KR102008400B1 - Polymer eletrolyte membrane - Google Patents

Abstract

The present invention provides a polymer electrolyte membrane, which comprises an air permeable support and an ion conductive polymer electrolyte. The air permeable support is an air permeable support having air permeability of 0.2 to 6 cfm and pore distribution of ±0.3 μm. According to the present invention, the air permeability and pore size distribution of the support used in the polymer electrolyte membrane can be adjusted to a predetermined value.

Description

Polymer Electrolyte Membrane {POLYMER ELETROLYTE MEMBRANE}

The present invention relates to a polymer electrolyte membrane having improved mechanical properties and performance and a method of manufacturing the same.

Recently, as it is known that nitrogen oxides and sulfur oxides generated during the exhaustion of resources and power generation by thermal power generation cause serious problems in environmental pollution, interest in environmentally friendly energy generation is increasing. As one of the environmentally friendly energy, a fuel cell is a chemical cell that converts chemical energy by oxidation of hydrogen and oxygen, which are fuels, into electrical energy.It is simple to operate, has high energy efficiency, has no noise during power generation, and produces pure water and It has an environmentally friendly feature of reusing reusable heat. Due to these advantages, it is widely used as a power source for home, automobile, and power generation.

Further, fuel cells generally have a structure in which a polymer electrolyte membrane is provided between an anode and a cathode. The polymer electrolyte membrane is prepared using a fluorine-based or hydrocarbon-based resin having ion conductivity. When the membrane is manufactured only with the ion conductive polymer, since the swelling by water in the use environment is large and the durability thereof is lowered, the research on the polymer electrolyte membrane which supplements the above point by using the ion conductive polymer and the support together in recent years has been actively conducted. It's going on.

The support used for the polymer electrolyte membrane uses an air permeable material. Since the air permeable support must maintain ion conductivity in the thickness direction, it is used as a method of filling the ion conductive polymer electrolyte into the pores of the air permeable support. At this time, the air permeability of the air permeable support is important. When the air permeability is too high, the mechanical properties of the support are lowered. When the air permeability is too low, the pores of the support are too small to fill the pores with the ion conductive polymer. In the case of nonwoven fabrics or nanomembrane, the pore size is mostly formed randomly and has high air permeability. However, irregularities in the pore size of the support cause non-uniform generation of ion channels, thereby degrading the performance of the electrolyte membrane, and high air permeability has a problem of deteriorating the mechanical properties of the electrolyte membrane.

The present invention has been made in view of the above problems, and an object thereof is to provide a polymer electrolyte membrane having improved mechanical properties and performance and a method of manufacturing the same.

MEANS TO SOLVE THE PROBLEM In order to achieve the said subject, the present inventors performed earnestly and found that the said objective can be achieved by using the support | carrier which has predetermined | prescribed air permeability and pore size distribution as a permeable support for a polymer electrolyte membrane. It was found out and completed this invention.

In other words, according to the present invention,

(1) an air permeable support and an ion conductive polymer electrolyte,

The polymer electrolyte membrane, wherein the air permeable support is an air permeable support having an air permeability of 0.2 to 6 cfm and a pore size distribution of ± 0.3 μm;

(2) the polymer electrolyte membrane according to (1), wherein the air permeable support preferably has an air permeability of 0.5 to 4 cfm;

(3) The polymer electrolyte membrane according to (1), wherein the air permeable support has an elastic modulus of 300 MPa or more;

(4) The polymer electrolyte membrane according to (1), wherein the air permeable support has an MD strength of 22 MPa or more;

(5) the polymer electrolyte membrane according to (1), wherein the air permeable support has a dynamic friction coefficient of 0.1 to 3.0;

(6) the polymer electrolyte membrane according to (1), wherein the air permeable support is heat treated at 100 ° C to 250 ° C;

(7) The polymer electrolyte membrane according to (1), wherein the air permeable support is subjected to chemical treatment for 5 minutes to 1 hour by placing the support in a solvent;

(8) The solvent is a single solvent or two or more mixed solvents selected from the group consisting of ethanol, methanol, propanol, N, N-dimethylformamide, N, N-dimethylacetamide and water, The polymer electrolyte membrane according to 8);

(9) A method for producing a polymer electrolyte membrane comprising an air permeable support and an ion conductive polymer electrolyte,

The air permeable support is subjected to heat treatment at 100 ° C. to 250 ° C. to produce an air permeability of 0.2 to 6 cfm and a pore size distribution of ± 0.3 μm;

(10) A method for producing a polymer electrolyte membrane comprising an air permeable support and an ion conductive polymer electrolyte,

The air permeable support is a method of producing a polymer electrolyte membrane, characterized in that through the step of chemical support for 5 minutes to 1 hour to put the support in a solvent, the air permeability of 0.2 to 6 cfm, ± 0.3 ㎛ pore size distribution ;

 (11) (9) or (10) comprising impregnating a solution comprising the ion conductive polymer electrolyte into an air permeable support having an air permeability of 0.2 to 6 cfm and a pore size distribution of ± 0.3 μm. A method for producing the described polymer electrolyte membrane;

This is provided.

According to the present invention, it is possible to provide a polymer electrolyte membrane having improved mechanical properties, including an air permeable support having a predetermined air permeability and pore size distribution, and improving the performance by uniformly inducing ion channels.

In addition, according to the present invention, the air permeability and pore size distribution of the support used in the polymer electrolyte membrane can be adjusted to a predetermined value.

1 is a view showing the pore size and pore size distribution of the air permeable support after heat treatment of the present invention.
2 is a diagram showing the pore size and pore size distribution of the air permeable support before processing.

Hereinafter, the present invention will be described in detail with reference to embodiments. However, this is presented as an example, by which the present invention is not limited, and the present invention is defined only by the scope of the following claims. In addition, even if it is the structure which is essential for implementing this invention, the detailed description is abbreviate | omitted about the structure which a person skilled in the art can easily implement from a well-known technique.

The polymer electrolyte membrane includes an air permeable support and an ion conductive polymer electrolyte. The air permeable support includes a plurality of pores, and is filled with an ion conductive polymer electrolyte in the pores. Here, as the air permeable support, a fibrous support including a plurality of pores, such as a nonwoven fabric having air permeability, is used, and such air permeable support generally has an air permeability of more than six. However, if the air permeability of the support is too large, the mechanical properties such as tensile strength and elastic modulus of the polymer electrolyte membrane are lowered. Therefore, in order to obtain a polymer electrolyte membrane having good mechanical properties, it is necessary to lower the air permeability of the support to an appropriate level. have. Thus, the polymer electrolyte membrane according to the present invention is the air permeability and pore size distribution of the support is adjusted, the air permeable support has an air permeability of 0.2 to 6 cfm.

The air permeability of the air permeable support used in the polymer electrolyte membrane according to the present invention can be lowered to an appropriate level by a method of applying heat treatment and / or chemical treatment to the air permeable support. The air permeability of the air permeable support thus processed is preferably 0.2 to 6 cfm, more preferably 0.5 to 4 cfm, and more preferably 1.0 to 3.4 cfm. If the air permeability of the support is less than the lower limit of the above range, the ion conductive polymer electrolyte is not well filled inside the pores of the support to produce a desired membrane, and if the upper limit of the above range is exceeded, the ion conductive polymer electrolyte is sufficiently attached to the support. There is a fear that a desired film cannot be produced because it is not included.

Moreover, the air permeable support body used for the polymer electrolyte membrane which concerns on this invention should just have an air permeability of 0.2-6 cfm, and there is no restriction | limiting in particular in the specific shape or material. As the polymer constituting the air permeable support, a single or two or more kinds of mixed polymers such as polyimide, polyamideimide, polyetherimide, polyethersulfone, polyvinylidene fluoride (PVdF), polyester, etc. may be used. Can be.

In addition, the air-permeable support is generally used non-woven fabric or nano-membrane with irregular pore size, such that when the pore size of the support is formed randomly, the performance of the resulting polymer electrolyte membrane is deteriorated and does not exhibit the desired physical properties. Accordingly, the air permeable support used in the polymer electrolyte membrane according to the present invention reduces the size of excessively large pores present on the surface of the support by applying heat treatment and / or chemical treatment, The pores of the size are made uniform in the pore size of the support without damaging the pores. As such, when the ion conductive polymer electrolyte is filled in the pores of the support having the uniform pore size, a uniform ion channel can be formed, thereby improving performance such as ion conductivity of the prepared polymer electrolyte membrane. The pore size distribution of the air permeable support is preferably ± 0.3 μm, more preferably ± 0.2 μm. As the pore size distribution of the support is smaller, that is, the pore size is uniform, resistance elements that may occur when the ion channel is formed may be reduced, thereby improving performance such as ion conductivity.

As shown in Fig. 1, the air-permeable support subjected to the heat treatment according to the present invention has a very small pore size distribution and the pore size is uniform, whereas in the case of the support before the processing of Fig. 2, the pore size is Unevenly scattered over a wide range.

Further, the air permeable support according to the present invention is an air permeable support having a predetermined range of air permeability and a uniform pore size by applying heat treatment or chemical treatment to a conventional air permeable support. As such, the polymer electrolyte membrane prepared by using an air permeable support having a predetermined range of air permeability and uniform pore size improves mechanical properties such as elastic modulus and tensile strength of the membrane, and uniformly induces ion channels to ion conductivity. The performance is improved. In particular, the elastic modulus and tensile strength of the polymer electrolyte membrane prepared using the air permeable support are improved because of the occurrence of entanglement between the supports.

The air permeable support may have a small pore size distribution so that the pore size is uniform and there is no particular limitation on the pore size. However, the air permeable support is preferably formed in the range of 0.05 to 10 μm in consideration of the mechanical strength and the ionic conductivity of the polymer electrolyte membrane. Do. If the pore size of the support is less than 0.05 μm, the ion conductive polymer electrolyte particles may not penetrate and the ion conductivity of the polymer electrolyte membrane may be lowered. If the pore size is more than 10 μm, the mechanical strength characteristics of the polymer electrolyte membrane may be degraded. have.

The air permeable support preferably exhibits an elastic modulus of 300 MPa or more, more preferably 350 MPa or more. Furthermore, the air permeable support preferably has a tensile strength of 20 MPa or more (MD direction), and more preferably has a tensile strength of 30 MPa or more. In the case of a support having a modulus of elasticity and tensile strength lower than the above range, there is a fear that a polymer electrolyte membrane exhibiting desired performance may not be obtained.

Moreover, it is preferable that an air permeable support body has a dynamic friction coefficient of 0.1-3.0. When the air permeable support has a kinetic friction coefficient within the above range, the support surface is flattened to have excellent smoothness, and the running property is favored at the time of continuous production, which makes it easy to manufacture.

In order to lower the air permeability of the air permeable support to an appropriate level and to uniform the pore size, a method of applying heat treatment and / or chemical treatment to the air permeable support can be used. There is no particular limitation on the heat treatment and chemical treatment method, but in the case of heat treatment, a method of heat treatment of the support at a temperature of 100 ° C. to 250 ° C. and within 10 minutes is preferable, and a temperature of 100 ° C. to 200 ° C. and 30 seconds More preferred is a method of heat treatment at a condition of from 5 minutes. In addition, in the case of chemical treatment, the support is placed in a solvent and chemically treated for 5 minutes to 1 hour, and more preferably 5 to 30 minutes. In chemical treatment, the support is immersed in a solvent for 5 minutes to 1 hour, taken out, washed with water appropriately, and then dried at a temperature of about 80 ° C. Here, the solvent may be, for example, a single solvent or two or more mixed solvents selected from the group consisting of ethanol, methanol, propanol, N, N-dimethylformamide, N, N-dimethylacetamide and water. It can be used without any special restrictions. By applying heat treatment and / or chemical treatment to the air permeable support, the air permeable support according to the present invention has an appropriate level of air permeability and uniform pore size, and thus the elastic modulus, tensile strength, and the like of the polymer electrolyte membrane to be produced. Performance such as mechanical properties and ion conductivity can be improved.

Although the thickness of an air permeable support body is not specifically limited, Usually, it is 1-100 micrometers, Preferably it is 3-60 micrometers. The thickness of the air permeable support can be adjusted as needed, but if the thickness of the support is too small, the mechanical strength of the membrane may be inferior. On the contrary, if the thickness of the support is too large, the resistance loss may increase when applied to the polymer electrolyte membrane.

Impregnation is mentioned as a method of filling an ion conductive polymer electrolyte into the pores of an air permeable support body. The impregnation method may be performed by immersing the air permeable support in a solution containing an ion conductive polymer electrolyte. In addition, the air permeable support may be formed by immersing the monomer or low molecular weight oligomer of the ion conductive polymer electrolyte and then in-situ polymerizing the monomer or low molecular weight oligomer in the air permeable support.

Impregnation temperature and time can be affected by various factors. For example, it may be influenced by the thickness of the support, the concentration of the ion conductive polymer electrolyte, the kind of the solvent, the concentration of the ion conductive polymer to be impregnated in the air permeable support, and the like. Further, the impregnation process may be performed at a temperature of 100 ° C. or less above the freezing point of the solvent, and preferably at room temperature of 70 ° C. or less.

The ion conductive polymer electrolyte may be a fluorine-based or hydrocarbon-based polymer without particular limitation, and may be selected from the group consisting of sulfonic acid groups, carboxylic acid groups, boronic acid groups, phosphoric acid groups, imide groups, sulfonimide groups, sulfonamide groups, and derivatives thereof. It may be a cation exchange polymer having a cation exchange group selected or an anion exchange polymer having an anion exchange group such as hydroxy ions, carbonates or bicarbonates. The ion exchanger equivalent is 500 to 1500 EW.

The cation exchange polymer includes a cation exchange group, a fluorine-based polymer containing fluorine in the main chain; Benzimidazole, polyamide, polyamideimide, polyimide, polyacetal, polyethylene, polypropylene, acrylic resin, polyester, polysulfone, polyether, polyethersulfone, polyetherimide, polycarbonate, polystyrene, polyphenylene Hydrocarbon-based polymers such as sulfide, polyether ether ketone, polyether ketone, polyaryl ether sulfone, polyphosphazene or polyphenylquinoxaline; Partially fluorinated polymers such as polystyrene-graft-ethylenetetrafluoroethylene copolymer or polystyrene-graft-polytetrafluoroethylene copolymer; Sulfone imides and the like.

The anion exchange polymer is capable of transporting anions such as hydroxy ions, carbonates or bicarbonates, and the anion exchange polymer is commercially available in the form of hydroxide or halide (generally chloride). As the anion exchange polymer, a metal hydroxide-doped polymer may be generally used. Specifically, poly (ethersulfone), polystyrene, vinyl-based polymer, poly (vinylchloride), poly (vinylidene fluoride) doped with metal hydroxide ), Poly (tetrafluoroethylene), poly (benzimidazole) or poly (ethylene glycol) and the like can be used, but is not limited thereto.

In the impregnation method, the solution containing the ion conductive polymer electrolyte is a solution of a melt or a solvent of the ion conductive polymer. In the case of a solution in which the solvent is mixed, the solvent includes alcohols such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, water, and the like. It includes, and may be used alone or a mixed solvent using two or more kinds. The viscosity is preferably 5 cP or more and 25,000 cP or less, and preferably 10 cP or more and 10,000 cP or less.

The method of impregnating the air permeable support with the ion conductive polymer electrolyte solution is not particularly limited, and there are various methods such as die coating, gravure coating, roll coating, comma coating, bar coating, dip coating, and die coating is most preferred. Furthermore, after impregnating the ion conductive polymer electrolyte into the air permeable support, heat treatment for drying is required. The temperature at this time can be dried by setting a drying temperature in accordance with the nature of the solvent of the ion conductive polymer electrolyte. When the solvent is ethanol, the solvent is slowly dried at 60 to 80 ° C. for 5 to 10 minutes. At this time, it is preferable that the temperature profile gradually increases. When initially dried at an excessively high temperature, cracks or pinholes may occur on the surface of the resulting polymer electrolyte membrane.

The polymer electrolyte membrane prepared by the above method requires a post processing process according to the type of the ion conductive polymer electrolyte. Post-processing processes include heat treatment, acid treatment, and the like, and may include single or multiple processes. In the case of heat treatment, the crystallinity of the ion conductive polymer may be increased to enhance mechanical properties or to improve durability. The heat treatment is carried out above the crystallization temperature of the ion conductive polymer. In addition, in the case of acid treatment, the sodium salt or potassium salt present in the ion conductive polymer end group can be carried out to convert to the acid form. The acid treatment may be performed by selecting one of strong acids such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and the like of 1M or more.

Further, according to the present invention, in the method for producing a polymer electrolyte membrane comprising an air permeable support and an ion conductive polymer electrolyte, the air permeable support is subjected to heat treatment at 100 ° C to 250 ° C, and 0.2 to 6 The air permeability of cfm has a pore size distribution of ± 0.3 μm. In addition, in the method for producing a polymer electrolyte membrane comprising an air permeable support and an ion conductive polymer electrolyte, the air permeable support is subjected to a chemical treatment for 5 minutes to 1 hour in a solvent, 0.2 to 6 cfm of air Permeability, ± 0.3 μm pore size distribution. The air permeable support prepared in this manner can improve the mechanical properties and performance of the membrane when used as a support for the polymer electrolyte membrane.

Furthermore, by using the polymer electrolyte membrane according to the present invention, it is possible to provide a fuel cell having a membrane electrode assembly (MEA), an anode, and a reducing electrode, and a fuel cell is generally a method known in the art to which the present invention pertains. It can employ | adopt and manufacture. Specifically, the fuel cell may include at least one electricity generating unit generating electricity through an oxidation reaction of a fuel and a reduction reaction of an oxidant; A fuel supply unit and an oxidant supply unit for supplying a fuel and an oxidant to the electricity generating unit, wherein the electricity generating unit includes a separator for supplying fuel and oxidant to both sides of the membrane electrode assembly and the membrane electrode assembly. In the fuel cell, since the membrane electrode assembly, the separator constituting the electricity generating unit, the fuel supply unit and the oxidant supply unit are generally used in the fuel cell, detailed description thereof will be omitted.

Example

An Example and a comparative example are given to the following, and this invention is demonstrated more concretely. However, the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Property evaluation method

1. Air permeability measurement

As for the air permeability of a support body, 3 or more samples of area 38 cm <^2> are measured on the conditions of 125 Pa of pressure by the ASTM D 737 method which is the air permeability measurement method of a fabric, and the average value is used. This can be measured with an Air Permeability Tester (FX 3300, Textest Instruments) that meets ASTM D 737. The unit uses cfm.

2. Pore size measurement

Capillary flow porometer, Porous materials, CFP-1200AE (CFP-1200AE), using the same sample is measured by taking three or more, the average value is used.

3. Measurement of elastic modulus and tensile strength

The elastic modulus and tensile strength of the air permeable support were measured according to ASTM D 882 using a universal testing machine (UTM-3365). Measure at least 5 places and use the average value.

4. Basis weight measurement

The basis weight of the specimen was measured according to KS K 0514. Using a circular specimen cutter, take a specimen of 100 cm ² area, measure the weight, and convert it into units of g / m ² . Measure at least 3 places and use the average value.

5. Measurement of dynamic friction coefficient

The dynamic friction coefficient of the air permeable support was measured according to ASTM D 1894. Three or more places are measured with a friction abrasion tester, and the average value is used.

6. Thickness measurement

In accordance with KS M ISO 4593, the thickness is measured with a measuring instrument displayed up to 0.001 μm at intervals of 1 cm in the width direction, and an average value is used.

7. Ionic Conductivity Measurement

The polymer electrolyte membrane is cut to size 1 x 4 cm and fixed to the measuring jig. The measuring jig is made of PTFE, and the electrode is made of platinum. The polymer electrolyte membrane fixed to the measuring jig was RH 100%. After treatment at 25 ° C. for 2 hours or more, the impedance is measured using an impedance measuring instrument (Bio Logic Science Instruments, Impedance Meter, SP-300), and then ion conductivity is calculated using the following equation. The average value of the value obtained by measuring five or more times from the same sample is used. Through this, the degree of ion channel formation can be evaluated.

<Equation 1>

Ionic Conductivity = L / (W * Z * R * 10 ^-4 ) [S / cm]

Where R is the measurement resistance (Ω), W is the longitudinal length of the electrolyte membrane (cm, 1 in the method), L is the length between the measurement electrodes (cm), and Z is the thickness of the prepared electrolyte membrane (μm). )

8. Hydrogen Permeability Measurement

In order to measure the hydrogen permeability of the membrane electrode assembly, it was measured in the unit cell form using LSV (Linear Sweep Voltammetry). Using a Scribner 850e instrument at 0.1V to 0.6V and a scan rate of 0.2 mV / s, H ₂ / N ₂ was added to the anode / reduction electrode at a temperature of 70 ° C and a relative humidity of 100% 1.5 / 2 SR (stoichiometry ratio) 1.5 / 2 Measure while supplying When the hydrogen permeability exceeds 2 mA / cm ² , hydrogen permeation occurs and there is a fear of deterioration in performance.

Example 1

(Air permeable support manufacturing method)

Air permeable PVdF supports having an air permeability of 6.4 cfm are processed using calender equipment. Set the temperature to 120 ° C. and heat treatment for 30 seconds without pressure. The air permeability of the processed support was 1.8 cfm.

(Polymer Electrolyte Membrane Manufacturing Method)

After applying the ion conductive polymer electrolyte (3M, Dyneon E-22397) with a bar coater on the substrate using an applicator, the heat-treated air permeable support was placed on the coated polymer electrolyte and dried in an oven at 80 ° C. for 5 minutes. do. Thereafter, the same ion conductive polymer electrolyte was again applied to the bottom coated membrane with a bar coater using an applicator, and then dried in an oven at 80 ° C. for 5 minutes. The dried membrane is heat treated at 150 ° C. for 5 minutes. In the polymer electrolyte membrane thus prepared, the air permeability, pore size and distribution of the support, the film thickness, the ionic conductivity, the tensile strength and the elastic modulus were measured by the above-described method, and the results are shown in Table 1.

(Method for manufacturing membrane electrode assembly (MEA))

On the produced polymer electrolyte membrane, a membrane electrode assembly in which an electrode layer was formed by using the decal method was prepared. At this time, the catalyst layer of the electrode is coated with a catalyst layer-forming composition comprising a platinum / carbon catalyst and a polymer electrolyte on a release film and dried to form a catalyst layer, and the release layer coated with a catalyst layer on both sides of the polymer electrolyte membrane Thereafter, hot pressing was carried out at a pressure of 5 kg / cm ² and a temperature of 100 ° C. to transfer the catalyst layer. Subsequently, a gas diffusion layer (GDL) was attached to both surfaces of the polymer electrolyte membrane to which the catalyst layer was bonded to prepare a membrane electrode assembly. At this time, the loading amount of the catalyst was 0.3 mg / cm ² . The hydrogen permeability was measured by the method mentioned above about the MEA manufactured in this way, and the result is shown in Table 1.

Example 2

(Air permeable support manufacturing method)

The air permeable PVdF support having an air permeability of 6.4 cfm was immersed in a mixed solution of 4: 6 mixed with DMF and ethanol, and after about 5 minutes, the support was taken out, washed with water and dried. The air permeability of the processed support was 2.0 cfm.

(Polymer Electrolyte Membrane Manufacturing Method)

Ion conductive polymer electrolyte (3M, Dyneon E-22397) was applied on the substrate with a bar coater using an applicator, and then the above chemically treated air permeable support was placed on the coated polymer electrolyte and dried in an 80 ° C. oven for 5 minutes. do. Thereafter, the same ion conductive polymer electrolyte was again applied to the bottom coated membrane with a bar coater using an applicator, and then dried in an oven at 80 ° C. for 5 minutes. The dried film is heat treated at 150 ° C. for 5 minutes. In the polymer electrolyte membrane thus prepared, the air permeability, pore size and distribution of the support, the film thickness, the ionic conductivity, the tensile strength and the elastic modulus were measured by the above-described method, and the results are shown in Table 1. In addition, MEA was prepared in the same manner as in Example 1 using the prepared polymer electrolyte membrane, and the hydrogen permeability was measured by the above-described method, and the results are shown in Table 1.

Comparative Example 1

(Polymer Electrolyte Membrane Manufacturing Method)

An ion conductive polymer electrolyte (3M, Dyneon E-22397) is applied on a substrate using a bar coater using an applicator, and then dried in an oven at 80 ° C. for 5 minutes. The dried membrane is heat treated at 150 ° C. for 5 minutes. In the polymer electrolyte membrane thus prepared, the air permeability, pore size and distribution of the support, the film thickness, the ionic conductivity, the tensile strength and the elastic modulus were measured by the above-described method, and the results are shown in Table 1. In addition, MEA was prepared in the same manner as in Example 1 using the prepared polymer electrolyte membrane, and the hydrogen permeability was measured by the above-described method, and the results are shown in Table 1.

Comparative Example 2

(Polymer Electrolyte Membrane Manufacturing Method)

Ion conductive polymer electrolyte (3M, Dyneon E-22397) was applied to the substrate with a bar coater using an applicator, and then an air-permeable support without heat treatment was placed on the coated polymer electrolyte, followed by 5 minutes in an 80 ° C. oven. To dry. Thereafter, the same ion conductive polymer electrolyte was again applied to the bottom coated membrane with a bar coater using an applicator, and then dried in an oven at 80 ° C. for 5 minutes. The dried membrane is heat treated at 150 ° C. for 5 minutes. In the polymer electrolyte membrane thus prepared, the air permeability, pore size and distribution of the support, the film thickness, the ionic conductivity, the tensile strength and the elastic modulus were measured by the above-described method, and the results are shown in Table 1. In addition, MEA was prepared in the same manner as in Example 1 using the prepared polymer electrolyte membrane, and the hydrogen permeability was measured by the above-described method, and the results are shown in Table 1.

Comparative Example 3

(Polymer Electrolyte Membrane Manufacturing Method)

A polymer electrolyte coated with an air permeable support that was coated with an ion conductive polymer electrolyte (3M, Dyneon E-22397) using a bar coater using an applicator on a substrate and then heat treated at 95 ° C. for 1 minute without pressure using a calender equipment. Place on top and dry in oven at 80 ° C. for 5 minutes. Thereafter, the same ion conductive polymer electrolyte was again applied to the bottom coated membrane with a bar coater using an applicator, and then dried in an oven at 80 ° C. for 5 minutes. The dried membrane is heat treated at 150 ° C. for 5 minutes. In the polymer electrolyte membrane thus prepared, the air permeability, pore size and distribution of the support, the film thickness, the ionic conductivity, the tensile strength and the elastic modulus were measured by the above-described method, and the results are shown in Table 1. In addition, MEA was prepared in the same manner as in Example 1 using the prepared polymer electrolyte membrane, and the hydrogen permeability was measured by the above-described method, and the results are shown in Table 1.

As is clear from Table 1, the polymer electrolyte membranes of Examples 1 and 2, in which the air permeability of the air permeable support is in a predetermined range and the pore size distribution of the support is ± 0.3 μm or less, the ion conductivity of the prepared polymer electrolyte membrane, hydrogen It can be seen that it is excellent in all of the transmittance, the tensile strength and the elastic modulus.

On the other hand, in the case of a polymer electrolyte membrane using a support having a large pore size distribution of the air permeable support and having a non-uniform pore size (Comparative Example 2), and a polymer electrolyte membrane prepared without using an air permeable support (Comparative Example) In 1), compared with Examples 1 and 2, it turns out that both the ionic conductivity, hydrogen permeability, tensile strength, and elastic modulus of a polymer electrolyte membrane are inferior.

In addition, although the air permeability of the air permeable support satisfies a predetermined range, the polymer electrolyte membrane having a non-uniform pore size such that the pore size distribution of the support exceeds ± 0.3 μm also has the ion of the polymer electrolyte membrane, as compared with Examples 1 and 2. It can be seen that the conductivity, hydrogen permeability, tensile strength and elastic modulus are all inferior.

Claims (11)

An air permeable support and an ion conductive polymer electrolyte,
Wherein the air permeable support is an air permeable support having an air permeability of 0.2 to 6 cfm and a pore size distribution of ± 0.3 μm. The method of claim 1,
The polymer electrolyte membrane, wherein the air permeable support has an air permeability of 0.5 to 4 cfm. The method of claim 1,
The polymer electrolyte membrane, wherein the air permeable support has an elastic modulus of 300 MPa or more. The method of claim 1,
The polymer electrolyte membrane, wherein the air permeable support has an MD strength of 22 MPa or more. The method of claim 1,
The polymer electrolyte membrane, wherein the air permeable support has a dynamic friction coefficient of 0.1 to 3.0. The method of claim 1,
The polymer permeable membrane, wherein the air permeable support is heat treated at 100 ° C to 250 ° C. The method of claim 1,
The polymer permeable membrane is the air permeable support, the support is placed in a solvent and chemically treated for 5 minutes to 1 hour. The method of claim 7, wherein
The polymer electrolyte membrane, wherein the solvent is a single solvent or a mixed solvent selected from the group consisting of ethanol, methanol, propanol, N, N-dimethylformamide, N, N-dimethylacetamide and water. In the method for producing a polymer electrolyte membrane comprising an air permeable support and an ion conductive polymer electrolyte,
The air permeable support is subjected to heat treatment at 100 ° C. to 250 ° C. to produce an air permeability of 0.2 to 6 cfm and a pore size distribution of ± 0.3 μm. In the method for producing a polymer electrolyte membrane comprising an air permeable support and an ion conductive polymer electrolyte,
The air permeable support is a method of producing a polymer electrolyte membrane, characterized in that through the step of chemical support for 5 minutes to 1 hour to put the support in a solvent, the air permeability of 0.2 to 6 cfm, ± 0.3 ㎛ pore size distribution . The method according to claim 9 or 10,
And impregnating the solution containing the ion conductive polymer electrolyte into an air permeable support having an air permeability of 0.2 to 6 cfm and a pore size distribution of ± 0.3 μm.

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