KR101143302B1 - Laminate Sheet for Battery Case and Lithium Secondary Battery Using The Same - Google Patents

Abstract

The laminate sheet used to manufacture the battery case according to the present invention comprises an outer coating layer / barrier layer / resin sealant layer, wherein the resin sealant layer is an inorganic filler and / or glass transition temperature (Tg) in a matrix of a heat-sealing material. It is a laminate sheet into which the organic filler which is more than the melting temperature of the said heat-sealing material is introduce | transduced.

Such a laminate sheet has excellent mechanical strength and can suppress corrosion of the barrier layer due to the collapse or cracking of the resin sealant layer in the heat-sealing process or use process, and ultimately the safety and life of the secondary battery using the same. Properties can be improved.

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, 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 A laminate sheet in which an inorganic filler and / or an organic filler having a glass transition temperature (Tg) of not less than the melting temperature of the heat-sealing material are introduced into a matrix of a heat-sealing material.

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. In particular, for pouch-type batteries that are easy to deform, low in manufacturing cost and light in weight. 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 can seal the accommodating part 11. The cover 12 is made up of.

Therefore, in the pouch type secondary battery, the electrode assembly is mounted on the accommodating part 11 of the battery case 10, and then bent at the connecting portion of the main body 13 and the lid 12 to seal the accommodating part 11. In order to manufacture the heat-sealing the sealing surface 3 and the cover 12 of the main body 13, except for the bent 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. When the exposed aluminum layer is in contact with the electrolyte or the electrode tab for the above reason, the insulation resistance is destroyed. When charge and discharge are performed in the energized state, as shown in FIG. 3, aluminum is oxidized to form a lithium aluminum 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, adverse effects 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 or the like.

Accordingly, there is a need for a technology that fundamentally prevents a problem of deterioration of battery performance such as cracking in a battery case due to oxidation or deterioration of a resin sealant layer that 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, it is an object of the present invention to provide a lithium secondary battery with improved reliability and performance by suppressing breakage and collapse of the inner insulating film 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, and as a result, the inorganic filler and / or glass transition temperature (Tg) in the matrix of the heat-sealing material in the resin sealant layer When introducing an organic filler that is higher than the melting temperature of the heat-sealing material, 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 an inorganic filler and / or glass transition temperature (Tg) in the matrix of the heat-sealing material ) Is composed of an organic filler having a temperature of at least the melting temperature of the heat-sealed material.

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.

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, since the matrix serves to ensure the insulation of the barrier layer, in order to suppress the invasion of the electrolyte, the moisture absorption is low and should not be expanded or eroded by the electrolyte.

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.

In the present invention, the resin sealant layer has a structure in which an inorganic filler and / or an organic filler whose glass transition temperature (Tg) is equal to or higher than the melting temperature of the heat-sealing material is introduced into the matrix of the heat-sealing material.

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) 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 ? ₃ SiO 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 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 polybutylene, polystyrene, polycarbonate, and ABS resin.

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 10 to 80% based on the thickness of the sealant layer.

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, 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 and 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, polyetherurethane, and the like 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 resin sealant layer has a thickness of 10 to 50 µm. 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.

Figure 2 is a schematic diagram of the cross-sectional structure of the laminate sheet according to an embodiment of the present invention.

Referring to FIG. 2, the laminate sheet 100 has a structure in which the barrier layer 120 is laminated between the outer coating layer 110 as the outermost layer and the heat sealable resin sealant layer 130. That is, the outer coating layer 110, the barrier layer 120, and the resin sealant layer 130 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 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 layer 130 forms 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, since the resin sealant layer 130 is a site where thermal fusion is performed, the material of the resin sealant layer 130 may be formed by using a matrix of CPP (non-stretched polypropylene film) having both electrolyte resistance and heat fusion as a matrix. have. Here, the filler 150 is introduced and uniformly distributed. The filler 150 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 150 is introduced to reinforce the strength of the laminate sheet, and by supporting the matrix, it is possible to prevent the resin sealant layer 130 from collapsing or cracking during thermal fusion. 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.

Figure 3 shows a schematic diagram of the cross-sectional structure of the laminate sheet further comprising an adhesive layer according to another embodiment of the present invention.

In this drawing, the adhesive layer 140 is formed between the outer coating layer 110 and the barrier layer 120 and between the barrier layer 120 and the resin sealant layer 130, but may be included only in any one of them.

4 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 lid 220 is formed on the other side thereof. It may be prepared in the form of a pouch provided. 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 part 230 of the main body excluding the bent portion is disposed. The pouch type battery case may be manufactured by heat-sealing the three surfaces and the lid 220.

In the secondary battery, after the electrode assembly 150 is mounted on the accommodating part 120 of the pouch-type secondary battery case 100, the resin sealant layers (see FIG. 3; 130) facing each other have an outer peripheral part of the accommodating part 210. It may be manufactured by forming a sealing portion by heat fusion in a state in contact with the inside of the cover 220 at 230.

As described above, the laminate sheet according to the present invention contains an organic or inorganic filler in the resin sealant layer to improve the mechanical strength of the laminate sheet, and by supporting the matrix, the resin sealant layer breaks or collapses during thermal fusion, resulting in insulation resistance. Deterioration can be prevented and surface corrosion of the barrier layer can be prevented from occurring.

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 of a structure in which the present invention further includes an adhesive layer according to another embodiment;

Figure 4 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 (17)

A laminate sheet used in the manufacture of a battery case, comprising an outer coating layer / barrier layer / resin sealant layer, wherein the resin sealant layer is a melting temperature of an inorganic filler and the heat-sealing material in a matrix of a heat-sealing material, 150 to 200 ° C. An organic filler having a higher glass transition temperature (Tg) is introduced. delete According to claim 1, wherein the matrix of the heat-sealing material is polyethylene (polyethylene), polyethylene acrylic acid (polyethylene acrylic acid), unstretched polypropylene (polyurethane), 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 characterized in that it is selected from the group consisting of Laminate sheet. The laminate sheet according to claim 1, wherein the organic filler is selected from the group consisting of polymer resins. 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 10 to 80% in size based on the thickness of the sealant layer. The method of claim 1, wherein the laminate sheet further comprises an adhesive layer between the outer coating layer and the barrier layer, or between the barrier layer and the resin sealant layer, or between the outer coating layer and the barrier layer and between the barrier layer and the resin sealant layer. Laminate sheet to make. 2. The laminate sheet of claim 1, wherein the outer coating 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 or physically or chemically and 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 resin sealant has a thickness of 10 to 50 µm. 2. 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) or a polyethylene terephthalate (PET) layer is provided on an outer surface of the outer coating layer. Laminate sheet. A battery case for a secondary battery using the laminate sheet according to claim 1. The secondary battery case according to claim 14, wherein the secondary battery case is formed in a pouch form 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 a cover form. A lithium secondary battery comprising the battery case and the electrode assembly according to claim 15. The lithium secondary battery of claim 16, wherein the secondary battery is used as a unit cell of a medium-large battery pack.

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