WO2013012290A2

WO2013012290A2 - Cover material for battery and method for manufacturing same

Info

Publication number: WO2013012290A2
Application number: PCT/KR2012/005824
Authority: WO
Inventors: 김홍건; 김기홍; 김정겸; 윤종윤
Original assignee: 한화케미칼 주식회사
Priority date: 2011-07-21
Filing date: 2012-07-20
Publication date: 2013-01-24
Also published as: WO2013012290A3

Abstract

The present invention provides a pouch-type cover material for a battery, comprising: an outermost layer; a barrier layer comprising aluminum or aluminum alloy plating; and an innermost layer, wherein an oxidized coating layer is formed on at least one surface of the barrier layer so that the battery has a surface resistance of at least 0.1 ㏀/㎠. The cover material effectively maintains a moisture-repellent property while effectively and significantly increasing durability to corrosion and electricity insulation.

Description

【Specification】

[Name of invention]

Battery packaging material and its manufacturing method [technical field]

The present invention is the outermost layer; A barrier layer comprising aluminum or aluminum alloy foil; And it relates to a battery packaging material including the innermost layer, and more particularly, to provide a battery packaging material and a manufacturing method thereof having an oxide film layer formed on at least one surface of the barrier layer exhibiting a surface resistance of at least O.lkQ / ciif. The packaging material has an effect of significantly improving corrosion resistance and electrical insulation while maintaining moisture barrier property.

Background Art

Because lithium ion secondary batteries use a liquid electrolyte, lithium ion secondary batteries use aluminum cans as packaging materials to prevent leakage of electrolyte and reduce the risk of explosion. Therefore, the lithium ion secondary battery is heavy and bulky due to the aluminum cans used as the packaging material, and even if the aluminum cans are used, the risk of explosion exists because of the use of an ionic liquid electrolyte. This has a low disadvantage. As a result, the company continues to research and develop to further increase energy density while reducing safety and volume.

Recently, a lithium polymer secondary battery has been developed as a battery which improves and supplements the disadvantages of the lithium ion secondary battery. Lithium polymer secondary batteries can be pouched to reduce the weight of batteries, thereby reducing production costs and increasing the shape of the batteries. Can be. Since the lithium polymer secondary battery uses a laminate pouch as a packaging material, the lithium polymer secondary battery can be thinned. These polymer batteries, notebooks, It is used in portable terminal devices (mobile phones, PDAs, etc.), video cameras, electric vehicles, energy storage batteries, robots, satellites, etc.

The structure of a lithium polymer secondary battery having such an advantage is that a laminated aluminum pouch, which is a packaging material, is connected to an electrode terminal (anode: A1, negative electrode: Ni or Cu) which is a metal, and an electrolyte is laminated therein. However, when the internal electrolyte is exposed to moisture, acid and heat are generated by hydrolysis. When the internal electrolyte is exposed to air, the internal electrolyte may combine with hydrogen to generate strong acidic toxic gas (Gas), causing the battery to explode. In addition, hydrofluoric acid (HF) in the electrolyte has a high penetration force, and passes through the polypropylene film layer, which is the innermost layer of the pouch, to reach the aluminum thin film layer and dissolve and corrode the aluminum thin film layer surface. When the surface of the aluminum thin film layer is corroded, the adhesion between the aluminum thin film layer and the innermost layer is reduced, and the innermost layer is peeled off, and the internal electrolyte is more exposed to air or moisture, thereby increasing the risk of explosion of the battery.

In order to prevent the peeling of the inner layer of the packaging material generated by the internal electrolyte, the surface of the aluminum thin film layer is treated with a chemical conversion treatment solution and then laminated with a thermoplastic resin to produce a packaging material.

On the other hand, the packaging material of the lithium polymer secondary battery is a multilayer including a can type formed by processing a metal and a base layer (or outermost layer) / aluminum layer (or barrier layer) / sealant layer (or innermost layer) as basic elements. The thing which produced the film on the pouch is used. A general battery packaging material is composed of an outermost layer made of a polyester resin and / or a polyamide resin, an inner layer of a barrier layer made of aluminum or an alloy thereof, or a thermoplastic resin.

Methyl carbonate (MC), dimethyl carbonate (DMC) and the like are used as the electrolyte of the polymer battery, and an acid such as hydrofluoric acid (HF) is generated by the reaction of the battery. Adhesiveness, moisture barrier, and electrical insulation between the aluminum film and the electrode to prevent lamination are required.

However, the barrier layer of the conventional lithium polymer secondary battery is ozone treatment, Attempts have been made to improve physical properties such as adhesion through plasma treatment, gamma ray treatment, heat treatment, or chemical treatment such as chromate or phosphate. However, a technique for improving acid resistance and electrical insulation, in particular, electrical insulation of the barrier layer is disclosed. It is difficult to find.

[Content of invention]

[Problem to solve]

In the present invention, by a barrier layer of aluminum or aluminum alloy thin film of a ^"polymer battery by performing the anodization (anodizing) forming a porous aluminum oxide film on the aluminum film, compared to the barrier layer by chromium chemical conversion adhesive It was possible to obtain a battery packaging material that improved the corrosion resistance, electrolytic resistance and electrical insulation while maintaining.

Accordingly, an object of the present invention is to provide a battery packaging material excellent in acid resistance and electrical insulation.

Another object of the present invention is to provide a method of manufacturing the battery packaging material.

[Measures of problem]

Aspect of this invention is an outermost layer, containing aluminum or an aluminum alloy, a barrier layer and an innermost layer comprising a, and comprises a porous oxide film layer formed of at least a positive electrode on one surface oxidation treatment (anodizing) of the barrier layer was 0.1 ^'kffi / cm ^It relates to a battery packaging material having a surface resistance of ^two or more.

One embodiment of the present invention relates to a method for producing a battery packaging material including a porous oxide film by performing anodizing (at least one surface) of the barrier layer.

According to the present invention, the barrier layer in which an oxide film is formed on aluminum is significantly improved in corrosion resistance, electrolytic resistance, and electrical insulation while maintaining adhesiveness as compared to the barrier layer formed by the conventional chemical conversion treatment. In addition, through the pores formed in the porous oxide film to improve the corrosion resistance, the specific surface area is properly Adjusted to provide a packaging material with improved adhesion.

【Effects of the Invention】

As described above, the present invention forms an oxide layer on the aluminum or aluminum alloy as a barrier layer using an anodizing method, while maintaining the moisture barrier property and adhesion of the barrier layer by conventional chemical conversion treatment, There is an effect of dramatically improving the insulation.

[Brief Description of Drawings]

1 is a schematic view showing an embodiment of a laminated structure of a battery packaging material having an oxide film layer according to the present invention.

2 is a schematic view showing another embodiment of a laminated structure of a battery packaging material having an oxide film layer according to the present invention.

3 is a schematic view showing still another embodiment of a laminated structure of a battery packaging material having an oxide film layer according to the present invention.

[Specific contents to carry out invention]

Hereinafter, the present invention will be described in more detail.

In one embodiment of the present invention, the battery packaging material includes an outermost layer, a barrier layer and an innermost layer containing aluminum or an aluminum alloy, and includes a porous oxide film layer formed by anodizing on at least one surface of the barrier layer and O The present invention relates to a battery packaging material having a surface resistance of .lkQ / oif or more.

The battery packaging material may be a battery packaging material for a pouch, and is preferably for a lithium polymer secondary battery.

In an embodiment of the present invention, as shown in Figure 1, ^' battery packaging material is the outermost layer 10 consisting of a PET layer 11 and a nylon layer 12; The innermost layer 18 composed of a barrier layer 13 on which a Crab oxide film layer 14 and a Crab oxide film layer 15 are formed, and a metal adhesive olefin resin layer 18 and a heat adhesive resin layer 19. This sequentially It has a laminated structure. .

In another embodiment of the present invention, as shown in Figure 2, the battery packaging material is the outermost layer 10 consisting of a PET layer 11 and 0-nylon layer 12; It has a structure in which the innermost layer 18 which consists of the barrier layer 13 in which only the 1st oxide film layer 14 was formed, and the metal adhesive olefin resin layer 18 and the heat-adhesive resin layer 19 was sequentially laminated. .

In another embodiment of the present invention, as shown in Figure 3, the battery packaging material is the outermost layer 10 consisting of a PET layer 11 and 0-nylon layer 12; It has a barrier layer 13 in which only the 2nd oxide film layer 15 was formed, the metal adhesive olefin resin layer 18, and a heat adhesive resin layer.

• When anodizing a thin film of aluminum or aluminum alloy, a porous oxide film having a thickness of 1 to several tens can be formed on the aluminum surface. In the present invention, the anodization conditions are adjusted to form the oxide film layers 14 and 16 on one surface or both surfaces of the aluminum constituting the barrier layer to have a surface resistance of at least O.lkQ / oif.

The oxide layer 14, 16 is porous, 0.2 to 10 / zm, preferably o. m to 5 // m, more preferably 0.5 / ffli to 1 /. If the thickness exceeds 10, it is not preferable because the oxide film tends to be damaged in implementing the continuous process.

In addition, the pore particle diameter of the oxide layer is l, 000 nm or less, for example, Iran to l, 000 nm, more preferably 200 nm or less, for example Iran to 200 nm, in terms of adhesion performance and electrical insulation properties. It can be seen that the corrosion resistance decreases as the unit size and size increase.

The specific surface area of the oxide film layer is preferably in the range of 0.5 mVg to 100 mVg. The larger the specific surface area of the oxide film layer, the better the adhesion. The specific surface area of the oxide film layer may be selected in an appropriate range in consideration of the improvement of adhesion and the prevention of delamination caused by hydrofluoric acid, electrolyte, and the like.

The porous oxide film has an improved surface area due to the pores, thereby significantly increasing the adhesion performance between the outermost layer (substrate layer) 10 and the innermost layer 17. In addition, since electrical insulation properties are exhibited, a new performance of electrical insulation can be given to the barrier layer 13.

Conventionally, the chemical conversion treatment layer formed by the chromatization treatment and the chemical conversion treatment method such as phosphate on the barrier layer does not have electrical insulation. Therefore, when the aluminum surface comes into contact with an electric current, electricity conduction occurs immediately. The functionality of the cell pouch can be further improved. For example, when aluminum of the barrier layer is exposed to an electrode or an electrolyte due to damage of the outermost layer (substrate layer) 10 and the innermost layer (silane layer) 17, the performance of the polymer battery is significantly reduced. However, if electrical insulation is provided as in the present invention, higher battery performance can be achieved.

According to the present invention, the outermost layer 10, barrier layer 13 and innermost layer 17 may be composed of all components known in the field of battery packaging materials.

Preferably, since the outermost layer 10 is used to protect the aluminum thin film used as the barrier layer 13 and to protect against pressure or force from the outside, weather resistance, chemical resistance, formability of the packaging material It is preferable to consist of the polyester-based resin layer 11 and / or the stretched polyamide-based resin layer 12 stretched in the biaxial direction in consideration of the above. As thickness of the said outermost layer 10, 5 omega -50 / im is preferable, More preferably, it is about l zm-30 / im. Too thin a thickness reduces the likelihood of pinholes in the filling itself and the protection against external forces.

Examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), copolyester, or polycarbonate (PC) film The biaxially stretched polyamide film resin includes nylon 6, nylon 6.6, a copolymer of nylon 6 and nylon 6.6, nylon 6.10 and polymethacrylylene amidamide (MXD 6), and the like. It may be composed of a single or multiple layers of one or more components selected from the group consisting of. In addition, if there is a polyolefin resin with improved heat resistance, weather resistance, and chemical resistance, it can be applied to form a layer. The outermost layer 10 is dry It adhere | attaches with the barrier layer 13 by methods, such as lamination and extrusion lamination.

The barrier layer is a charge for preventing gas and water vapor from penetrating into the lithium battery from the outside, and pinholes and processability of the barrier layer.

In order to stabilize (pouch formation and embossing) and to have pin holes, a composite of aluminum or nickel with a thickness of about 15 or more, or an inorganic compound such as silicon oxide or alumina may be added. Can be.

In the present invention, the barrier layer 13 is preferably a foil of aluminum or aluminum alloy having a thickness of 20 to 80 in consideration of workability. The aluminum foil is preferably a 10, 80 alloy-based aluminum foil because the high purity series has excellent processability. In addition, the aluminum substrate may optionally include silicon, boron, germanium, arsenic, antimony, copper, magnesium, manganese, zinc, lithium, iron, chromium, vanadium, titanium, bismuth, .potassium, tin, lead zirconium, nickel, cobalt and It may be an alloy containing an element selected from the group consisting of a combination thereof.

According to the present invention, the barrier layer 13 is subjected to anodization of aluminum foil to give an electrical insulation function to form porous oxide films 14 and 16.

The aluminum surface is preferably washed with alkali for the purpose of removing oil. It is a method of changing the surface of aluminum metal into alumina ceramic using electrochemical method. When the method is applied, the aluminum metal itself is oxidized and converted into alumina ceramic, and the surface of the aluminum is stronger than steel and wear resistance is better than that of hard chromium plating. It does not peel off like plating or coating (coating), and the changed alumina ceramic surface has excellent electrical insulation (1500Volt) and electricity flows well inside.

The anodizing treatment may be used in various ways such as sulfuric acid method, hydroxyl method, chromic acid method, phosphoric acid method or boric acid method. For example, the anodization current density of 0.5A / dm ² to 50A / dm, using an electrolyte solution of from about 10 ^° C ^'to 35 ^° C comprising sulfuric acid, chromic acid, boric acid, dioxane, or in a common acid compound The reaction can be made in, and the process can be performed in about 5 seconds to 60 minutes. The oxide layer thus treated is a porous oxide (A1 ₂ 0 ₃ ) layer, which has the inherent function of the barrier layer, and improves electrical insulation, acid resistance, metal adhesion, and wear resistance. ^'

The oxide film layers 14 and 16 treated according to the present invention exhibit electrical insulation properties, and firmly adhere the aluminum foil and the olefinic resin layer having metal adhesion to the oxide film layer by hydrofluoric acid generated by hydrolysis of the electrolyte solution and the electrolyte solution. The lamination can be prevented while preventing the lamination.

In the present invention, the innermost layer 17 is polyolefin-based, polycetylene-based, polypropylene-based, polybutylene-based, ethylene copolymer, propylene copolymer, polyester-based, polyamide-based, polycarbonate-based, fluorine-based, silicone-based , Acrylic, ethylene-propylene-diene-monomer rubber (EPDM) and mixtures thereof. Preferably, it is a polyolefin resin layer or the mixed resin layer of polybutadiene and a polyolefin. In the present invention, the innermost layer 17 is coextruded without using the barrier layer and the adhesive, and the coextrusion is performed by the extrusion coating method under the conditions of the die and screw temperature in the range of 300 ^° C. in the locrc, The sealant layer (the innermost layer) can be bonded to the metal without an adhesive in the molten state, and the thickness thereof is preferably between 200 and 200 for reasons of strength reinforcement and interlayer peeling during heat sealing of the battery.

The innermost layer 17 may be composed of a composite layer using a film such as PET, polyolefin film, nylon, or the like depending on its function. For example, as shown in Figs. 1 to 3, the metal adhesive olefin resin layer 18 and the heat adhesive resin layer 19 can be formed in multiple layers.

The metal adhesive olefin resin layer (intermediate layer) 18 is a modified polyolefin resin, and forms a layer containing a mixture of ethylene and modified propylene, modified butadiene, acrylic acid or methacrylic acid, modified acrylic acid, or the like alone or singly. You can.

The heat adhesive resin layer (the innermost layer) 19 is a lithium battery. For the purpose of thermal bonding in the state of protruding the metal tab bonded to the anode and the cathode respectively to the main body Low density polyethylene, high density polyethylene, linear low density polyethylene, ethylene copolymers, ethylene-propylene copolymers, polybutadiene, ethylene-butadiene-propylene copolymers, propylene resins and the like may be used alone or in combination.

In another embodiment of the present invention, a method for manufacturing a battery packaging material including an outermost layer, a barrier layer including an aluminum or aluminum alloy foil, and an innermost layer, wherein anodizing is performed on at least one surface of the barrier layer. It provides a battery packaging material comprising the step of forming an aluminum oxide film.

In addition, the manufacturing method may further include performing dry lamination on one surface and the outermost layer of the barrier layer, and co-extruding the innermost layer on the other surface of the barrier layer. Anodizing the aluminum or aluminum alloy foil of the barrier layer in an electrolyte solution containing 0.1% to 25% of the specific acid solution of the present invention for 5 seconds to 60 minutes at a current density of 0.5A / dm ² to 50A / dm ² Performing anodizing roll to prepare an aluminum oxide film layer; Dry laminating a surface and an outermost layer of the barrier layer having the coating layer; And coextruding the innermost layer to another surface of the barrier layer having the coating layer.

The anodizing treatment is to treat the aluminum or aluminum alloy of the barrier layer in an electrolyte solution containing 0.1% to 25% of the acid solution, and the acid of the electrolyte solution which can be used for the anodizing treatment may be sulfuric acid, chromic acid, It may be at least one selected from the group consisting of phosphoric acid, oxalic acid and phosphoric acid, for example, 10-25% sulfuric acid, 0.1-10% oxalic acid, 5-15% phosphoric acid or 2-15% It may be chromic acid, and in the case of using a sulfuric acid solution may be used by adding an additional oxalic acid.

The anodization treatment is 0.5A / dm ^! It can be carried out at 5 seconds to 60 minutes with a current density of from 50 A / dm ² .

The temperature of the electrolyte solution is 10 ^° C to 35 ^° C, more preferably 15 ^° C 3 to 3 ⁽ rc, may be a non-uniform thickness of the aluminum oxide filmworm if outside the numerical range and the problem of pore size control. The coextrusion has a die and screw temperature of 100 ^° C to 300 ^° C Under the condition of the innermost layer resin may be carried out by extruding together with the barrier layer in a molten state.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the protection scope of the present invention is not limited to the following examples.

Example 1

The outermost layer was composed of PET (about 6) / 0-nylon (about 15), and a soft aluminum foil of 80 alloy series degreasing treatment having a thickness of about 50 mm 3 was used as the barrier layer. The aluminum foil was reacted for about 2 minutes at a current density of about lA / dnf using an electrolyte solution of about 20 ^° C. in which 0.4% of oxalic acid was added as an additive to sulfuric acid concentration 1, and a thickness of about 0.5 was applied to both sides of aluminum. An aluminum oxide forming soft aluminum foil having a film of aluminum oxide (A1 ₂ 0 ₃ ) having was prepared.

The outermost layer and the barrier layer were laminated by a dry lamination method of injecting a urethane-based adhesive between the two layers, drying them, and bonding each other at a constant temperature and pressure. The barrier layer and the innermost layer had a metal adhesive olefin resin layer therebetween, and co-extruded the adhesive resin in a molten state with a high temperature T-die to manufacture a battery packaging material.

The coextrusion was carried out by an extrusion coating method with a die and screw temperature of about 210 ^° C to coat the anodized aluminum oxide film and the heat-adhesive resin layer in-line. As the metal adhesive olefin resin layer, a mixed resin of modified ethylene and modified propylene was used.

Example 2 was the same as in Example 1 except that the current density and reaction time were changed to lA / dm ² and 3 minutes, respectively, to perform anodization, and the thickness of the obtained oxide film was about 0.8im. Was carried out. Example 3 is the same as in Example 1 except that the current density and reaction time are changed to lA / dm ² and 4 minutes, respectively, to perform anodization, and the thickness of the obtained oxide film is about 1 卿. Was carried out.

Example 4 was carried out in the same manner as in Example 1 except that the current density and reaction time were changed to lA / dm ² and 20 minutes, respectively, to perform anodization, and the thickness of the obtained oxide film was about 5. It was.

TABLE 1

Example 5 was carried out in the same manner except that the electrolyte solution used in Example 3 was treated with 3% chromic acid instead of the mixed solution of sulfuric acid and oxalic acid.

Example 6 was carried out in the same manner except that the electrolyte solution used in Example 3 was treated with 10% phosphoric acid instead of the mixed solution of sulfuric acid and oxalic acid.

Example 7 was carried out in the same manner as in Example 3, except that the electrolyte solution used in Example 3 was treated with oxalic acid of 5> instead of the mixed solution of sulfuric acid and oxalic acid.

Comparative Example 1

The soft aluminum foil of the dealloyed 80 alloy series having a thickness of about 50 used in Example 1 was carried out in the same manner except that aluminum foil without an oxide film was used. Comparative Example 2

A soft aluminum foil of a dealloyed 80 alloy series having a thickness of about 50iffli used in Example 1 was used as a barrier layer, and a chemical conversion solution was coated on one surface of the barrier layer by a reverse roll coating method (thickness 0. an) and dried (heat treated) at 230 ^° C. for 10 seconds to form an anticorrosion layer 120.

In Comparative Example 2, a trivalent chemical conversion film was obtained, and an electrical conduction test of a specimen (5 × 5 cm) was performed by a current application method, and the results are shown in Table 1 below.

Experimental Example 1

The physical properties of the battery packaging material prepared according to Examples 1 to 7 and Comparative Examples 1 to 2 were tested in the following manner and the results were displayed.

1) energization test

An electrical conduction test of the specimen (5 × 5 cm) was performed by the current application method, the results are shown in Table 2 below.

2) Surface resistance test by resistance measurement

Surface resistance was measured by the resistance measurement method for the specimen (5X5cm) of the battery packaging material according to Examples 1 to 7 and Comparative Examples 1 to 2, the results are shown in Table 2 below.

3) Adhesion Test

Adhesion was tested by the peel test method of the innermost layer and aluminum on the specimen (5x5cm) of the battery packaging material according to Examples 1 to 7 and Comparative Examples 1 to 2, the results are shown in Table 2 below.

TABLE 2

4) Corrosion Resistance Test

For specimens (5 X 5 cm) of the battery packaging material according to Examples 1 to 7 and Comparative Examples 1 to 2, NaCl (3.5%) was impregnated with aluminum for each surface treatment to check the presence of corrosion and to perform a corrosion resistance test. The results are shown in Table 3 below.

Corrosion level

O: Brownish corrosion is observed in very small areas but does not affect function

Δ: Partially brownish brown corrosion is observed and affects the function somewhat. X: A lot of brownish brown corrosion is observed.

5) electrolyte solution test

With respect to the specimen (5X5cm) of the battery packaging material according to Examples 1 to 7 and Comparative Examples 1 to 2, the electrolytic solution test was performed by visually impregnating an anodizing film in the electrolyte (DMC + MC + LiPF ₆ ), The results are shown in Table 3 below.

6) Crack occurrence

With respect to the specimen (5X5cm) of the battery packaging material according to Examples 1 to 7 and Comparative Examples 1 to 2, after bending the specimen 10 times or more at 90 ^° , The anodizing film was visually checked and tested for cracks, and the results are shown in Table 3 below. In Table 3, X is an indication that no crack has occurred, and Δ is an indication of the occurrence of microcracks.

TABLE 3

As shown in the above table, unlike Comparative Example 2 having the chromium chemical conversion layer as a barrier layer, Examples 1 to 7 of a battery packaging material including an aluminum oxide film as a barrier layer instead of the chromium chemical conversion layer are used for anodizing treatment. Corrosion does not occur, it can be seen that the resistance to corrosion is improved when used in the battery later.

Instead of the electrolyte solution of 20 ^° C used to form the aluminum oxide film on the surface of the aluminum foil in Example 1, using an electrolyte solution of 25 ^° C in Example 8 and an electrolyte solution of 30 ^° C in Example 9 Except that, substantially the same as in Example 1, the reaction was performed at a current density of about lA / dm ² for about 2 minutes to form a film of aluminum oxide (A1 ₂ 0 ₃ ) having a thickness of about 0.5, on both surfaces of the aluminum. Aluminum oxide-forming soft aluminum foil was prepared, and a battery packaging material using the same. <Example 10>

When forming an aluminum oxide film on the surface of the aluminum foil in Example 1, to produce an aluminum foil having an aluminum oxide film on the surface in the same manner as in Example 1, except that the voltage was treated with 1.5A / dm, A battery packaging material using the same was prepared.

When forming an aluminum oxide film on the surface of the aluminum foil in Example 1, the aluminum oxide on the surface in the same manner as in Example 1 except that the electrolyte solution was treated with 5% oxalic acid instead of sulfuric acid and oxalic acid mixed solution An aluminum foil having a film was produced, and a battery packaging material using the same was produced.

As the barrier layer, an aluminum foil having an aluminum oxide film on its surface was prepared in the same manner as in Example 1 except that the oxide film was used as it was without forming an oxide film on the aluminum alloy-based soft aluminum foil having a thickness of about 50. And the battery packaging material using this was manufactured. <Test Example ² >

1) Pore size of oxide film

The pore sizes of the oxide films prepared according to Examples 1, 8 and 9 were measured by SEM and shown in Table 4.

2) Salt water test (corrosion test)

Sodium chloride for the oxide film prepared according to Examples 1, 8 and 9 above

An anodizing film was impregnated with 3.5% solution to visually check the salt water test. The corrosion degree was measured according to the following criteria, and the results are shown in Table 4 below.

<Corrosion degree> © ： No corrosion

o: Dark brown corrosion is observed in very small areas but does not affect function

Δ: Partially brownish corrosion is observed, slightly affecting function

X ： A considerable part of brownish corrosion is observed. Function cannot be achieved.

TABLE 4

3) Specific surface area test

By changing the surface area of the porous anodic oxide film prepared according to Examples 1, 10 and 11, Comparative Example 4, the specific surface area test of the specimen according to the embodiment was carried out by BET measuring equipment (Autosorb-iQX Quantachrome instruments) of 77K, N2. It was measured by gas, and the results are shown in Table 5 below.

4) Adhesion Test

In Example 1, 10 and 11, Comparative Example 4 to the porous anodized film (5X5cin) prepared in accordance with the peel test method of the innermost layer and the aluminum (Peel) test method, the results are shown in Table 5 below It was.

TABLE 5

As can be seen from Tables 2 to 5, the barrier layer in which an oxide film is formed on aluminum according to the present invention has corrosion resistance, electrolytic resistance, and electrical insulation while maintaining adhesiveness as compared to the barrier layer by conventional chromium chemical conversion treatment. The result is a dramatic improvement. In addition, it can be seen that the corrosion resistance decreases as the unit pore size increases, and the adhesion strength increases as the specific surface area increases. .

[Description of the code]

10: outermost layer 11: PET layer

12 ： 0-nylon layer 13: barrier layer

14: first oxide film layer 15: aluminum layer

16: second oxide layer 17: innermost layer

18: olefin resin layer 19: heat adhesive resin layer

Claims

[Patent Claims]

[Claim 1]

Outermost layer, including barrier layer and innermost layer containing aluminum or aluminum alloy, ^_

A battery packaging material comprising an aluminum oxide film layer formed on at least one surface of the barrier layer and having a surface resistance of 0.11 Ω / α ² or more.

[Claim 2]

The method of claim 1,

The thickness of the oxide film layer is a battery packaging material, characterized in that 0.2 to 10.

[Claim 3]

The method of claim 1,

The coating layer is a battery packaging material containing pores having a pore particle diameter of lnm to l, 000nm.

[Claim 4]

The method of claim 3,

The coating layer is a battery packaging material containing pores having a pore size of lnm to 200nm.

[Claim 5]

The method of claim 1,

The coating layer is a battery packaging material having a specific surface area in the range of 0.5m7g to 100mVg. . ·

[Claim 6]

The method of claim 1,

The coating layer is a battery packaging material that is formed by anodizing at least one surface of the aluminum or aluminum alloy.

[Claim 7]

The method of claim 1,

A battery packaging material having a thickness of the barrier layer of 20 to 80 / mm 3.

[Claim 8]

According to claim 1,

The outermost layer is a battery packaging material comprising a stretched polyester resin, a stretched polyamide resin or a mixture thereof. ^■

[Claim 9]

The method of claim 1,

The innermost layer is polyolefin, polyethylene, polypropylene, polybutylene, ethylene copolymer, propylene copolymer, polyester, polyamide, polycarbonate, fluorine, silicone, acrylic, ethylene-propylene-diene A battery packaging material comprising at least one resin selected from the group consisting of monomer rubbers (EPra «) and combinations thereof.

[Claim 10]

As a manufacturing method of a battery packaging material comprising an outermost layer, a barrier layer containing aluminum or an aluminum alloy, and an innermost layer,

And anodizing the at least one surface of the barrier layer to form an aluminum oxide film.

[Claim 11]

The method of claim 10,

Wherein the anodizing is a method of manufacturing a battery packaging material that is performed for 5 minutes to 60 minutes at a current density of 0.5A / dm to 50A / dm ² .

[Claim 12] ^■

The method of claim 10,

Wherein the anodizing is a method of manufacturing a battery packaging material that is carried out in an electrolyte solution containing an acid of 0.1% to 25% concentration.

[Claim 13]

The method of claim 12,

Temperature of the electrolyte solution is a method for producing a battery packaging material in the range of 10 ^° C to 35 ^° C.

[Claim 14] The method of claim 12,

The acid is a method for producing a battery packaging material of at least one selected from the group consisting of sulfuric acid, chromic acid, phosphoric acid, boric acid and oxalic acid.

[Claim 15]

The method of claim 10,

Dry lamination of one surface and the outermost layer of the barrier layer, and co-extruded the innermost layer on the other surface of the barrier layer.

[Claim 16]

The method of claim 15,

The co-extrusion step is a battery packaging material manufacturing method of co-extrusion in a molten state by interposing an adhesive resin between the barrier layer and the innermost layer.

[Claim 17]

The method of claim 15,

The coextrusion step is a method for producing a battery packaging material that is carried out under the conditions of the die and screw temperature is 100 ^° C to 300 ^° C.