pollution in the environment).

Hereinafter, a method for manufacturing the stacked film layer will be described in detail. FIG. 2A to FIG. 2C are schematic cross-sectional views illustrating a flow of a method for manufacturing a stacked film layer according to an embodiment of the present invention.

First, referring to FIG. 2A, a metal layer 140 is provided, and a first protective layer 130A and a second protective layer 130B are formed on the first surface S1 and the second surface S2 of the metal layer 140 facing each other, respectively. In one embodiment, the metal layer 140 includes, for example, an aluminum film or a steel film. In one embodiment, the thickness of the metal layer 140 is, for example, 25 micrometers to 40 micrometers.

In one embodiment, the thickness of the first protective layer 130A and the second protective layer 130B is, for example, between 0.05 μm and 1.2 μm. In one embodiment, the surface roughness of the first protective layer 130A and the second protective layer 130B is, for example, between 0.09 micrometers and 0.30 micrometers. In the present invention, the material of the first protective layer 130A and the second protective layer 130B includes polysilazane, wherein the polysilazane has a repeating unit represented by the above formula (I). For example, in one embodiment, a polysilazane having a repeating unit represented by the formula (I) is coated on the first surface S1 and the second surface S2 of the metal layer 140 by a coating process. Then, the first protective layer 130A and the second protective layer 130B are completely cured into a hard coating layer having a dense structure by heating and humidifying, so as to be formed on the first surface S1 and the second surface S2 of the metal layer 140, respectively. A corrosion-resistant film. It is worth noting that the polysilazane having the repeating unit represented by the above formula (I) uses water vapor and heat as the driving force for curing, and forms (Si-N) / (Si-O) during curing. A thin film of a cross-linked network such as / (Si-CH ₃ ) / (Si-O-Si) / (Si-N) / (NH), and a hard and dense protective layer is formed on the surface of the metal layer 140. In one embodiment, the coating process includes dipping coating, roll coating, blade coating, bar coating, and slit die. Slot die coating or spraying coating.

As shown in FIG. 2B, a first resin layer 110 is provided, and then a first adhesive layer 120 is formed between the first resin layer 110 and the first protective layer 130A, so that the first resin layer 110 is adhered to the metal layer 140 to have a first The first surface S1 of the protective layer 130A. In this embodiment, the material of the first resin layer 110 is, for example, polypropylene. In one embodiment, the thickness of the first resin layer 110 is, for example, 30 μm to 80 μm.

For example, the first adhesive layer 120 is formed by, for example, a coating process or a coating process. In one embodiment, the thickness of the first adhesive layer 120 is, for example, 3 μm to 15 μm.

In one embodiment, when the material of the first adhesive layer 120 is, for example, acid-modified polyolefin (mPO), modified polyurethane (mPU), or modified styrene-ethylene / butene block copolymer (mSEBS) Through a coating process, the acid-modified polyolefin, modified polyurethane, or modified styrene-ethylene / butene block copolymer is coated on the first protective layer 130A away from the first of the metal layer 140 The first adhesive layer 120 is formed on the surface of the surface S1; the surface of the first adhesive layer 120 that is far from the first surface S1 of the metal layer 140 is directly placed on the first resin layer 110 and then directly pressed to make the first The resin layer 110 is directly bonded to the first protective layer 130A through the first adhesive layer 120, that is, the first resin layer 110 is bonded to the metal layer 140 and has the first surface S1 of the first protective layer 130A. In another embodiment, through a coating process, an acid-modified polyolefin, modified polyurethane, or modified styrene-ethylene / butene block copolymer can also be applied to the first resin layer. 110 to form a first adhesive layer 120; and then place the surface of the first adhesive layer 120 away from the first resin layer 110 directly on the first protective layer 130A and press directly to make the first resin layer 110 directly adhere The first protective layer 130A, that is, the first resin layer 110 is adhered to the metal layer 140 and has the first surface S1 of the first protective layer 130A. The coating process includes roll coating, blade coating, slide coating, slot-die or wire rod coating. cloth.

However, the present invention is not limited thereto. In other embodiments, when the material of the first adhesive layer 120 is, for example, acid-modified polypropylene (mPP) or maleic anhydride-grafted polypropylene (MA-g-PP), Through a coating process, acid-modified polypropylene or maleic anhydride-grafted polypropylene is coated on the surface of the first protective layer 130A away from the first surface S1 of the metal layer 140 to form a first adhesive layer 120 ; And then placing the surface of the first adhesive layer 120 away from the first surface S1 of the metal layer 140 directly on the first resin layer 110, heating and increasing the pressure, and making the first resin layer 110 transparent through a heat-compression process. The first adhesive layer 120 is directly attached to the first protective layer 130A, that is, the first resin layer 110 is attached to the first layer S1 of the metal layer 140 having the first protective layer 130A. In other embodiments, through a coating process, acid-modified polypropylene or maleic anhydride-grafted polypropylene can also be applied to the first resin layer 110 to form a first adhesive layer 120; and then The surface of the first adhesive layer 120 that is far from the first resin layer 110 is directly placed on the first protective layer 130A, and then the temperature and pressure are increased, and the first resin layer 110 is directly passed through the first adhesive layer 120 by a thermal compression bonding process. The first protective layer 130A is bonded to the first protective layer 130A, that is, the first resin layer 110 is bonded to the metal layer 140 and has the first surface S1 of the first protective layer 130A.

Finally, as shown in FIG. 2C, a second resin layer 160 is provided, and a second adhesive layer 150 is formed between the second resin layer 160 and the second protective layer 130B, so that the second resin layer 160 is adhered to the metal layer 140. The second surface S2 of the second protective layer 130B. In one embodiment, the material of the second resin layer 160 is, for example, nylon or polyethyleneimine. In one embodiment, the thickness of the second resin layer 160 is, for example, 15 μm to 25 μm.

For example, the second adhesive layer 150 is formed by, for example, a coating process. In one embodiment, the second adhesive layer 150 is coated on the surface of the second resin layer 160 or on the surface of the second protective layer 130B away from the second surface S2 of the metal layer 140 through a coating process. The second resin layer 160 is directly adhered to the second protective layer 130B through the second adhesive layer 150, that is, the second resin layer 160 is adhered to the second surface S2 of the metal layer 140 having the second protective layer 130B. In one embodiment, the material of the second adhesive layer 150 is, for example, a modified acrylic resin. In one embodiment, the thickness of the second adhesive layer 150 is, for example, 3 μm to 5 μm. The coating process includes roller coating, blade coating, swash plate coating, extrusion coating or wire rod coating. So far, the stacked film layer of the present invention has been completed.

In addition, in the foregoing manufacturing method, the first resin layer 110 is formed on the metal layer 140 and then the second resin layer 160 is formed as an example. However, the present invention is not limited to this. In other embodiments, the second resin layer 160 may be formed on the metal layer 140 first, and then the first resin layer 110 may be formed.

3 is a schematic cross-sectional view of a stacked film layer according to another embodiment of the present invention. Please refer to FIG. 3 and FIG. 1 at the same time. The stacked film layer 200 shown in FIG. 3 is similar to the stacked film layer 100 shown in FIG. 1, so similar or identical components are represented by similar or identical component symbols, and the related description is no longer To repeat. In some embodiments, the stacked film layer 200 of FIG. 3 includes a first resin layer 110, a first adhesive layer 120, a first protective layer 130A, a metal layer 140, a second adhesive layer 150, and a second resin layer 160.

As shown in FIG. 3, in the stacked film layer 200, the first resin layer 110, the first adhesive layer 120, and the first protective layer 130A are located on the first surface S1 of the metal layer 140, and the second adhesive layer 150 and the second The resin layer 160 is located on the second surface S2 of the metal layer 140, wherein the first surface S1 and the second surface S2 are two opposite surfaces of the metal layer 140. Specifically, the metal layer 140 is disposed between the first resin layer 110 and the second resin layer 160, the first protective layer 130A is located between the first resin layer 110 and the metal layer 140, and the first adhesive layer 120 is located at the first A resin layer 110 is between the first protective layer 130A and a second adhesive layer 150 is between the metal layer 140 and the second resin layer 160.

Specifically, the first resin layer 110 is adhered to the first surface S1 of the metal layer 140 having the first protective layer 130A through the first adhesive layer 120; and the second resin layer 160 is directly adhered through the second adhesive layer 150. Bonded to the second surface S2 of the metal layer 140. In some embodiments, disposing the first protective layer 130A as a corrosion-resistant layer on the first surface S1 of the metal layer 140 can isolate the metal layer 140 from the battery core, thereby preventing the metal layer 140 from being affected. Acidic substances generated by the electrolyte corrode and cause delamination between stacked film layers and battery leakage. In addition, the manufacturing process of the protective layer (ie, the first protective layer 130A) in this embodiment does not require the use of a processing solution containing phosphorus or heavy metals, and there is no doubt about superior nutrition or heavy metal pollution. In other words, the stacking film layer 200 of FIG. 3 does not include the second protective layer 130B. In addition to preventing the metal layer 140 from being corroded by the acidic substance generated by the electrolyte, the layering between the stacking film layers and battery leakage can be further improved. Reduce overall film thickness.

The following description includes Comparative Examples 1 to 7 of the present invention and comparative examples as a control group of the present invention. For the materials and thicknesses of the stacked film layers of Examples 1 to 7 and Comparative Examples, please refer to Table 1 below. < Example >

Please refer to the above for the structure and manufacturing method of stacked film layers. Hereinafter, features of the present invention will be described more specifically with reference to Examples 1 to 7. Although the following embodiments 1 to 7 are described, the materials used, their amounts and ratios, processing details, processing flow, and the like can be appropriately changed without going beyond the scope of the present invention. Therefore, the present invention should not be interpreted restrictively by the examples described below. Example 1

Polysilazane (PSZ) having a repeating unit represented by formula (I) was applied to two opposite surfaces of an aluminum film as a metal layer at room temperature, and then in an environment with water vapor The polysilazane coated on the surface of the aluminum film is completely cured to form a first protective layer and a second protective layer. The aluminum film has a thickness of about 40 microns, and the first protective layer and the second protective layer are cured. The protective layers each have a film thickness of about 1.2 microns. Next, a modified styrene-ethylene / butene block copolymer (mSEBS) was coated on one surface of a polypropylene film (PP film) as an inner layer, and the polypropylene film was further provided with modified styrene. -After the surface of the ethylene / butene block copolymer is placed on the first protective layer of the aluminum film, pressure bonding is performed to pass the polypropylene film through the modified styrene-ethylene / butene block copolymer. Adheres to the first protective layer, wherein the modified styrene-ethylene / butene block copolymer is used as the first adhesive layer to have a film thickness of about 3 to 5 micrometers, and the polypropylene film has about 40 micrometers Of film thickness. Finally, the modified acrylic resin is coated on one surface of the nylon film as an outer layer, and then the surface of the nylon film having the modified acrylic resin is placed on the second protective layer of the aluminum film, and then the coating is performed. Pressure bonding, so that the nylon film passes through the modified acrylic resin and is bonded to the second protective layer, wherein the modified acrylic resin is used as the second adhesive layer to have a film thickness of about 3 microns to 5 microns, and The nylon film has a film thickness of about 25 microns. The stacked film layer of the present invention is completed through the above steps, wherein the stacked film layer is in order from the inner layer (close to the inner core of the battery) to the outer layer in order of a first resin layer, a first adhesive layer, a first protective layer, a metal layer, and a second protection Layer, a second adhesive layer, and a second resin layer.

In addition, in the above steps, atomic force microscopy (AFM) was used to perform surface roughness tests on the metal layer, the first protective layer, and the second protective layer in the stacked film layer. The measurement results are shown in Table 1. . Example 2 to Example 5

The stacked film layers of Examples 2 to 5 were prepared in the same steps as in Example 1. However, the difference is that the film thicknesses of the first protective film and the second protective film are changed (as shown in Table 1). Example 6

The stacked film layer of Example 6 was prepared by the same steps as those of Example 1. However, the difference is that the material of the first adhesive layer is replaced by modified polyurethane (mPU), and the film thicknesses of the first protective film and the second protective film are changed (as shown in Table 1). Example 7

The stacked film layer of Example 7 was prepared in the same steps as in Example 1. However, the difference is that the material of the first adhesive layer is replaced with maleic anhydride grafted polypropylene (MA-g-PP), and the first resin layer, the first adhesive layer, the first protective film, and the first adhesive layer are changed. The thickness of the two protective films (as shown in Table 1). Comparative example

At room temperature, a modified styrene-ethylene / butene block copolymer was coated on one surface of a polypropylene film as an inner layer, and then the polypropylene film was modified with styrene-ethylene / butylene. The surface of the olefin block copolymer is placed on one surface of an aluminum film as a metal layer, and then bonded under pressure to pass the polypropylene film through the modified styrene-ethylene / butene block copolymer to the aluminum. The film is fitted. The aluminum film has a film thickness of about 40 microns, the modified styrene-ethylene / butene block copolymer as the first adhesive layer has a film thickness of about 3 to 5 microns, and the polypropylene film has about 40 microns Of film thickness. Next, the modified acrylic resin is coated on one surface of the nylon film as an outer layer, and then the surface of the nylon film having the modified acrylic resin is placed on the other surface of the aluminum film with respect to the first adhesive layer. After the application, press bonding is performed to make the nylon film pass through the modified acrylic resin and be bonded to the aluminum film. The modified acrylic resin has a film of about 3 to 5 microns as the second adhesive layer. And the nylon film has a film thickness of about 25 microns. Through the above steps, the stacked film layer of the comparative example is completed, and the first resin layer, the first adhesive layer, the metal layer, the second adhesive layer, and the second resin layer are sequentially formed from the inner layer (close to the battery core) to the outer layer. That is, the stacked film layer of the comparative example does not have the first and second protective layers.

In the above steps, an atomic force microscope (AFM) was used to perform a surface roughness test on the metal layer in the stacked film layer of the comparative example. The measurement results are shown in Table 1. Table 1         <TABLE border = "1" borderColor = "# 000000" width = "85%"> <TBODY> <tr> <td> </ td> <td> <b> Example </ b> <b> 1 < / b> </ td> <td> <b> Example </ b> <b> 2 </ b> </ td> <td> <b> Example </ b> <b> 3 </ b > </ td> <td> <b> Example </ b> <b> 4 </ b> </ td> <td> <b> Example </ b> <b> 5 </ b> < / td> <td> <b> Example </ b> <b> 6 </ b> </ td> <td> <b> Example </ b> <b> 7 </ b> </ td > <td> <b> Comparative example </ b> </ td> </ tr> <tr> <td> <b> Second </ b> <b> Resin layer </ b> </ td> < td> material </ td> <td> nylon </ td> <td> nylon </ td> <td> nylon </ td> <td> nylon </ td> <td> nylon </ td> <td> Nylon </ td> <td> Nylon </ td> <td> Nylon </ td> </ tr> <tr> <td> Thickness (μm) </ td> <td> 25 </ td> <td> 25 </ td> <td> 25 </ td> <td> 25 </ td> <td> 25 </ td> <td> 25 </ td> <td> 25 </ td> <td> 25 < / td> </ tr> <tr> <td> <b> Second </ b> <b> Adhesive layer </ b> </ td> <td> Material </ td> <td> Modified acrylic Acrylic resin </ td> <td> modified acrylic resin </ td> <td> modified acrylic resin </ td> <td> modified acrylic resin </ td> <td> modified Acrylic resin </ td> <td> modified acrylic resin </ td> <td> modified acrylic resin </ td> <td> modified acrylic resin </ td> </ tr > <tr> <td> Thickness (μm) </ td> <td> 3-5 </ td> <td> 3-5 </ td> <td> 3-5 </ td> <td> 3-5 </ td> <td > 3-5 </ td> <td> 3-5 </ td> <td> 3-5 </ td> <td> 3-5 </ td> </ tr> <tr> <td> <b > Second </ b> <b> Protection layer </ b> </ td> <td> Material </ td> <td> PSZ </ td> <td> PSZ </ td> <td> PSZ </ td> <td> PSZ </ td> <td> PSZ </ td> <td> PSZ </ td> <td> PSZ </ td> <td> </ td> </ tr> <tr> <td > Thickness (μm) </ td> <td> 1.2 </ td> <td> 0.60 </ td> <td> 0.30 </ td> <td> 0.10 </ td> <td> 0.05 </ td> < td> 0.30 </ td> <td> 0.30 </ td> <td> </ td> </ tr> <tr> <td> Surface roughness (μm) </ td> <td> 0.09 </ td> <td> 0.10 </ td> <td> 0.13 </ td> <td> 0.22 </ td> <td> 0.30 </ td> <td> 0.13 </ td> <td> 0.13 </ td> <td > </ td> </ tr> <tr> <td> <b> Metal layer </ b> </ td> <td> Material </ td> <td> Aluminum film </ td> <td> Aluminum film </ td> <td> Aluminum film </ td> <td> Aluminum film </ td> <td> Aluminum film </ td> <td> Aluminum film </ td> <td> Aluminum film </ td> < td> Aluminum film </ td> </ tr> <tr> <td> Thickness (μm) </ td> <td> 40 </ td> <td> 40 </ td> <td> 40 </ td> <td> 40 </ td> <td> 40 </ td> <td> 40 </ td> <td> 40 </ td> <td> 40 </ td> </ tr> <tr> <td> Surface roughness (μm) </ td> <td> 0.28 </ td> <td> 0.28 </ td > <td> 0.28 </ td> <td> 0.28 </ td> <td> 0.28 </ td> <td> 0.28 </ td> <td> 0.28 </ td> <td> 0.28 </ td> < / tr> <tr> <td> <b> first </ b> <b> protective layer </ b> </ td> <td> material </ td> <td> PSZ </ td> <td> PSZ </ td> <td> PSZ </ td> <td> PSZ </ td> <td> PSZ </ td> <td> PSZ </ td> <td> PSZ </ td> <td> </ td> </ tr> <tr> <td> Thickness (μm) </ td> <td> 1.2 </ td> <td> 0.60 </ td> <td> 0.30 </ td> <td> 0.10 </ td> <td> 0.05 </ td> <td> 0.30 </ td> <td> 0.30 </ td> <td> </ td> </ tr> <tr> <td> Surface roughness (μm) < / td> <td> 0.09 </ td> <td> 0.10 </ td> <td> 0.13 </ td> <td> 0.22 </ td> <td> 0.30 </ td> <td> 0.13 </ td > <td> 0.13 </ td> <td> </ td> </ tr> <tr> <td> <b> First </ b> <b> Adhesive layer </ b> </ td> <td > Materials </ td> <td> mSEBS </ td> <td> mSEBS </ td> <td> mSEBS </ td> <td> mSEBS </ td> <td> mSEBS </ td> <td> mPU </ td> <td> MA-g-pp </ td> <td> mSEBS </ td> </ tr> <tr> <td> Thickness (μm) </ td> <td> 3-5 </ td> <td> 3-5 </ td> <td> 3-5 </ td> <td> 3-5 </ td> <td> 3-5 </ td> <td> 3-5 </ td> <td> 15 </ td> <td> 3-5 </ td> </ tr> <tr> <td> <b> First </ b> <b> Adhesive layer </ b> </ td> <td> material </ td> <td> PP </ td> <td> PP </ td> <td> P P </ td> <td> PP </ td> <td> PP </ td> <td> PP </ td> <td> PP </ td> <td> PP </ td> </ tr> < tr> <td> Thickness (μm) </ td> <td> 40 </ td> <td> 40 </ td> <td> 40 </ td> <td> 40 </ td> <td> 40 < / td> <td> 40 </ td> <td> 35 </ td> <td> 40 </ td> </ tr> </ TBODY> </ TABLE>

Next, peel strength test, penetration test, electrolyte resistance test, and heat-sealing characteristic test were performed on the stacked film layers of Examples 1 to 7 and Comparative Examples, respectively. The items were measured in the following manner, and The test results are shown in Table 2. ＜ Peeling strength test ＞

The stacked film layers of Examples 1 to 7 and Comparative Examples were cut into test samples having a width of 15 mm. Next, a universal testing machine (made by Shimadzu Scientific Instruments Co., Ltd. (SHIMADZU); equipment name: AG-1S) was used to peel the first resin layer (inner layer) and the metal layer in each test sample at a speed of 50 mm / min. A peel strength test was performed at an angle of 180 degrees, and the test samples were stretched to a tensile length of 50 mm. Among them, the tensile length is an intermediate value of 6 test samples. According to the standards set by the general industry, the peel strength of the first resin layer (inner layer) and the metal layer is usually greater than 5 N / 15 mm. Therefore, in this peel strength test, if the peel strength of the first resin layer (inner layer) and the metal layer is greater than 5 N / 15 mm, it is marked as "○" in Table 2; if the first resin layer (inner layer) If the peel strength from the metal layer is less than or equal to 5 N / 15 mm, it is marked as "×" in Table 2. ＜ Deepness Test 1 ＞

The stacked film layers of Examples 1 to 7 and Comparative Examples were prepared as test samples having a growth width of 8 cm × 10 cm, respectively. Next, cold-shell testing is performed on each test sample at a pressure of 6 kg, and the test samples are drawn to a depth of more than 5 mm. After the cold punching shell test, observe whether the test sample has holes or delamination. In this penetration test, if no holes or delamination occurred in the test sample, it is marked as "○" in Table 2. If a hole or delamination occurred in the test sample, it is marked as "X" in Table 2. ＜ Deepness Test 2 ＞

The stacked film layers of Examples 1 to 7 and Comparative Examples were prepared as test samples having a growth width of 8 cm × 10 cm, respectively. Next, cold-shell testing is performed on each test sample at a pressure of 6 kg, and the test samples are drawn to a depth of more than 5 mm. After the cold punching shell test, the surface coating of the metal layer of the test sample was observed by SEM for cracks and peeling. In this penetration test, if the test sample does not crack or fall off, it is marked as "○" in Table 2. If the test sample cracks but does not fall off, it is marked as "△" in Table 2. When the sample cracked and fell off, it was marked as "×" in Table 2. ＜ Anti-electrolyte test 1 ＞

The stacked film layers of Examples 1 to 7 and Comparative Examples were prepared as test samples having a growth width of 10 cm × 10 cm, respectively. Next, the first resin layer (inner layer) of each test sample was immersed in an electrolyte (DEC / EMC / EC = 1/1/1 (wt%) + LiPF ₆ ) at a temperature of 85 degrees Celsius, and left to stand 1 day. Next, the peel strength test was performed on the first resin layer (inner layer) and the metal layer of the test sample. In this peel strength test, if the peel strength of the first resin layer (inner layer) and the metal layer is greater than 3 N / 15 mm, it is marked as "○" in Table 2. The peel strength of the layer is between 2 N / 15 mm and 3 N / 15 mm, and it is marked as "△" in Table 2. If the peel strength of the first resin layer (inner layer) and the metal layer is less than 2 N / 15 mm, marked "×" in Table 2. ＜ Anti-electrolyte test 2 ＞

The stacked film layers of Examples 1 to 7 and Comparative Examples were prepared as test samples having a growth width of 10 cm × 10 cm, respectively. Next, the first resin layer (inner layer) of each test sample was immersed in an electrolyte (DEC / EMC / EC = 1/1/1 (wt%) + LiPF ₆ ) at a temperature of 75 degrees Celsius, and left to stand 7 days. Next, observe whether the first resin layer (inner layer) of the test sample is delaminated. In this electrolyte resistance test, if there is no delamination in the first resin layer (inner layer), it is marked as "○" in Table 2. If there is some delamination in the first resin layer (inner layer), it is indicated in the table. It is marked as "△" in 2; if the first resin layer (inner layer) has severe delamination, it is marked as "×" in Table 2. ＜ Heat sealing characteristics test ＞

The stacked film layers of Examples 1 to 7 and Comparative Examples were cut into test samples having a width of 15 mm. Then, in a high temperature and high pressure environment, heat-sealing procedures are performed on the test samples, so that the first resin layers (inner layers) of the test samples are individually joined, that is, a single test is performed using high heat and high pressure. The first resin layers (inner layers) of the samples were welded to each other. Universal resin tester (made by Shimadzu Scientific Instruments Co., Ltd. (SHIMADZU); equipment name: AG-1S) heat-sealed first resin layer (inner layer)-first resin layer (inner layer) interface in each test sample Here, a peel strength test at an angle of 180 degrees was performed at a peel speed of 50 mm / min, and the test samples were stretched to a tensile length of 50 mm. If the first resin layer (inner layer)-the peel strength of the first resin layer (inner layer) is greater than 50 N / 15 mm, it is marked as "○" in Table 2. If the first resin layer (inner layer)-the first If the peel strength of the resin layer (inner layer) is less than or equal to 50 N / 15 mm, it will be marked as "×" in Table 2. Table 2         <TABLE border = "1" borderColor = "# 000000" width = "85%"> <TBODY> <tr> <td> </ td> <td> <b> Example </ b> <b> 1 < / b> </ td> <td> <b> Example </ b> <b> 2 </ b> </ td> <td> <b> Example </ b> <b> 3 </ b > </ td> <td> <b> Example </ b> <b> 4 </ b> </ td> <td> <b> Example </ b> <b> 5 </ b> < / td> <td> <b> Example </ b> <b> 6 </ b> </ td> <td> <b> Example </ b> <b> 7 </ b> </ td > <td> <b> Comparative example </ b> </ td> </ tr> <tr> <td> <b> Peel strength test </ b> </ td> <td> ○ </ td> < td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> </ tr> <tr> <td> <b> Punch </ b> <b> Deep Test </ b> <b> 1 </ b> </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> </ tr> <tr> <td> <b> Dash </ b> <b> Deep Test </ b> <b> 2 </ b> </ td> <td> △ </ td> <td> △ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ < / td> <td>-* </ td> </ tr> <tr> <td> <b> Anti-electrolyte test </ b> <b> 1 </ b> </ td> <td> ○ < / td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> △ </ td> <td> ○ </ td> <td> ○ </ td > <td> × </ td> </ tr> <tr> <td> <b> Anti-electrolytic Liquid test </ b> <b> 2 </ b> </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> △ </ td> <td> ○ </ td> <td> ○ </ td> <td> × </ td> </ tr> <tr> <td> <b> Heat-seal characteristics </ b> <b> Test </ b> </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> <td> ○ </ td> </ tr> </ TBODY> </ TABLE> *: No surface coating (ie: no With the first protective layer or the second protective layer), the comparative example cannot perform the test of the penetration test 2.       

As can be seen from Table 2, compared to the comparative example, Example 1-7 also maintained a good performance in tests such as peel strength test, penetration test 1, heat seal characteristic test, etc. This shows the stacked film layers of Example 1-7 Has good bonding strength and moldability. In addition, as can be seen from Table 2, compared to the comparative example, Examples 1-7 have better performance in tests such as the depth test 2 and the electrolyte resistance test 1-2. This indicates that Examples 1-7 The stacked film has good chemical resistance. ＜ Electrolytic corrosion resistance test ＞

FIG. 4A to FIG. 4D and FIG. 5A to FIG. 5B are SEM images of the test surface of the experimental group and the control group before and after the electrolyte simulation test to prove the corrosion resistance of the protective layer of the invention. Specifically, the experimental group of the present invention is a two-layer film layer having an aluminum film as a metal layer and a protective layer formed on the surface thereof (see Table 1, the metal layer of Example 3 and the first / second Two protective layers), and the control group of the present invention is a single-layered film layer, which has only an aluminum film as a metal layer (see Table 1, the metal layer of the comparative example).

First, before the electrolyte corrosion resistance test, the test surfaces of the experimental and control film layers of the present invention were observed through SEM, and are shown in FIGS. 4A and 4B, respectively. It is obvious from the SEM image of FIG. 4A that the protective layer on the aluminum film in the experimental group of the present invention has a dense structure (the upper right corner of FIG. 4A is a partial enlarged SEM image thereof, the upper layer is the protective layer and the lower layer is metal Layer) and a flat surface.

Next, the experimental group and the control group were immersed in a simulated electrolyte environment (the electrolyte (DEC / EMC / EC = 1/1/1 (wt%) + LiPF ₆ ) + 20% RO water), and left to stand for 4 minutes. After a few days, the test surface conditions of the film layers of the experimental group and the control group of the present invention were observed using SEM, and shown in FIG. 5A and FIG. 5B, respectively. Referring to FIGS. 4A and 5A at the same time, it can be known that the test surface of the film layer of the experimental group is only slightly etched, that is, a small amount of the protective layer is peeled off; therefore, it can be seen that the protective layer of the present invention does have corrosion resistance. On the other hand, referring to FIGS. 4B and 5B at the same time, it can be known that the test surface of the control layer ’s film layer was severely etched, causing the aluminum film to break (the upper right corner of FIG. 5B is a partial enlarged SEM image thereof).

In summary, the stacked structure of the present invention can effectively prevent the metal layer from being generated by the electrolyte by forming at least a hard protective layer with a dense structure and corrosion resistance on the surface of the metal layer (near the battery core). The delamination between stacked film layers and battery leakage caused by the corrosion of acidic materials, thereby improving the life and safety of the stacked film layers. In addition, the manufacturing process of the hard protective layer of the present invention does not require the use of a processing solution containing phosphorus or heavy metals, and there is no doubt about superior nutrition or heavy metal contamination. Therefore, compared with the conventional manufacturing process of the stacked structure, The stacked film layer of the present invention has a more environmentally friendly manufacturing process.

Although the present invention has been disclosed as above with the examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.

100, 200‧‧‧ stacked film layers

110, 210‧‧‧ first resin layer

120, 220‧‧‧ first adhesive layer

130A, 230A‧‧‧First protective layer

130B‧‧‧Second protective layer

140, 240‧‧‧ metal layer

150, 250‧‧‧Second adhesive layer

160, 260‧‧‧Second resin layer

S1‧‧‧First surface

S2‧‧‧Second surface

FIG. 1 is a schematic cross-sectional view of a stacked film layer according to an embodiment of the present invention. FIG. 2A to FIG. 2C are schematic cross-sectional views illustrating a flow of a method for manufacturing a stacked film layer according to an embodiment of the present invention. 3 is a schematic cross-sectional view of a stacked film layer according to another embodiment of the present invention. 4A to 4B are scanning electron microscope (SEM) images of the test surfaces of the experimental group and the control group of the present invention before the electrolyte simulation test. 5A to 5B are SEM images of the test surfaces of the experimental group and the control group of the present invention after the electrolyte simulation test.

Claims (11)

A stacked film layer includes: a metal layer having a first surface and a second surface opposite to each other; a first resin layer on the first surface of the metal layer; a second resin layer on the first layer On the second surface of the metal layer; and a first protective layer between the metal layer and the first resin layer, wherein the material of the first protective layer includes polysilazane. The stacked film layer according to item 1 of the patent application scope, wherein the thickness of the first protective layer is between 0.05 micrometer and 1.2 micrometer. The stacked film layer according to item 1 of the patent application scope, wherein the surface roughness of the first protective layer is between 0.09 micrometers and 0.30 micrometers. The stacked film layer according to item 1 of the patent application scope, wherein the thickness of the first resin layer is between 20 micrometers and 80 micrometers. The stacked film layer according to item 1 of the patent application scope, wherein the thickness of the metal layer is 30 micrometers to 40 micrometers. The stacked film layer according to item 1 of the patent application scope, wherein the thickness of the second resin layer is 15 μm to 25 μm. The stacked film layer according to item 1 of the patent application scope further includes: a first adhesive layer between the first resin layer and the first protective layer, wherein the thickness of the first adhesive layer is 3 micrometers to 15 μm; and a second adhesive layer between the metal layer and the second resin layer, wherein the thickness of the second adhesive layer is 3 μm to 5 μm. The stacked film layer according to item 1 of the patent application scope further includes: a second protective layer between the metal layer and the second resin layer, wherein the material of the second protective layer includes polysilazane. The stacked film layer according to item 8 of the patent application scope, wherein the thickness of the second protective layer is between 0.05 micrometer and 1.2 micrometer. The stacked film layer according to item 8 of the scope of patent application, wherein the surface roughness of the second protective layer is between 0.09 micrometers and 0.30 micrometers. The stacked film layer according to item 8 of the scope of patent application, further comprising: a first adhesive layer between the first resin layer and the first protective layer, wherein the thickness of the first adhesive layer is 3 micrometers to 15 μm; and a second adhesive layer between the second resin layer and the second protective layer, wherein the thickness of the second adhesive layer is 3 μm to 5 μm.