KR20100058243A - Ploymer membrane, method for manufacturing the membrane and membrane electrode assembly including the membrane - Google Patents

Abstract

PURPOSE: A polymer membrane, a manufacturing method thereof, and a membrane electrode assembly including thereof are provided to accelerate a catalyst reaction by enabling water generated from a reduction electrode to be absorbed on the surface of the membrane. CONSTITUTION: A polymer membrane comprises the following: a hydrophobic asymmetric supporter(14) in a single layer with a first surface and a second surface facing each other; and a pore(15) exposed on the first or the second surface while penetrating the supporter. The size of the pore exposed on the first surface is smaller than the size of the pore on the second surface. The hydrophobic asymmetric supporter contains a hydrophilic polymer located on the pore.

Description

Polymer electrolyte membrane, method for manufacturing polymer electrolyte membrane and membrane-electrode assembly with polymer electrolyte membrane {Ploymer membrane, Method for manufacturing the membrane and Membrane electrode assembly including the membrane}

The present invention relates to a fuel cell, and more particularly, to a membrane-electrode assembly having a polymer electrolyte membrane, a method for producing a polymer electrolyte membrane, and a polymer electrolyte membrane.

Fuel cells are highly efficient electrochemical systems that convert chemical energy into electrical energy. An advantage of fuel cells over other sources of electrical energy is their high efficiency and environmental friendliness.

The fuel cell may include a polymer electrolyte membrane which is a passage through which hydrogen ions move. However, in the polymer electrolyte membrane, water is accumulated on the local side of the polymer electrolyte membrane by water generated from the cathode, and the catalytic reaction is suppressed, thereby reducing the performance of the fuel cell.

An object of the present invention for solving the above problems is to provide a membrane-electrode assembly comprising a polymer electrolyte membrane, a method for producing a polymer electrolyte membrane, and a polymer electrolyte membrane which can improve the performance of a fuel cell by enabling water management of the polymer electrolyte membrane. It is.

The present invention for achieving the above object is a monolayer hydrophobic asymmetric support having a first surface and a second surface facing each other, the support is a first surface and the second surface of the support facing each other through the support It provides a polymer electrolyte membrane having pores exposed in the plane, the size of the pores exposed in the first surface is smaller than the size of the pores exposed in the second surface and comprises a hydrophilic polymer located in the pores.

The voids can gradually increase in size from the first side to the second side. The hydrophobic asymmetric support may be prepared using a polymer of BPPO, PI, PVDF or IEC 1.5 or less, and the polymer of IEC 1.5 or less may be SPPO, SPES, SPEK, SPEEK or SPS. In addition, the hydrophilic polymer may be SPPO, SPES, SPEK, SPEEK or SPS of IEC 1.5 or higher.

According to another aspect of the present invention, there is provided a step of forming a single layer hydrophobic asymmetric support having a first side and a second side, the support passing through the support and facing each other of the support and A polymer having pores exposed in the second surface, wherein the size of the pores exposed in the first surface is small compared to the size of the pores exposed in the second surface and comprising placing a hydrophilic polymer in the pores It provides a method for producing an electrolyte membrane.

The asymmetric support can be formed using a phase transition method. The phase transfer method may be performed by reaction of a solvent and a non-solvent. Positioning the hydrophilic polymer in the voids may be used in the pore filling method.

The present invention for achieving the above another object is a single layer hydrophobic asymmetric support disposed between the anode and the cathode and the anode and the cathode, the first surface and the second surface, the support is A pore penetrating the support and exposed in the first and second facing surfaces of the support, wherein the size of the void exposed in the first surface is smaller than the size of the void exposed in the second surface; and It provides a membrane-electrode assembly comprising a polymer electrolyte membrane having a hydrophilic polymer located in the voids. The cathode may be disposed in contact with the second surface of the asymmetric support.

A first surface and a second surface facing each other, and having a void exposed in the first and second surfaces facing each other, the size of the voids exposed in the first surface being exposed in the second surface. A polymer electrolyte membrane including a small asymmetric support and a hydrophilic polymer positioned in the asymmetric support was prepared, compared to the size of the pores. Then, the first hydrophobic surface of the polymer electrolyte membrane prepared as described above was disposed in contact with the anode, and the second hydrophilic surface was disposed in contact with the reduction electrode. As a result, water generated in the cathode may not be accumulated in the cathode, and may be absorbed from the surface of the polymer electrolyte membrane in the hydrophilic region, and thus the catalytic reaction may be actively progressed to improve the performance of the fuel cell. In addition, since water absorbed in the hydrophilic region of the polymer electrolyte membrane may be moved toward the anode by diffusion, it is possible to continuously supply moisture to the anode, thereby facilitating the movement of ions.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, with reference to the accompanying drawings, it will be described in detail a preferred embodiment of the present invention. Hereinafter, the same reference numerals are used for the same components in the drawings, and duplicate descriptions of the same components are omitted.

Example 1

1A to 1D are schematic diagrams illustrating a method of manufacturing a polymer electrolyte membrane according to an embodiment of the present invention.

Referring to FIG. 1A, a hydrophobic polymer solution may be prepared by dissolving a hydrophobic polymer in a first solvent. The hydrophobic polymer may be a polymer of BPPO (brominated poly (2,6-dimethyl-1,4-phenylene oxide)), PI (polyimide), PVDF (poly (vinylidene fluoride)) or IEC (ion exchange capacity) 1.5 or less have. The polymer having an ion exchange capacity (IEC) 1.5 or less may exhibit an ion exchange capacity of 1.5 or less. Specifically, the polymer of IEC 1.5 or less may include sulfonated poly (2,6-dimethyl-1,4-phenylene oxide) (SPPO), sulfonated polythersulfone (SPES), sulfonated poly (etherketone) (SPEK), and poly (etheretherketone) SPEEK. ) Or sulfonated polystyrene (SPS). The first solvent may be N-methylpyrrolidone (NMP), dimethylformamide (DMF) or N, N -dimethylacetamide ( N, N -dimethyl acetamide; DMAc).

By using the hydrophobic polymer solution it can be prepared an asymmetric support (14 in Fig. 1b). The asymmetric support (14 in Figure 1b) can be prepared using a phase transition method. Specifically, the phase transition method casts a hydrophobic polymer solution on the glass plate 11 to form a hydrophobic polymer film 12, and then immersed the glass plate 11 having the hydrophobic polymer film 12 formed in a coagulation solution 13. Can be done. The coagulating solution 13 may contain a non-solvent, specifically a solvent that cannot dissolve the hydrophobic polymer. The coagulating solution 13 may further contain a solvent capable of dissolving the hydrophobic polymer together with the non-solvent. When the solvent is mixed with the nonsolvent as the coagulating solution 13, the phase transition rate can be adjusted, and thus the size of the pores of the hydrophobic polymer membrane 12 can be controlled. The non-solvent may be distilled water, and the solvent may be N-methylpyrrolidone, dimethylformamide or N, N-dimethylacetamide.

Specifically, the glass plate 11 on which the hydrophobic polymer film 12 is formed may be immersed in a mixed solution of a non-solvent and a solvent for first phase transition, and the first phase transition glass plate 11 may be immersed in a non-solvent for secondary phase transition. .

That is, when the hydrophobic polymer film 12 cast on the glass plate 11 is immersed in the coagulation solution 13, the reaction is performed by the reaction of the respective solvents and nonsolvents contained in the hydrophobic polymer film 12 and the coagulation solution 13. The surface of the hydrophobic polymer film 12 may be phase shifted to gel. At this time, the surface of the hydrophobic polymer film 12 may be provided with a plurality of micropores. The micropores may serve as a passage through which the non-solvent flows into the hydrophobic polymer membrane 12.

The non-solvent introduced through the micropores may gel the inside of the hydrophobic polymer membrane 12. However, since the non-solvent-solvent reaction is slower as the hydrophobic polymer membrane 12 enters the surface, the phase transition speed may be slow. Therefore, since the pore size increases as the phase transition speed decreases, the voids (15 in FIG. 1B) of the hydrophobic polymer membrane 12 may gradually increase in the direction from the first surface to the second surface.

Referring to FIG. 1B, an asymmetric support 14 made through FIG. 1A is provided. Asymmetric support 14 according to an embodiment of the present invention may be provided in a single layer having a first surface and a second surface facing each other, and through the support 14 to the mutual support of the support 14 It may have a void 15 exposed in the opposing first and second surfaces. In addition, the air gap 15 may gradually increase in size from the first surface to the second surface direction.

Referring to FIG. 1C, a hydrophilic polymer (16 of FIG. 1D) may be positioned within the pores of the asymmetric support 14. The hydrophilic polymer (16 of FIG. 1D) may be a polymer of IEC 1.5 or higher, and specifically, may be SPPO, SPES, SPEK, SPEEK, or SPS. The hydrophilic polymer (16 in FIG. 1D) may be positioned in the cavity 15 of the asymmetric support 14 using pore filling.

Specifically, in the pore filling method, a hydrophilic polymer solution may be prepared by dissolving a hydrophilic polymer in a second solvent and casting the same on a glass plate 11 to form a hydrophilic polymer membrane 17. The second solvent may be N-methylpyrrolidone, dimethylformamide or N, N-dimethylacetamide.

The asymmetric support 14 produced through FIGS. 1A and 1B may have solubility by the second solvent contained in the hydrophilic polymer film 17. Thus, the hydrophilic polymer film 17 containing the second solvent has an affinity for the asymmetric support 14 and also due to the capillary force caused by the voids 15, the hydrophilic polymer (16 in FIG. 1D). May be spontaneously moved and filled in the pores 15 of the asymmetric support 14.

However, the asymmetric support 14 may have solubility in the second solvent of the hydrophilic polymer film 17, thereby damaging the asymmetric support 14. Therefore, the hydrophilic polymer may be dissolved in a saturated state with respect to the second solvent and then the hydrophilic polymer membrane 17 may be formed so that the asymmetric support 14 is no longer dissolved in the second solvent.

Further, in addition to the method of dissolving the hydrophilic polymer in a saturated state with respect to the second solvent as described above, a crosslinking step may be performed in forming the asymmetric support 14 in FIG. 1A.

For example, the crosslinking may be performed by immersing the asymmetric support 14 in the crosslinking solution to induce covalent or ionic bonds. The immersion time may be 3 hours to 15 hours. The crosslinking solution may be ammonia or diamine (diamine) solution, the diamine solution is 1,6-diaminohexane (1,6-diaminohexane), ethylenediamine (ethylenediamine) or p -phenylenediamine ( p- phenylendiamine). When the asymmetric support 14 is crosslinked as described above, the strength of the asymmetric support 14 may be improved so that the asymmetric support 14 may not be damaged by the second solvent.

The hydrophilic polymer (16 of FIG. 1D) may then dry the asymmetric support 14 located in the void 15. The drying may be performed for 5 hours to 15 hours at a temperature of 50 ℃ to 80 ℃.

The dried hydrophilic polymer (16 in FIG. 1D) may be acid-treated with the asymmetric support 14 positioned in the pore 15 to prepare a polymer electrolyte membrane. The acid treatment may be performed to replace the salt ions (Na ⁺ , K ⁺ , alkyl amonium ions) of the sulfone portion included in the polymer electrolyte membrane with hydrogen. In the acid treatment, the polymer electrolyte membrane was immersed in 2N aqueous sulfuric acid (H ₂ SO ₄ ) solution, 1N nitric acid (HNO ₃ ) solution, or 1N hydrochloric acid (HCl) solution for 24 hours, washed in distilled water, and then distilled water for 24 hours. It can be performed as immersion in. In addition, the polymer electrolyte membrane may be added to a 0.5 molar sulfuric acid (H ₂ SO ₄ ) aqueous solution to boil for 2 hours.

Referring to FIG. 1D, a polymer electrolyte membrane 10 prepared through FIG. 1C is provided. In the polymer electrolyte membrane 10, the hydrophilic polymer 16 may be located in the pores (15 of FIG. 1B) of the hydrophobic asymmetric support 14. That is, the polymer electrolyte membrane 10 is formed of a single layer having first and second surfaces facing each other, and penetrates through the polymer electrolyte membrane 10 to form a hydrophobic asymmetric support 14 and a hydrophilic polymer 16. May be formed to intersect. In addition, the hydrophilic polymer 16 exposed in the first and second surfaces facing each other of the polymer electrolyte membrane 10 has the size of the hydrophilic polymer 16 exposed in the first surface exposed in the second surface. Compared to the size of the hydrophilic polymer 16 can be. That is, the size of the hydrophilic polymer 16 may be gradually increased in the direction from the first surface to the second surface.

Both surfaces of the polymer electrolyte membrane prepared as described above may have different hydrophilicities. That is, the second surface having the large pore size of the asymmetric support 14 may exhibit hydrophilicity because the area of the hydrophilic polymer 16 filled in the asymmetric support 14 is larger than the total area of the polymer electrolyte membrane 10. The first surface having a smaller pore size of the asymmetric support 14 has a larger hydrophobic polymer area than the total area of the polymer electrolyte membrane 10, and thus may exhibit hydrophobicity. Therefore, the polymer electrolyte membrane 10 may be disposed between the anode and the cathode to prevent drying and flooding of water generated at each of the anode and the cathode, and to improve the performance of the fuel cell. .

In addition, the hydrophilic polymer 16 having a higher degree of sulfonation than the hydrophobic polymer has good ion conductivity and facilitates the movement of hydrogen. On the other hand, since methanol cannot pass through the asymmetric support 14, when the polymer electrolyte membrane is directly applied to a methanol fuel cell, there is an effect of reducing the methanol transmittance.

Preparation Example 1 Preparation of Polymer Electrolyte Membrane

As hydrophobic polymer, BPPO was dissolved in N-methylpyrrolidone at 20wt% to prepare a hydrophobic polymer solution. The hydrophobic polymer solution was cast on a glass plate and immersed in a solution of N-methylpyrrolidone and water in a 4: 6 mixture to perform a first phase transition reaction to prepare a membrane. In this case, the first phase transition reaction was carried out for 6 hours. Subsequently, the membrane subjected to the first phase transition reaction was immersed in distilled water to perform a second phase transition reaction to prepare an asymmetric support having a thickness of 40 μm. In this case, the second phase transition reaction was performed for 3 hours. The asymmetric support was then crosslinked by immersion in ammonia solution for 3 hours and then dried. Drying of the asymmetric support was carried out for 12 hours at a temperature of 50 ℃.

Subsequently, SPPO of IEC 2.5 was dissolved in 40 wt% of N-methylpyrrolidone as a hydrophilic polymer to prepare a hydrophilic polymer solution. The hydrophilic polymer solution was cast on a glass plate with a thickness of 80 μm. After the asymmetric support was placed on the hydrophilic polymer solution, a temperature of 50 ° C. was added to induce pore filling. After the pore filling, the hydrophilic polymer solution on the surface of the asymmetric support was removed using a Teflon film, and then dried at 80 ° C. for 12 hours to prepare a polymer electrolyte membrane. Subsequently, the polymer electrolyte membrane was immersed in 1N HCl solution, followed by acid treatment for 12 hours, followed by sufficient washing with distilled water.

2A is a SEM image showing a cross section of an asymmetric support according to an embodiment of the invention.

Referring to Figure 2a, it can be seen that the asymmetric support is composed of a single layer having a first surface and a second surface facing each other, and has a pore passing through the support. In addition, it can be seen that the void gradually increases in the direction from the first surface to the second surface.

2B and 2C are SEM images showing the surface of the asymmetric support.

2B and 2C, the first surface of the asymmetric support has a small size of the voids 13, and has tens of nanometers in size (FIG. 2B), and the second surface of the asymmetric support has a size of the voids 13. It can be seen that it is large and has a size of several tens of microseconds (FIG. 2C).

3 is an SEM image showing a cross section of an asymmetric support impregnated with a hydrophilic polymer according to an embodiment of the present invention.

Referring to Figure 3, it can be seen that the hydrophilic polymer is well embedded in the asymmetric support by the method prepared according to an embodiment of the present invention.

4A and 4B are schematic diagrams showing contact angles on both sides of an asymmetric support impregnated with a hydrophilic polymer according to an embodiment of the present invention.

4a and 4b, it can be seen that the first surface of the asymmetric support impregnated with the hydrophilic polymer has a small hydrophilicity due to the small area of the hydrophilic polymer, and has a high contact angle of 65 ° in contact with water (FIG. 4a). ). In addition, it can be seen that the second surface of the asymmetric support impregnated with the hydrophilic polymer has a large hydrophilic polymer and a high hydrophilicity, and a contact angle contacting with water is 52 °, which is smaller than that of the surface of FIG. 4A (FIG. 4A). 4b). Therefore, since the contact angles of both surfaces of the polymer electrolyte membrane according to the embodiment of the present invention are different, it is determined that water can be controlled by using the hydrophilicity of the membrane.

Example 2

5 is a cross-sectional view illustrating a membrane-electrode assembly according to another embodiment of the present invention.

Referring to FIG. 5, the membrane-electrode assembly may include an anode electrode 20, a cathode electrode 30, and a polymer electrolyte membrane 10 disposed between the anode electrode 20 and the cathode electrode 30. .

The anode 20 and the cathode 30 may be formed by mixing a supported catalyst, an ionomer, and a fourth solvent to prepare an ink catalyst, and coating the same on a porous support. The supported catalyst may be a mixture of a carbon material and a platinum catalyst. The ionomer is a material having a cation exchange group, and the cation exchange group may be a sulfonic acid group or a carboxyl group. The third solvent may be water, alcohol or perchloric acid solution. The anode 20 and the cathode 30 may be formed using a spray method, a painting method, a doctor blade method, or a transfer method.

The polymer electrolyte membrane 10 may be the same as the polymer electrolyte membrane 10 prepared according to Example 1. That is, the polymer electrolyte membrane 10 has a single layer of hydrophobic asymmetric support 14 having a first surface and a second surface facing each other, and the support 14 penetrates the support 14 to support the support ( 14) having pores exposed in opposite first and second faces, wherein the size of the pores exposed in the first face is smaller than the size of the pores exposed in the second face and is hydrophilic in the pores. It may be a membrane on which the polymer 16 is located.

Both surfaces of the polymer electrolyte membrane 10 may have different hydrophilicities. That is, the second surface having a large pore size may have high hydrophilicity, and the first surface having a small pore size may have high hydrophobicity. Therefore, in the membrane-electrode assembly, the first surface of the polymer electrolyte membrane 10 is in contact with the surface of the oxide electrode 20, and the second surface of the polymer electrolyte membrane 10 is the reduction electrode ( 30) can be placed in contact with the face.

As a result, water generated in the reduction electrode 30 is not accumulated in the reduction electrode 30 and can be absorbed from the surface of the polymer electrolyte membrane in the second surface, that is, the hydrophilic region, and thus the catalytic reaction proceeds actively. Thus, the performance of the fuel cell can be improved. In addition, since water absorbed in the hydrophilic region of the polymer electrolyte membrane may be moved toward the anode 20 by diffusion, it is possible to continuously supply the moisture to the anode 20, thereby facilitating the movement of ions. Can be.

Preparation Example 2 Preparation of Membrane-Electrode Assembly (SPA)

A catalyst ink was prepared by mixing a 40 wt% Pt / C supported catalyst, 5 wt% Nafion ionomer solution, and isopropyl alcohol (IPA). The catalyst ink was dispersed using ultrasonic waves and then applied to each electrode support to prepare an anode and a cathode. In this case, the platinum content of the anode and the cathode was 0.4 mg / cm ² and the electrode area was 5 cm ² . The polymer electrolyte membrane was prepared according to Preparation Example 1.

The first surface of the polymer electrolyte membrane showing hydrophobicity was disposed in contact with the anode, and the second surface of the polymer electrolyte membrane showing hydrophilicity was disposed in contact with the reduction electrode to prepare a membrane-electrode assembly.

The membrane electrode assembly thus prepared was installed in a unit cell. The unit cell was performed at a temperature of 60 ° C., and performance was measured while supplying oxygen and hydrogen.

Preparation Example 3 Preparation of Membrane-Electrode Assembly (SPC)

The same procedure as in Preparation Example 2 was performed, except that the first surface of the polymer electrolyte membrane having hydrophobicity was placed in contact with the reduction electrode and the second surface of the polymer electrolyte membrane having hydrophilicity was placed in contact with the anode. Prepared.

6 is a graph showing I-V of the membrane-electrode assembly according to Preparation Examples 2 and 3. FIG.

Referring to FIG. 6, the maximum current density was 4.3 A / cm ² when the fuel cell was operated by arranging SPA under humidification conditions (Production Example 2). Moreover, when the fuel cell was operated by arranging by SPC (Production Example 3), the maximum current density was 3.2 A / cm ² . Therefore, when the surface having high hydrophilicity was placed in contact with the reduction electrode (Production Example 2), the performance improvement of about 34% was shown compared to the case where the surface having high hydrophobicity was disposed in contact with the reduction electrode (Production Example 3). .

7 is a graph showing voltage characteristics over time of the polymer electrolyte membrane according to Preparation Examples 2 and 3. FIG.

Referring to FIG. 7, when the fuel cell was operated for 20 minutes in a non-humidified condition, the voltage was kept constant when placed in SPA (Production Example 2), and the voltage was maintained in SPC (Production Example 3). After about 10 minutes had elapsed, the voltage dropped sharply. Accordingly, it can be seen that when the fuel cell is operated by bringing a polymer electrolyte membrane having a high hydrophilicity into contact with a reduction electrode (Production Example 2), the performance of the fuel cell is improved and stability is maintained. The reason why the stability is maintained is as described above by placing a surface having high hydrophilicity on the reduction electrode (Production Example 2), since water generated in the reduction electrode can be absorbed in the hydrophilic polymer electrolyte membrane and moved to the anode by diffusion. In addition, the anode can be continuously supplied with water to facilitate the movement of ions. In addition, since the cathode is prevented from accumulating water, the catalytic reaction may be actively progressed, and thus the performance of the fuel cell may be improved.

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 or scope of the present invention as defined by the following claims It can be understood that

1A to 1D are schematic diagrams illustrating a method of manufacturing a polymer electrolyte membrane according to an embodiment of the present invention.

2A is a SEM image showing a cross section of an asymmetric support according to an embodiment of the invention.

2B and 2C are SEM images showing the surface of the asymmetric support.

3 is a SEM image showing a cross section of an asymmetric support impregnated with a hydrophilic polymer according to an embodiment of the present invention.

4A and 4B are schematic diagrams showing contact angles on both sides of an asymmetric support impregnated with a hydrophilic polymer according to an embodiment of the present invention.

5 is a cross-sectional view illustrating a membrane-electrode assembly according to another embodiment of the present invention.

6 is a graph showing I-V of the membrane-electrode assembly according to Preparation Example 2. FIG.

7 is a graph showing the voltage characteristics over time of the polymer electrolyte membrane according to Preparation Example 2.

<Description of the symbols for the main parts of the drawings>

10: polymer electrolyte membrane 14: asymmetric support

15: pore 16: hydrophilic polymer

20: anode 30: cathode

Claims (17)

A single layer of hydrophobic asymmetric support having a first side and a second side facing each other, the support having air gaps passing through the support and exposed in the first and second facing sides of the support; The size of the voids exposed in the first face is smaller than the size of the voids exposed in the second face; And A polymer electrolyte membrane comprising a hydrophilic polymer located in the voids. The method of claim 1, The pore has a portion whose size gradually increases in the direction from the first surface to the second surface. The method of claim 1, The hydrophobic asymmetric support is a polymer electrolyte membrane prepared using BPPO, PI, PVDF, or a polymer of IEC 1.5 or less. The method of claim 3, wherein The polymer of IEC 1.5 or less is a polymer electrolyte membrane of SPPO, SPES, SPEK, SPEEK or SPS. The method of claim 1, The hydrophilic polymer is a polymer electrolyte membrane of SPPO, SPES, SPEK, SPEEK or SPS of IEC 1.5 or higher. Forming a monolayer hydrophobic asymmetric support having a first side and a second side, the support having pores exposed through the support and exposed in the first and second facing sides of the support, The size of the voids exposed in the first surface is smaller than the size of the voids exposed in the second surface; And A method of manufacturing a polymer electrolyte membrane comprising placing a hydrophilic polymer in the pores. The method of claim 6, The asymmetric support is a method for producing a polymer electrolyte membrane formed by using a phase transition method. The method of claim 7, wherein The phase transition method is a method for producing a polymer electrolyte membrane is carried out by the reaction of a solvent and a non-solvent. The method of claim 6, Positioning the hydrophilic polymer in the pores is a method for producing a polymer electrolyte membrane using a pore filling method. The method of claim 6, The hydrophobic asymmetric support is a method for producing a polymer electrolyte membrane prepared using BPPO, PI, PVDF, or a polymer of IEC 1.5 or less. The method of claim 10, The method of producing a polymer electrolyte membrane wherein the polymer of IEC 1.5 or less is SPPO, SPES, SPEK, SPEEK or SPS. The method of claim 6, The hydrophilic polymer is a method of producing a polymer electrolyte membrane of SPPO, SPES, SPEK, SPEEK or SPS of IEC 1.5 or higher. An anode and a cathode; And A single layer of hydrophobic asymmetric support disposed between the anode and the cathode, the support having a first surface and a second surface, the support penetrating the support within the first and second facing surfaces of the support; A membrane comprising a polymer electrolyte membrane having an exposed pores, the size of the pores exposed in the first surface is smaller than the size of the pores exposed in the second surface, and has a hydrophilic polymer located in the pores- Electrode assembly. The method of claim 13, The cathode is a membrane electrode assembly disposed in contact with the second surface of the asymmetric support. The method of claim 13, The hydrophobic asymmetric support is a membrane-electrode assembly prepared using BPPO, PI, PVDF, or a polymer of IEC 1.5 or less. The method of claim 15, The polymer below the IEC 1.5 is SPPO, SPES, SPEK, SPEEK or SPS membrane-electrode assembly. The method of claim 13, The hydrophilic polymer is a membrane-electrode assembly of SPPO, SPES, SPEK, SPEEK or SPS of IEC 1.5 or higher.

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