KR20120086038A - Electrode assembly for secondary battery - Google Patents

Abstract

PURPOSE: A jelly-roll type electrode assembly is provided to prevent the reduction of battery performance, to easily manufacture the battery, and to improve thermal resistance, and cycle performance. CONSTITUTION: A jelly-roll type electrode assembly(200) is manufactured by winding a positive electrode(30), a first separator(10), a negative electrode(40), and a second separator(20) sequentially. The first separator and the second separator comprises a porous substrate, and a porous coating layer(11) which is a mixture of an inorganic material particles and binder polymers, formed on only one side of the porous substrate. Porous coating layers of the first separator and the second separator are arranged to face a negative electrode, and independently comprise a polyolefin-based porous substrate.

Description

Electrode assembly for secondary battery {Electrode assembly for secondary battery}

The present invention relates to a jelly-roll type electrode assembly for a lithium secondary battery, and more particularly, to a jelly-roll type electrode assembly for a lithium secondary battery having improved heat resistance in which a PET tape for preventing heat shrinkage is attached to a separator.

Recently, interest in energy storage technology is increasing. As the field of application extends to the energy of mobile phones, camcorders, notebook PCs, and even electric vehicles, efforts for research and development of electrochemical devices are becoming more concrete. The electrochemical device is the most attracting field in this respect, and the development of a secondary battery capable of charging and discharging has been the focus of attention, and in recent years in the development of such a battery in order to improve the capacity density and specific energy The research and development of the design of the battery is progressing.

Among the secondary batteries currently applied, lithium secondary batteries developed in the early 1990s have a higher operating voltage and significantly higher energy density than conventional batteries such as Ni-MH, Ni-Cd, and sulfuric acid-lead batteries using aqueous electrolytes. I am in the spotlight.

In general, a lithium secondary battery has a structure in which a unit cell composed of a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode is laminated or wound and built in a case of a metal can or laminate sheet, and an electrolyte is injected or impregnated therein. It is comprised by doing.

The electrode assembly of the positive electrode / separation membrane / cathode structure constituting the secondary battery is largely divided into a jelly-roll type (winding type) and a stack type (lamination type) according to its structure. A folding electrode assembly (jelly roll) wound between a long sheet-like cathode and an anode coated with an active material through a separator, and a stack type in which a plurality of anodes and cathodes of a predetermined size were sequentially stacked with a separator therebetween. It is classified as an electrode assembly. Among them, the jelly-roll type electrode assembly has the advantages of easy manufacturing and high energy density per weight.

The polyolefin-based porous substrate commonly used as a separator in such a jelly-roll type lithium ion battery exhibits extreme heat shrinkage behavior at a temperature of 100 degrees or more due to material properties and manufacturing process characteristics including stretching. Thus, a method of improving the heat resistance by introducing an organic-inorganic composite layer into the separator has been proposed, but problems such as deterioration of battery performance, generation of winding failure in the winding process, and desorption of inorganic particles in the battery assembly process have occurred. .

Accordingly, an object of the present invention is to provide a jelly-roll type electrode assembly with improved heat resistance, which prevents battery performance and is easy to manufacture.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, in this invention, an anode, a 1st separator, a cathode, and a 2nd separator are laminated | stacked one by one sequentially, and the said 1st separator and the said 2nd separator are both a porous base material and only one surface of the said porous base material. And a porous coating layer formed of a mixture of inorganic particles and a binder polymer, wherein the first separator and the second separator provide a jelly-roll type electrode assembly in which all of the porous coating layers thereof face the cathode. .

The porous substrate may be a polyolefin-based porous substrate, it is preferable to use polyethylene, polypropylene, polybutylene and polypentene as the polyolefin-based porous substrate.

As the inorganic particles, inorganic particles having a dielectric constant of 5 or more, inorganic particles having lithium ion transfer ability, and the like may be used.

Inorganic particles having a dielectric constant of 5 or more include BaTiO ₃ , Pb (Zr _x , Ti _{1 -x} ) O ₃ (PZT, 0 <x <1), Pb _{1 - x} La _x Zr _{1 -y} Ti _y O ₃ (PLZT hafnia, 0 <x <1, 0 <y <1), (1-x) Pb (Mg 1/3 Nb 2/3) O 3 -xPbTiO 3 (PMN-PT, 0 <x <1), ( HfO ₂ ), SrTiO ₃ , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZrO ₂ , SiO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , SiC, TiO ₂ , and the like are preferably used.

In addition, the inorganic particles having a lithium ion transfer ability are lithium phosphate (Li ₃ PO ₄ ), lithium titanium phosphate (Li _x Ti _y (PO ₄ ) ₃ , 0 <x <2, 0 <y <3), lithium aluminum Titanium phosphate (Li _x Al _y Ti _z (PO ₄ ) ₃ , 0 <x <2, 0 <y <1, 0 <z <3), (LiAlTiP) _x O _y series glass (0 <x <4, 0 <y <13), lithium lanthanum titanate (Li _x La _y TiO ₃ , 0 <x <2, 0 <y <3), lithium germanium thiophosphate (Li _x Ge _y P _z S _w , 0 <x <4, 0 <y <1, 0 <z <1, 0 <w <5), lithium nitride (Li _x N _y , 0 <x <4, 0 <y <2), SiS ₂ (Li _x Si _y S _z , 0 <x <3, 0 <y <2, 0 <z <4) Series glass and P ₂ S ₅ (Li _x P _y S _z , 0 <x <3, 0 <y <3, 0 <z <7) It is preferable to use series glass etc.

The binder polymer may be polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polymethylmethacrylate, Polybutylacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate, polyvinyl alchol, ethylene vinyl acetate copolymer (polyethylene-co- vinyl acetate, polyethylene oxide, polyarylate, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethylflu Lan (cyanoethylpullulan), cyanoethyl Cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan, carboxyl methyl cellulose and low molecular weight compounds with a molecular weight of 10,000 g / mol or less Can be used.

The composition ratio of the inorganic particles to the binder polymer is preferably 10:90 to 99: 1 by weight, respectively.

The present invention also provides a secondary battery having a case for sealingly accommodating the electrode assembly together with the jelly-roll electrode assembly and an electrolyte.

The present invention, which is a jelly-roll type electrode assembly having a separator having a porous coating layer surrounding the cathode, uses a separator having an organic-inorganic porous coating layer having excellent heat resistance, and thus has excellent enthusiasm stability of the battery, and the porous coating layer is formed only on the end face of the separator. Because of the excellent breathability, the organic-inorganic porous coating layer of the separator is better than the cycle characteristics when the contact directly with the anode.

In addition, the present invention prevents contact between the porous coating layer and the core during the winding process, thereby preventing winding failure due to different surface friction characteristics, and the outermost portion of the electrode assembly is disposed because the separator is not exposed to the porous coating layer. Desorption of the coating layer can be prevented, and since the frictional force is not increased, it is easy to assemble the battery by combining with the battery case.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate exemplary embodiments of the invention and, together with the description of the invention, It should not be construed as limited.
1 is a cross-sectional view of a jelly-roll type electrode assembly using a separator without a porous coating layer according to an embodiment.
2 is a cross-sectional view of a jelly-roll type electrode assembly using a separator having a porous coating layer according to an embodiment.
3 is a cycle characteristic graph of Example 1 and Comparative Example 1 of the present invention.
4 is a SEM photograph of the surface of the separator of Example 1 of the present invention.
5 is a SEM photograph of the surface of the separator of Comparative Example 1 of the present invention.

Hereinafter, the present invention will be described in detail with reference to the drawings. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

1 is a cross-sectional view of a jelly-roll type electrode assembly using a separator in which a porous coating layer is not formed according to an embodiment, and FIG. 2 illustrates a jelly using a separator having only one surface of a porous coating layer contacting a cathode according to the present invention. A cross-sectional view of a rolled electrode assembly is shown. However, the configuration described in the embodiments and drawings described below are only the most preferred embodiment of the present invention and do not represent all of the technical idea of the present invention, which can be replaced at the time of the present application It should be understood that there may be various equivalents and variations.

In general, a jelly-roll type electrode assembly used in a cylindrical battery or the like is manufactured by stacking and winding a positive electrode, a negative electrode, and a separator. Such an electrode assembly is shown in FIG. 1.

Referring to FIG. 1, the jelly-roll type electrode assembly 100 in which the positive electrode 30 and the negative electrode 40 and the separators 10 and 20 interposed between the electrode plates are wound together is the positive electrode 30 and the separator 10. ) Has a rolled-up core. When the jelly-roll type electrode assembly 100 generates heat during charging or use, the separator 10, which is generally stretched and manufactured, undergoes thermal contraction, and the positive electrode 30 is the negative electrode 40. ), There is a risk of fire due to short circuit.

Referring to FIG. 2, in the jelly-roll type electrode assembly 200 of the present invention, an anode 30, a first separator 10, a cathode 40, and a second separator are sequentially stacked and wound up, and the first separator is stacked. Both the 10 and the second separator 20 have porous coating layers 11 and 21 made of a mixture of inorganic particles and a binder polymer on only one surface of the porous substrate and the porous substrate, and the first separator 10 And the second separator 20 are arranged such that all of these porous coating layers 11 and 21 face the cathode 40.

The separators 10 and 20 of the present invention include a porous substrate and porous coating layers 11 and 21 made of a mixture of inorganic particles and a binder polymer on one surface of the porous substrate. Since the porous coating layer is excellent in heat resistance, it serves to prevent thermal contraction of the separator. In many cases, a separator having a porous coating layer has a porous coating layer formed on both sides thereof, but a separator having both porous coating layers formed on both sides has a problem of lowering air permeability, and is manufactured by dip coating. In most cases, it was difficult to manufacture a uniform porous coating layer. However, the separators 10 and 20 of the present invention have a porous coating layers 11 and 21 formed on only one surface thereof, and thus have excellent breathability, and are manufactured using the slot die coating method, thereby providing a porous coating layer having a uniform thickness and breathability. Easy to provide

The porous coating layer of the present invention is a porous coating layer composed of a mixture of inorganic particles and a binder polymer, the binder polymer is attached to each other (that is, the binder polymer is connected and fixed between the inorganic particles, so that the inorganic particles can remain bound to each other) In addition, the porous coating layer is bound to the porous substrate by the binder polymer. The inorganic particles of the porous coating layer are present in the closest-filled structure substantially in contact with each other, and the interstitial volume generated when the inorganic particles are in contact with each other becomes pores of the porous coating layer. In particular, the porous coating layer of the present invention is not in direct contact with the positive electrode, it was found that the cycle characteristics are better than the contact with the positive electrode, and also excellent porosity.

The present invention is laminated in the order of the positive electrode 30, the first separator 10, the negative electrode 40 and the second separator 20, and wound around one end of the core (mandrel) to roll the jelly-roll type electrode assembly To prepare. At this time, when the porous coating layer and the core is in contact with each other, adhesion may occur between the core and the porous coating layer, so that a poor winding-roll-shaped electrode assembly may be produced, but the present invention provides a separator having a single-side porous coating layer. In this case, the porous coating layer is laminated toward the cathode so that the porous coating layer does not come into direct contact with the core.

The wound jelly-roll type electrode assembly is finally inserted into a battery case to manufacture a battery. A battery case, such as a cylindrical, square, or pouch type, using a can is used. If the frictional force of the assembly surface is large, assembly may not be easy. However, the outermost surface of the jelly-roll type electrode assembly of the present invention does not have a large friction force because the separator of the surface on which the porous coating layer is not formed is disposed. In addition, when the porous coating layer is exposed on the outermost surface of the jelly-roll type electrode assembly, detachment of the porous coating layer may occur due to friction when inserted into the battery case, but the jelly-roll type electrode assembly of the present invention has a porous coating layer on the outermost surface thereof. Since it is not exposed, desorption can be prevented.

The porous substrate used in the present invention can be used including a polyolefin-based porous substrate, it is preferable to use polyethylene, polypropylene, polybutylene and polypentene as such a polyolefin-based porous substrate.

As the inorganic particles, inorganic particles having a dielectric constant of 5 or more, inorganic particles having lithium ion transfer ability, and the like may be used.

Inorganic particles having a dielectric constant of 5 or more include BaTiO ₃ , Pb (Zr _x , Ti _{1 -x} ) O ₃ (PZT, 0 <x <1), Pb _{1 - x} La _x Zr _{1 -y} Ti _y O ₃ (PLZT hafnia, 0 <x <1, 0 <y <1), (1-x) Pb (Mg 1/3 Nb 2/3) O 3 -xPbTiO 3 (PMN-PT, 0 <x <1), ( HfO ₂ ), SrTiO ₃ , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZrO ₂ , SiO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , SiC, TiO ₂ , and the like are preferably used.

In addition, the inorganic particles having a lithium ion transfer ability are lithium phosphate (Li ₃ PO ₄ ), lithium titanium phosphate (Li _x Ti _y (PO ₄ ) ₃ , 0 <x <2, 0 <y <3), lithium aluminum Titanium phosphate (Li _x Al _y Ti _z (PO ₄ ) ₃ , 0 <x <2, 0 <y <1, 0 <z <3), (LiAlTiP) _x O _y series glass (0 <x <4, 0 <y <13), lithium lanthanum titanate (Li _x La _y TiO ₃ , 0 <x <2, 0 <y <3), lithium germanium thiophosphate (Li _x Ge _y P _z S _w , 0 <x <4, 0 <y <1, 0 <z <1, 0 <w <5), lithium nitride (Li _x N _y , 0 <x <4, 0 <y <2), SiS ₂ (Li _x Si _y S _z , 0 <x <3, 0 <y <2, 0 <z <4) Series glass and P ₂ S ₅ (Li _x P _y S _z , 0 <x <3, 0 <y <3, 0 <z <7) It is preferable to use series glass etc.

The binder polymer may be polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polymethylmethacrylate, Polybutylacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate, polyvinyl alchol, ethylene vinyl acetate copolymer (polyethylene-co- vinyl acetate, polyethylene oxide, polyarylate, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethylflu Lan (cyanoethylpullulan), cyanoethyl Cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan, carboxyl methyl cellulose and low molecular weight compounds with a molecular weight of 10,000 g / mol or less Can be used.

The composition ratio of the inorganic particles to the binder polymer is preferably 10:90 to 99: 1 by weight, respectively.

The present invention also provides a secondary battery having a case for sealingly accommodating the electrode assembly together with the jelly-roll electrode assembly and an electrolyte.

The positive electrode and the negative electrode of the present invention are not particularly limited, and according to a conventional method known in the art, the electrode active material may be prepared in a form bound to the electrode current collector. Non-limiting examples of the positive electrode active material of the electrode active material may be a conventional positive electrode active material that can be used for the positive electrode of the conventional electrochemical device, in particular lithium manganese oxide, lithium cobalt oxide, lithium nickel oxide, lithium iron oxide or combinations thereof It is preferable to use one lithium composite oxide. Non-limiting examples of the negative electrode active material may be a conventional negative electrode active material that can be used for the negative electrode of the conventional electrochemical device, in particular lithium metal or lithium alloys, carbon, petroleum coke, activated carbon, Lithium adsorbents such as graphite or other carbons are preferred. Non-limiting examples of the positive electrode current collector is a foil made by aluminum, nickel or a combination thereof, and non-limiting examples of the negative electrode current collector by copper, gold, nickel or copper alloy or a combination thereof Foils produced.

Electrolyte that may be used in the electrode assembly of the present invention is A ⁺ B ^- A salt of the structure, such as, A ⁺ comprises Li ^+, Na ^+, an alkali metal cation or an ion composed of a combination thereof, such as K ⁺ and B ^- is _{^{PF 6 -, BF 4 -,}} Cl -, Br -, I -, ClO 4 -, AsF 6 -, CH 3 CO 2 -, CF 3 SO 3 -, N (CF 3 SO 2) 2 -, C ( Salts containing ions consisting of anions such as CF ₂ SO ₂ ) ₃ ^- or a combination thereof are propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), dimethyl sulfoxide, acetonitrile, dimethoxyethane, diethoxyethane, tetrahydrofuran, N-methyl-2-pyrrolidone (NMP), ethylmethylcarbonate (EMC), gamma butyrolactone (g- Butyrolactone) or a mixture thereof, or dissolved in an organic solvent, but is not limited thereto. The electrolyte injection may be performed at an appropriate stage in the battery manufacturing process, depending on the manufacturing process and the required physical properties of the final product. That is, it may be applied before the battery assembly or at the end of battery assembly.

Electrolyte that may be used in the electrode assembly of the present invention is A ⁺ B ^- A salt of the structure, such as, A ⁺ comprises Li ^+, Na ^+, an alkali metal cation or an ion composed of a combination thereof, such as K ⁺ and B ^- is _{^{PF 6 -, BF 4 -,}} Cl -, Br -, I -, ClO 4 -, AsF 6 -, CH 3 CO 2 -, CF 3 SO 3 -, N (CF 3 SO 2) 2 -, C ( Salts containing ions consisting of anions such as CF ₂ SO ₂ ) ₃ ^- or a combination thereof are propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), dimethyl sulfoxide, acetonitrile, dimethoxyethane, diethoxyethane, tetrahydrofuran, N-methyl-2-pyrrolidone (NMP), ethylmethylcarbonate (EMC), gamma butyrolactone (g- Butyrolactone) or a mixture thereof, or dissolved in an organic solvent, but is not limited thereto. The electrolyte injection may be performed at an appropriate stage in the battery manufacturing process, depending on the manufacturing process and the required physical properties of the final product. That is, it may be applied before the battery assembly or at the end of battery assembly.

The battery case used in the present invention may be adopted that is commonly used in the art, there is no limitation on the appearance according to the use of the battery, for example, cylindrical, square, pouch type or coin using a can (coin) type and the like.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Example

Manufacturing example . Single sided porous coating layer Separator  Produce

18: 1 wt% of Al ₂ O ₃ and BaTiO ₃ mixed with polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP) and cyanoethylpolyvinylalcohol in a 9: 1 mixture 2 wt% of one organic was dissolved in acetone to prepare a slurry. The slurry was coated on one surface of a 312HT film manufactured by SK Corporation, a polyolefin-based film, and dried to form a porous coating layer having a thickness of 3 μm.

Example  1. Electrode assembly in which the porous coating layer is in contact with the cathode

Anode manufacturing

A positive electrode mixture slurry was prepared by adding 94 wt% of LiCoO ₂ as a cathode active material, 3 wt% of carbon black as a conductive agent, and 3 wt% of PVdF as a binder to a solvent, N-methyl-2pyrrolidone (NMP). The positive electrode mixture slurry was coated and dried on a thin film of aluminum (Al), which is a positive electrode current collector having a thickness of about 20 μm, which is a positive electrode current collector.

Cathode manufacturing

A negative electrode mixture slurry was prepared by adding carbon powder as a negative electrode active material, PVdF as a binder, and carbon black as a conductive agent at 96 wt%, 3 wt%, and 1 wt%, respectively, to NMP as a solvent. The negative electrode mixture slurry was coated and dried on a thin film of copper (Cu), which is a negative electrode current collector having a thickness of 10 μm, to prepare a negative electrode.

Battery manufacturing

The positive electrode, the negative electrode, and the separator prepared in the above production example are laminated in the order of the positive electrode, the separator, the negative electrode, and the separator, and the porous coating layers of all the separators are disposed to face the negative electrode, wound, and jelly-roll in the form of FIG. 2. An electrode assembly was prepared to prepare a cell.

A lithium secondary battery was prepared by injecting an ethylene carbonate / propylene carbonate / diethyl carbonate (EC / PC / DEC = 30: 20: 50 wt%)-based electrolyte solution in which 1 M lithium hexafluorophosphate (LiPF6) was dissolved. Prepared.

Comparative example  1. Electrode assembly with porous coating layer in contact with anode

A lithium secondary battery was manufactured in the same manner as in Example 1, except that the porous coating layers of all the separators were disposed to contact the positive electrode.

Test Example  1. Cycle Characteristics

Repeated charge / discharge of the batteries of Example 1 and Comparative Example 1 is shown in Figure 3 the results for the cycle characteristics.

3 shows that the battery of Example 1 in which the porous coating layer is in contact with the negative electrode has better cycle characteristics than Comparative Example 1. FIG.

Test Example  2. Separator  Surface inspection

After repeating charging / discharging the batteries of Example 1 and Comparative Example 1, the batteries were disassembled to separate the separators, and SEM photographs of the surfaces of these separators were taken and shown in FIGS. 4 and 5, respectively.

4 and 5, it can be seen that the surface of the separator of Example 1, in which the coating layer was in contact with the cathode, maintained pores, whereas a large number of pores on the surface of the separator of Comparative Example 1 were blocked. there was.

10: first separator 11: porous coating layer
20: second separator 30: positive electrode
40: cathode 100: jelly-roll type electrode assembly
200: jelly-roll type electrode assembly

Claims (9)

The positive electrode, the first separator, the negative electrode and the second separator are sequentially stacked and wound up,
Both the first separator and the second separator are formed only on one surface of the porous substrate and the porous substrate, and include a porous coating layer made of a mixture of inorganic particles and a binder polymer,
And the first separator and the second separator are arranged such that all of their porous coating layers face the cathode. The method of claim 1,
The porous substrate of the first separator and the second separator, each independently, a jelly-roll type electrode assembly comprising a polyolefin-based porous substrate. The method of claim 2,
The polyolefin-based porous substrate is a jelly-roll electrode assembly, characterized in that formed of any one polymer selected from the group consisting of polyethylene, polypropylene, polybutylene and polypentene. The method of claim 1,
The inorganic particles of the porous coating layer of the first separator and the second separator are each independently an inorganic particle selected from the group consisting of inorganic particles having a dielectric constant of 5 or more, inorganic particles having a lithium ion transfer ability, and mixtures thereof. Jelly-roll electrode assembly characterized in that. The method of claim 4, wherein
The inorganic particles having a dielectric constant of 5 or more include BaTiO ₃ , Pb (Zr _x , Ti _{1- x} ) O ₃ (PZT, 0 <x <1), Pb _{1 - x} La _x Zr _{1 -y} Ti _y O ₃ (PLZT hafnia, 0 <x <1, 0 <y <1), (1-x) Pb (Mg 1/3 Nb 2/3) O 3 -xPbTiO 3 (PMN-PT, 0 <x <1), ( HfO ₂ ), SrTiO ₃ , SnO ₂ , CeO ₂ , MgO, NiO, CaO, ZnO, ZrO ₂ , SiO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , SiC and TiO ₂ Jelly-roll type electrode assembly, characterized in that the particles or a mixture of two or more thereof. The method of claim 4, wherein
The inorganic particles having a lithium ion transfer ability include lithium phosphate (Li ₃ PO ₄ ), lithium titanium phosphate (Li _x Ti _y (PO ₄ ) ₃ , 0 <x <2, 0 <y <3), and lithium aluminum titanium phosphate (Li _x Al _y Ti _z (PO ₄ ) ₃ , 0 <x <2, 0 <y <1, 0 <z <3), (LiAlTiP) _x O _y series glass (0 <x <4, 0 <y <13), lithium lanthanum titanate (Li _x La _y TiO ₃ , 0 <x <2, 0 <y <3), lithium germanium thiophosphate (Li _x Ge _y P _z S _w , 0 <x <4 , 0 <y <1, 0 <z <1, 0 <w <5), lithium nitride (Li _x N _y , 0 <x <4, 0 <y <2), SiS ₂ (Li _x Si _y S _z , 0 <x <3, 0 <y <2, 0 <z <4) Series glass and P ₂ S ₅ (Li _x P _y S _z , 0 <x <3, 0 <y <3, 0 <z <7) Jelly-roll type electrode assembly, characterized in that any one of the inorganic particles selected from the group consisting of glass or a mixture of two or more thereof. The method of claim 1,
The binder polymer of the porous coating layer of the first separator and the second separator are each independently polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-trichloroethylene ( polyvinylidene fluoride-co-trichloroethylene, polymethylmethacrylate, polybutylacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate, polyvinylacetate Vinyl alcohol, ethylene vinyl co-vinyl acetate, polyethylene oxide, polyarylate, cellulose acetate, cellulose acetate butyrate ), Cellulose Acetate Pro Cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan, carl Jelly-roll type electrode assembly, characterized in that any one of a binder polymer selected from the group consisting of carboxyl methyl cellulose and a low molecular weight compound having a molecular weight of 10,000 g / mol or less or a mixture of two or more thereof. The method of claim 1,
The composition ratio of the inorganic particles to the binder polymer of the porous coating layer of the first separator and the second separator are independently 10:90 to 99: 1 by weight, characterized in that the jelly-roll electrode assembly. The jelly-roll electrode assembly of any one selected from claim 1 to claim 8; And a case for sealingly accommodating the electrode assembly together with an electrolyte.

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