KR20100099538A - Laminate sheet for battery case and lithium secondary battery using the same - Google Patents

Abstract

PURPOSE: A laminate sheet for a battery case and a lithium secondary battery using the same are provided to prevent the deterioration of an insulation resistor due to the breakdown of a resin sealant layer in a thermal fusion process. CONSTITUTION: A laminate sheet includes an outer coating layer(110), a barrier layer(120), and a resin sealant layer(130,140). The resin sealant layer has two layered structure of the matrix made of thermal fusion materials. An inorganic filler(160) and/or organic filler with a glass transition temperature above the fusion temperature of the thermal fusion materials is inserted into the matrix of one layer. The resin sealant layer includes a first resin sealant layer and a second resin sealant layer.

Description

Laminate sheet for battery case and lithium secondary battery using same {Laminate Sheet for Battery Case and Lithium Secondary Battery Using the Same}

The present invention relates to a laminate sheet for a battery case and a lithium secondary battery using the same, and more particularly to a laminate sheet used in the manufacture of a battery case, including an outer coating layer / barrier layer / resin sealant layer, the resin sealant layer Laminate having a structure of two or more layers of the matrix of the heat-sealing material, and having an organic filler having a inorganic filler and / or a glass transition temperature (Tg) of the matrix of any one or more layers thereof being higher than the melting temperature of the heat-sealing material. It is about a sheet.

As technology development and demand for mobile devices have increased, the demand for secondary batteries as energy sources has been rapidly increasing. Many researches have been conducted on lithium secondary batteries with high energy density and discharge voltage among such secondary batteries. .

Lithium secondary batteries are largely classified into cylindrical batteries, square batteries, pouch-type batteries, and the like according to their appearance, and may also be classified into lithium ion batteries, lithium ion polymer batteries, and lithium polymer batteries, depending on the type of electrolyte.

Due to the recent trend toward the miniaturization of mobile devices, there is an increasing demand for thinner rectangular batteries and pouch-type batteries. Interest is high.

Generally, a pouch type battery refers to a battery in which an electrode assembly and an electrolyte are sealed inside a pouch type case of a laminate sheet including a resin layer and a metal layer. The electrode assembly accommodated in the battery case has a structure of jelly-roll type (winding type), stacking type (lamination type), or composite type (stack / folding type). The pouch-type secondary battery forms an accommodating part for mounting an electrode assembly on a laminate sheet, and heat-seazes a separate sheet which is separated from the sheet or a sheet extending therefrom while the electrode assembly is mounted on the accommodating part. It is made by doing.

Referring to FIG. 1, the battery case 10 is integrated with a main body and a main body in which an accommodating part 11 for mounting an electrode assembly (not shown) is formed and which can seal the accommodating part 11. It consists of a cover 12 in the form.

Therefore, the pouch-type secondary battery is bent to attach the electrode assembly to the accommodating portion 11 of the battery case 10 and then bend at the connection portion between the main body and the lid 12 and bend to seal the accommodating portion 11. It is manufactured by heat-sealing the three surfaces of the sealing portion 13 and the lid 12 of the main body 13 except for the portion.

At this time, when the resin sealant layers corresponding to the innermost layer apply heat to the sealing portions of the main body and the cover, the main body and the cover are joined and sealed by fusion while the resin sealant layer is melted.

However, free radicals may be generated in the resin sealant layer constituting the battery case by the high temperature heat applied in the thermal fusion process. Accordingly, deterioration such as oxidation of the resin sealant layer or generation of fine cracks may occur.

In this case, since the sealing property of the battery is reduced, a problem may occur in that the electrolyte may leak to the outside or external moisture may penetrate into the battery, which may shorten the life of the battery and cause serious problems in the safety of the battery. Can be. If the exposed aluminum barrier layer is in contact with the electrolyte or the electrode tab for the same reason as above, the insulation resistance is destroyed. When charge and discharge are performed in the energized state, aluminum is oxidized to form a lithium aluminum alloy (Li-Al alloy). In addition, the aluminum alloy is eluted with the electrolyte solution, and fine pores are formed in the aluminum barrier layer.

As a result, moisture introduced through the outer coating layer having no moisture barrier property is introduced into the battery case through fine cracks formed in the aluminum layer, resulting in swelling of the battery, and as a result, the safety of the lithium secondary battery and penetration into the battery. Alternatively, problems such as swelling of the battery, deterioration of life characteristics, deterioration of long-term storage characteristics, and reduction of insulation resistance may occur due to diffused moisture.

Therefore, there is a need for a technology that fundamentally prevents a problem of deterioration of battery performance such as cracking of the battery case due to oxidation or deterioration of the resin sealant layer which may be caused during thermal fusion, and to secure battery stability. This is high.

The present invention aims to solve the problems of the prior art and the technical problem that has been requested from the past.

Specifically, an object of the present invention is to provide a lithium secondary battery having improved reliability and performance by suppressing breakage and collapse of the resin sealant layer and preventing corrosion of the metal barrier layer located therein.

The present inventors have tried various methods to minimize the occurrence of cracking of the resin sealant layer and corrosion of the metal layer of the laminate sheet, the resin sealant layer is composed of two or more matrices of heat-sealing material, any one of these When introducing an inorganic filler and / or an organic filler having a glass transition temperature (Tg) above the melting temperature of the heat-sealing material in the above matrix, it was confirmed that all the desired objects can be satisfied and the present invention has been completed. .

Accordingly, the present invention is a laminate sheet used in the manufacture of a battery case, comprising an outer coating layer / barrier layer / resin sealant layer, the resin sealant layer is a structure of two or more layers of a matrix of a heat-sealing material, any one of these The inorganic filler and / or the organic filler whose glass transition temperature (Tg) is more than the melting temperature of the said heat-sealing material are introduce | transduced in the matrix of layers or more.

As such, by introducing a predetermined organic and inorganic filler into the resin sealant layer to be subjected to thermal fusion, the resin sealant layer collapses or cracks due to pressure and high temperature exposure of a heat sealing tool during fabrication of the battery using the same. It can suppress that insulation resistance is destroyed while this occurs. Therefore, the barrier layer can be prevented from being exposed from the resin sealant layer to suppress corrosion of the barrier layer, thereby improving the lifespan characteristics of the battery, and suppressing swelling. It is possible to manufacture a lithium secondary battery with improved performance compared to the conventional.

On the other hand, when the resin sealant layer is formed in a multilayer structure of two or more layers, not only the adhesiveness during thermal fusion can be further improved, but also another resin sealant layer even when collapse or crack occurs in the innermost resin sealant layer. Thereby, the barrier layer can be prevented from being exposed, which has the advantage of high reliability.

In the present invention, the resin sealant layer is composed of a multilayer structure of two or more layers, preferably two to four layers, more preferably located on the innermost side with the first resin sealant layer facing the barrier layer. It may be a double layer structure of the second resin sealant layer.

Since the heat fusion is preferably made at a temperature of 150 ℃ to 200 ℃, the matrix of the thermal fusion material is made of a material having a melting point in the temperature range. In addition, the matrix serves to ensure the insulation of the barrier layer, so that the hygroscopicity is low in order to suppress the penetration of the electrolyte solution and should not be expanded or eroded by the electrolyte solution.

Preferred examples of the matrix of the heat-sealing material, polyethylene, polyethylene acrylic acid, casted polypropylene, polyurethane (polyurethane), polypropylene, polyamide , Polyamide-imide, polyimide, and mixtures or copolymers thereof, but are not limited thereto.

The resin sealant layer of the multilayer structure is composed of a matrix of a heat-sealing material, and an inorganic filler and / or an organic filler having a glass transition temperature (Tg) of at least one of the heat-sealing material is introduced into the matrix of any one layer. Has a structure. The filler is introduced is not particularly limited, and may be included in each of the multi-layer structure, but is preferably introduced in the layer facing the barrier layer in terms of ensuring the insulating property and the adhesive force during the heat welding.

The organic and inorganic fillers support the structure of the matrix in the process of thermal fusion to improve mechanical strength, thereby preventing the resin sealant layer from collapsing or cracking in the resin sealant layer. As a result, it is possible to prevent the barrier layer from reacting with the electrolyte solution to prevent the barrier layer from corroding.

The kind of the inorganic filler is not particularly limited, and preferred examples thereof include Al ₂ O ₃ , ZnO, ZnS, SiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , MgO, CaO, Y ₂ O ₃ , TiO ₂ , Sb ₂ O ₃ , BaTiO ₃ , SrTiO ₃ , Pb (Zr, Ti) O ₃ (PZT), Pb _1-x La _x Zr _1-y Ti _y O ₃ (PLZT), Fe ₃ O ₄ , (Co, Ni) O- (Cr, Fe) ₂ O ₃ , PbCrO ₄ , ZnCrO ₄ , BaCrO ₄ , CdS, FeO (OH) · nH ₂ O, TiO ₂ -NiO-Sb ₂ O ₃ , Pb (CN) ₂ , Ca ₂ PbO ₄ , Al, Fe, Sn-2PbO-Sb ₂ O ₅ , V-SnO ₂ , V-ZrO ₂ , Pr-ZrSiO ₄ , CrSbO ₄ or Cr ₂ WO ₆ -TiO ₂ , ZrSO ₄ coated CdS or (CdZn) S , PbCrO ₄ PbO, PbCrO ₄ PbMoO _{4 ,} PbSO ₄ , Fe ₂ O ₃ + FeO, Fe ₂ O ₃ + MnO ₂ + Mn ₃ O ₄ , ZnO · (Al, Cr, Fe) ₂ O ₃ , Fe ₂ O ₃ , Pb ₃ O ₄ , HgS, CdS + CdSe, CdS + HgS, 2Sb ₂ S ₃ , Sb ₂ O ₃ , Co ₃ (PO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ 4H ₂ O, Co ₃ (PO _{4) 2 · 8H 2 O,} 3NaAl SiO 4 Na 2 S 2, Fe 4 [Fe (CN 6) 3] · nH 2 O, CoO · nAl 2 O 3, CoO · nSnO 2 mMgO (n = 1.5 ~ 3.5, m = 2-6), Co ₃ O ₄ + SiO ₂ + Al ₂ O ₃ + Fe ₂ O ₃ + NiO + MnO, CoO-nAl ₂ O ₃ or (Co, Zn) O-nAl ₂ O ₃ , 2 ( Co, Zn) OSiO ₂ , V-ZrSiO ₄ , Cr ₂ O ₃ , Cr ₂ O (OH) ₄ , Cu (CH ₃ CO ₂ ) ₂ 3CuO (AsO ₂ ) ₂ , CoO-ZnO-MgO, (Co, Zn) O · (Al, Cr) ₂ O ₃ , 3CaO-Cr ₂ O ₃ · 3SiO ₂ , (Al, Cr) ₂ O ₃ , Sb-SnO ₂ , Co, Ni-ZrSiO ₄ , Mn, P-α-Al ₂ O ₃ , ZnO · (Al, Cr ) ₂ O ₃ , Cr-CaOSnO ₂ · SiO ₂ , Fe-ZrSiO ₄ , Cr, Co-CaO · SnO ₂ · SiO ₂ , ZrSiO ₄ coated Cd (S, Se), ZnS, Zn ₂ SiO ₄ , ( Zn, Cd) S, CaS, SrS, CaWO ₄ , SiC and Si ₃ N _{4 It} may be one or two or more selected from the group consisting of.

In one preferred embodiment, the inorganic filler is activated carbon, zeolite, alumina, which can adsorb moisture in the battery without reacting with the electrolyte and the electrode active material and without degrading the performance of the battery. , Silica gel, silica gel, molecular sieve, magnesia (MgO), titanium dioxide (titania: TiO ₂ ) may be one or two or more selected from the group consisting of.

Such an inorganic filler absorbs moisture present in the battery itself, thereby preventing corrosion of the barrier layer and preventing generation of harmful substances such as HF, thus preventing battery performance, lifetime characteristics, and battery deterioration. can do.

In addition, the organic filler may be a material having a glass transition temperature of higher than the melting temperature of the thermal fusion material, preferably a glass transition temperature of 160 ~ 250 ℃. If the glass transition temperature of the organic filler is equal to or lower than the melting temperature of the heat-sealing material, it is difficult to maintain the shape of the organic filler at the temperature and pressure at the time of thermal welding, and thus it is difficult to achieve the effects as described above. Examples of such organic fillers include, but are not limited to, polymer resins such as polystyrene and polycarbonate.

On the other hand, if the content of the filler is too small, it may be difficult to exert the effect of the addition, if the content of the filler is too large, the heat sealability during sealing may be lowered. In addition, if the particle size of the filler is too small, it may be difficult to uniformly distribute in the matrix by agglomeration and may not exert an effect of supporting the resin sealant layer against pressure in the heat fusion process. On the contrary, if the particle size is too large, heat fusion is difficult. It is not preferable because it causes the increase of the thickness of the resin sealant layer. Thus, the content of the filler is preferably 0.1 to 30% by weight based on the total weight of the resin sealant layer, the average particle diameter (D50) of the filler is preferably 0.001 ㎛ to 10.0 ㎛.

The method of introducing the organic and inorganic fillers into the matrix is not particularly limited. For example, when the resin sealant layer is manufactured by a melt extrusion method, a melt extrusion process may be performed by mixing a predetermined organic and inorganic filler with a raw material. have. In some cases, in order to increase the binding force of the filler to the matrix, the surface of the filler may be treated with a silane compound or the like.

The outer coating layer is required to have excellent resistance from the external environment in order to protect the battery from the outside, so excellent tensile strength and weather resistance to the thickness is required. For example, polyester-based resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP), etc. Polyolefin resin, polystyrene resin such as polystyrene, polyvinyl chloride resin, polyvinylidene chloride resin and the like can be used. These materials may be used alone or in combination of two or more, and polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and the like may be preferably used.

The barrier layer may be aluminum or an aluminum alloy to exert a function of improving the strength of the battery case in addition to the function of preventing the inflow or leakage of foreign substances such as gas, moisture, and the like, for example, the alloy number 8079, 1N30, 8021, 3003, 3004, 3005, 3104, 3105 and the like, and these may be used alone or in combination of two or more. Among them, 8079, 1N30, 8021 and 3004 can be particularly preferably used as the metal foil of the barrier layer.

In general, polyolefin resins such as polypropylene have low adhesion to metals, so that the surface of the barrier layer facing the resin sealant layer may be chemically and / or physically treated to form a plurality of irregularities in order to improve adhesion. Can be. Such irregularities can be formed, for example, by sand blasting, chemical etching, or the like on the surface of the barrier layer, and can improve the adhesion by securing a larger surface area. Although the size of the unevenness is not particularly limited, it is preferable that the size of the unevenness is 10 to 200 ㎛ to provide a high bonding force between the layers.

The laminate sheet may have a structure further comprising an adhesive layer between the outer coating layer and the barrier layer and / or between the barrier layer and the resin sealant layer. The adhesive layer serves to complement the adhesion between the barrier layer, the outer coating layer, and the barrier layer and the resin sealant layer.

As the adhesive layer, for example, an adhesive including a resin such as epoxy, phenol, melamine, polyimide, polyester, urethane, polyethylene terephthalate copolymer, and polyetherurethane may be used (modified). A melt-extruded resin layer formed by melt-extrusion coating of polypropylene or (modified) polyethylene resin can be used.

In the laminate sheet according to the present invention, the outer coating layer has a thickness of 5 to 40 µm, the barrier layer has a thickness of 20 to 150 µm, and the thickness of each of the resin sealant layers is preferably 3 to 30 µm, It is preferable that the total thickness of a sealant layer is 10-50 micrometers. If the thicknesses are too thin, it is difficult to expect the blocking function and the strength improvement of the material, on the contrary, too thick is not preferable because of the poor workability and causing an increase in the thickness of the sheet.

In one preferred example, the laminate sheet according to the present invention may be a high strength laminate sheet having a needle penetration of about 7.0 kgf or more. In a preferred example of such a high strength laminate sheet, the barrier layer of the barrier layer is made of aluminum alloy, the outer coating layer is made of polyethylene naphthalate (PEN) or polyethylene tere on the outer surface of the outer coating layer of polyethylene naphthalate (PEN) The sheet provided with the phthalate (PET) layer is mentioned.

The high-strength laminate sheet is configured such that the barrier layer of the metal foil, which has a main function of preventing the inflow or leakage of a conventional material, has a function of improving the strength of the battery case in addition to the blocking function and is provided on the outer coating layer or its outer surface. It further has high strength by further including a separate resin layer.

The needle penetrating force means a penetrating force measured by the FTMS 101C reference measurement method, whereas a conventional laminated sheet battery case has a needle penetrating force of approximately 5.0 kgf, and the battery case is at least 7.0 kgf or more, preferably 7.0 to It has a needle penetration of 10.0 kgf, more preferably 7.0-8.5 kgf. The needle penetrating force of the above range can be said to be a range in which the safety of the battery is ensured in response to the possibility of the battery being damaged by various needle members when the battery is used.

When the battery case made of the high-strength laminate sheet is used, even when a pack case including only the top cap and the bottom cap is used, the battery case may have a high mechanical strength comparable to that of the box-type pack case. Therefore, a battery pack having a high volumetric efficiency and a relatively high capacity can be provided.

The present invention also provides a battery case for a secondary battery using a laminate sheet.

The secondary battery case may be preferably a pouch type, which may be manufactured by forming an accommodating part on which one side of the laminate sheet may be seated by deep drawing and bending the other side in the form of a cover.

In addition, the present invention provides a lithium secondary battery after mounting the electrode assembly in the accommodating portion of the pouch-type secondary battery case. For example, the resin sealant layer may be sealed by heat-sealing the resin sealant layer on the outer circumferential surface of the lid and the lid of the secondary battery case. The lithium secondary battery may be used as a medium-large battery pack by connecting two or more batteries as unit cells.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings, but the scope of the present invention is not limited thereto.

2 and 3 are schematic diagrams of the cross-sectional structure of the laminate sheet according to one embodiment of the present invention.

Referring to these drawings, in the laminate sheet 100, the outer coating layer 110, the barrier layer 120, the first resin sealant layer 130, and the second resin sealant layer 140 are laminated in order from the outside.

Since the outer coating layer 110 forms the outer surface of the battery case, it requires tensile strength and weather resistance to stably protect the electrode assembly against the external environment, and is made of polyethylene terephthalate (PET) or stretched nylon (Ony). The coating layer 110 can satisfy this requirement.

The barrier layer 120 is a layer that blocks gas, moisture, and the like including air, and is excellent in formability, can be given a predetermined strength, and can block moisture or air, and is preferably aluminum, aluminum alloy, and copper. Etc. can be used. In some cases, the surface of the barrier layer 120 facing the first resin sealant layer 130 may be chemically and / or physically treated to form fine concavities and convexities, thereby increasing the bonding force therebetween.

Since the resin sealant layers 130 and 140 form the inside of the accommodating part and the cover in the pouch case, resistance to the lithium-containing electrolyte is required. At the same time, the second resin sealant layer 140 is a site where thermal fusion is performed, and the additional first resin sealant layer 130 that complements the second resin sealant layer 140 is the second resin sealant layer 140. Since it is preferable that the material can have affinity with, the material of each of the resin sealant layers 130 and 140 may be made by using a CPP (non-stretched polypropylene film) having the same electrolytic solution and heat sealability as a matrix. have.

In the laminate sheet 100 according to FIG. 2, a filler 160 is introduced into the first resin sealant layer 130 facing the barrier layer 120, and the laminate sheet 101 according to FIG. 3 is disposed inside the battery. The filler 160 is introduced into the second resin sealant layer 140 to be positioned.

The filler 160 may be an inorganic filler and / or an organic filler having a glass transition temperature (Tg) equal to or higher than the melting temperature of the heat-sealed material.

In this way, the filler 160 is introduced into the resin sealant layers 130 and 140, thereby reinforcing the strength of the laminate sheet, and supporting the matrix to collapse the resin sealant layers 130 and 140 during thermal fusion. Alternatively, cracks can be prevented. In addition, since the electrolyte may minimize contact with the barrier layer 120, the insulation resistance may be improved, and ultimately, the safety of the secondary battery using the electrolyte may be improved. Meanwhile, in the drawings, the thicknesses of the layers of the resin sealant layers 130 and 140 are the same, but the thicknesses of the layers may be set in consideration of adhesiveness.

4 is a schematic diagram of a cross-sectional structure of a laminate sheet additionally including an adhesive layer according to another embodiment of the present invention.

In the laminate sheet 102, the adhesive layer 150 is formed between the outer coating layer 110 and the barrier layer 120, and between the barrier layer 120 and the first resin sealant layer 130, but any one of them May be included only.

5 schematically illustrates a process of manufacturing a secondary battery using the secondary battery case 100 according to one embodiment of the present invention.

The secondary battery case 200 forms an accommodating part 210 in which the electrode assembly 300 can be seated by deep drawing on one side of the laminate sheet (see FIGS. 2 and 3), and the cover 220 is provided on the other side thereof. It can be prepared in the form of a pouch. The electrode assembly 300 is mounted on the accommodating part 210 of the secondary battery case 200, the cover 220 is bent to cover the accommodating part 210, and the sealing except the bent portion of the accommodating part 210 is sealed. The second resin sealant layer (see FIG. 2) 140 facing each other in a state in contact with the three surfaces of the portion 230 and the inside of the lid 220 may be manufactured by heat-sealing to form a sealing portion.

As described above, the laminate sheet according to the present invention improves the mechanical strength of the laminate sheet while exhibiting excellent adhesion by containing an organic or inorganic filler in at least one layer in a resin sealant layer of two or more multilayer structures, By supporting the matrix, it is possible to prevent the resin sealant layer from breaking or disintegrating during thermal fusion and to lower the insulation resistance, and to prevent surface corrosion of the barrier layer.

Those skilled in the art to which the present invention pertains will be able to perform various applications and modifications within the scope of the present invention based on the above contents.

1 is a schematic diagram of a typical pouch type battery case;

2 is a schematic diagram of a cross-sectional structure of a laminate sheet according to one embodiment of the present invention;

3 is a schematic diagram of a cross-sectional structure of a laminate sheet according to another embodiment of the present invention;

4 is a schematic diagram of a cross-sectional structure of a laminate sheet having a structure in which an adhesive layer is further included according to another embodiment of the present invention;

5 is a schematic diagram of a process of forming a secondary battery using a pouch-type battery case according to an embodiment of the present invention.

Claims (19)

A laminate sheet for use in the manufacture of a battery case, comprising an outer coating layer / barrier layer / resin sealant layer, wherein the resin sealant layer has a structure of two or more layers of a matrix of a heat-sealing material, and inorganic material in a matrix of any one or more of these layers A laminate sheet comprising an organic filler having a filler and / or a glass transition temperature (Tg) equal to or higher than the melting temperature of the heat-sealing material. The laminate sheet according to claim 1, wherein the resin sealant layer has a double layer structure of a first resin sealant layer facing the barrier layer and a second resin sealant layer located on the innermost side. 3. The laminate sheet according to claim 2, wherein the filler is introduced into the first resin sealant layer. The laminate sheet according to claim 1, wherein the thermal fusion temperature is 150 to 200 ° C. According to claim 1, wherein the matrix of the heat-sealing material is polyethylene (polyethylene), polyethylene acrylic acid (polyethylene acrylic acid), stretched polypropylene (casted polypropylene), polyurethane (polyurethane), polypropylene (polypropylene), polyamide ( Laminate sheet, characterized in that at least one selected from the group consisting of polyamide, polyamide-imide, polyimide and mixtures or copolymers thereof. The method of claim 1, wherein the inorganic filler is Al ₂ O ₃ , ZnO, ZnS, SiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , MgO, CaO, Y ₂ O ₃ , TiO ₂ , Sb ₂ O ₃ , BaTiO ₃ , SrTiO ₃ , Pb (Zr, Ti) O ₃ (PZT), Pb _1-x La _x Zr _1-y Ti _y O ₃ (PLZT), Fe ₃ O ₄ , (Co, Ni) O- (Cr, Fe ) ₂ O ₃ , PbCrO ₄ , ZnCrO ₄ , BaCrO ₄ , CdS, FeO (OH) · nH ₂ O, TiO ₂ -NiO-Sb ₂ O ₃ , Pb (CN) ₂ , Ca ₂ PbO ₄ , Al, Fe, Sn-2PbO-Sb ₂ O ₅ , V-SnO ₂ , V-ZrO ₂ , Pr-ZrSiO ₄ , CrSbO ₄ or Cr ₂ WO ₆ -TiO ₂ , ZrSO ₄ coated CdS or (CdZn) S, PbCrO ₄ PbO, PbCrO ₄ PbMoO _{4 ,} PbSO ₄ , Fe ₂ O ₃ + FeO, Fe ₂ O ₃ + MnO ₂ + Mn ₃ O ₄ , ZnO · (Al, Cr, Fe) ₂ O ₃ , Fe ₂ O ₃ , Pb ₃ O ₄ , HgS, CdS + CdSe, CdS + HgS, 2Sb ₂ S ₃ , Sb ₂ O ₃ , Co ₃ (PO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ 4H ₂ O, Co ₃ (PO ₄ ) ₂ · 8H ₂ O _{, 3NaAl SiO 4 Na 2 S 2} , Fe 4 [Fe (CN 6) 3] · nH 2 O, CoO nAl 2 O 3, CoO · nSnO 2 mMgO (n = 1.5 ~ 3.5, m = 2 ~ 6), Co ₃ O ₄ + SiO ₂ + Al ₂ O ₃ + Fe ₂ O ₃ + NiO + MnO, CoO-nAl ₂ O ₃ or (Co, Zn) O-nAl ₂ O ₃ , 2 (Co, Zn) O · SiO ₂ , V-ZrSiO ₄ , Cr ₂ O ₃ , Cr ₂ O (OH) ₄ , Cu (CH ₃ CO ₂ ) ₂ 3CuO (AsO ₂ ) ₂ , CoO-ZnO-MgO, (Co, Zn) O. (Al, Cr) ₂ O ₃ , 3CaO-Cr ₂ O ₃ · 3SiO ₂ , (Al, Cr) ₂ O ₃ , Sb-SnO ₂ , _{Co, Ni-ZrSiO 4, Mn} , P-α-Al 2 O 3, ZnO · (Al, Cr) 2 O 3, Cr-CaO · SnO 2 · SiO 2, Fe-ZrSiO 4, Cr, Co-CaO · SnO ₂ SiO ₂ , ZrSiO ₄ coated Cd (S, Se), ZnS, Zn ₂ SiO ₄ , (Zn, Cd) S, CaS, SrS, CaWO ₄ , SiC and Si ₃ N ₄ Laminate sheet characterized by the above-mentioned. The laminate sheet of claim 1, wherein the organic filler is selected from the group consisting of polystyrene and polycarbonate. The laminate sheet according to claim 1, wherein the content of the filler is 0.1 to 30% by weight based on the total weight of the resin sealant layer. The laminate sheet according to claim 1, wherein the average particle diameter (D50) of the filler is 0.001 µm to 10.0 µm. 2. The laminate sheet of claim 1, wherein the laminate sheet further comprises an adhesive layer between the outer coating layer and the barrier layer and / or between the barrier layer and the resin sealant layer. 2. The laminate sheet of claim 1, wherein said outer covering layer is nylon or polyethylene terephthalate. The laminate sheet according to claim 1, wherein the barrier layer is aluminum or an aluminum alloy. The laminate sheet according to claim 1, wherein the surface of the barrier layer facing the resin sealant is chemically and / or physically treated to form a plurality of irregularities. The laminate sheet according to claim 1, wherein the outer coating layer has a thickness of 5 to 40 µm, the barrier layer has a thickness of 20 to 150 µm, and the total thickness of the resin sealant layer is 10 to 50 µm. The barrier layer of claim 1, wherein the barrier layer is made of an aluminum alloy, and the outer coating layer is made of polyethylene naphthalate (PEN) and / or the polyethylene terephthalate (PET) layer is provided on an outer surface of the outer coating layer. Laminate sheet characterized by the above-mentioned. A battery case for a secondary battery using the laminate sheet according to claim 1. The battery case for a secondary battery of claim 16, wherein the battery case for the secondary battery is formed in a pouch-type form by forming an accommodating part on which one side of the laminate sheet can be seated by deep drawing and bending the other side in a cover form. . A lithium secondary battery comprising a battery case and an electrode assembly according to claim 17. The lithium secondary battery of claim 18, wherein the secondary battery is used as a unit cell of a medium-large battery pack.

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