KR20110129113A - Polymer electrolyte nanofiber web - Google Patents

Abstract

PURPOSE: A polyelectrolyte nanofiber web is provided to strongly adhere an ion conductor and to continuously maintain ion conductivity. CONSTITUTION: A polyelectrlyte nanofiber web contains: hydrocarbon porous support(10) in a web form; a porous compound layer which is attached at one side or both sides of the porous support and has a web form with 0.01-0.15 S/cm of ion conductivity; and an ion conductor which is impregnated in the porous support.

Description

Polymer electrolyte nanofiber web

The present invention relates to a polymer electrolyte nanofiber web, and more particularly, to a polymer electrolyte nanofiber web usable in an electrolyte membrane for a fuel cell.

Porous nanofiber webs have a wide surface area and excellent porosity, and thus can be used for various purposes. For example, the porous nanofiber webs can be used for water purification filters, air purification filters, composite materials, and battery separators. In particular, such a porous nanofiber web can be usefully applied to fuel cell membranes for automobiles.

A fuel cell is a battery that converts chemical energy generated by oxidation of a fuel into electrical energy directly, and has been in the spotlight as a next-generation energy source due to its high energy efficiency and eco-friendly features with low emission of pollutants. Such a fuel cell generally has a structure in which an anode and a cathode are formed on both sides of an electrolyte membrane.

Representative examples of automotive fuel cells include a hydrogen ion exchange membrane fuel cell using hydrogen gas as a fuel. Since the electrolyte membrane used in the hydrogen ion exchange membrane fuel cell is a passage through which hydrogen ions generated from the anode are transferred to the cathode, the conductivity of the hydrogen ions should be excellent. In addition, the electrolyte membrane must have excellent separation ability to separate hydrogen gas supplied to the anode and oxygen supplied to the cathode, and also have excellent mechanical strength, shape stability, and chemical resistance, and have low resistance loss at high current density. Such characteristics are required. In particular, the fuel cell for automobiles should be excellent in heat resistance so as not to rupture the electrolyte membrane when used for a long time at high temperature.

As an electrolyte membrane for fuel cells currently used, a perfluorosulfonic acid resin (Nafion, Nafion, trade name) (hereinafter referred to as 'nafion resin') is a fluorine resin. However, Nafion resins have a weak mechanical strength, so that when used for a long time, pinholes are generated, thereby lowering energy conversion efficiency. Attempts have been made to increase the film thickness of Nafion resin in order to reinforce mechanical strength. However, in this case, the resistance loss is increased, and there is a problem in that the economy is inferior as expensive materials are used.

In order to solve this problem, an electrolyte membrane having improved mechanical strength by impregnating a porous polytetrafluoroethylene resin (Teflon, Teflon, trade name) (hereinafter referred to as 'Teflon resin') with an ion conductor as an ion conductor has been proposed. There is a bar. In this case, the mechanical strength is relatively higher than that of the electrolyte membrane composed of Nafion resin alone, but there is a problem that the ionic conductivity is somewhat reduced. In addition, since the Teflon resin is very low adhesion, there is a disadvantage in that the separation between hydrogen and oxygen decreases as the adhesion between the Teflon resin and the Nafion resin decreases with the change of operating conditions such as temperature or humidity during fuel cell operation. . In addition, since the price of not only Nafion resin but also porous Teflon resin is expensive, there is a problem in that economic feasibility in mass production.

In order to solve this problem, general-purpose hydrocarbon resins such as polyethylene, polypropylene, polysulfone, polyethersulfone, polyvinylidene fluoride are used instead of teflon resin, and sulfonic acid groups are used instead of Nafion resin as an ion conductor. An electrolyte membrane has been proposed to reduce the production cost by using a low-cost hydrocarbon resin.

However, in this case, although the production cost can be reduced, the economic efficiency can be improved. However, the film-type hydrocarbon-based membrane prepared by the nonwoven fabric or the conventional separation membrane manufacturing method is difficult to thin, the porosity is reduced, and the pore size is controlled. This is not an easy problem.

In particular, there is a problem that the ion conductivity is lowered as the ion conductor is not smoothly impregnated into the pores of the hydrocarbon-based membrane and the attached ion conductor is separated from the membrane due to repeated expansion and contraction.

According to the present invention, an ion conductor is easily impregnated and strongly adhered to the thin film and the pore size, and is made of a fiber aggregate form having excellent porosity, a porous compound layer having excellent ion conductivity, and having a fiber aggregate form is formed on one surface. Since the conductivity can be continuously maintained, an object of the present invention is to provide a polymer electrolyte nanofiber web that can be used in various fields such as electrolyte membranes for fuel cells.

The present invention for achieving the above object is a hydrocarbon-based porous support having a fiber aggregate form; A porous compound layer attached to one or both surfaces of the porous support and having a fiber aggregate form having an ionic conductivity of 0.01 to 0.15 S / cm; And it provides a polymer electrolyte nanofiber web comprising an ion conductor impregnated in the porous support to which the porous compound layer is attached.

The present invention has the following effects.

First, the polymer electrolyte nanofiber web according to the present invention has an effect of easily thinning and easily adjusting the pore size.

Second, the polymer electrolyte nanofiber web according to the present invention has an effect of continuously maintaining excellent ion conductivity by easily impregnated and strongly bonded to the ion conductor.

The polymer electrolyte nanofiber web having such excellent physical properties can be used in an electrolyte membrane for fuel cells requiring weight reduction, high efficiency, and chemical resistance.

1 is a cross-sectional view of a polymer electrolyte nanofiber web according to an embodiment of the present invention.
2 is a schematic diagram of an electrospinning apparatus according to an embodiment of the present invention.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. Therefore, the present invention encompasses all changes and modifications that come within the scope of the invention as defined in the appended claims and equivalents thereof.

Hereinafter, a polymer electrolyte nanofiber web according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

1 is a cross-sectional view of a polymer electrolyte nanofiber web according to an embodiment of the present invention.

The polymer electrolyte nanofiber web of the present invention includes a hydrocarbon-based porous support 10 having a fiber aggregate form. Since the hydrocarbon-based porous support 10 is insoluble in a conventional organic solvent, there is an advantage of excellent chemical resistance. In addition, since it is hydrophobic, its shape is not easily changed by moisture in an environment of high humidity, and thus it may be suitable for use in an electrolyte membrane for a fuel cell.

The electrolyte membrane for the fuel cell must include the ion conductor 30 to smoothly move the ions. In other words, it may be desirable to fill the fine pores of the membrane with the ion conductor 30 in order to move the ions smoothly.

However, since the conventional ion conductor 30 is hydrophilic, it does not adhere smoothly to the hydrocarbon-based porous support 10, and since the adhesive strength is weak, there is a problem that the ion conductivity is poor as it is easily separated from the membrane. That is, the ion conductor 30 is impregnated in the pores of the hydrocarbon-based porous support 10, even if the ion conductor 30 is not easily attached to the pores of the hydrocarbon-based porous support 10 due to different physical and chemical properties. As the adhesive strength decreases, when the membrane expands and contracts repeatedly due to humidity and heat, the layers may be separated, thereby decreasing the ionic conductivity.

In order to solve such a problem, the polymer electrolyte nanofiber web of the present invention includes a porous compound layer 20 having a fiber aggregate form having an ion conductivity of 0.01 to 0.15 S / cm having excellent affinity with the ion conductor 30.

The porous compound layer 20 serves to help the ion conductor 30 to be uniformly impregnated into the pores of the hydrocarbon-based porous support 10 in a short time. That is, the porous compound layer 20 may serve to improve the affinity of the interface between the hydrocarbon-based porous support 10 and the ion conductor 30 like a surfactant. However, conventional surfactants may cause deterioration of the performance of fuel cells or the like if they remain in the membrane. Accordingly, these surfactants must be removed from the membrane. However, when the surfactant is removed from the membrane as described above, the performance of the fuel cell may be degraded because the process is complicated and the physical properties such as porosity change.

However, the porous compound layer 20 of the fiber aggregate form as shown in the present invention does not need to be removed because it is made of a polymer having excellent ion conductivity, and is attached to the hydrocarbon-based porous support 10 as a thin film of fiber aggregate form. It may serve to help the ion conductor 30 to be smoothly and uniformly impregnated. Accordingly, the porous compound layer 20 may provide an advantage of improving the performance of the fuel cell and the like and eliminating the need for a separate removal process.

The porous compound layer 20 may be attached to one surface of the hydrocarbon-based porous support 10, both sides of the hydrocarbon-based porous support 10 to more easily impregnate the ion conductor 30 and improve the ion conductivity. It can be attached to.

The porous compound layer 20 may include a fluorine compound. In particular, the porous compound layer 20 may have a repeating unit including -CF ₂ -or -CHF- in the main chain to facilitate the impregnation of the ion conductor 30 more. As such, when the porous compound layer 20 is made of a compound containing fluorine, not only affinity with the ion conductor 30 but also greatly improve ion conductivity. As such a fluorine compound, polyfluorovinylidene (PVDF) can be used.

In addition, the porous compound layer 20 may include a non-fluorine-based compound. In particular, the porous compound layer 20 is insoluble in an organic solvent having a dielectric constant of 2.0 to 58 at room temperature in order to improve the affinity of the ion conductor 30 and the hydrocarbon-based porous support 10, and includes a -OH functional group. Compound. As the non-fluorine compound, polyvinyl alcohol (PVA) may be used.

Since the hydrocarbon-based porous support 10 is manufactured through electrospinning, it is possible to easily obtain a thin web of fibers having a thin diameter, and thus have a porosity of 30% or more. As such, as having a porosity of 30% or more, since the specific surface area of the hydrocarbon-based porous support 10 increases, the ion conductor 30 may be easily impregnated. On the other hand, the hydrocarbon-based porous support 10 may have a porosity of 90% or less. If the porosity of the hydrocarbon-based porous support 10 exceeds 90%, the morphological stability is lowered so that the subsequent process proceeds smoothly. It may not be. The porosity was calculated by the ratio of the air volume to the total volume as shown in the following equation. In this case, the total volume was calculated by measuring the width, length, and thickness of a sample in the form of a rectangular shape, the air volume was obtained by subtracting the volume of the polymer inverted from the density after measuring the mass of the sample from the total volume.

Porosity (%) = (air volume / total volume) × 100

The hydrocarbon-based porous support 10 may have an average thickness of 5 ~ 40 ㎛. If the average thickness of the hydrocarbon-based porous support 10 is less than 5 ㎛ may significantly decrease the mechanical strength and form stability, while if the average thickness of the hydrocarbon-based porous support 10 exceeds 40 ㎛ lightweight and integration will fall Can be.

The hydrocarbon-based porous support 10 may include a fiber having an average diameter of 0.01 ~ 5 ㎛. In order for the hydrocarbon-based porous support 10 to have the porosity and the average thickness as described above, the fibers forming the porous support 10 may have an average diameter in the range of 0.01 to 5 ㎛. If the fiber has an average diameter of less than 0.01 μm, the mechanical strength may be reduced, while if the average diameter of the island exceeds 5 μm, the porosity may be significantly reduced and the thickness may be thick. The average diameter of the fiber is calculated from the average of 50 fiber diameters by using an electron scanning microscope (Scanning Electron Microscope, JSM6700F, JEOL).

The hydrocarbon-based porous support 10 may be made of polyimide. The polyimide may have an imidation ratio of 90% or more. As such, the porous support 10 made of polyimide having an imidation ratio of 90% or more may have a melting point of 400 ° C. or more. If the melting point of the porous support 10 is less than 400 ° C., the heat resistance may be easily deformed at high temperatures as the heat resistance thereof is lowered. Accordingly, the fuel cell manufactured using the porous support 10 may be degraded. In addition, when the heat resistance of the porous support 10 is lowered, there may be a problem that the product to which it is applied is broken due to abnormal heat generation during use and explodes.

When used in the electrolyte membrane of a fuel cell that requires high stability as described above, it may be preferable that the polyimide porous support 10 has a melting point of 400 ~ 800 ℃. If the melting point of the polyimide porous support 10 exceeds 800 ° C., the manufacturing process may not proceed smoothly, and thus economic efficiency may be reduced.

In addition, since the polyimide porous support 10 has excellent dimensional stability, the strain on the x, y, and z axes is small, and chemical and heat resistance is excellent even in a humidified environment. Accordingly, the polyimide porous support 10 can maintain the adhesive force at the interface between the membrane and the electrode for a long time by maintaining its shape even when the ion conductor 30 is expanded by humidification.

The porous compound layer 20 may be made of a fiber having an average diameter of 0.1 to 3 ㎛. If the average diameter of the fiber is less than 0.1 μm, the manufacturing process is difficult and the affinity with the ion conductor 30 may not be greatly improved. On the other hand, when the average diameter of the fiber exceeds 3 μm, since the excellent porosity cannot be obtained, the ion conductor 30 may not be smoothly attached.

The porous compound layer 20 may have an average thickness of 3 μm or less. That is, when the average thickness of the porous compound layer 20 exceeds 3 μm, the ion conductor 30 may not be uniformly impregnated into the pores of the porous support 10 as the ion conductor 30 does not penetrate smoothly initially.

The porous compound layer 20 made of fibers having the diameter as described above and manufactured under optimal conditions to be described below may have a porosity of 60 to 99%. If the porosity of the porous compound layer 20 is less than 60%, the affinity with the ion conductor 30 may be reduced, whereas if the porosity of the porous compound layer 20 exceeds 99%, the ion conductor 30 is void. May not penetrate smoothly into.

Such a ratio of the porosity of the porous compound layer 20 and the porosity of the above-described hydrocarbon-based porous support 10 may be desirable to have an appropriate range. That is, it may be preferable that the porosity of the porous compound layer 20 is slightly higher than that of the hydrocarbon-based support, so that the ion conductor 30 can smoothly penetrate into the pores of the hydrocarbon-based support. Accordingly, the porosity ratio of the porous compound layer 20 to the porosity of the hydrocarbon-based porous support 10 may be 1.1 or more. If the porosity ratio is less than 1.1, since the porous compound layer 20 interferes with the penetration of the ion conductor 30, the ion conductor 30 may be formed only in the pores of the porous compound layer 20, thereby decreasing durability. That is, when the ion conductor 30 is attached only to the surface of the porous compound under driving conditions of high temperature and high humidity, the ion conductor 30 may be separated as the expansion and contraction are repeated.

In the polymer electrolyte nanofiber web of the present invention, the ion conductor 30 is impregnated in the hydrocarbon-based porous support having the porous compound layer described above.

The ion conductor 30 may include a repeating unit of —CF ₂ — or —CHF— and a functional group of —SO ₃ H in the main chain. In particular, Nafion may be used as the ion conductor 30. The Nafion has excellent ionic conductivity by itself and strongly adheres to the hydrocarbon-based porous support 10 to which the porous compound layer 20 is attached, so that the polymer electrolyte nanofiber web to which the Nafion is applied can also have excellent ionic conductivity. There is this.

The ion conductor 30 may have a water content of 40 to 80%. That is, the ion conductor 30 has such a moisture content and has an excellent affinity with the porous compound layer. If the water content of the ion conductor 30 is less than 40%, the fuel cell may not exhibit sufficient performance. On the other hand, if the water content of the ion conductor 30 is more than 80%, it is excessively sensitive to moisture. Can be degraded.

The ion conductor 30 may be impregnated with a content of 30 to 90% by weight. If the content of the ion conductor 30 is less than 30% by weight, excellent ion conductivity may not be obtained. On the other hand, if the content of the ion conductor 30 is more than 90% by weight, the polymer electrolyte nanofiber web may have high temperature and high humidity. As it is easily deformed, durability may be reduced.

As such, the polymer electrolyte nanofiber web including the ion conductor 30 may greatly improve the performance of a fuel cell or the like as it has an ion conductivity of 0.10 to 0.15 S / cm.

In addition, the polymer electrolyte nanofiber web may have a peel strength of 5 N / cm. That is, since the polymer electrolyte nanofiber web has a high peel strength of 5 N / cm or more, even when used for a long time in an electrolyte membrane for a fuel cell, each layer is not separated, thereby maintaining excellent ion conductivity.

Next, a method of manufacturing a polymer electrolyte nanofiber web according to an embodiment of the present invention will be described in detail with reference to FIG. 2. 2 is a schematic diagram of an electrospinning apparatus according to an embodiment of the present invention.

Since the polymer electrolyte nanofiber web of the present invention is manufactured by electrospinning, the porosity may be high and the thin film may have excellent characteristics.

First, a hydrocarbon-based polymer is dissolved in an organic solvent to prepare a spinning solution.

The hydrocarbon-based polymer may be a polyimide precursor. The porous support 10 which is insoluble in organic solvents such as polyimide cannot be directly manufactured through an electrospinning process. In other words, polyimide, which is insoluble in organic solvents, is insoluble in organic solvents, making it difficult to produce spinning solutions. Therefore, a polyimide support having insolubility in organic solvents may be prepared by preparing a fiber aggregate using a polyimide precursor that is well soluble in an organic solvent and then imidating the fiber aggregate.

As the polyimide precursor, polyamic acid may be used. The polyamic acid may be prepared by mixing diamine in a solvent, adding dianhydride thereto, and polymerizing the diamine. The dianhydride may be pyromellyrtic dianhydride (PMDA), benzophenonetetracarboxylic dianhydride (BTDA), ODPA (4,4′-oxydiphthalic anhydride), BPDA (biphenyltetracarboxylic dianhydride), or SIDA (bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride It may be used to include at least one of). In addition, the diamine may be one containing at least one of ODA (4,4'-oxydianiline), p-PDA (p-penylene diamine), or o-PDA (openylene diamine).

Solvents for dissolving the polyamic acid include m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, A solvent including at least one of diethyl acetate, tetrahydrofuran (THF), chloroform, and γ-butyrolactone may be used.

By using the electrospinning apparatus as shown in Figure 2 the spinning solution to prepare a fiber assembly consisting of fibers having an average diameter of 0.01 to 5 ㎛. That is, the spinning solution is supplied to the spinning unit using a fixed volume pump 1 in a solution tank in which spinning solution is stored in a predetermined amount, and the spinning solution is discharged through the nozzle 2 of the spinning unit and coagulated at the same time (4) may be formed and the solidified fibers 4 may be focused at the collector 5 to produce a porous support 10 in the form of a fiber aggregate.

If the fiber assembly is made of a polyimide precursor, the method of manufacturing the porous support 10 may further include an imidization process. The imidation step may include a step of thermal imidization, chemical imidization, or a combination of thermal imidization and chemical imidization.

Subsequently, a porous compound layer 20 having a fiber aggregate form consisting of fibers having an average diameter of 0.1 to 3 μm is attached to one or both surfaces of the porous support 10. The porous compound layer 20 may be attached to the porous support 10 in various ways. In particular, the porous compound layer 20 may be attached to the porous support 10 using an electrospinning process. That is, after preparing a spinning solution by dissolving a fluorine-based or non-fluorine-based compound having an ion conductivity of 0.01 to 0.15 in an organic solvent, the spinning solution is spun and solidified using the electrospinning apparatus shown in FIG. The fiber 4 may be attached to the porous support 10 positioned on the collector 5 to attach the porous compound layer 20 to the porous support 10.

As such, by attaching the porous compound layer 20 to the porous support 10 through an electrospinning process, the adhesion between the porous support 10 and the porous compound layer 20 can be greatly improved, and the process is simple. As a result, the economy is excellent, and the porosity can be easily adjusted.

Subsequently, the electrolyte nanofiber web is manufactured by impregnating the ion conductor 30 in the porous support 10 to which the porous compound layer 20 is attached. More specifically, the porous support 10 to which the porous compound layer 20 is attached is immersed in a solution of an ion conductor 30 such as Nafion once or several times, and then left under reduced pressure to remove air bubbles and then dried. The polymer electrolyte nanofiber web may be manufactured through the process. The polymer electrolyte nanofiber web prepared as described above may contain 30 to 90% by weight of the ion conductor 30.

Since the polymer electrolyte nanofiber web impregnated with the ion conductor 30 can smoothly move ions, the performance can be greatly improved when used in an electrolyte membrane for a fuel cell.

Hereinafter, the effects of the present invention will be described in more detail with reference to Examples and Comparative Examples. These examples are merely to aid the understanding of the present invention and do not limit the scope of the present invention.

Example  One

After dissolving the polyamic acid in dimethylformamide solvent to prepare a 12 wt% spinning solution, it is spun through a metering pump (1) through a nozzle (2) installed in the electrospinning apparatus and then to the high voltage generator (3) By scattering in the state where the electric field is applied to form a solidified fiber (4), and the thus formed solidified fibers (4) to the collector (5) to prepare a polyimide precursor fiber aggregate (10). At this time, the applied voltage was 15 kV and the spinning distance was 15 cm. The fiber aggregate 10 had an average pore 12 of 1.5 μm, an average thickness of 30 μm, and an average fiber diameter of 0.8 μm.

Subsequently, the polyimide precursor fiber aggregate 10 was heat-treated for 10 minutes in a hot press maintained at a temperature of 400 ° C. to prepare a polyimide porous support 10.

Subsequently, polyfluorovinylidene was dissolved in dimethylformamide to prepare a spinning solution having a concentration of 17% by weight, and the spinning solution was electrospun to obtain a fiber having an average diameter of 0.3 µm, and the fiber was used as the polyimide Through the process of seating on one surface of the porous support 10, a polyimide porous support having a porous compound layer 20 having an average thickness of 3 ㎛ was laminated.

Subsequently, the porous compound layer 20 was laminated on the other side of the polyimide porous support 10 using the same method as described above.

Subsequently, the porous support 10 having the porous compound layer 20 laminated on both surfaces thereof was immersed twice for 20 minutes in a solution of Nafion ion conductor 30, and then left for 1 hour under reduced pressure at 80 ° C. Drying in hot air for 3 hours to prepare a polymer electrolyte nanofiber web.

Example  2

In Example 1 described above, a polymer electrolyte nanofiber web was prepared by the same method as Example 1 except for using polyvinyl alcohol instead of polyfluorovinylidene and using a spinning solution made by dissolving it in water.

Comparative example

In Example 1, the polymer electrolyte nanofibers were prepared in the same manner as in Example 1, except that the process of laminating the polyfluorovinylidene porous compound layer 20 on the polyimide porous support 10 was omitted. The web was prepared.

Physical properties of the polymer electrolyte nanofiber webs prepared by Examples and Comparative Examples were measured by the following method and are shown in Table 1 below.

Thickness measurement

Prepare a sample of size 100cm × 500cm, measure the thickness of 1cm × 5cm in the left and right direction from the upper left corner of the sample, measure the thickness continuously at 1cm horizontal interval, and average the result. Was obtained. At this time, the thickness measurement was measured directly using a thickness measuring device (model name: G, brand name: PEACOCK) that is a contact measuring instrument, the number of measurements per sample was 20 times.

Ionic Conductivity (S / cm) Measurement

Ionic conductance of the polymer electrolyte nanofiber web was measured by the constant current four-terminal method. Specifically, the ion conductivity of the polyelectrolyte nanofiber web is characterized by the difference in the AC potential generated at the center while applying a constant alternating current to both ends of the polyelectrolyte nanofiber web in a chamber controlled at a temperature of 80 ° C. and 100% relative humidity. It measured and obtained.

Peel Strength (N / cm) Measurement

Peel strength of the polymer electrolyte nanofiber web was measured according to KS M ISO 8510-2 using a universal testing machine (Lloyd LR5K).

Moisture Content (%) Measurement

The water content of the polymer electrolyte nanofiber web was measured from the following equation.

Moisture Content (%) = [(Wet Weight-Dry Weight) / Dry Weight] × 100

division Ion Conductivity (S / cm) Moisture content (%) Peel Strength (N / cm) Example 1 0.13 42 5.5 Example 2 0.12 45 5.1 Comparative example 0.08 35 4.5

1: metering pump 2: nozzle
3: high voltage generating unit 4: solidified fiber
5: collector 10: porous support
20 porous layer 30 ion conductor

Claims (12)

A hydrocarbon-based porous support having a web form;
A porous compound layer attached to one or both surfaces of the porous support and having a web form having an ionic conductivity of 0.01 to 0.15 S / cm; And
A polymer electrolyte nanofiber web comprising an ion conductor impregnated in the porous support to which the porous compound layer is attached. The method of claim 1,
The porous compound layer is a polymer electrolyte nanofiber web comprising a fluorine-based compound having a repeating unit containing -CF ₂ -or -CHF-. The method of claim 1,
The porous compound layer is a polymer electrolyte nanofiber web comprising a non-fluorine-based compound insoluble in an organic solvent having a dielectric constant of 2.0 to 58 at room temperature and containing -OH groups. The method of claim 1,
The hydrocarbon-based porous support is made of a fiber having an average diameter of 0.01 to 5 ㎛ and a polymer electrolyte nanofiber web, characterized in that it has an average thickness of 5 to 40 ㎛. The method of claim 1,
The hydrocarbon-based porous support is a polymer electrolyte nanofiber web comprising polyimide. The method of claim 1,
The porous compound layer is made of a fiber having an average diameter of 0.1 to 3 ㎛ and a polymer electrolyte nanofiber web, characterized in that having an average thickness of 3 ㎛ or less. The method of claim 1,
The hydrocarbon-based porous support has a porosity of 30 to 90%, the porous compound layer has a porosity of 60 to 99%, and a porosity ratio of the porous compound layer to the hydrocarbon-based porous support is 1.1 or more. Textile web. The method of claim 1,
The ion conductor is a polymer electrolyte nanofiber web, characterized in that it comprises a Nafion, which is impregnated in a content of 30 to 90% by weight. The method of claim 1,
The ion conductor is a polymer electrolyte nanofiber web comprising a repeating unit of -CF ₂ -or -CHF- and a functional group of -SO ₃ H in the main chain. The method of claim 1,
The ion conductor is a polymer electrolyte nanofiber web, characterized in that having a water content of 40 to 80%. The method of claim 1,
The polymer electrolyte nanofiber web has a polymer electrolyte nanofiber web, characterized in that it has an ion conductivity of 0.10 to 0.15 S / cm. The method of claim 1,
The polymer electrolyte nanofiber web has a peel strength of 5 N / cm or more.

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