KR20210001421A - Seperator and method for preparing the same - Google Patents

Abstract

The present invention relates to a separation membrane and a manufacturing method thereof. More specifically, since the separation membrane has an adhesive nanofiber coating layer formed on both sides of a base part, the separation membrane can be applied without limitation to the separation membrane of an electrochemical device. In particular, when the separation membrane including the adhesive nanofiber coating layer is applied to a water capacitor including an aqueous electrolyte, it is possible to minimize a decrease in energy performance and improve adhesion between the electrode and the separation membrane at the same time.

Description

Separator and its manufacturing method {SEPERATOR AND METHOD FOR PREPARING THE SAME}

The present invention relates to a separator and a method of manufacturing the same.

Electrochemical capacitors are devices that store electrical energy by forming an electrical double layer between the surface of an electrode and an electrolyte. In this case, since electricity is not generated by a chemical reaction like a battery and is simply stored by an electric double layer, it does not damage the electrode itself, so the lifespan is long, and the charge/discharge time is not long, so that a large amount of current can be stored in a short time. However, the energy density that can be stored is low because it uses physical adsorption of ions. Therefore, this device is an important electrical storage device when high power is required.

In particular, the necessity of an energy storage device having an appropriate energy density and output is increasing recently. As an energy storage device having higher energy density than conventional capacitors and higher output than general lithium-ion batteries, studies on super capacitors are being conducted.

These supercapacitors can be simply classified into electrical doublelayer capacitors (EDLC) and pseudo capacitors according to the method of energy storage mechanism. In particular, the water capacitor may exhibit a larger specific capacitance by using a surface oxidation-reduction reaction. As described above, various studies on water capacitors using reversible oxidation/reduction reactions at the electrode/electrolyte interface have been conducted.

In general, an energy storage device includes a structure in which a plurality of cells are stacked, and at this time, adhesion between the separator and the electrode is required, and if sufficient adhesion is not made during the adhesion, the electrode or the separator may be separated, and an irregular shape Can be stacked.

Among the energy storage devices, the adhesion method by PVDF (polyvinylidene fluoride) coating, which is an adhesion method mainly used in water capacitors using an aqueous electrolyte, has excellent adhesion due to the hydrophobic properties of the PVDF coating, but greatly deteriorates the performance of the electrode. There is a problem to let you.

Japanese Patent Laid-Open No. 2018-147769 discloses a separator in which a porous layer including a binder resin and cellulose fibers is formed on at least one surface, but there is a problem in that the performance of the electrode is deteriorated due to the hydrophobic property of the binder resin.

In addition, Korean Patent Application Publication No. 2013-0091781 discloses a separator in which a slurry including a hydrophilic polymeric binder and cellulose fibers is formed, but there is also a problem in that the performance of the electrode is deteriorated.

Accordingly, there is a need to develop a technology capable of bonding an electrode and a separator in an energy storage device, in particular, a technology capable of bonding an electrode and a separator without deteriorating the energy characteristics of a water capacitor using an aqueous electrolyte.

Japanese Patent Publication No. 2018-147769 Korean Patent Publication No. 2013-0091781

As a result of conducting various studies to solve the above problems, the present inventors formed a coating layer containing adhesive nanofibers prepared in the form of nanofibers of an adhesive polymer on both sides of a porous support containing a polyolefin resin Was prepared, and it was confirmed that when the prepared separator was applied to a water capacitor using an aqueous electrolyte, the adhesive performance was excellent and the energy characteristics were not reduced.

Accordingly, an object of the present invention is to provide a separator having excellent adhesion performance and a method for manufacturing the same without deteriorating the energy performance of the electrode.

In addition, another object of the present invention is to provide an electrochemical device including such a separator.

In order to achieve the above object, the present invention comprises a substrate portion: and an adhesive nanofiber coating layer formed on both sides of the substrate portion, Provide a separator.

The adhesive nanofiber coating layer may include adhesive nanofibers including an adhesive polymer.

The adhesive polymer may include one or more selected from the group consisting of polyvinylidene fluoride (PVDF), polyvinyl butyral (PVB), polyvinyl alcohol (PVA), and polyacrylic acid (PA).

The diameter of the adhesive nanofiber may be 50 to 200 nm.

The thickness of the adhesive nanofiber coating layer may be 0.5 to 20 μm.

The content of the adhesive nanofiber may be 1 to 10% by weight based on the total weight of the adhesive nanofiber coating layer.

The base portion is a porous film, non-woven fabric, or a mixture of two or more selected from the group consisting of polyolefin-based resins, fluorine-based resins, polyester-based resins, polyacrylonitrile resins, cellulose-based materials, and copolymers thereof. It may include a layered structure of more than one layer.

The present invention also includes the steps of (S1) dissolving the adhesive polymer in a solvent to form a spinning solution for forming adhesive nanofibers; (S2) forming adhesive nanofibers using the spinning solution, and applying it to one surface of the substrate; (S3) forming an adhesive nanofiber coating layer on both surfaces of the substrate by repeating the process of winding and unwinding the substrate portion coated with the adhesive nanofibers; comprising, a method for manufacturing a separator Provides.

The solvents include dimethyl carbonate, dimethyl formamide, N-methyl formamide, sulfolane (tetrahydrothiophene-1,1-dioxide), 3-methylsulfolane, N-butyl sulfone, dimethyl sulfoxide, pyloridinone ( HEP), dimethylpiperidone (DMPD), N-methyl pyrrolidinone (NMP), N-methyl acetamide, dimethyl acetamide (DMAc), dimethylformamide (DMF), diethylacetamide (DEAc) dipropylacet One selected from the group consisting of amide (DPAc), ethanol, propanol, butanol, hexanol, ethylene glycol, tetrachloroethylene, propylene glycol, toluene, trpentine, methyl acetate, ethyl acetate, petroleum ether, acetone, cresol and glycerol It may be an organic solvent containing the above.

The present invention also provides an electrochemical device including the separation membrane.

The electrochemical device may be a Pseudo Capacitor.

According to the separator of the present invention, since the adhesive nanofiber coating layer is formed on both sides of the base portion, when applied to a separator of an electrochemical device, adhesion between the electrode and the separator can be improved.

In addition, the adhesive nanofiber coating layer has a porous structure including pores formed by adhesive nanofibers, and has a large specific surface area, so that it can exhibit excellent adhesive properties even when a small amount of nanofibers is applied.

In addition, since both the adhesive nanofiber coating layer and the substrate portion have a porous structure, it does not interfere with the movement of the electrolyte, so that energy reduction of the electrochemical device can be minimized. When water is used as an electrolyte, resistance increases when coating with a hydrophobic polymer having adhesive properties in the water capacitor, and the output of the capacitor rapidly decreases. In addition, when bonding using a hydrophilic polymer having adhesive properties, it is used as an electrolyte. Dissolution, elution, or swelling occurs due to the used water, so that the output gradually decreases during the charging and discharging process of the capacitor, but the separator of the present invention can prevent such a problem.

In addition, since the separator according to the present invention has a structure in which adhesive nanofiber coating layers including adhesive nanofibers are formed on both sides of the substrate portion on both sides, a positive electrode, a negative electrode, and a separator are sequentially stacked to provide sufficient battery cells. Can be stacked. When the anode, the cathode, and the separator are sequentially stacked, it is possible to manufacture a capacitor with a high energy density, and there is an effect of stably charging and discharging.

1 is a schematic diagram showing a cross-section of a separator according to an embodiment of the present invention.
2 shows SEM (scanning electron microscope) images of the separation membranes of Example 1 and Comparative Example 3.

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

Separator

The present invention relates to a separator applicable to an electrochemical device.

1 is a schematic diagram showing a cross-section of a separator according to an embodiment of the present invention.

Referring to FIG. 1, the separation membrane 1 may have an adhesive nanofiber coating layer 20 formed on both surfaces of a base portion 10.

In the present invention, the adhesive nanofiber coating layer may include adhesive nanofibers including an adhesive polymer. That is, the adhesive nanofiber may mean that an adhesive polymer is manufactured in the form of nanofibers. The adhesive nanofiber coating layer has a porous structure formed by the adhesive nanofibers, in other words, the adhesive nanofiber coating layer may include adhesive nanofibers and pores.

In the present invention, the adhesive polymer may allow sufficient adhesion between the separator and the electrode, so that the separator or the electrode does not come off.

The adhesive polymer is polyvinylidene fluoride (PVDF), polyvinyl butyral (PVB), polyvinyl alcohol (PVA), polyacrylic acid (PA), fluoride- Hexafluoropropylene (polyvinylidene fluoride-co-hexafluoropropylene, PVDF-HFP), polyvinylidene fluoride-co-trichloroethylene, polymethylmethacrylate, polyacrylonitrile ), polyvinylacetate, ethylene vinyl acetate copolymer (polyethylene-covinylacetate), polyimide, and polyethylene oxide.It may be at least one hydrophobic binder selected from the group consisting of.

In the present invention, since the adhesive nanofiber is included in the adhesive nanofiber coating layer to have a high specific surface area, the adhesive strength can be improved by substantially increasing the adhesive area between the separator and the electrode. In addition, due to the nanofibers, even after the separator is adhered to the electrode, the adhesive nanofiber coating layer maintains a porous shape including pores, so that the electrolyte can smoothly move through the pores, thereby reducing the energy of the electrochemical device. The reduction can be minimized.

The diameter of the nanofibers may be 50 to 200 nm, preferably 60 to 150 nm, more preferably 70 to 100 nm. When the diameter of the nanofibers is less than 50 nm, the durability of the adhesive nanofiber coating layer may be deteriorated, and when the diameter of the nanofibers is more than 200 nm, the effect of increasing the specific surface area is insignificant, so that the adhesion may be difficult to improve, and the electrolyte may be difficult to move. That is, when the diameter of the nanofibers exceeds 200 nm, it is difficult to pass lithium ions contained in the solution solution through the pores of the porous structure formed by the nanofibers, thereby reducing energy performance.

In addition, the adhesive nanofiber may be included in an amount of 1 to 10% by weight, preferably 1 to 6% by weight, more preferably 2 to 5% by weight, based on the total weight of the adhesive nanofiber coating layer. If the content of the adhesive nanofiber is less than 1% by weight, the porous structure is not formed in the desired shape in the adhesive coating layer, making it difficult to move the electrolyte, thereby reducing the energy performance of the electrochemical device, and the adhesion may be reduced. In addition, if it exceeds 10% by weight, durability may decrease when the separator and the electrode are adhered.

In the present invention, the adhesive nanofiber coating layer may have a thickness of 0.5 to 20 µm, preferably 0.5 to 5 µm, and more preferably 0.5 to 1 µm. When the thickness of the adhesive nanofiber coating layer is less than 0.5 µm, durability may decrease when the separator and the electrode are bonded, and when it exceeds 20 µm, the adhesive nanofiber coating layer may act as a resistance in the electrochemical device.

In addition, the adhesive nanofiber coating layer has a porous structure, and the porosity of the pores may be 50 to 95%, preferably 75 to 95%, more preferably 85 to 95%. If the porosity is less than 50%, the mobility of the electrolyte is small, so that the performance of the electrochemical device may be deteriorated. If the porosity is greater than 95%, durability may be reduced when the separator and the electrode are bonded.

In the present invention, the substrate portion may be a porous support, and specifically, the substrate portion from the group consisting of a polyolefin resin, a fluorine resin, a polyester resin, a polyacrylonitrile resin, a cellulose-based material, and a copolymer thereof. Any one or a mixture of two or more selected may include a porous film, a nonwoven fabric, or a laminated structure of two or more layers.

The polyolefin-based resin may be one or more selected from polyethylene, polypropylene, polybutylene and polypentene, and the fluorine-based resin may be one or more selected from polyvinylidene fluoride and polytetrafluoroethylene, and the The polyester resin may be at least one selected from polyethylene terephthalate and polybutylene terephthalate.

In addition, the base portion may be a porous support having a porosity of 10 to 80% by volume, or 30 to 60% by volume of micropores having an average pore diameter of 0.01 to 20 μm, or 0.01 to 1 μm. Excellent mechanical strength can be maintained by including micropores having an average pore diameter in the above range within the above-described porosity range, and ionic material can more smoothly move between the positive electrode and the negative electrode of the battery.

Method of manufacturing a separator

The present invention also includes the steps of (S1) dissolving the adhesive polymer in a solvent to form a spinning solution for forming adhesive nanofibers; (S2) forming adhesive nanofibers using the spinning solution and applying them to one surface of the substrate; (S3) forming an adhesive nanofiber coating layer on both surfaces of the substrate by repeating the process of winding and unwinding the substrate portion coated with the adhesive nanofibers; comprising, a method for manufacturing a separator It is about.

In the above (S1), the adhesive polymer may be dissolved in a solvent to prepare a spinning solution for forming adhesive nanofibers. At this time, the type of the adhesive polymer is the same as previously mentioned.

The solvent may be an organic solvent, and the organic solvent is dimethyl carbonate, dimethyl formamide, N-methyl formamide, sulfolane (tetrahydrothiophene-1,1-dioxide), 3-methylsulfolane, N-butyl Sulfone, dimethyl sulfoxide, pyrolidinone (HEP), dimethyl piperidone (DMPD), N-methyl pyrrolidinone (NMP), N-methyl acetamide, dimethyl acetamide (DMAc), dimethylformamide (DMF), Diethylacetamide (DEAc) Dipropylacetamide (DPAc), ethanol, propanol, butanol, hexanol, ethylene glycol, tetrachloroethylene, propylene glycol, toluene, trpentin, methyl acetate, ethyl acetate, petroleum ether, acetone, It may be one or more selected from the group consisting of cresol and glycerol, preferably dimethylformamide (DMF) or a mixed solvent of dimethylformamide and ethanol.

The concentration of the spinning solution may be 10 to 25%, preferably 12 to 23%, more preferably 15 to 20%, based on the weight of the solid content. If the concentration of the spinning solution is less than 10%, it is not applied in the form of nanofibers, and is applied to the separator in the form of polymer beads, thereby blocking the surface of the separator. When the concentration of the spinning solution is 25% or more, the concentration of the polymer solution increases and the viscosity increases. Due to this, it is impossible to apply nanofibers, or fibers having a micrometer diameter other than nanofibers may be formed. In this case, the output of the capacitor can be reduced by acting as a resistor at the electrode.

In the step (S2), the adhesive nanofiber may be formed and applied to one surface of the substrate. In this case, the adhesive nanofiber may be performed by electrospinning, solution blowing, or force spinning using a centrifugal force using the spinning solution prepared in step (S1), but is not limited thereto. A commonly used nanofiber manufacturing method can be used. That is, while the adhesive nanofiber is formed by the spinning solution, it may be applied to one surface of the substrate.

In the step (S3), the process of winding and unwinding the substrate on which the adhesive nanofibers are applied is repeated to apply the nanofibers to form an adhesive nanofiber coating layer on both sides of the substrate. can do.

That is, after applying the adhesive nanofibers to one surface of the substrate, the winding and unwinding processes may be repeated so that the adhesive nanofibers can be newly applied to the other surface.

Electrochemical device

The present invention also relates to an electrochemical device including the separation membrane. The electrochemical device may be a water capacitor including an aqueous electrolyte.

An electrochemical device according to an aspect of the present invention includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, and the separator is a porous separator according to an embodiment of the present invention.

Such an electrochemical device includes all devices that undergo an electrochemical reaction, and specific examples include all types of primary and secondary batteries, fuel cells, solar cells, or capacitors such as supercapacitor devices. Particularly, among the secondary batteries, lithium secondary batteries including lithium metal secondary batteries, lithium ion secondary batteries, lithium polymer secondary batteries or lithium ion polymer secondary batteries are preferred.

The positive electrode and the negative electrode to be applied together with the porous separator of the present invention are not particularly limited, and an electrode active material may be prepared in a form bound to an electrode current collector according to a conventional method known in the art. As a non-limiting example of the positive electrode active material among the electrode active materials, a conventional positive electrode active material that can be used for the positive electrode of a conventional electrochemical device may be used, and in particular, lithium manganese oxide, lithium cobalt oxide, lithium nickel oxide, lithium iron oxide, or a combination thereof It is preferable to use one lithium composite oxide. As a non-limiting example of the negative electrode active material, a conventional negative electrode active material that can be used for the negative electrode of a conventional electrochemical device may be used, and in particular, lithium metal or lithium alloy, carbon, petroleum coke, activated carbon, Lithium adsorption materials such as graphite or other carbons are preferred. Non-limiting examples of the positive electrode current collector include aluminum, nickel, or a foil manufactured by a combination thereof, and non-limiting examples of the negative electrode current collector include copper, gold, nickel, or a copper alloy or a combination thereof. Manufactured foils and the like.

The electrolytic solution that can be used in the electrochemical device of the present invention may be an aqueous electrolytic solution containing water. In addition, further to the electrolytic solution is A ⁺ B ^- A salt of the structure, such as, A ⁺ is Li ^+, Na ^+, K ⁺ comprises an alkaline metal cation or an ion composed of a combination thereof, such as, 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 (CF 2 SO 2 ) A salt containing an ion consisting of an anion or a combination thereof such as ₃ ^- is 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), ethylmethyl carbonate (EMC), gamma butyrolactone (g-butyrolactone) Alternatively, there may be dissolved or dissociated in an organic solvent composed of a mixture thereof, but is not limited thereto.

The electrolyte injection may be performed at an appropriate step in the battery manufacturing process according to the manufacturing process and required physical properties of the final product. That is, it can be applied before battery assembly or at the final stage of battery assembly.

The present invention also provides a battery module including the water capacitor as a unit cell.

The battery module can be used as a power source for medium and large-sized devices that require high temperature stability, long cycle characteristics, and high capacity characteristics.

Examples of the medium and large-sized devices include a power tool that is powered by an omniscient motor and moves; Electric vehicles including electric vehicles (EV), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like; Electric two-wheeled vehicles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf cart; Power storage systems, etc., but are not limited thereto.

Hereinafter, preferred embodiments are presented to aid the understanding of the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. It is natural that changes and modifications fall within the scope of the appended claims.

Example 1: Preparation of a separator having an adhesive nanofiber coating layer formed on both sides

As a raw material for forming an adhesive coating layer on both sides of the separator, the adhesive polymer is 16% by weight of PVDF (Zheijijiang, Zheflon FL2606) in a mixed solvent in which DMF (dimethylformamide) and acetone are mixed in a weight ratio of 50:50. It was dissolved in to prepare a spinning solution. Using an electrospinning machine (Nano NC, Electrospinning machine), PVDF nanofibers with a diameter of 90 nm were prepared as the nanofibers, and PVDF nanofibers were formed by the spinning process and applied to one surface of the substrate. As the substrate part, a polyolefin-based porous support (Vilene) was used.

Thereafter, by winding the polyolefin-based porous support so that the surface on which the PVDF nanofibers are applied is wound inside, the PVDF nanofibers are applied to the other surface of the polyolefin-based porous support to which the coating liquid is not applied. Applied.

By repeating the above winding and unwinding process three times, an adhesive nanofiber layer having a thickness of 1.0 μm was formed on both surfaces of the polyolefin-based porous support to prepare a powder film.

Example 2: Manufacture of a water capacitor including a separator having an adhesive nanofiber coating layer formed on both sides

70% by weight of LiMn ₂ O ₄ as a positive electrode active material, 20% by weight of acetylene black as a conductive material, and 10% by weight of polyvinylidene fluoride (PVDF) as a binder, and N- A positive electrode mixture slurry was prepared by adding methylpyrrolidone (NMP, N-Methylpyrrolidone). The positive electrode mixture slurry was coated on a nickel (Ni) thin film of a positive electrode current collector having a thickness of about 10 μm, dried to prepare a positive electrode, and then roll press to manufacture a positive electrode.

In addition, LiTi ₂ (PO ₄ ) ₃ as a negative electrode active material, polyvinylidene fluoride (PVDF, polyvinylidene fluoride) as a binder, and acetylene black as a conductive material in 70% by weight, 10% by weight and 20% by weight, respectively. Then, it was added to N-methylpyrrolidone (NMP, N-Methylpyrrolidone) as a solvent to prepare a negative electrode mixture slurry. The negative electrode mixture slurry was coated on a nickel (Ni) thin film of a negative electrode current collector having a thickness of about 10 μm, dried to prepare a negative electrode, and then roll press to prepare a negative electrode.

After sequentially stacking the anode, the separator prepared in Example 1, and the cathode, a water capacitor was manufactured using a thermocompression bonding method. It was compressed to a thickness of 60° C. and 150 μm, and an aqueous electrolyte containing 1M Li ₂ SO ₄ , which is an aqueous electrolyte, was used as the electrolyte.

Comparative Example 1

A separator was prepared in the same manner as in Example 1, except that adhesive nanofibers having a diameter of 220 nm prepared by the electrospinning process were used.

Comparative Example 2

A water capacitor was manufactured in the same manner as in Example 2, except that the separator prepared in Comparative Example 1 was used instead of the separator prepared in Example 1.

Comparative Example 3

A polyolefin-based porous support (Vilene) having no adhesive nanofiber coating layer formed on both sides was prepared as a separator.

Comparative Example 4

A water capacitor was manufactured in the same manner as in Example 2, except that the separator of Comparative Example 3 was used instead of the separator prepared in Example 1.

Experimental Example 1: Confirmation of the surface of the separator

The surfaces of the separator prepared in Example 1, on which the adhesive nanofiber coating layer was formed on both sides, and the separator prepared in Comparative Example 3, in which the adhesive nanofiber coating layer was not formed on both sides, were observed.

2 shows SEM (scanning electron microscope) images of the separation membranes of Example 1 and Comparative Example 3.

2, in the case of the separator of Example 1, nanofibers having an average diameter of 64.3 ± 20.1 nm were observed, and it can be seen that an adhesive nanofiber coating layer including adhesive nanofibers formed on the surface of the separator was formed. .

On the other hand, in the case of the separator of Comparative Example 1, fibers having an average diameter of 1.90 μm were observed, indicating that the adhesive nanofiber coating layer was not formed on the surface of the separator.

Experimental Example 2: Measurement of energy density

For the water capacitors manufactured in Example 2, Comparative Example 2, and Comparative Example 4, respectively, energy density (Specific energy) was measured using a constant current measurement method (Biologic Co., Ltd.), and is shown in Table 1 below.

Energy output
(Specific energy, kW/kg) 2 kW/kg 4 kW/kg Comparative Example 2 54.9 50.8 Comparative Example 4 64.0 61.6 Example 2 66.9 60.3

Referring to Table 1, it can be seen that a water capacitor including a separator having an adhesive nanofiber coating layer formed on both sides as in Example 2 minimizes energy output deterioration. In the case of Comparative Example 2, which is a water capacitor including a separator to which an adhesive nanofiber having a diameter of 220 nm is applied, it can be seen that the energy output is significantly reduced compared to Comparative Examples 4 and 2.

In the above, although the present invention has been described by limited embodiments and drawings, the present invention is not limited thereto, and the technical idea of the present invention and the following description by those of ordinary skill in the art to which the present invention pertains. It goes without saying that various modifications and variations are possible within the equivalent range of the claims to be made.

1: separator
10: base
20: adhesive nanofiber coating layer

Claims (12)

Base; And an adhesive nanofiber coating layer formed on both sides of the substrate portion; Separator. The method of claim 1,
The adhesive nanofiber coating layer is a separator comprising an adhesive nanofiber containing an adhesive polymer. The method of claim 2,
The adhesive polymer is polyvinylidene fluoride (PVDF), polyvinyl butyral (PVB), polyvinyl alcohol (PVA), polyacrylic acid (PA), fluoride- Hexafluoropropylene (polyvinylidene fluoride-co-hexafluoropropylene, PVDF-HFP), polyvinylidene fluoride-co-trichloroethylene, polymethylmethacrylate, polyacrylonitrile ), polyvinyl acetate (polyvinylacetate), ethylene vinyl acetate copolymer (polyethylene-covinylacetate), polyimide (polyimide) and polyethylene oxide (polyethylene oxide) that comprises at least one selected from the group consisting of. The method of claim 1,
The diameter of the adhesive nanofiber is 50 to 200 nm, the separator. The method of claim 1,
The thickness of the adhesive nanofiber coating layer is 0.5 to 20 ㎛, the separator. The method of claim 2,
The content of the adhesive nanofibers is 1 to 10% by weight based on the total weight of the adhesive nanofiber coating layer, the separator. The method of claim 1,
The base portion is a porous film, non-woven fabric, or a mixture of two or more selected from the group consisting of polyolefin-based resins, fluorine-based resins, polyester-based resins, polyacrylonitrile resins, cellulose-based materials and copolymers thereof. A separation membrane comprising a layered structure or more. (S1) dissolving the adhesive polymer in a solvent to form a spinning solution for forming adhesive nanofibers;
(S2) forming adhesive nanofibers using the spinning solution, and applying it to one surface of the substrate;
(S3) forming an adhesive nanofiber coating layer on both surfaces of the substrate by repeating the process of winding and unwinding the substrate portion coated with the adhesive nanofibers; comprising, a method for manufacturing a separator . The method of claim 8,
The solvent is dimethyl carbonate, dimethyl formamide, N-methyl formamide, sulfolane (tetrahydrothiophene-1,1-dioxide), 3-methylsulfolane, N-butyl sulfone, dimethyl sulfoxide, pyloridinone (HEP), dimethylpiperidone (DMPD), N-methylpyrrolidinone (NMP), N-methyl acetamide, dimethyl acetamide (DMAc), dimethylformamide (DMF), diethylacetamide (DEAc) dipropyl 1 selected from the group consisting of acetamide (DPAc), ethanol, propanol, butanol, hexanol, ethylene glycol, tetrachloroethylene, propylene glycol, toluene, trpentine, methyl acetate, ethyl acetate, petroleum ether, acetone, cresol and glycerol An organic solvent containing more than one species, a method for producing a separation membrane. The method of claim 8,
The concentration of the spinning solution is 10 to 25% based on the weight of the solid content, the method of manufacturing a separation membrane. An electrochemical device comprising the separator of any one of claims 1 to 7. The method of claim 11,
The electrochemical device is an electrochemical device that is a Pseudo Capacitor.

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