KR101915339B1 - Separator, separator-electrode composite and electrochemical device comprising the same - Google Patents

Abstract

A porous polymer substrate, a porous coating layer formed on at least one surface of the porous polymer substrate, and an electrode adhesion layer formed on the porous coating layer, wherein the electrode adhesion layer is formed of polymeric binder fibers.

Description

TECHNICAL FIELD The present invention relates to a separator, a separator-electrode composite, and an electrochemical device including the separator,

The present invention relates to a separation membrane, a separation membrane-electrode composite, and an electrochemical device including the same, and more particularly, to a separation membrane, a separation membrane-electrode composite having improved adhesion to an electrode, ≪ / RTI >

Recently, interest in energy storage technology is increasing. As the application fields of cell phones, camcorders, notebook PCs and even electric vehicles are expanding, efforts for research and development of electrochemical devices are becoming more and more specified.

The electrochemical device is one of the most attracting fields in this respect. Of these, the development of a rechargeable secondary battery has become a focus of attention. In recent years, in order to improve the capacity density and the specific energy, Research and development on the design of electrodes and batteries are underway.

Among the currently applied secondary batteries, the lithium secondary battery developed in the early 1990s has advantages such as higher operating voltage and higher energy density than conventional batteries such as Ni-MH, Ni-Cd and sulfuric acid-lead batteries using an aqueous electrolyte solution . However, such a lithium ion battery has a safety problem such as ignition and explosion when using an organic electrolytic solution, and is disadvantageous in that it is difficult to manufacture. Recently, the lithium ion polymer battery improves the weak point of the lithium ion battery and is considered as one of the next generation batteries. However, since the capacity of the battery is relatively low as compared with the lithium ion battery, especially the discharge capacity at the temperature is insufficient, Is urgently required.

Such electrochemical devices are produced in many companies, but their safety characteristics are different. It is very important to evaluate the safety and safety of these electrochemical devices. The most important consideration is that the electrochemical device should not injure the user in case of malfunction. For this purpose, the safety standard strictly regulates the ignition and fuming in the electrochemical device. In the safety characteristics of an electrochemical device, there is a high possibility that explosion may be caused when the electrochemical device is overheated and thermal runaway occurs or the separator penetrates. Particularly, a polyolefin-based porous substrate commonly used as a separator of an electrochemical device exhibits extreme heat shrinkage behavior at a temperature of 100 DEG C or more due to characteristics of the manufacturing process including material properties and elongation, . ≪ / RTI >

In order to solve the safety problem of such an electrochemical device, a separator in which a porous coating layer is formed by coating a mixture of inorganic particles and a binder polymer on at least one surface of a porous substrate having a plurality of pores has been proposed. In the separator, the inorganic particles in the porous porous coating layer formed on the porous substrate serve as a kind of spacer capable of maintaining the physical shape of the porous coating layer, thereby suppressing the heat shrinkage of the porous substrate upon overheating of the electrochemical device. In addition, there is an empty space between the inorganic particles to form micropores.

As such, since a formed separator is required to be bonded to an electrode with a stack and a folding structure in a process, a considerable amount of the adhesive layer must be exposed on the porous substrate layer, which is advantageous for bonding.

However, there is a difficulty in controlling the process of forming a gradient of the coating solution concentration in the thickness direction at the time of forming the adhesive layer by the currently used humidifying separation method. When the coating solution is applied to the separation membrane, the coating solution is applied to the porous substrate or the porous polymer coating layer There is a problem that the electric resistance is absorbed.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and provides a separation membrane including an electrode adhesive layer formed of polymeric binder fibers and minimizing pore clogging while preventing the adhesive layer composition from being absorbed by the porous polymer base material and the porous coating layer.

In addition, the electrode adhesive layer includes polymer binder fibers having an optimal average diameter, and provides excellent cell stability along with improvement of adhesion between the electrode and the separator.

Other objects and advantages of the present invention will become apparent from the following description. It is also to be easily understood that the objects and advantages of the present invention can be realized by the means or method described in the claims, and the combination thereof.

According to one aspect of the present invention, there is provided a porous polymer substrate comprising a porous polymer substrate, a porous coating layer formed on at least one surface of the porous polymer substrate, and an electrode adhesive layer formed on an upper surface of the porous coating layer, A separation membrane formed of a binder fiber is provided.

The average diameter of the polymeric binder fibers may be larger than the pore diameter of the porous polymer base material and the pore diameter of the porous coating layer.

The average diameter of the polymeric binder fibers may be 50 nm or more.

Wherein the polymeric binder fiber is selected from the group consisting of polyvinylidene fluoride polymer, styrene butadiene rubber, polytetrafluoroethylene, polyethylene glycol, polypropylene glycol, toluene diisocyanate, polymethylmethacrylate, polyacrylonitrile, polyvinylpyrrolidone, Polyvinyl acetate, ethylene-co-vinyl acetate, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose , Pullulan, carboxyl methyl cellulose, acrylonitrile-styrene-butadiene copolymer, and polyimide.

The porous coating layer may include inorganic particles and a binder polymer.

The inorganic particles may be any inorganic particles selected from inorganic particles having a dielectric constant of 5 or more and inorganic particles having lithium ion transporting ability, or a mixture of two or more thereof

Wherein the inorganic particles having a constant of dielectric constant of 5 or more are BaTiO ₃ , Pb (Zr, Ti) O ₃ (PZT), Pb _{1 -x} La _x Zr _{1 -y} Ti _y O ₃ , MgO, NiO (0 <y <1), Pb (Mg _1/3 Nb _2/3 ) O ₃ -PbTiO ₃ (PMN-PT), HfO ₂ , SrTiO ₃ , SnO ₂ , CeO ₂ , , CaO, ZnO, ZrO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , SiC and TiO ₂ , or a mixture of two or more thereof.

Wherein the inorganic particles having lithium ion transferring ability are selected from the group consisting of 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 < 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 , x <4, 0 <y < 1, 0 <z <1, 0 <w <5), lithium nitrides _{(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 < 0 < z < 7) series glass.

The binder polymer may be an organic binder polymer or an aqueous binder polymer.

The water-based binder may include a water-dispersible binder polymer and a water-soluble binder polymer.

According to another aspect of the present invention, there is provided a separation membrane-electrode composite including one of the separation membranes and an improved electrode on the upper surface of the separation membrane electrode-bonding layer.

The electrode may be a cathode or an anode.

According to another aspect of the present invention, there is provided an electrochemical device including the above membrane-electrode composite.

The electrochemical device may be a secondary battery.

The present invention can prevent the polymeric binder of the electrode adhesive layer from being absorbed by the porous polymer base material and the porous coating layer without lowering the thermal stability of the separation membrane by forming an electrode adhesive layer including a fiber- The increase in resistance has the advantage of improving the phenomenon and improving the stability of the separator.

In addition, by including the polymer binder fibers having an average diameter of 50 nm or more, a sufficient adhesive force can be obtained while the amount of the adhesive is minimized due to the entanglement between the polymeric binder fibers and the interaction with the surface of the porous coating layer.

In addition, by minimizing the binder of the electrode adhesive layer, the binder in contact with the electrode can be minimized, thereby preventing deterioration in performance of the battery due to the electrode adhesive layer.

Hereinafter, the present invention will be described in detail. Prior to that, the terms or words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms. It should be construed in the meaning and concept consistent with the technical idea of the present invention based on the principle that the concept of the term can be appropriately defined in order to explain it by a method. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention, and not all of the technical ideas of the present invention are described. Therefore, It should be understood that various equivalents and modifications may be present.

The separation membrane according to one aspect of the present invention comprises a porous polymer base material and a porous coating layer formed on at least one side of the porous polymer base material and an electrode adhesive layer formed on the upper surface of the porous coating layer, A separator is provided.

The porous polymer base may be a porous polymer film base or a porous polymer nonwoven base.

The porous polymeric film substrate may be a porous polymeric film made of a polyolefin such as polyethylene or polypropylene. The polyolefin porous polymeric film substrate exhibits a shutdown function at a temperature of, for example, 80 to 130 ° C.

At this time, the polyolefin porous polymer film may be formed by mixing polyolefin-based polymers such as polyethylene, polypropylene, polybutylene, and polypentene, such as high density polyethylene, linear low density polyethylene, low density polyethylene and ultra high molecular weight polyethylene, .

In addition, the porous polymeric film substrate may be produced by molding various polymeric materials such as polyester in addition to polyolefin. In addition, the porous polymeric film substrate may have a structure in which two or more film layers are laminated, and each film layer may be formed of a polymer such as polyolefin or polyester described above, or a polymer in which two or more polymers are mixed have.

In addition, the porous polymer film base and the porous nonwoven base material may be formed of a material selected from the group consisting of polyethyleneterephthalate, polybutyleneterephthalate, polyester, polyacetal, polyamide, Polycarbonate, polyimide, polyetheretherketone, polyethersulfone, polyphenylene oxide, polyphenylenesulfide, polyethylenenaphthalene, polyetherketone, polyetherketone, polyetherketone, And the like may be used alone or in the form of a mixture thereof.

The thickness of the porous substrate is not particularly limited, but is preferably from 5 to 50 nm. The size of the pores present in the porous substrate should be smaller than that of the polymer binder fiber of the electrode adhesive layer, preferably 0.001 to 50 nm, The porosity is preferably 0.1 to 99%.

In the separation membrane according to an embodiment of the present invention, the porous coating layer may be formed on one side or both sides of the porous polymer base material, and may include inorganic particles and a binder polymer. The interstitial volume is formed between the inorganic particles, and the interstitial volume between the inorganic particles becomes an empty space to form pores. do.

That is, the binder polymer adheres the inorganic particles to each other so that the inorganic particles can remain bonded to each other. For example, the binder polymer bonds and fixes the inorganic particles. In addition, the pores of the porous coating layer are formed as interstitial volumes between the inorganic particles as voids, and the pores of the porous coating layer are formed as pores formed by the inorganic particles substantially enclosed in the packed structure (closed packed or densely packed) It is the space defined by the particles. A path through which lithium ions necessary for operating the battery through the pores of the porous coating layer can be provided.

The inorganic particles are not particularly limited as long as they are electrochemically stable. That is, the inorganic particles usable in the present invention are not particularly limited as long as oxidation and / or reduction reaction does not occur in the operating voltage range of the applied electrochemical device (for example, 0 to 5 V based on Li / Li ⁺ ). Particularly, when inorganic particles having a high dielectric constant are used as the inorganic particles, the dissociation of the electrolyte salt, for example, the lithium salt in the liquid electrolyte, can be increased, and the ion conductivity of the electrolyte can be improved.

For the reasons stated above, the inorganic particles may include high-permittivity inorganic particles having a dielectric constant of 5 or more, preferably 10 or more, or inorganic particles having lithium ion transferring ability or a mixture thereof.

Nonlimiting examples of 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, 0 <x <} 1, 0 <y <1), (1-x) Pb (Mg 1/3 Nb 2/3) O 3 -xPbTiO 3 (PMN-PT, 0 <x <1), Wherein the metal oxide selected from the group consisting of hafnia (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 Inorganic particles such as one or a mixture of two or more of them not only exhibit a high dielectric constant characteristic with a dielectric constant of 100 or more but also exhibit piezoelectricity in which a charge is generated when a certain pressure is applied and then a potential is generated, ), It is possible to prevent internal short-circuiting of both electrodes due to an external impact, thereby improving the stability of the electrochemical device.

In addition, the inorganic particles having lithium ion transferring ability mean inorganic particles containing a lithium element and having a function of transferring lithium ions without storing lithium. Non-limiting examples of inorganic particles having lithium ion transferring ability include lithium phosphate (Li ₃ PO ₄ ), lithium titanium phosphate (Li _x Ti _y (PO ₄ ) ₃ , 0 <x < 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 (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 Mani Titanium (Li _x Ge _y P _z S _{w, 0 <x <4,} 0 <y <1, 0 <z <1, 0 <w <5), lithium nitrides _{(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 < y < 3, 0 < z < 7) series glass or a mixture thereof. When the above-mentioned high-permittivity inorganic particles and inorganic particles having lithium ion transferring ability are mixed, their synergistic effect can be doubled.

The inorganic particle size of the porous coating layer is not limited, but it is preferably in the range of 0.001 to 10 nm for the formation of a coating layer having a uniform thickness and proper porosity.

The polymeric binder for forming the porous coating layer may be any organic binder polymer or an aqueous binder polymer, although inorganic binders and binders that can be used in the formation of the porous coating layer may be used without limitation.

Non-limiting examples of the organic binder polymer include polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene (polyvinylidene fluoride- ), Polymethylmethacrylate, polybutylacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate, ethylene vinyl acetate copolymer (polyethylene polyvinyl acetate, polyvinyl acetate, polyvinyl acetate, polyvinyl acetate, polyethylene oxide, polyarylate, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, No ethylfuran (cya noethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan, and carboxyl methyl cellulose. The term &quot; methylcellulose &quot;

The aqueous binder polymer includes a water-dispersible binder polymer that does not dissolve in water but has dispersibility, and a water-soluble binder polymer that is soluble in water.

The water-dispersible binder polymer may be a rubber or a water-dispersible (meth) acrylic polymer. The polymer is excellent in elasticity and functions as a buffer against changes in the volume during charging / discharging of electricity. Also, since the adhesive strength is excellent, it is possible to maintain the structure of the electrode for a long time even if the electrode is used for a long time.

Non-limiting examples of such rubbers include styrene butadiene rubber (SBR), acrylonitrile-butadiene rubber, and acrylonitrile-butadiene-styrene rubber. It is preferable to use at least one selected from the group.

The water-dispersible (meth) acrylic polymer may be at least one selected from the group consisting of polyethyl acrylate, polyethyl methacrylate, polypropyl acrylate, polypropyl methacrylate, polyisopropyl acrylate, polyisopropyl methacrylate, , One selected from the group consisting of polybutyl methacrylate, polyhexyl acrylate, polyhexyl methacrylate, polyethylhexyl acrylate, polyethylhexyl methacrylate, polylauryl acrylate and polylauryl methacrylate Or more.

The water-soluble binder polymer plays a role of smoothly coating the slurry on the porous polymer base material, and increases the dispersibility of the inorganic particles and the water-dispersible binder polymer used together. That is, in the slurry for separator coating according to the present invention, the water-dispersible binder polymer binds the inorganic particles and, at the same time, the water-soluble binder facilitates the binding between the inorganic particles and the inorganic particles and the porous polymer base material, An excellent separator can be provided.

Examples of the water-soluble polymer which can be used in the present invention include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, ethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, Phosphorylated starch, and casein. These compounds may be used in combination.

The composition ratio of the inorganic particles and the binder polymer in the porous coating layer of the separator according to an exemplary embodiment of the present invention is preferably in the range of 50:50 to 99: 1, more preferably 70:30 to 95: 5 . When the content ratio of the inorganic particles to the binder polymer is less than 50:50, the content of the polymer is increased and the improvement of the thermal stability of the separator may be deteriorated. In addition, the pore size and porosity due to the reduction of the void space formed between the inorganic particles may be reduced, resulting in deterioration of the final cell performance. If the content of the inorganic particles exceeds 99 parts by weight, the fillerability of the porous coating layer may be weakened because the content of the binder polymer is too small. The peeling resistance of the porous coating layer composed of the inorganic particles and the binder polymer may be weakened. The thickness of the porous coating layer composed of the inorganic particles and the binder polymer is not particularly limited, but is preferably in the range of 0.001 to 20 mu m.

The pore diameter is preferably smaller than the average diameter of the polymeric binder fibers of the electrode adhesive layer, and the porosity is preferably in the range of 10 to 99%. The pore diameter and porosity mainly depend on the size of the inorganic particles. For example, when inorganic particles having a particle size of 1 nm or less are used, the pores formed are also about 1 nm or less. Such a pore structure is filled with an electrolyte solution to be injected at a later stage, and the filled electrolyte serves as an ion transfer function.

In the separation membrane according to an embodiment of the present invention, an electrode adhesion layer is provided on the upper surface of the porous coating layer, and the electrode adhesion layer serves to bond the electrode and the separation membrane. At this time, the electrode adhesive layer includes a polymer binder in a fiber form in order to prevent the adhesive layer composition from penetrating into the pores of the porous coating layer or the pores of the porous substrate to block the pores.

At this time, since the polymer binder fibers contained in the electrode adhesive layer can be mutually entangled, they are not absorbed into the pores, and in order to more completely block the absorption into the porous polymer base material or the porous coating layer, the average diameter of the polymeric binder fibers, The pore diameter of the substrate and the pore diameter of the porous coating layer are preferably 50 nm, more preferably 50-100 nm.

When the diameter of the polymeric binder fiber is less than 50 nm, there is a problem that the binder for forming the electrode-adhesive layer is absorbed by the porous polymer base material or the porous coating layer and the resistance increases.

The polymeric binder fiber forming the electrode bonding layer may be coated on the surface of the porous coating layer and may be bonded to the electrode without limitation. Preferably, the polymeric binder fiber is a polyvinylidene fluoride polymer, styrene butadiene rubber, polytetrafluoroethylene, Polyethylene glycol, polyethylene glycol, polypropylene glycol, toluene diisocyanate, polymethylmethacrylate, polyacrylonitrile, polyvinylpyrrolidone, polyvinylacetate, ethylene-co-vinyl acetate, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, Cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose, pullulan, carboxyl methyl cellulose, acrylonitrile-styrene-butadiene copolymer and polyimide to Emitter may be at least one selected.

According to another aspect of the present invention, there is provided a separation membrane-electrode composite including the above-described separation membrane and an electrode formed on an upper surface of the electrode adhesion layer of the separation membrane, wherein the electrode may be a cathode or an anode.

The cathode or the anode may include an electrode current collector and an electrode active material layer, and the electrode current collector may include stainless steel; aluminum; nickel; titanium; Fired carbon; Copper; Stainless steel surface-treated with carbon, nickel, titanium or silver, aluminum-cadmium alloy, or the like can be used.

At this time, the electrode active material layer used for the cathode is composed of LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , LiCoPO ₄ , LiFePO ₄ , LiNiMnCoO _2, and LiNi _{1 -x-yz} Co _x M _y M2 _z O ₂ X, y and z are independently selected from the group consisting of Al, Ni, Co, Fe, Mn, V, Cr, Ti, W, Ta, Mg and Mo, 0? X <0.5, 0? Y <0.5, 0? Z <0.5, 0 <x + y + z? 1).

In addition, the electrode active material layer used for the anode may be made of natural graphite, artificial graphite, a carbonaceous material, a lithium-containing titanium composite oxide (LTO), metals such as Si, Sn, Li, Zn, Mg, Cd, Ce, ); An alloy composed of the metal (Me); An oxide of the metal (Me) (MeOx); And a composite of the metal (Me) and carbon, and the like.

At this time, the cathode and the anode use an electrode composition including an electrode active material, a binder, a solvent and optionally a conductive material to form an electrode active material layer on the current collector. At this time, the method of forming the electrode active material layer may be a method of directly coating the electrode active material composition on the current collector or a method of coating the electrode active material composition on a separate support and drying and then peeling the film from the support to form a film on the current collector There is a way to laminate. Here, the support may be any support capable of supporting the active material layer. Examples of the support include mylar film, polyethylene terephthalate (PET) film, and the like.

The binder, the conductive material, and the solvent may be those conventionally used in the production of lithium secondary batteries.

Specifically, the binder may include vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethylmethacrylate ) And mixtures thereof can be used. Examples of the conductive material include carbon black or acetylene black, and examples of the solvent include acetone and N-methylpyrrolidone.

According to another aspect of the present invention, there is provided an electrochemical device including the above-described membrane-electrode composite, wherein the electrochemical device includes all devices that perform an electrochemical reaction, and specific examples thereof include all kinds of primary, A capacitor, such as a battery, a fuel cell, a solar cell, or a super capacitor element. Particularly, the secondary battery is preferably a lithium secondary battery including a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.

While the present invention has been described with reference to the particular embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, And various modifications and variations are possible within the scope of the appended claims.

Claims (14)

Porous polymeric substrates;
A porous coating layer formed on at least one surface of the porous polymer substrate; And
And an electrode bonding layer coated on the upper surface of the porous coating layer,
Wherein the porous coating layer comprises inorganic particles and a binder polymer,
Wherein the electrode adhesive layer is formed of a polymeric binder fiber,
Wherein the polymeric binder fiber has a diameter larger than a pore diameter of the porous polymer substrate and a pore diameter of the porous coating layer.
delete The method according to claim 1,
Wherein the average diameter of the polymeric binder fibers is 50 nm or more. The method according to claim 1,
Wherein the polymeric binder fiber is selected from the group consisting of polyvinylidene fluoride polymer, styrene butadiene rubber, polytetrafluoroethylene, polyethylene glycol, polypropylene glycol, toluene diisocyanate, polymethylmethacrylate, polyacrylonitrile, polyvinylpyrrolidone, Polyvinyl acetate, ethylene-co-vinyl acetate, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethylpullulan, cyanoethylpolyvinyl alcohol, cyanoethyl cellulose, cyanoethyl sucrose , Pullulan, carboxyl methyl cellulose, acrylonitrile-styrene-butadiene copolymer, and polyimide. The method according to claim 1,
Wherein the porous coating layer comprises inorganic particles and a binder polymer. 6. The method of claim 5,
Wherein the inorganic particles are inorganic particles selected from inorganic particles having a dielectric constant of 5 or more and inorganic particles having a lithium ion transporting ability, or a mixture of two or more thereof. The method according to claim 6,
Wherein the inorganic particles having a dielectric constant of 5 or more are 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 0 <x <1, 0 < y <1), (1-x) Pb (Mg 1/3 Nb 2/3) O 3 -xPbTiO 3 (PMN-PT, 0 <x <1), hafnia (HfO ₂ ), at least one inorganic particle selected from the group consisting of 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 Or a mixture of two or more thereof. The method according to claim 6,
Wherein the inorganic particles having lithium ion transferring ability are selected from the group consisting of 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 < 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 , x <4, 0 <y < 1, 0 <z <1, 0 <w <5), lithium nitrides _{(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 < 0 < z < 7) series glass. 6. The method of claim 5,
Wherein the binder polymer is an organic binder polymer or an aqueous binder polymer. 10. The method of claim 9,
Wherein the water-based binder comprises a water-dispersible binder polymer and a water-soluble binder polymer. 11. A separation membrane-electrode composite comprising a separation membrane according to any one of claims 1 to 10 and an electrode formed on an upper surface of the electrode adhesion layer of the separation membrane. 12. The method of claim 11,
Wherein the electrode is a cathode or an anode. 11. An electrochemical device comprising the membrane-electrode composite of claim 11. 14. The method of claim 13,
Wherein the electrochemical device is a secondary battery.