KR20130110569A - The electrolyte membrane for and method for preparing the same - Google Patents

Abstract

PURPOSE: A polymer electrolyte membrane has high durability, radical resistance, improved electric conductivity, and improved lifetime and has reliability for the long term use of a cation exchange membrane fuel cell. CONSTITUTION: A polymer electrolyte membrane comprises a polyimide porous nanofiber web support; an ion conductor filled in the porous nanofiber web support; an oxidation stabilizer which is one selected from a phenol-based oxidation stabilizer, an amine-based oxidation stabilizer, sulfur-based oxidation stabilizer, and a combination thereof. The porous nanofiber web support is a polyimide porous nanofiber support. The ion conductor is polyarylene ether sulfone-based ion conductor or polyetherethersulfone ion conductor. The oxidation stabilizer is a phenol-derived oxidation stabilizer.

Description

Polymer electrolyte membrane and manufacturing method thereof {THE ELECTROLYTE MEMBRANE FOR AND METHOD FOR PREPARING THE SAME}

The present invention relates to a polymer electrolyte membrane and a method of manufacturing the same. More specifically, the present invention provides a polymer electrolyte membrane and a method for manufacturing the same, which can prevent a decrease in conductivity due to oxidation of an ion conductor by radicals generated in a cathode of a proton exchange membrane fuel cell and a decrease in battery performance.

Recently, due to the rapid spread of portable electronic devices and wireless communication devices, a lot of interest and research has been progressed in the development of a fuel cell as a battery as a portable power supply source, a fuel cell for a pollution-free automobile and a power generation fuel cell as a clean energy source.

A fuel cell is an energy conversion device that converts chemical energy of a fuel directly into electrical energy. In other words, the fuel cell is a power generation method that uses fuel gas (hydrogen, methanol, or other organic material) and oxidizing agent (oxygen or air), and generates electric power by using electrons generated during the redox reaction. It is being researched and developed as the next generation energy source due to the eco-friendly features with low emission of pollutants and pollutants.

Low-humidity polymer electrolyte fuel cells (PEMFCs) powered by hydrogen can operate over a wide temperature range, simplifying cooling devices and sealing parts, and using low-humidity hydrogen as fuel, minimizing the use of humidifiers. In addition, it has been spotlighted as a vehicle and home power supply for its advantages such as fast driving. In addition, it is a high output fuel cell with a higher current density than other types of fuel cells. It operates at a wide range of temperatures, has a simple structure, and has fast startup and response characteristics.

The fuel cell is typically formed as a stack or assembly of membrane electrode assemblies, each comprising an electrolyte membrane, an anode electrode and a cathode electrode, and any other components. Fuel cell membrane electrode assemblies are typically in electrical contact with each electrode to allow diffusion of reactants to the electrode, and a porous electrically conductive sheet material known as a gas diffusion layer, gas diffusion substrate or gas diffusion backing. Also includes. When the electrocatalyst is coated on the electrolyte membrane, the membrane electrode assembly is said to include a catalyst coating. In other cases, when the electrocatalyst is coated on the gas diffusion layer, the membrane electrode assembly is said to include a gas diffusion electrode. The functional components of the fuel cell are usually arranged in the order of conductive electrode plates, gas diffusion backings, anode electrodes, membranes, cathode electrodes, gas diffusion backings, and conductive electrode plates.

Such a fuel cell is composed of a continuous composite of a membrane electrode assembly in which a hydrogen ion exchange membrane is interposed between an anode and a cathode, and a separator that collects and supplies fuel for generated electricity. In the anode, hydrogen or methanol, which is a fuel, is supplied and reacts on the electrode catalyst to generate hydrogen ions (H +, protons). In the cathode, hydrogen ions and oxygen that pass through the hydrogen ion exchange membrane are combined to generate pure water.

Long-term stability of the electrolyte membrane is very important for fuel cells. For example, the lifetime goal for a stationary fuel cell application is 40,000 hours of operation. Conventional membranes, which are known to be used throughout the industry, degrade over time by degradation and subsequent dissolution of the ion-exchange polymer in the membrane, thereby degrading the solubility and performance of the membrane. This degradation is believed to be at least partly a result of the reaction with hydrogen peroxide (H ₂ O ₂ ) radicals generated during fuel cell operation of the ion-exchange polymer in the membrane or electrode. Fluoropolymer membranes are generally considered to be more stable during fuel rolling operations than hydrocarbon membranes that do not contain fluorine, but even perfluorinated ion-exchange polymers degrade in use. And deterioration of the fluoride ion-exchange polymer are also believed to be the result of the reaction of the polymer with hydrogen peroxide.

Thus, by reducing or preventing deterioration of the proton exchange membrane or membrane electrode assembly due to its interaction with the hydrogen peroxide radical, performance is maintained while remaining stable and available for a longer period of time, resulting in reduced fuel cell cost There is a need to develop a way to be.

In the related art, Prior Patent Document 1 (10-2008-0039615A) relates to an electrolyte membrane including carbon nanotubes dispersed in a matrix of a hydrogen ion conductive polymer, and removes hydroxy radicals by the carbon nanotubes. It is. However, there is a problem in that it is difficult to commercialize because it is difficult to disperse the carbon nanotubes in the matrix of the hydrogen ion conductive polymer.

Prior Patent Document 2 (10-2007-0056324A) relates to a polymer electrolyte membrane for a fuel cell including a polymer matrix in which an oligomer is crosslinked and a nano-sized proton conductive polymer present in the polymer matrix. The sulfonic acid group may be replaced by radicals generated in or the aromatic ring may cause a decrease in conductivity and a decrease in performance of the fuel cell.

KR 10-2008-0039615 A KR 10-2007-0056324 A

An object of the present invention is the electrolyte membrane commonly used in proton-exchange membrane fuel cells, the electrical conductivity is reduced by the radicals generated from the cathode, which may cause a decrease in the performance of the fuel cell, while having resistance to radicals High durability. Provided is a polymer electrolyte membrane having improved electrical conductivity and lifespan of a fuel cell.

Another object of the present invention to provide a method for producing the polymer electrolyte membrane.

Polymer electrolyte membrane according to an embodiment of the present invention is a porous nanofiber web (Polyimide porous nanofiber web) support, an ion conductor filled in the porous nanofiber web support, and phenolic oxidation stabilizer, amine-based oxidation stabilizer, sulfur-based oxidation It includes an oxidative stabilizer which is any one selected from the group consisting of a stabilizer, a phosphorus oxidative stabilizer and a combination thereof.

The polymer electrolyte membrane may include 0.1 to 5 parts by weight of the oxidative stabilizer based on 100 parts by weight of the ion conductor.

The ion conductor consists of sulfonated polyimide, sulfonated polyarylethersulfone, sulfonated polyetheretherketone, sulfonated polybenzimidazole, sulfonated polysulfone, sulfonated polystyrene, sulfonated polyphosphazene and combinations thereof It may be any one selected from the group.

The phenolic oxidative stabilizer is 2,6-di-t-butyl-p-cresol, pentaerythryl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] , 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, octadecyl-3- (3,5-di-t-butyl 4-hydroxyphenyl) propionate, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio ) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2-thio-diethylene bis [3- (3,5-di -t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di -t-butyl-4-hydroxy-benzylphosphonate diethyl ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate and 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspir [5,5] it may be in any one selected from undecane, and combinations thereof.

The amine oxidative stabilizer is monooctyldiphenylamine, monononyldiphenylamine, 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4 Dialkyldiphenylamines such as 4,4'-diheptyl diphenylamine, 4,4'-dioctyldiphenylamine, and 4,4'-dinonyldiphenylamine, tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetra Octyldiphenylamine, tetranonyldiphenylamine, α-naphthylamine, phenyl-α-naphthylamine, but also butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α-naph It may be any one selected from the group consisting of tilamine, heptylphenyl-α-naphthylamine, octylphenyl-α-naphthylamine, nonylphenyl-α-naphthylamine, and combinations thereof.

The sulfur-based oxidative stabilizer is pentaerythryl tetrakis (3-laurylthiopropionate), distearyl 3,3'- thiodipropionate, dilauryl 3,3'- thiodipropionate and It may be any one selected from the group consisting of dismyristyl 3,3'- thiodipropionate and combinations thereof.

The phosphorus oxidative stabilizer is tris (nonylphenyl) phosphite, tris (2,4-di-t- butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,6-di-t-butyl- 4-methylphenyl) pentaerythritol diphosphite and combinations thereof may be any one selected from the group consisting of.

The porous support is made of nylon, polyimide, polybenzoxazole, polyethylene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, polyarylene ether sulfone, polyether ether ketone, copolymers thereof, and combinations thereof. It may include any one selected from the group.

The porous nanofiber web support is a polyimide porous nanofiber support,

The ion conductor may be a polyarylene ether sulfone type ion conductor or a polyether ether sulfone type ion conductor, and the oxidative stabilizer may be a polymer electrolyte which is a phenolic oxidative stabilizer.

According to another exemplary embodiment of the present invention, a method for preparing a polymer electrolyte membrane includes a phenolic oxidizing stabilizer, an amine oxidizing stabilizer, a sulfur oxidizing stabilizer, and a phosphorus oxidizing stabilizer, based on 100 parts by weight of an ion conductor and 100 parts by weight of the ion conductor. A dissolution solution preparing step of dissolving 0.1 to 5 parts by weight of an oxidative stabilizer, which is any one selected from the group consisting of 100 to 2000 parts by weight of a polar solvent, and filling the solution with a porous nanofiber web support. To include the steps.

The polar solvent may be any one selected from the group consisting of dimethyl acetamide, dimethyl formamide, N-methyl pyrrolidine, and combinations thereof.

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

Polymer electrolyte membrane according to an embodiment of the present invention is a porous nanofiber web (Polyimide porous nanofiber web) support, an ion conductor filled in the porous nanofiber web support, and phenolic oxidation stabilizer, amine-based oxidation stabilizer, sulfur-based oxidation It includes an oxidative stabilizer which is any one selected from the group consisting of a stabilizer, a phosphorus oxidative stabilizer and a combination thereof.

The porous support comprises a collection of nanofibers connected three-dimensionally irregularly and discontinuously, and thus comprises a plurality of uniformly distributed pores. The porous support composed of a plurality of pores uniformly distributed thus has excellent gas or ionic conductivity.

The pore size of the pores formed in the porous support may be in the range of 0.05 to 30 탆. If the pore size is less than 0.05 탆, the ion conductivity of the polymer electrolyte may be lowered, The mechanical strength of the polymer electrolyte may be lowered.

Also, the porosity indicating the degree of formation of pores of the porous support may be formed within a range of 50 to 98%. When the porosity of the porous support is less than 50%, the ionic conductivity of the polymer electrolyte may drop, and when the porosity exceeds 98%, the mechanical strength and the shape stability of the polymer electrolyte may decrease.

The porosity (%) can be calculated by the ratio of the air volume to the total volume of the porous support, as shown in Equation 1 below.

[Equation 1]

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

In this case, the total volume of the porous support is calculated by measuring the width, length, and thickness of a sample of a porous support in the form of a rectangular shape, and the air volume of the porous support is inverted from the density after measuring the mass of the sample of the porous support. One polymer volume can be obtained by subtracting the total volume of the porous support.

The porous support is composed of a collection of nanofibers connected three-dimensionally irregularly and discontinuously, and the average diameter of the nanofibers may range from 0.005 to 5 mu m. If the average diameter of the nanofibers is less than 0.005 탆, the mechanical strength of the porous support may deteriorate. If the average diameter of the nanofibers exceeds 5 탆, the porosity of the porous support may not be easily controlled.

Wherein the nanofiber is selected from the group consisting of nylon, polyimide, polybenzoxazole, polyethylene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, polyarylene ether sulfone, polyetheretherketone, And the present invention is not limited thereto.

The porous support may be formed to a thickness of 5 to 20㎛. When the thickness of the porous support is less than 5 μm, the mechanical strength and shape stability of the polymer electrolyte may be deteriorated. When the thickness of the porous support is more than 20 μm, the resistance loss of the polymer electrolyte may be increased.

The polymer electrolyte membrane includes an ion conductor filled in the porous support.

When operating a proton exchange membrane fuel cell, radicals formed at the cathode side move to the electrolyte membrane, and the aromatic ring is broken by the addition reaction to the aromatic ring of the polymer ion conductor, or the sulfonic acid group is dropped by the reaction with the sulfonic acid group to decrease the conductivity. You can. In addition, deterioration with the chain reaction of the radicals may reduce the life of the fuel cell.

Therefore, when the polymer ion conductor includes any one selected from the group consisting of the phenolic oxidative stabilizer, the amine oxidative stabilizer, the sulfur oxidative stabilizer, the phosphorus oxidative stabilizer, and a combination thereof, the oxidative stabilizer is included in the oxidative stabilizer. By releasing the hydrogen ions, radicals formed at the cathode may be combined with the hydrogen ions to inhibit and stabilize a radical reaction, thereby protecting the main chain of the polymer ion conductor and the sulfonic acid group included in the polymer ion conductor. In addition, the oxidative stabilizer can remain in a stable form through the resonance effect and rearrangement of the electrons even after reacting with the radicals to suppress the chain radical reaction, and to suppress the problem of degradation due to the radical reaction.

When the oxidation stabilizer is included in less than 0.1 parts by weight with respect to 100 parts by weight of the polymer ionic conductor including the sulfonic acid group, it is difficult to effectively remove the radicals, and thus the conductivity may not be prevented. The stabilizer may act as an impurity for the ion conductor in excess, and thus the conductivity may be lowered. Preferably the oxidative stabilizer may be added in 1 to 3 parts by weight. It is because there is no influence in a conductivity maintenance effect and an ion conductor in the said range, and the durability improvement effect is the most outstanding.

The ion conductor is to perform an ion conduction function which is a main function of the polymer electrolyte membrane. The ion conductor may be preferably a hydrocarbon-based polymer having excellent ion conduction function and advantageous in terms of cost, but the present invention is not limited thereto. . In particular, a hydrocarbon-based material that is soluble in an organic solvent may be more preferably used for facilitating the process of filling the ion conductor in the pores of the porous support.

The ion conductor consists of sulfonated polyimide, sulfonated polyarylethersulfone, sulfonated polyetheretherketone, sulfonated polybenzimidazole, sulfonated polysulfone, sulfonated polystyrene, sulfonated polyphosphazene and combinations thereof It may be any one selected from the group, but the present invention is not limited thereto.

On the other hand, when a hydrocarbon-based material is used as the ion conductor and a hydrocarbon-based material is used as the porous support, the hydrocarbon-based material included in the ion conductor and the hydrocarbon-based material included in the porous support may be composed of the same material system. In particular, when S-PI (sulfonated polyimide) is used as the ion conductor and polyimide is used as the porous support, adhesion between the ion conductor and the porous support may be improved.

As a specific example of the oxidative stabilizer, the phenolic oxidative stabilizer is 2,6-di-t-butyl-p-cresol, pentaerythryl tetrakis [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, octadecyl-3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 2 , 4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2-thio-diethylene bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro Cinnamid), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate diethyl ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate And 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyljade ] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane and combinations thereof, and the amine oxidative stabilizer is monooctyldi. Phenylamine, monononyldiphenylamine, 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4,4'-diheptyldiphenylamine, Dialkyldiphenylamines such as 4,4'-dioctyldiphenylamine and 4,4'-dinononyldiphenylamine, tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, tetranonyldiphenyl Amine, α-naphthylamine, phenyl-α-naphthylamine, but also butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α-naphthylamine, heptylphenyl-α-naph Tylamine, octylphenyl-α-naphthylamine, nonylphenyl-α-naphthylamine, and any combination thereof. The sulfur-based oxidative stabilizer is pentaerythryl tetraki. (3-laurylthiopropionate), distearyl 3,3'-thiodipropionate, dilauryl 3,3'-thiodipropionate and dismyristyl 3,3'-thiodipropionate Nate and a combination thereof, and the phosphorus oxidative stabilizer is tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol It may be any one selected from the group consisting of diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and combinations thereof.

The antioxidant is not particularly limited to the above examples, and can be appropriately selected in consideration of the electrolyte type, the pluton conductivity and the strength of the electrode, and can be used in combination of two or more. In the case of the antioxidant, the effect of removing the radicals generated from the cathode is effective, and the durability of the electrolyte may be further improved.

According to another exemplary embodiment of the present invention, a method for preparing a polymer electrolyte membrane includes a phenolic oxidizing stabilizer, an amine oxidizing stabilizer, a sulfur oxidizing stabilizer, and a phosphorus oxidizing stabilizer, based on 100 parts by weight of an ion conductor and 100 parts by weight of the ion conductor. A dissolution solution preparing step of dissolving 0.1 to 5 parts by weight of an oxidative stabilizer, which is any one selected from the group consisting of 100 to 2000 parts by weight of a polar solvent, and filling the solution with a porous nanofiber web support. To include the steps.

First, the dissolving step is to dissolve 100 to 2000 parts by weight of 100 parts by weight of the polymer ion conductor and 0.1 to 5 parts by weight of the oxidizing stabilizer with respect to the polymer ion conductor.

Specific examples of the oxidative stabilizer are the same as those mentioned in the polymer electrolyte membrane.

Next, the dissolving step is to dissolve the ion conductor containing the oxidative stabilizer in a polar solvent (100 to 2000 parts by weight).

The polar solvent may be any one selected from the group consisting of dimethyl acetamide, dimethyl formamide, N-methyl pyrrolidine, and combinations thereof. In the case of the polar solvent there is an advantage of excellent filling properties for the porous nanofiber web support.

Next, the filling step is to fill the solution to the polyimide porous nanofiber web support, the filling method may be any of the conventional filling method used for preparing a polymer ion conductor. Preferably, by the spray method, the duct blade method, the screen printing method, the laminating method may be excellent in contact between the polyimide porous nanofiber web support and the solution.

The polymer electrolyte membrane according to the present invention increases the resistance to radicals by adding an antioxidant to prevent degradation of performance due to radicals. In addition, durability of the electrolyte membrane can be increased, and reliability for long-term use of the proton exchange membrane fuel cell can be ensured.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[ Manufacturing example : Example  And Comparative example  Produce]

According to Table 1, an oxidative stabilizer was added to the ion conductor, and the ionic conductor to which the oxidative stabilizer was added was dissolved in a polar solvent to prepare the polymer electrolytes of Examples, Comparative Examples 1 and 2.

The single membrane according to Table 1 below is a single membrane according to a conventional electrolyte production method not filled in the polyimide porous nanofiber web support, and the reinforcement composite membrane is prepared by filling the solution with the polyimide porous nanofiber web support. .

Example Comparative Example 1 Comparative Example 2 Ion Conductor ¹⁾ 100 100 100 Polar solvent ^{2 )} 400 400 400 Oxidation Stabilizer ^{3 )} 2 - - Single membrane - O - Reinforced Composite Membrane O - O

(Parts by weight)

1) Ion conductor: Polyarylene ether sulfone type ion conductor.

2) Polar solvent: Dimethyl acetamide.

3) Oxidation stabilizer: Phenol-based oxidation stabilizer.

[ Experimental Example  One: Fenton  Test( Fenton's test )result]

Fenton test is a method for measuring radical resistance to electrolytes. The polymer electrolytes of Examples and Comparative Examples prepared according to Table 1 were immersed in a Fenton solution in which 2 ppm of iron sulfate heptahydrate was added to 3% by weight of hydrogen peroxide, and the film was deteriorated by radicals at 80 ° C. The phenomenon was tested over time.

When visually confirmed, the time at which the holes or fragments occurred was recorded as the first degradation time, and the time of complete melting was designated as the complete decomposition time.

Example Comparative Example 1 Comparative Example 2 Primary Degradation 36 hours 8 hours 24 hours Complete decomposition More than 100 hours 25 hours 100 hours

Referring to Table 2 above, In Comparative Example 1, the polymer electrolyte membrane prepared as a single membrane had little resistance to radicals, and Comparative Example 2 was prepared as a composite reinforcement membrane, and thus the mechanical strength was superior to that of Comparative Example 1, but the first reduction time was It occurred at a relatively early time point. However, in Example 1, the first reduction time was the longest, and complete decomposition did not occur until more than 100 hours, indicating that the polymer electrolyte membrane according to Example 1 had excellent resistance to radicals.

[ Experimental Example  2: conductivity experiment]

Hydrogen ion conductivity was evaluated using the polymer electrolyte membrane according to the above Examples and Comparative Examples.

Hydrogen ion conductivity was measured at 80 ° C. by a 90% humidification and four-electrode method through a resistance measuring device. The results are shown in Table 3 below.

Example Comparative Example 1 Comparative Example 2 Ion Conductivity @ 80 ℃ 0.12S / cm 0.12S / cm 0.12S / cm

Referring to Table 3, it can be seen that the above example shows the same ion conductivity as Comparative Examples 1 and 2 while improving the resistance to radicals including an oxidative stabilizer. Therefore, even in the case of Example 1, it is possible to improve the mechanical properties and the resistance to radicals without reducing the effect on the ionic conductivity.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of right.

Claims (11)

Porous porous nanofiber web support,
An ion conductor filled in the porous nanofiber web support, and
It includes an oxidative stabilizer which is any one selected from the group consisting of phenolic oxidative stabilizer, amine oxidative stabilizer, sulfur-based oxidative stabilizer, phosphorus oxidative stabilizer and combinations thereof
Polymer electrolyte membrane. The method of claim 1, wherein
The polymer electrolyte membrane
With respect to 100 parts by weight of the ion conductor,
Wherein the oxidation stabilizer is included in 0.1 to 5 parts by weight
Polymer electrolyte membrane. The method of claim 1,
The ion conductor consists of sulfonated polyimide, sulfonated polyarylethersulfone, sulfonated polyetheretherketone, sulfonated polybenzimidazole, sulfonated polysulfone, sulfonated polystyrene, sulfonated polyphosphazene and combinations thereof Which one is chosen from the group
Polymer electrolyte membrane. The method of claim 1,
The phenolic oxidative stabilizer is 2,6-di-t-butyl-p-cresol, pentaerythryl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] , 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, octadecyl-3- (3,5-di-t-butyl 4-hydroxyphenyl) propionate, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio ) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2-thio-diethylene bis [3- (3,5-di -t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di -t-butyl-4-hydroxy-benzylphosphonate diethyl ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate and 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspir [5,5] undecane, and in that the at least one selected from the group consisting of
Polymer electrolyte membrane. The method of claim 1,
The amine oxidative stabilizer is monooctyldiphenylamine, monononyldiphenylamine, 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4 Dialkyldiphenylamines such as 4,4'-diheptyl diphenylamine, 4,4'-dioctyldiphenylamine, and 4,4'-dinonyldiphenylamine, tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetra Octyldiphenylamine, tetranonyldiphenylamine, α-naphthylamine, phenyl-α-naphthylamine, but also butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α-naph Any one selected from the group consisting of tilamine, heptylphenyl-α-naphthylamine, octylphenyl-α-naphthylamine, nonylphenyl-α-naphthylamine, and combinations thereof
Polymer electrolyte membrane. The method of claim 1,
The sulfur-based oxidative stabilizer is pentaerythryl tetrakis (3-laurylthiopropionate), distearyl 3,3'- thiodipropionate, dilauryl 3,3'- thiodipropionate and Dimyristyl 3,3'- thiodipropionate and any one selected from the group consisting of
Polymer electrolyte membrane. The method of claim 1,
The phosphorus oxidative stabilizer is tris (nonylphenyl) phosphite, tris (2,4-di-t- butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,6-di-t-butyl- 4-methylphenyl) pentaerythritol diphosphite and any one selected from the group consisting of
Polymer electrolyte membrane. The method of claim 1,
The porous support is made of nylon, polyimide, polybenzoxazole, polyethylene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, polyarylene ether sulfone, polyether ether ketone, copolymers thereof, and combinations thereof. To include any one selected from the group
Polymer electrolyte membrane. The method of claim 1,
The porous nanofiber web support is a polyimide porous nanofiber support,
The ion conductor is a polyarylene ether sulfone ion conductor or a polyether ether sulfone ion conductor, and
The oxidative stabilizer is a phenolic oxidative stabilizer
Polymer electrolyte membrane. 100 parts by weight of an ion conductor and
0.1 to 5 parts by weight of an oxidizing stabilizer, which is any one selected from the group consisting of a phenolic oxidative stabilizer, an amine oxidative stabilizer, a sulfur oxidative stabilizer, a phosphorus oxidative stabilizer, and a combination thereof, based on 100 parts by weight of the ion conductor.
A dissolving step of dissolving 100 to 2000 parts by weight of a polar solvent, and
It comprises a filling step of filling the solution to the porous nanofiber web support
Method for producing a polymer electrolyte membrane. The method of claim 10,
The polar solvent is any one selected from the group consisting of dimethyl acetamide, dimethyl formamide, N-methyl pyrrolidine, and combinations thereof.
Method for producing a polymer electrolyte membrane.