KR20040047420A - Ionomer/Clay NanoComposite Proton Exchange Membrane, preparation method thereof and fuel cell containing the same - Google Patents

Abstract

PURPOSE: Provided is a proton-conductive polymer membrane, which has excellent electrochemical properties, thermal stability and mechanical properties, and is capable of reducing methanol cross-over. CONSTITUTION: The proton-conductive polymer membrane comprises 100 parts by weight of a fluoropolymer having a pendant sulfonate group, and 1-10 parts by weight of demineralized clay that is interlayer-separated into a nano-sized planar structure and has an aspect ratio of 1/1000 to 1/30. The proton-conductive polymer membrane is manufactured by the method comprising the steps of: dissolving a proton-conductive polymer having a pendant sulfonate group into an organic solvent; dispersing clay treated with a demineralizing agent into a separate organic solvent; mixing both solutions and stirring them to obtain a mixed solution; and forming a membrane by using the mixed solution.

Description

Proton-conducting polymer membrane, preparation method thereof, membrane-electrode assembly using same and fuel cell comprising same {Ionomer / Clay NanoComposite Proton Exchange Membrane, preparation method etc. and fuel cell containing the same}

The present invention relates to a proton conductive polymer membrane, and more particularly, to a proton conductive polymer membrane which reduces methanol crossover and has excellent mechanical properties, a method of manufacturing the same, a membrane-electrode assembly using the same, and a fuel cell including the same.

In recent years, along with environmental problems, exhaustion of energy sources, and the practical use of fuel cell vehicles, development of high-performance fuel cells with high energy efficiency and operation at room temperature and reliability are urgently required. Accordingly, there is also a demand for the development of polymer membranes that can increase the efficiency of fuel cells.

A fuel cell is a power generation system that directly converts energy generated by electrochemical reaction between fuel and oxidant into electrical energy. It is a molten carbonate electrolyte fuel cell operating at high temperature (500 to 700 ° C), and phosphoric acid operating near 200 ° C. Electrolyte fuel cells, alkali electrolyte fuel cells operating at room temperature to about 100 ° C. or lower, and polymer electrolyte fuel cells.

The polymer electrolyte fuel cell includes a direct exchange fuel cell (Proton Exchange Membrane Fuel Cell (PEMFC)) using hydrogen gas as a fuel and a direct methanol fuel cell using liquid methanol directly supplied to the anode. Fuel Cell: DMFC). The polymer electrolyte fuel cell is a future clean energy source that can replace fossil energy, and has high power density and energy conversion efficiency. In addition, since it can operate at room temperature and can be miniaturized and sealed, it can be widely used in fields such as pollution-free automobiles, household power generation systems, mobile communication equipment, medical equipment, military equipment, and space business equipment.

PEMFC is a power generation system for producing direct current electricity from the electrochemical reaction of hydrogen and oxygen, the basic structure of such a cell is shown in FIG.

Referring to FIG. 1, a fuel cell has a structure in which a proton conductive polymer membrane 11 is interposed between an anode and a cathode.

The proton conductive polymer membrane 11 has a thickness of 50 to 200 µm and is made of a solid polymer electrolyte, and the anode and the cathode are respectively supported by the support layers 14 and 15 for supplying the reactor, and the oxidation / reduction reaction of the reactor. It consists of a gas diffusion electrode (hereinafter referred to collectively referred to as a gas diffusion electrode ") of the catalyst layers 12, 13, which occur. Reference numeral 16 in Fig. 1 has a groove for gas injection. A carbon sheet, which also functions as a current collector.

In the PEMFC having the structure as described above, an oxidation reaction occurs at the anode while hydrogen, which is a reactive gas, is converted into hydrogen ions and electrons. At this time, hydrogen ions are transferred to the cathode via the proton conductive polymer membrane 11.

On the other hand, in the cathode, a reduction reaction occurs and oxygen molecules receive electrons and are converted into oxygen ions, and oxygen ions react with hydrogen ions from the anode to be converted into water molecules. As shown in FIG. 1, catalyst layers 12 and 13 are formed on support layers 14 and 15, respectively, in the gas diffusion electrode of PEMFC. At this time, the support layers (14) and (15) are made of carbon cloth or carbon paper, and are surface-treated to facilitate the passage of water delivered to the reactor body and the proton conductive polymer membrane 11 and water generated as a result of the reaction.

On the other hand, the direct methanol fuel cell (DMFC) has the same structure as the above-described PEMFC, but instead of hydrogen as a reactor, liquid methanol is supplied to the anode, whereby an oxidation reaction occurs due to the role of a catalyst, which causes hydrogen ions and hydrogen ions. Electrons and carbon dioxide are generated. Although DMFC has lower battery efficiency than PEMFC, it has the advantage that methanol can be used directly without reforming fuel. It is thinner and can be used at a low volume. It is suitable for use as a power source. The principle of generating electricity in the fuel cell is as shown in the reaction equation 1 methanol and water is supplied to the anode (anode) is adsorbed to the platinum catalyst of the cathode and the hydrogen ions and electrons are generated by the oxidation reaction.

CH ₃ OH + H ₂ O -----> 6H + + CO ₂ + 6e-

At this time, the generated electrons reach the cathode along the external circuit, and the hydrogen ions pass through the polymer electrolyte membrane and are transferred to the anode. At the positive electrode, the oxygen molecules receive electrons transferred to the positive electrode and are reduced to oxygen ions as in Scheme 2, and the reduced oxygen reacts with hydrogen ions to generate electricity while producing water.

^{_{3 / 2O 2 + 6e - ----}} > 3O 2 -

_{^{3O 2 - + 6H + ---->}} 3H 2 O

Proton-conducting polymer membranes for fuel cells are electrically insulators, but act as mediators for transferring hydrogen ions from the cathode to the anode during cell operation, and at the same time separate the fuel gas or liquid from the oxidant gas. Therefore, the proton conductive polymer membrane for fuel cell should have excellent mechanical properties and electrochemical stability, and the mechanical properties as a conductive membrane, thermal stability at operating temperature, manufacturability as a thin membrane for reducing resistance, and small expansion effect when containing liquid. Requirements must be met. Currently, a fluorine-based membrane having a fluorinated alkylene in the main chain and a sulfonic acid group at the terminal of the fluorinated vinyl ether side chain is used as such a polymer membrane (for example, manufactured by Nafion and Dupont). However, since the price is very expensive, not only is it difficult to apply to fuel cells for automobiles, but when methanol is used as a fuel, there is a problem that methanol cross-overs the polymer membrane and degrades the overall fuel cell performance. Methanol crossover is shown in Scheme 3. Since methanol is similar in size and polarity to water and molecules, methanol, which has not been oxidized at the cathode, penetrates the proton-conducting polymer membrane hydrated with water in the liquid or gas state at the same time and reaches the anode, thereby reducing the performance of the fuel cell. Results in. More specifically, 1) methanol flowing from the cathode does not oxidize, but passes through the anode, resulting in loss of fuel. 2) carbon dioxide gas is generated during oxidation at the anode, causing poisoning of platinum using a catalyst. 3 A) Oxygen gas loss occurs because oxygen is required at the anode, and 4) the voltage is reduced at the anode.

CH ₃ OH + 3 / 2O ₂ -----> CO ₂ + 2H ₂ O

In the case of using a Nafion membrane, a thickness of 175 μm or more is used to prevent the methanol crossover. However, increasing the thickness decreases the ionic conductivity and has the disadvantage of increasing the cost of the proton conductive polymer membrane. Therefore, various polymer materials have been researched that are excellent in electrochemical properties and thermal stability and can supplement the above problems. Typical examples of the heat-resistant aromatic polymer include polybenzimidazole, polyether sulfone, and polyether ketone, but each of these aromatic polymers is very rigid and difficult to dissolve, making it difficult to prepare a film. have.

Therefore, the first technical problem to be achieved by the present invention is to provide a proton conductive polymer membrane which is excellent in electrochemical properties, thermal stability and mechanical properties, and can reduce the methanol crossover.

The second technical problem to be achieved by the present invention is to provide a method for producing the proton conductive polymer membrane.

The third technical problem to be achieved by the present invention is to provide a membrane-electrode assembly using the proton conductive polymer membrane.

A fourth technical object of the present invention is to provide a fuel cell including the membrane-electrode assembly.

1 shows the structure of a proton conductive polymer membrane fuel cell.

2 is a schematic diagram of a proton conductive polymer membrane according to the present invention.

3 is a graph showing the methanol permeability of the proton conductive polymer membrane according to Examples 1 to 4 and Comparative Example 1 of the present invention.

FIG. 5 is a graph showing current-voltage curves at 70 ° C. of a fuel cell manufactured using the proton conductive polymer membranes according to Examples 1 to 4 and Comparative Example 1 of the present invention.

6 is a graph illustrating a current-voltage curve at 30 ° C. of a fuel cell manufactured using the proton conductive polymer membranes according to Examples 1 to 4 and Comparative Example 1 of the present invention.

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

11 hydrogen ion exchange membrane 12 anode catalyst layer

13 Cathode Catalytic Layer 14 Anode Support Layer

15 ... cathode support layer 16 ... carbon plate

The present invention to achieve the first technical problem

Fluorine-based polymer having a sulfonic acid group in the side chain; And

Provided is a proton conductive polymer membrane which is treated with an organic agent, is separated into a nano-sized plate-like structure, and contains 1 to 10 parts by weight based on 100 parts by weight of the clay having a ratio of 1/1000 to 1/30 of a short axis and a long axis.

According to one embodiment of the present invention, the clay is pyrophylite-talc, montmorilonite (MMT), vermiculit, illite, mica Or brittle mica, and preferably dispersed in the proton conductive polymer membrane.

In addition, the organic agent is preferably an alkylamine having 1 to 20 carbon atoms, alkylene diamine having 1 to 20 carbon atoms, quaternary alkyl ammonium having 1 to 20 carbon atoms, alkyl ammonium salt having 1 to 20 carbon atoms, or aminohexane.

In addition, the thickness of the polymer film is preferably 30 to 125㎛.

The present invention to achieve the second technical problem

Dissolving a proton conductive polymer having a sulfonic acid group in a side chain in an organic solvent;

Dispersing the organic agent-treated clay in a separate organic solvent;

Mixing and stirring the respective solutions to obtain a mixed solution; And

It provides a method for producing a proton conductive polymer membrane comprising the step of forming a polymer membrane using the mixed solution.

According to a preferred embodiment of the present invention, the organic solvent is N-methyl-2-pyrrolidinone (NMP), dimethylformamide (DMF), dimethyl acetamide (DMA), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), acetone, methyl ethyl ketone (MEK), tetramethylurea, trimethyl phosphate, butyrolactone, isophorone, carbitol acetate, methyl isobutyl ketone, N-butyl acetate, cyclohexanone, diacetone alcohol, di It is preferably isobutyl ketone, ethyl acetoacetate, glycol ether, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, or mixtures thereof.

In addition, the mixing ratio of the clay in the mixed solution is preferably 1 to 10 parts by weight based on 100 parts by weight of the polymer.

The present invention provides a fuel cell membrane-electrode assembly manufactured using the polymer membrane according to the present invention in order to achieve the third technical problem.

The present invention provides a fuel cell including the membrane-electrode assembly in order to achieve the fourth technical problem.

Hereinafter, the present invention will be described in more detail.

The proton conductive polymer membrane according to the present invention is a composite polymer electrolyte membrane prepared by dispersing the organically treated clay in a solution state and mixing it with a polymer solution having proton conductivity, followed by evaporation of the solvent to form a membrane.

According to the present invention, the clay, which is a layered clay mineral, is separated into a nano-sized plate, which is a basic unit, dispersed and separated in a proton conductive polymer membrane, thereby significantly increasing the mechanical properties of the polymer membrane, while significantly reducing the permeability of methanol in liquid or gaseous phase. It is characterized by. That is, when the nano-sized plate clay is peeled off in the proton conductive polymer membrane, the contact surface area of the organic polymer and the inorganic clay is widened, thereby increasing the intermolecular attraction and improving mechanical properties.

If the plate-shaped clay having a ratio of uniaxial and long axes of 1/1000 to 1/30 is peeled off in the proton conductive polymer membrane, it acts as a barrier to methanol permeation as shown in Fig. 2, which significantly reduces the crossover of gas or liquid methanol. . When the ratio of the short axis and the long axis is less than 1/1000, there is a disadvantage in that it is difficult to disperse and disperse in the polymer membrane, and when the ratio is greater than 1/30, the peeled clay does not act as a diffusion barrier between gas and liquid, so that the resolution is remarkably decreased. Because it is not desirable.

Most of the clay is layered silicate, and the basic structure is composed of a combination of silica tetrahedral sheets and alumina octahedral sheets, and these two sheets form a layered structure through hydroxyl condensation. In the case of silicate, pyrophylite-talc, montmorilonite (MMT), vermiculit, illite, and mica depending on the degree of internal negative charge Or the brittle mica group. In particular, MMT has a structure in which Mg ²⁺ , Fe ²⁺ , Fe ³⁺ ions are substituted for Al ³⁺ ions in the alumina octahedron sheet, and Al ³⁺ ions are substituted for Si ⁴⁺ ions in the silicate tetrahedron sheet, and the overall negative charge Will be It also contains cations and water molecules that can be exchanged between the silicate layers to balance the charge as a whole. Plate silicates are very difficult to peel and disperse in polymer resin due to the strong van der Waals force. When low amount of organic agent is inserted between silicate layers, the polymer resin is easily penetrated. Because of the role of these polymer resins, peeling and dispersion are easy.

According to the method for producing a proton conductive polymer membrane according to the present invention, the organic clay is immersed in the polymer solution, and the solvent penetrates the layers of the clay so that the clay sheet is peeled and dispersed, and the clay is placed in the polymer resin during the drying process. The nanocomposite polymer membrane prepared by the above method improves strength, flame retardancy, flame resistance, abrasion resistance, and high temperature stability without damaging the basic physical properties of the polymer. For example, in 1987 Toyota CRDL, using 12-aminolauric acid-treated clay, tensile strength and modulus of elasticity were increased by about 100% without deterioration of impact strength. In addition, Professor Giannelis of Cornell University developed a clay / polycaprolactone nanocomposite and measured the water vapor permeability. An improvement effect was obtained. This is a result of lowering the permeability of molecules by lengthening the water vapor transmission path due to the sheet-like structure of the glare.

Clay has been known to be able to swell by water at an interlayer distance of 0.24 nm, but not to penetrate any other organic matter. In order to swell the interlayer distance of the clay to facilitate the intermediate penetration of the organics, an organic agent comprising a cation head and a lipophilic end group is used. The cation of the organic agent serves to exchange metal ions present in the silicate layer structure, and the lipophilic groups of the end groups can increase the interaction with the organic material and increase the interlayer distance to facilitate the intercalation of the organic material. . In the present invention, in order to disperse the clay in the proton conductive polymer solution, the clay treated with at least one carbon 20 organic agent having a lipophilic end group and a cationic head is used.

Fluorine-based polymers used in the present invention are commercially available as fluorine-based membranes having fluorinated alkylenes in the main chain and sulfonic acid groups at the ends of the fluorinated vinyl ether side chains. Nafion under the trade name of Dupont de Nemours.

Method for producing a proton conductive polymer membrane according to the present invention is as follows. First, the proton conductive polymer described above is dissolved in an organic solvent to prepare a 5 wt% to 10 wt% solution. In the above, an organic solvent that can be used for the production of a proton conductive polymer solution is N-methyl-2-pyrrolidinone (NMP), dimethylformamide (DMF), dimethyl acetamide (dimethyl acetamide (DMA), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), acetone, methyl ethyl ketone (MEK), tetramethylurea, trimethyl phosphate , Butyrolactone, isophorone, carbitol acetate, methyl isobutyl ketone, N-butyl acetate, cyclohexanone, Diacetone alcohol, diisobutyl ketone, ethyl acetoacetate, glycol ether, propylene carbonate, ethylene There is a carbonate (ethylene carbonate), dimethyl carbonate (dimethylcarbonate), diethyl carbonate (diethylcarbonate) and mixtures thereof.

Clays used to increase mechanical strength and reduce methanol crossover include pyrophylite-talc, montmorilonite (MMT), vermiculit, illite, Mica, brittle mica, and the like, and in the present invention, montmorillonite is preferably used. As the organic agent used for the organic treatment of the clay, alkylamines having 1 to 20 carbon atoms, alkylene diamines having 1 to 20 carbon atoms, quaternary ammonium salts having 1 to 20 carbon atoms or aminohexane can be used. Examples thereof include methylamine hydrochloride, propyl amine, butyl amine, octyl amine, decyl amine, dodecyl amine, hexadecyl amine, octadecyl amine, N-methyl octadecyl amine, and the like.

Examples of alkylene diamines include 1,6-hexamethylene diamine, 1,12-dodecane diamine, and quaternary alkyl ammoniums include dimethyl quaternary ammonium, benzyl quaternary ammonium, 2-ethylhexyl quaternary ammonium, bis- 2-hydroxyethyl quaternary ammonium, methyl quaternary ammonium; alkylammonium salts include tetramethylammonium chloride, octadecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, dioctadecyl dimethyl ammonium bromide, bis (2-hydride) Oxyethyl) methyl octadecyl ammonium, 1-hexadecylpyridium chloride, etc. can be used, and 6-aminohexane, 12-aminohexane, etc. can be used as aminohexane.

In the present invention, the clay may be used by treating the clay with the above-mentioned organic agent, but the clay which has already been organicized may be directly used. Examples of such organically processed clays include Cloisite 10A, Cloisite 15A, Cloisite 20A, Cloisite 25A, Cloisite 30B, and the like, as Southern trade names, and Cloisite 10A is preferable. Then, the organically treated clay is dispersed using the solvent described above, and then mixed with 1 to 10 parts by weight of the proton conductive polymer solution. When the amount of clay is less than 1 part by weight, it is not preferable because the degree of dispersion is small and methanol permeability is increased. When the amount of clay is more than 10 parts by weight, it is preferable because the excess clay is dispersed in the proton conductive polymer membrane and adversely affects the proton conductivity. Not. Next, the mixed polymer solution may be prepared into a film having a desired thickness by using a solution casting method or a heat compression method, and the thickness of the polymer film is preferably in the range of 30 to 125 μm. In the case of conventional polymer membranes such as Nafion, a thickness of 175 μm or more is used to suppress methanol crossover, but as the thickness increases, the proton conductivity decreases and the cost of the polymer membrane increases, but according to the present invention. In the case of the polymer membrane, the mechanical properties are improved due to the role of the plate-shaped clay in nano units, and methanol crossover is remarkably reduced, thereby achieving an excellent effect even if the thickness of the polymer membrane is thin.

Hereinafter, the present invention will be described in more detail with reference to preferred examples and test examples, but the present invention is not limited thereto.

Example 1

5 g of Nafion solution was prepared by dissolving 5 g of Nafion 117 (produced by Nafion 117, manufactured by Dupont) in 95 ml of dimethylacetamide (DMA). Next, 5 g of organically treated clay Cloisite 10A (manufactured by Southern) was dispersed in 95 ml of dimethylacetamide, and then dispersed using a sonicator to prepare a 5 wt% clay dispersion. Next, 10 g of the proton conductive polymer solution and 0.1 g of the dispersed clay dispersion were mixed and ultrasonically applied for 10 minutes using a sonicator, followed by stirring at 80 ° C. for 12 hours to uniformly peel and disperse the clay. The prepared proton conductive polymer / clay solution. After proton conductive polymer / clay nanocomposite solution prepared as described above was film cast, a proton conductive polymer membrane was prepared by evaporating the solvent for 4 hours in an oven maintained at about 100 ° C.

Example 2

A proton conductive polymer membrane was prepared in the same manner as in Example 1, except that 0.3 g of the clay dispersion was mixed with respect to 10 g of the polymer solution.

Example 3

A proton conductive polymer membrane was prepared in the same manner as in Example 1, except that 0.5 g of the clay dispersion was mixed with respect to 10 g of the polymer solution.

Example 4

A proton conductive polymer membrane was prepared in the same manner as in Example 1, except that 1 g of a clay dispersion was mixed with respect to 10 g of the polymer solution.

Comparative Example 1

A commercial Nafion 117 (thickness = 175 μm) proton conductive polymer membrane manufactured by Dupont was treated with 100 ° C hydrogen peroxide for 3 hours to remove surface contaminants, and then treated with 100M 1M sulfuric acid solution for 2 hours and stored in deionized water. Was

Test Example 1

Elongation Measurement

The mechanical properties of the proton conductive polymer membranes prepared in Examples 1 to 4 and Comparative Example 1 were evaluated according to ASTM 638 or ASTM 882. In this case, the machine parameters were as follows, and the elongation is shown in FIG. 3.

Cross head speed: 25 cm / min

Grip distance: 6.35 cm

Temperature: 25 ℃

Humidity: 50%

As can be seen in Figure 3, the elongation of the proton conductive polymer membrane according to the present invention was significantly increased compared to Comparative Example 1, it can be seen that excellent mechanical properties.

Test Example 2

Measurement of Methanol Crossover

Methanol crossover of the proton conductive polymer membranes prepared in Examples 1 to 4 and Comparative Example 1 was measured using the difference between the reflectivity index of water and methanol. The proton conductive polymer membrane was placed between the 5% methanol solution and the deionized water, and the amount of methanol transmitted through the proton conductive polymer membrane was measured using a difference in refractive index, and is shown in FIG. 4.

As shown in Figure 4 it can be seen that the amount of methanol crossover of the proton conductive polymer membrane according to the present invention is significantly reduced compared to the comparative example.

Test Example 3

Measurement of hydrogen ion conductivity

Ionic conductivity of the proton conductive polymer membranes prepared according to Examples 1 to 4 and Comparative Example 1 of the present invention was measured by a constant current four terminal method. Measure the hydrogen ion conductivity of the specimen by measuring the difference in alternating potential generated in the center of the specimen while applying a specimen with a size of 1 X 5 cm and a thickness of 50 µm to both ends of a constant AC current specimen in a room with controlled temperature and humidity. 5 is shown. As shown in FIG. 5, the ion conductivity of the proton conductive polymer membrane according to the present invention has a value similar to that of Comparative Example 1.

Test Example 4

Battery performance test

Membrane-electrode assembly (MEA) was prepared by coating a commercial catalyst electrode layer on both sides of the proton conductive polymer membranes prepared in Examples 1 to 4 and Comparative Example 1 by hot-press method. The electrode used was a single-sided ELAT electrode available from E-TEK Inc., using a platinum-rubidium black catalyst for the cathode and a platinum black catalyst for the anode. The conditions used for the hot-press were fixed by applying a pressure of about 60 kg / cm ² at 140 ° C. for 5 minutes. Silicon-coated glass fiber gaskets were placed above and below the membrane-electrode assembly and press-sealed with a current collector plate made of carbon to assemble the unit cell. In the unit cell experiment, methanol introduced into the negative electrode was fixed at a concentration of 3M, the positive electrode used high purity oxygen, and the supply pressure was tested at 30 psi. The performance of the cell was tested at 70 ° C., respectively, and the results are shown in FIG. 6. It was.

As shown in Figure 6 it can be seen that the battery using a proton conductive polymer membrane according to the present invention shows a higher current density than the comparative example can be produced a fuel cell with excellent performance.

As described above, the proton-conducting polymer membrane according to the present invention can maintain excellent mechanical properties even at a thinner thickness than the conventional polymer membrane, thereby reducing the amount of proton-conducting polymer used, thereby achieving an economic effect. In addition, since nano-sized plate clays are dispersed, they act as a barrier to methanol crossovers, which significantly reduces methanol crossovers, thereby improving battery performance and lifespan. On the other hand, the method of manufacturing a proton conductive polymer membrane according to the present invention is simple in the manufacturing process, it is excellent in mass production characteristics and can secure the economics of the process.

Claims (9)

Fluorine-based polymer having a sulfonic acid group in the side chain; And A proton conductive polymer membrane comprising 1 to 10 parts by weight of clay, treated with an organizing agent, separated into a nano-sized plate-like structure, and having a ratio of 1/1000 to 1/30 of a short axis and a long axis based on 100 parts by weight of the polymer. The method of claim 1, wherein the clay is pyrophylite-talc, montmorilonite (MMT), vermiculit, illite, mica, or bro Little mica (brittle mica), characterized in that the proton conductive polymer membrane is dispersed in the proton conductive polymer membrane. The method according to claim 1, wherein the organic agent is an alkylamine having 1 to 20 carbon atoms, alkylene diamine having 1 to 20 carbon atoms, quaternary ammonium having 1 to 20 carbon atoms, alkyl ammonium salt having 1 to 20 carbon atoms or aminohexane Proton conductive polymer membrane. The proton conductive polymer membrane of claim 1, wherein the polymer membrane has a thickness of 30 μm to 125 μm. Dissolving a proton conductive polymer having a sulfonic acid group in a side chain in an organic solvent; Dispersing the organic agent-treated clay in a separate organic solvent; Mixing and stirring the respective solutions to obtain a mixed solution; And Method of producing a proton conductive polymer membrane comprising the step of forming a polymer membrane using the mixed solution. The method of claim 5, wherein the organic solvent is N-methyl-2-pyrrolidinone (NMP), dimethylformamide (DMF), dimethyl acetamide (DMA), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) , Acetone, methyl ethyl ketone (MEK), tetramethylurea, trimethyl phosphate, butyrolactone, isophorone, carbitol acetate, methyl isobutyl ketone, N-butyl acetate, cyclohexanone, diacetone alcohol, diisobutyl ketone , Ethyl acetoacetate, glycol ether, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, or a mixture thereof. The method of claim 5, wherein the mixing ratio of the clay solution in the mixed solution is 1 to 10 parts by weight based on the polymer solution. A membrane-electrode assembly for a fuel cell manufactured using the polymer membrane according to any one of claims 1 to 4. A fuel cell comprising the membrane-electrode assembly according to claim 8.