KR102300431B1 - composite for production of perfluorinated sulfonic acid ionomer, perfluorinated sulfonic acid ionomer using the same, complex electrolyte membrane for PEMFC containing the same and membrane electrode assembly for PEMFC containing the same - Google Patents

Abstract

The present invention relates to a composition for manufacturing a perfluorinated sulfonic acid ionomer, the perfluorinated sulfonic acid ionomer using the same, a complex electrolyte membrane for PEMFC containing the same, and a membrane-electrode assembly for PEMFC containing the same. More specifically, the present invention relates to a composition for manufacturing a perfluorinated sulfonic acid ionomer not only has excellent safety, but also has improved durability, the perfluorinated sulfonic acid ionomer using the same, a complex electrolyte membrane for PEMFC containing the same, and a membrane-electrode assembly for PEMFC containing the same.

Description

A composition for manufacturing a perfluorinated sulfonated ionomer, a perfluorinated sulfonated ionomer using the same, a composite electrolyte membrane for PEMFC including the same, and a membrane-electrode assembly for PEMFC including the same same, complex electrolyte membrane for PEMFC containing the same and membrane electrode assembly for PEMFC containing the same}

The present invention relates to a composition for preparing a perfluorinated sulfonated ionomer, a perfluorinated sulfonated ionomer using the same, a composite electrolyte membrane for PEMFC including the same, and a PEMFC membrane-electrode assembly including the same, which has excellent safety and durability The improved composition for preparing a perfluorinated sulfonated ionomer, a perfluorinated sulfonated ionomer using the same, a composite electrolyte membrane for PEMFC including the same, and a PEMFC membrane-electrode assembly including the same.

A fuel cell is a power generation system that directly converts chemical energy generated by the electrochemical reaction of fuel (hydrogen or methanol) and oxidizing agent (oxygen) into electrical energy. is being researched and developed. Fuel cells can be used by selecting high-temperature and low-temperature fuel cells depending on the application field, and are generally classified according to the type of electrolyte. For high-temperature applications, solid oxide fuel cells (SOFC), molten carbonate There is a fuel cell (Molten Carbonate Fuel Cell, MCFC), and for low-temperature applications, an alkaline electrolyte fuel cell (AFC) and a polymer electrolyte fuel cell (PEMFC) are being developed.

미만의 낮은 작동온도, 고체 전해질 사용으로 인한 누수문제 배제, 빠른 시동과 응답 특성, 및 우수한 내구성 등의 장점으로 휴대용, 차량용, 및 가정용 전원장치로 각광을 받고 있다. 특히 다른 형태의 연료전지에 비하여 전류밀도가 큰 고출력 연료전지로서, 소형화가 가능하기 때문에 휴대용 연료전지로의 연구가 계속 진행되고 있다.If the polymer electrolyte fuel cell is subdivided, the hydrogen ion exchange membrane fuel cell (PEMFC) uses hydrogen gas as a fuel, and direct methanol is used by supplying liquid methanol as a direct fuel to the anode. Direct Methanol Fuel Cell (DMFC) and the like. Polymer electrolyte fuel cell is 100

Due to its advantages such as low operating temperature, elimination of leakage problems due to the use of solid electrolyte, fast start-up and response characteristics, and excellent durability, it is in the spotlight as a portable, vehicle, and home power supply device. In particular, as a high-output fuel cell having a higher current density than other types of fuel cells, research on a portable fuel cell is ongoing because it can be miniaturized.

The unit cell structure of such a fuel cell has a structure in which an anode (anode) and a cathode (cathode, an oxygen electrode) are coated on both sides of an electrolyte membrane composed of a polymer material, which is a membrane-electrode assembly (Membrane). Electrode Assembly (MEA). This membrane-electrode assembly (MEA) is a part where the electrochemical reaction of hydrogen and oxygen occurs, and is composed of a reducing electrode, an oxide electrode, and an electrolyte membrane, that is, an ion conductive electrolyte membrane (eg, a hydrogen ion conductive electrolyte membrane).

At the anode, hydrogen or methanol, which is a fuel, is supplied to cause an oxidation reaction of hydrogen to generate hydrogen ions and electrons. .

This membrane-electrode assembly has a form in which the electrode catalyst layers of the anode and the cathode are coated on both sides of the ion conductive electrolyte membrane, and the material constituting the electrode catalyst layer is Pt (platinum) or Pt-Ru (platinum-ruthenium), etc. of the catalyst material is supported on a carbon carrier. Membrane-electrode assembly (MEA), which can be seen as a key component of the electrochemical reaction of a fuel cell, uses an ion-conducting electrolyte membrane and a platinum catalyst, which have a high cost composition, and is directly related to power production efficiency. It is regarded as the most important part in improving the performance and price competitiveness of

The conventional method for manufacturing MEA, which is generally used, is to prepare a paste by mixing a catalyst material, a hydrogen ion conductive binder, that is, a fluorine-based Nafion ionomer, and water and / or an alcohol solvent, This is coated on carbon cloth or carbon paper that serves as an electrode support for supporting the catalyst layer and a gas diffusion layer at the same time, and then dried and thermally fused to a hydrogen ion conductive electrolyte membrane.

In the catalyst layer, the oxidation-reduction reaction of hydrogen and oxygen by a catalyst; movement of electrons by the adhered carbon particles; securing a passage for supplying hydrogen, oxygen and moisture and for discharging excess gas after reaction; The movement of oxidized hydrogen ions and the like must occur simultaneously. Moreover, in order to improve the performance, it is necessary to reduce the activation polarization by increasing the area of the triple phase boundary where the feed fuel meets the catalyst and the ion conductive polymer electrolyte membrane, and the interface between the catalyst layer and the electrolyte membrane and the catalyst layer It is necessary to uniformly bond the interface between the gas diffusion layer and the gas diffusion layer to reduce Ohmic polarization at the interface. Therefore, in order to improve the performance of the fuel cell by maximally reducing the interfacial resistance between the catalyst layer and the electrolyte membrane, there must be bonding strength between the catalyst layer and the electrolyte membrane during MEA manufacturing, as well as the interfacial bonding between the catalyst layer and the electrolyte membrane during fuel cell operation. should be maintained

Accordingly, in recent years, technology for uniformly bonding the interface between the catalyst layer and the electrolyte membrane and the interface between the catalyst layer and the gas diffusion layer has been actively developed, but the interface uniformity is still limited.

In addition, in the case of the MEA having the above-described structure, since an electrolyte membrane having a thick thickness is generally used, the transfer of hydrogen ions may be delayed, and thus performance may be deteriorated.

In addition, as the movement of hydrogen ions and the duration of use of the fuel cell increase, the interface between the catalyst layer and the electrolyte membrane and the interface between the catalyst layer and the gas diffusion layer are weakened, resulting in separation from each other. Accordingly, when applied to a fuel cell, the performance of the fuel cell may be deteriorated.

In order to shorten the movement time of hydrogen ions, etc., it is necessary to reduce the thickness of the electrolyte membrane, and for this purpose, there is a method of thinning the thickness of the porous support constituting the electrolyte membrane. In addition to this significantly reduced, there was a problem in that economical and commercial properties were lowered due to a high defect rate during the manufacture of the support.

US Registered Patent No. US3282875 (Registration Date: 1966.11.01)

The present invention provides a composition for preparing a perfluorinated sulfonated ionomer having excellent physical properties, and a composition for preparing a perfluorinated sulfonated ionomer with improved stability and durability of a composite electrolyte membrane for PEMFC by including a perfluorinated sulfonated ionomer using the same, and a perfluorinated sulfonated ionomer using the same An object of the present invention is to provide an ionomer, a composite electrolyte membrane for PEMFC including the same, and a membrane-electrode assembly for PEMFC including the same.

In order to solve the above problems, the composition for preparing a perfluorinated sulfonated ionomer of the present invention may include tetrafluoroethylene (TFE), a compound represented by the following Chemical Formula 1, a compound represented by the following Chemical Formula 2, and a radical initiator. .

[Formula 1]

In Formula 1, n is 4 or 5.

[Formula 2]

In Formula 2, m is 4, 5 or 6.

In a preferred embodiment of the present invention, the radical initiator is a bis(fluoroacyl) peroxide-based compound, a bis(chlorofluoroacyl)peroxide-based compound, a dialkyl peroxydicarbonate-based compound, a diacyl peroxide-based compound, It may include at least one selected from a peroxyester-based compound, an azo-based compound, and a persulfate-based compound.

In a preferred embodiment of the present invention, the composition for preparing a perfluorinated sulfonated ionomer of the present invention may further include a hydrolyzing agent and an acid-forming agent.

In a preferred embodiment of the present invention, the compound represented by the following Chemical Formula 1-1 and the compound represented by the following Chemical Formula 2-1 may be included in a weight ratio of 1:0.45 to 1.24.

[Formula 1-1]

In Formula 1-1, n is 4.

[Formula 2-1]

In Formula 2-1, m is 4.

In a preferred embodiment of the present invention, the compound represented by the following Chemical Formula 1-1 and the compound represented by the following Chemical Formula 2-2 may be included in a weight ratio of 1:0.62 to 1.38.

[Formula 1-1]

In Formula 1-1, n is 4.

[Formula 2-2]

In Formula 2-2, m is 5.

In a preferred embodiment of the present invention, the compound represented by the following Chemical Formula 1-1 and the compound represented by the following Chemical Formula 2-3 may be included in a weight ratio of 1:0.85 to 1.60.

[Formula 1-1]

In Formula 1-1, n is 4.

[Formula 2-3]

In Formula 2-3, m is 6.

In a preferred embodiment of the present invention, the compound represented by the following Chemical Formula 1-2 and the compound represented by the following Chemical Formula 2-1 may be included in a weight ratio of 1:0.47 to 1.21.

[Formula 1-2]

In Formula 1-2, n is 5.

[Formula 2-1]

In Formula 2-1, m is 4.

In a preferred embodiment of the present invention, the compound represented by the following Chemical Formula 1-2 and the compound represented by the following Chemical Formula 2-2 may be included in a weight ratio of 1:0.64 to 1.36.

[Formula 1-2]

In Formula 1-2, n is 5.

[Formula 2-2]

In Formula 2-2, m is 5.

In a preferred embodiment of the present invention, the compound represented by the following Chemical Formula 1-2 and the compound represented by the following Chemical Formula 2-3 may be included in a weight ratio of 1:0.64 to 1.30.

[Formula 1-2]

In Formula 1-2, n is 5.

[Formula 2-3]

In Formula 2-3, m is 6.

Meanwhile, the perfluorinated sulfonated ionomer of the present invention may include a polymer including a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4, and a repeating unit represented by the following Chemical Formula 5.

[Formula 3]

[Formula 4]

In Formula 4, n is 4 or 5.

[Formula 5]

In Formula 5, m is 4, 5 or 6.

In a preferred embodiment of the present invention, the polymer may include a repeating unit represented by the following Chemical Formula 6, and the polymer may have a weight average molecular weight of 20,000 to 10,000,000.

[Formula 6]

In Formula 6, n is 4 or 5, m is 4, 5 or 6, x, y and z are molar ratios, 1: 0.01 to 1: 0.01 to 1, and is a rational number of x, y and z. The order of bonding of each constituent unit may be randomly modified.

In a preferred embodiment of the present invention, the polymer may have an _{equivalent weight of -SO 3} H group (EW: equivalent weight) of 500 to 1200.

Furthermore, the composite electrolyte membrane for PEMFC of the present invention may include a support layer, a first electrolyte layer formed on one surface of the support layer, and a second electrolyte layer formed on the other surface of the support layer.

In a preferred embodiment of the present invention, at least one of the first electrolyte layer and the second electrolyte layer may include the perfluorinated sulfonated ionomer of the present invention.

In a preferred embodiment of the present invention, the composite electrolyte membrane for PEMFC of the present invention may have a durability of 1.5 to 10 μmol/hr·g as measured by the Fenton test.

In a preferred embodiment of the present invention, the composite electrolyte membrane for PEMFC of the present invention may have an ionic conductivity of 0.07 to 0.2 S/cm.

Meanwhile, the membrane-electrode assembly for PEMFC of the present invention may include an anode (oxidation electrode), a composite electrolyte membrane for PEMFC of the present invention, and a cathode (reduction electrode).

In a preferred embodiment of the present invention, the PEMFC membrane-electrode assembly of the present invention may have a hydrogen permeability of 1.0 to 2.6 mA/cm².

Furthermore, the polymer electrolyte membrane fuel cell of the present invention includes the PEMFC membrane-electrode assembly and the separator of the present invention, and an electricity generator that generates electricity through an electrochemical reaction of fuel and an oxidizer, and supplies fuel to the electricity generator It may include a fuel supply unit and an oxidizer supply unit for supplying the oxidizer to the generator.

On the other hand, the method for producing a perfluorinated sulfonated ionomer of the present invention is a first step of adding and stirring deionized water, a compound represented by the following formula (1) and a compound represented by the following formula (2) into the reactor, tetrafluoro A second step of introducing roethylene (TFE) gas into the reactor to replace the internal atmosphere of the reactor with a TFE gas atmosphere, adding a radical initiator into the reactor to prepare a compound containing _{-SO 2 F group} Step 3 and _{immersing the compound containing the -SO 2} F group in a solution containing a hydrolyzing agent to prepare a compound containing a sulfonate group, and immersing the compound containing the sulfonate group in a solution containing an acid-forming agent A fourth step of preparing a polymer including a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4, and a repeating unit represented by the following Chemical Formula 5 may be included.

[Formula 1]

In Formula 1, n is 4 or 5.

[Formula 2]

In Formula 2, m is 4, 5 or 6.

[Formula 3]

[Formula 4]

In Formula 4, n is 4 or 5.

[Formula 5]

In Formula 5, m is 4, 5 or 6.

In a preferred embodiment of the present invention, the polymer of the method for preparing a perfluorinated sulfonated ionomer of the present invention includes a repeating unit represented by the following Chemical Formula 6, and the polymer may have a weight average molecular weight of 20,000 to 10,000,000.

[Formula 6]

In Formula 6, n is 4 or 5, m is 4, 5 or 6, x, y and z are molar ratios, 1: 0.01 to 1: 0.01 to 1, and is a rational number of x, y and z. The order of bonding of each constituent unit may be randomly modified.

Furthermore, in another method for producing a perfluorinated sulfonated ionomer of the present invention, the first step of adding and stirring deionized water and a compound represented by the following Chemical Formula 1 into the reactor, tetrafluoroethylene (TFE) gas A second step of replacing the internal atmosphere of the reactor with a TFE gas atmosphere by introducing it into the reactor, a third step of introducing a radical initiator into the reactor, and adding and stirring the compound represented by the following Chemical Formula 2 inside the reactor by the fourth step and the sulfonate base was immersed in a compound containing the group -SO ₂ F to the solution containing the released hydrolytically produce a compound containing a sulfonic acid base, and to prepare a compound containing an -SO ₂ F A fifth step of preparing a polymer comprising a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4 and a repeating unit represented by the following Chemical Formula 5 by immersing the compound containing may include

[Formula 1]

In Formula 1, n is 4 or 5.

[Formula 2]

In Formula 2, m is 4, 5 or 6.

[Formula 3]

[Formula 4]

In Formula 4, n is 4 or 5.

[Formula 5]

In Formula 5, m is 4, 5 or 6.

In a preferred embodiment of the present invention, the polymer of the method for preparing another perfluorinated sulfonated ionomer of the present invention includes a repeating unit represented by the following Chemical Formula 6, and the polymer may have a weight average molecular weight of 20,000 to 10,000,000.

[Formula 6]

In Formula 6, n is 4 or 5, m is 4, 5 or 6, x, y and z are molar ratios, 1: 0.01 to 1: 0.01 to 1, and is a rational number of x, y and z. The order of the combination of each constituent unit may be randomly modified.

The composite electrolyte membrane for PEMFC containing the perfluorinated sulfonated ionomer of the present invention has excellent ionic conductivity, and a Proton Exchange Membrane Fuel Cell (PEMFC) using the same can have excellent physical properties.

In addition, the composite electrolyte membrane for PEMFC containing the perfluorinated sulfonated ionomer of the present invention has a high water content and thus is easy to process and has improved hydrogen permeability.

In addition, the composite electrolyte membrane for PEMFC containing the perfluorinated sulfonated ionomer of the present invention has excellent safety and improved durability.

1 is a schematic diagram of a composite electrolyte membrane for PEMFC according to a preferred embodiment of the present invention.
2 is a schematic diagram of a membrane-electrode assembly for PEMFC according to a preferred embodiment of the present invention.

Hereinafter, with reference to the accompanying drawings, the embodiments of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily implement them. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and the same reference numerals are added to the same or similar elements throughout the specification.

The perfluorinated sulfonic acid ionomer (PFSA ionomer) of the present invention will be described first.

The perfluorinated sulfonated ionomer of the present invention is an ionomer included in the electrolyte layer of the composite electrolyte membrane for PEMFC of the present invention to be described later, and is represented by a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4, and a repeating unit represented by the following Chemical Formula 5 It may include a polymer including a repeating unit, preferably a polymer including a repeating unit represented by the following formula (6).

[Formula 3]

[Formula 4]

In Formula 4, n is 4 or 5.

[Formula 5]

In Formula 5, m is 4, 5 or 6.

[Formula 6]

In Formula 6, n is 4 or 5, m is 4, 5 or 6, and x, y and z are molar ratios, and a rational number of 1: 0.01 to 1: 0.01 to 1, preferably 1: 0.05 to 0.5: a rational number of 0.05 to 0.5, more preferably 1: 0.1 to 0.4: a rational number of 0.1 to 0.4, still more preferably 1: 0.12 to 0.3: a rational number of 0.12 to 0.3, even more preferably 1: 0.15 to 0.25 : It may be a rational number of 0.15 to 0.25.

If the molar ratio of x and y is less than 1: 0.01, there may be a problem of ionic conductivity, and if it exceeds 1:1, there may be problems such as compatibility, film forming characteristics, moldability and durability. In addition, if the molar ratio of x and z is less than 1: 0.01, there may be a problem of ionic conductivity, and if it exceeds 1:1, there may be a problem of durability.

In addition, in Formula 6, the order of bonding of each structural unit according to x, y, and z may be randomly modified.

In addition, the polymer of the perfluorinated sulfonated ionomer of the present invention has a weight average molecular weight of 20,000 to 10,000,000, preferably a weight average molecular weight of 50,000 to 5,000,000, more preferably a weight average molecular weight of 80,000 to 1,000,000, still more preferably a weight average molecular weight of 100,000 to 500,000, even more preferably, the weight average molecular weight may be 140,000 to 160,000, and if the weight average molecular weight of the polymer is less than 20,000, there may be problems with durability and mechanical properties, and if the weight average molecular weight exceeds 10,000,000, there may be problems with moldability. can

In addition, the perfluorinated sulfonated ionomer of the present invention has _{a chemical equivalent of -SO 3} H group (EW: equivalent weight) of 500 to 1200, preferably 500 to 1000, more preferably 550 to 900, still more preferably 600 ~ 800, even more preferably may be 650 ~ 750, if _{the chemical equivalent of -SO 3} H group is less than 500, there may be a problem in durability and mechanical properties, and if it exceeds 1200, there may be a problem of ionic conductivity have.

On the other hand, the above-mentioned perfluorinated sulfonated ionomer of the present invention is a composition for preparing a perfluorinated sulfonated ionomer comprising tetrafluoroethylene (TFE), a compound represented by the following Chemical Formula 1, a compound represented by the following Chemical Formula 2, and a radical initiator It can be manufactured using

[Formula 1]

In Formula 1, n is 4 or 5.

[Formula 2]

In Formula 2, m is 4, 5 or 6.

In addition, the composition for preparing a perfluorinated sulfonated ionomer of the present invention may include the compound represented by Formula 1 and the compound represented by Formula 2 in a weight ratio of 1:0.45 to 1.60, and if, the compound represented by Formula 2 If it contains less than 0.45 weight ratio, there may be a problem of ionic conductivity, and if it exceeds 1.60 weight ratio, there may be a problem of reduced durability.

Specifically, the composition for preparing a perfluorinated sulfonated ionomer of the present invention contains the compound represented by the following Chemical Formula 1-1 and the compound represented by the following Chemical Formula 2-1 in a weight ratio of 1: 0.45 to 1.24, preferably 1: 0.6 to 1.1 by weight. , more preferably 1: 0.75 to 0.95 weight ratio, even more preferably 1: 0.75 to 0.82 weight ratio.

[Formula 1-1]

In Formula 1-1, n is 4.

[Formula 2-1]

In Formula 2-1, m is 4.

In addition, the composition for preparing a perfluorinated sulfonated ionomer of the present invention comprises a compound represented by the following Chemical Formula 1-1 and a compound represented by the following Chemical Formula 2-2 in a weight ratio of 1: 0.62 to 1.38, preferably 1: 0.8 to 1.2 by weight, More preferably, it may be included in a weight ratio of 1: 0.9 to 1.1, even more preferably 1: 0.9 to 0.98 by weight.

[Formula 1-1]

In Formula 1-1, n is 4.

[Formula 2-2]

In Formula 2-2, m is 5.

In addition, the composition for preparing a perfluorinated sulfonated ionomer of the present invention comprises a compound represented by the following Chemical Formula 1-1 and a compound represented by the following Chemical Formula 2-3 in a weight ratio of 1: 0.85 to 1.60, preferably 1: 1.0 to 1.45 by weight, More preferably, it may be included in a weight ratio of 1:15 to 1.32, still more preferably 1:15 to 1.2 by weight.

[Formula 1-1]

In Formula 1-1, n is 4.

[Formula 2-3]

In Formula 2-3, m is 6.

In addition, the composition for preparing a perfluorinated sulfonated ionomer of the present invention comprises a compound represented by the following Chemical Formula 1-2 and a compound represented by the following Chemical Formula 2-1 in a weight ratio of 1: 0.47 to 1.21, preferably 1: 0.6 to 1.1 by weight, More preferably 1: 0.75 to 0.92 weight ratio, even more preferably 1: 0.75 to 0.82 weight ratio.

[Formula 1-2]

In Formula 1-2, n is 5.

[Formula 2-1]

In Formula 2-1, m is 4.

In addition, the composition for preparing a perfluorinated sulfonated ionomer of the present invention contains the compound represented by the following Chemical Formula 1-2 and the compound represented by the following Chemical Formula 2-2 in a weight ratio of 1: 0.64 to 1.36, preferably 1: 0.8 to 1.2 by weight, More preferably, it may be included in a weight ratio of 1: 0.91 to 1.1, still more preferably 1: 0.91 to 0.98 by weight.

[Formula 1-2]

In Formula 1-2, n is 5.

[Formula 2-2]

In Formula 2-2, m is 5.

In addition, the composition for preparing a perfluorinated sulfonated ionomer of the present invention comprises a compound represented by the following Chemical Formula 1-2 and a compound represented by the following Chemical Formula 2-3 in a weight ratio of 1: 0.64 to 1.30, preferably 1: 0.8 to 1.2 by weight, More preferably, it may be included in a weight ratio of 1: 0.9 to 1.04, still more preferably 1: 0.9 to 0.95 by weight.

[Formula 1-2]

In Formula 1-2, n is 5.

[Formula 2-3]

In Formula 2-3, m is 6.

The radical initiator of the composition for preparing a perfluorinated sulfonated ionomer of the present invention serves to generate radicals to cause radical chain polymerization, and as It may include at least one selected from compound, dialkyl peroxydicarbonate-based compound, diacyl peroxide-based compound, peroxyester-based compound, perfluoroperoxide-based compound, azo-based compound, and persulfate-based compound, preferably For example, it may include at least one selected from a perfluoroperoxide-based compound and a persulfate-based compound.

As a dialkyl peroxydicarbonate-based compound, it may include at least one selected from dimethyl peroxydicarbonate, diethyl peroxydicarbonate, and dipropyl peroxydicarbonate, and diacyl peroxide It may include diacetyl peroxide as a compound, and as a peroxyester compound, Bis(Pentafluoro propionyl)peroxide, Bis(trifluoromethyl)peroxide It may include at least one selected from oxyanhydride (Bis (trifluoromethyl) peroxyanhydride), and as a perfluoro peroxide-based compound, bis (perfluoro-t-butyl) peroxide (Bis (perfluoro-t-butyl) peroxide), bis (trifluoromethyl) peroxide (Bis (trifluoromethyl) Peroxide) may include at least one selected from, and azobis-2-methylpropanenitrile (Azobisisobutyronitrile, AIBN) and may include at least one selected from potassium persulfate (KPS: Potassium persulfate) and ammonium persulfate (APS: Ammonium persulfate) as the persulfate-based compound.

Meanwhile, the composition for preparing a perfluorinated sulfonated ionomer of the present invention may further include deionized water.

In addition, the composition for preparing a perfluorinated sulfonated ionomer of the present invention may further include a hydrolyzing agent and an acid-forming agent.

_{The hydrolyzing agent is a -SO 2} F group prepared by polymerization of tetrafluoroethylene (TFE), a compound represented by Formula 1 and a compound represented by Formula 2, included in the composition for preparing a perfluorinated sulfonated ionomer of the present invention. It serves to hydrolyze the compound containing the compound to be converted into a compound containing a sulfonate group, and may include a basic compound. In this case, the basic compound may include at least one selected from lithium hydroxide, sodium hydroxide and potassium hydroxide, and preferably lithium hydroxide.

The acid-forming agent serves to convert a compound containing a sulfonate group prepared through a hydrolyzing agent into a compound containing a -SO ₃ H group, and may include at least one selected from hydrochloric acid and sulfuric acid.

On the other hand, as a preferred embodiment of the method for preparing the perfluorinated sulfonated ionomer of the present invention, the first to fourth steps are included.

First, as the first step of the method for producing a perfluorinated sulfonated ionomer of the present invention, deionized water, a compound represented by the following formula (1) and a compound represented by the following formula (2) may be added and stirred into the reactor. have.

[Formula 1]

In Formula 1, n is 4 or 5.

[Formula 2]

In Formula 2, m is 4, 5 or 6.

At this time, preferably an autoclave may be used as the reactor, and the agitation is 150 to 450 rpm, preferably 200 to 400 rpm, more preferably 250 to 350 rpm for 15 minutes to 45 minutes, preferably It may be carried out for 20 minutes to 40 minutes, more preferably 25 to 35 minutes.

In addition, the compound represented by Formula 1 and the compound represented by Formula 2 are introduced into the reactor in a weight ratio of 1: 0.45 to 1.60.

Specifically, the compound represented by the following Chemical Formula 1-1 and the compound represented by the following Chemical Formula 2-1 are in a weight ratio of 1: 0.45 to 1.24, preferably 1: 0.6 to 1.1 by weight, more preferably 1: 0.75 to 0.95 by weight. , more preferably 1: 0.75 to 0.82 may be added in a weight ratio.

[Formula 1-1]

In Formula 1-1, n is 4.

[Formula 2-1]

In Formula 2-1, m is 4.

In addition, the compound represented by the following formula 1-1 and the compound represented by the following formula 2-2 are in a weight ratio of 1: 0.62 to 1.38, preferably 1: 0.8 to 1.2 by weight, more preferably 1: 0.9 to 1.1 by weight, Even more preferably, it may be added in a weight ratio of 1: 0.9 to 0.98.

[Formula 1-1]

In Formula 1-1, n is 4.

[Formula 2-2]

In Formula 2-2, m is 5.

In addition, the compound represented by the following formula 1-1 and the compound represented by the following formula 2-3 are in a weight ratio of 1: 0.85 to 1.60, preferably 1: 1.0 to 1.45 by weight, more preferably 1: 1.15 to 1.32 by weight, Even more preferably, it may be added in a weight ratio of 1:15 to 1.2.

[Formula 1-1]

In Formula 1-1, n is 4.

[Formula 2-3]

In Formula 2-3, m is 6.

In addition, the compound represented by the following formula 1-2 and the compound represented by the following formula 2-1 are in a weight ratio of 1: 0.47 to 1.21, preferably 1: 0.6 to 1.1 by weight, more preferably 1: 0.75 to 0.92 by weight, Even more preferably, it may be added in a weight ratio of 1: 0.75 to 0.82.

[Formula 1-2]

In Formula 1-2, n is 5.

[Formula 2-1]

In Formula 2-1, m is 4.

In addition, the compound represented by Formula 1-2 and the compound represented by Formula 2-2 are in a weight ratio of 1: 0.64 to 1.36, preferably 1: 0.8 to 1.2 by weight, more preferably 1: 0.91 to 1.1 by weight, Even more preferably, it may be added in a weight ratio of 1: 0.91 to 0.98.

[Formula 1-2]

In Formula 1-2, n is 5.

[Formula 2-2]

In Formula 2-2, m is 5.

In addition, the compound represented by the following formula 1-2 and the compound represented by the following formula 2-3 are in a weight ratio of 1: 0.64 to 1.30, preferably 1: 0.8 to 1.2 by weight, more preferably 1: 0.9 to 1.04 by weight, Even more preferably, it may be added in a weight ratio of 1: 0.9 to 0.95.

[Formula 1-2]

In Formula 1-2, n is 5.

[Formula 2-3]

In Formula 2-3, m is 6.

After performing the first step of the method for producing the perfluorinated sulfonated ionomer of the present invention, the inside of the reactor may be vacuumed to remove moisture, and then purged with nitrogen gas again. (Such a process can be repeated 2 to 5 times.)

Next, as a second step of the method for producing a perfluorinated sulfonated ionomer of the present invention, tetrafluoroethylene (TFE) gas is introduced into the reactor to replace the internal atmosphere of the reactor with a TFE gas atmosphere. can

Specifically, in the second step, TFE gas is first introduced into the reactor, and the pressure inside the reactor is 0.005 to 0.1 MPa, preferably 0.007 to 0.05 MPa, more preferably 0.008 to 0.03 MPa. can do.

Next, the inside of the reactor is vacuumed to remove moisture, and then, the pressure inside the reactor is 0.4 to 1.2 MPa, preferably 0.6 to 1.0 MPa, more preferably 0.7 to 0.9 MPa until the TFE gas may be introduced into the reactor.

Finally, heat is applied to the inside of the reactor at a rate of 3° C./min to 7° C./min, preferably 4° C./min to 6° C./min, so that the temperature inside the reactor is 30 to 40° C., preferably 33 to 37 It can be heated up until it becomes °C.

Next, as the third step of the method for preparing the perfluorinated sulfonated ionomer of the present invention, a radical initiator is introduced into the reactor to prepare a compound including _{-SO 2 F group.}

As mentioned above, the radical initiator is a bis (fluoroacyl) peroxide compound, a bis (chlorofluoroacyl) peroxide compound, a dialkyl peroxydicarbonate compound, a diacyl peroxide compound, a peroxyester compound, It may include at least one selected from perfluoroperoxide-based compounds, azo-based compounds and persulfate-based compounds, and preferably include at least one selected from perfluoroperoxide-based compounds and persulfate-based compounds, , The radical initiator may be mixed with deionized water and used as a radical initiator solution. In this case, the radical initiator solution may contain 0.1 to 2% by weight of the radical initiator, preferably 0.5 to 1.5% by weight.

_{On the other hand, when preparing a compound containing a -SO 2} F group through the third step of the method for producing a perfluorinated sulfonated ionomer of the present invention, the inside of the reactor is 3° C./min to 7° C./min, preferably 4° C. By applying heat at a rate of /min ~ 6 ℃ / min, the temperature inside the reactor is raised to 40 ~ 60 ℃, preferably 45 ~ 55 ℃, it can be maintained until the completion of the production reaction, The reaction may be carried out for 1 to 5 hours, preferably 2 to 4 hours.

_{Additionally, the compound containing -SO 2} F group prepared in the third step may be repeatedly washed with distilled water to remove foreign substances and unreacted substances.

Finally, as the fourth step of the method for preparing the perfluorinated sulfonated ionomer of the present invention, the _{compound containing the -SO 2} F group prepared in the third step is immersed in a solution containing a hydrolyzing agent to include a sulfonate group. A compound is prepared, and the compound containing the sulfonate group is immersed in a solution containing an acid-forming agent to include a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4, and a repeating unit represented by the following Chemical Formula 5 A polymer can be prepared, and preferably a polymer including a repeating unit represented by the following formula (6) can be prepared.

[Formula 3]

[Formula 4]

In Formula 4, n is 4 or 5.

[Formula 5]

In Formula 5, m is 4, 5 or 6.

[Formula 6]

In Formula 6, n is 4 or 5, m is 4, 5 or 6, and x, y and z are molar ratios, a rational number of 1: 0.01 to 1: 0.01 to 1, preferably 1: 0.05 to 0.5: a rational number of 0.05 to 0.5, more preferably 1: 0.1 to 0.4: a rational number of 0.1 to 0.4, still more preferably 1: 0.12 to 0.3: a rational number of 0.12 to 0.3, even more preferably 1: 0.15 to 0.25 : It may be a rational number of 0.15 to 0.25, and the order of bonding of each constituent unit according to x, y, and z may be randomly modified.

In addition, the polymer has a weight average molecular weight of 20,000 to 10,000,000, preferably a weight average molecular weight of 50,000 to 5,000,000, more preferably a weight average molecular weight of 80,000 to 1,000,000, still more preferably a weight average molecular weight of 100,000 to 500,000, even more preferably a weight average The molecular weight may be 140,000 to 160,000.

Specifically, in the fourth step of the method for producing a perfluorinated sulfonated ionomer of the present invention, _{the compound containing the -SO 2} F group prepared in the third step is hydrolyzed through a hydrolyzing agent to convert the -SO ₂ F group into a sulfonate group. It is a process of substituting a _{sulfonate group with a -SO 3} H group through an acid-forming agent.

A solution containing a hydrolyzing agent is a material in which the aforementioned hydrolyzing agent is mixed with a solvent, and a solution containing an acid-forming agent is a material in which the aforementioned acid-forming agent is mixed in a solvent, and the solvent is water or a mixture of water and a polar solvent. It may be a mixed solvent. The polar solvent may be alcohol (methanol, ethanol, etc.) or dimethyl sulfoxide.

Furthermore, as another preferred embodiment of the method for producing a perfluorinated sulfonated ionomer of the present invention, the first to fifth steps are included.

First, as a first step of the method for producing a perfluorinated sulfonated ionomer of the present invention, deionized water and a compound represented by the following Chemical Formula 1 may be added and stirred into the reactor.

[Formula 1]

In Formula 1, n is 4 or 5.

At this time, preferably an autoclave may be used as the reactor, and the agitation is 150 to 450 rpm, preferably 200 to 400 rpm, more preferably 250 to 350 rpm for 15 minutes to 45 minutes, preferably It may be carried out for 20 minutes to 40 minutes, more preferably 25 to 35 minutes.

After performing the first step of the method for producing the perfluorinated sulfonated ionomer of the present invention, the inside of the reactor may be vacuumed to remove moisture, and then purged with nitrogen gas again. (Such a process can be repeated 2 to 5 times.)

Next, as a second step of the method for producing a perfluorinated sulfonated ionomer of the present invention, tetrafluoroethylene (TFE) gas is introduced into the reactor to replace the internal atmosphere of the reactor with a TFE gas atmosphere. can

Specifically, in the second step, TFE gas is first introduced into the reactor, and the pressure inside the reactor is 0.005 to 0.1 MPa, preferably 0.007 to 0.05 MPa, more preferably 0.008 to 0.03 MPa. can do.

Next, the inside of the reactor is vacuumed to remove moisture, and then, the pressure inside the reactor is 0.4 to 1.2 MPa, preferably 0.6 to 1.0 MPa, more preferably 0.7 to 0.9 MPa until the TFE gas may be introduced into the reactor.

Finally, heat is applied to the inside of the reactor at a rate of 3° C./min to 7° C./min, preferably 4° C./min to 6° C./min, so that the temperature inside the reactor is 30 to 40° C., preferably 33 to 37 It can be heated up until it becomes °C.

Next, as the third step of the method for preparing the perfluorinated sulfonated ionomer of the present invention, a radical initiator may be introduced into the reactor.

As mentioned above, the radical initiator is a bis (fluoroacyl) peroxide compound, a bis (chlorofluoroacyl) peroxide compound, a dialkyl peroxydicarbonate compound, a diacyl peroxide compound, a peroxyester compound, It may include at least one selected from perfluoroperoxide-based compounds, azo-based compounds and persulfate-based compounds, and preferably include at least one selected from perfluoroperoxide-based compounds and persulfate-based compounds, , The radical initiator may be mixed with deionized water and used as a radical initiator solution. In this case, the radical initiator solution may contain 0.1 to 2% by weight of the radical initiator, preferably 0.5 to 1.5% by weight.

After adding the radical initiator to the inside of the reactor in the third step, heat is applied to the inside of the reactor at a rate of 3° C./min to 7° C./min, preferably 4° C./min to 6° C./min to increase the temperature inside the reactor. The temperature may be increased to 40 to 60° C., preferably 45 to 55° C., and maintained for 30 to 90 minutes, preferably 45 to 75 minutes.

Next, as a fourth step of the method for producing a perfluorinated sulfonated ionomer of the present invention, a compound represented by the following Chemical Formula 2 is added into the reactor and stirred to prepare a compound including a _{—SO 2 F group.}

[Formula 2]

In Formula 2, m is 4, 5 or 6.

In this case, the compound represented by Formula 2 may be added in an amount of 0.45 to 1.60 by weight based on 1 weight of the compound represented by Formula 1 added in the first step.

Specifically, the compound represented by the following Chemical Formula 1-1 is in a weight ratio of 0.45 to 1.24, preferably in a weight ratio of 0.6 to 1.1, more preferably in a weight ratio of 0.75 to 0.95, and still more preferably in a weight ratio of the compound represented by the following Chemical Formula 2-1 to 1 by weight of the compound represented by the following Chemical Formula 1-1. For example, it may be added in a weight ratio of 0.75 to 0.82.

[Formula 1-1]

In Formula 1-1, n is 4.

[Formula 2-1]

In Formula 2-1, m is 4.

In addition, with respect to 1 weight of the compound represented by the following formula 1-1, 0.62 to 1.38 weight ratio of the compound represented by the following formula 2-2, preferably 0.8 to 1.2 weight ratio, more preferably 0.9 to 1.1 weight ratio, even more preferably may be added in a weight ratio of 0.9 to 0.98.

[Formula 1-1]

In Formula 1-1, n is 4.

[Formula 2-2]

In Formula 2-2, m is 5.

In addition, with respect to 1 weight of the compound represented by the following formula 1-1, 0.85 to 1.60 weight ratio of the compound represented by the following formula 2-3, preferably 1.0 to 1.45 weight ratio, more preferably 1.15 to 1.32 weight ratio, even more preferably may be added in a weight ratio of 1.15 to 1.2.

[Formula 1-1]

In Formula 1-1, n is 4.

[Formula 2-3]

In Formula 2-3, m is 6.

In addition, with respect to 1 weight of the compound represented by the following formula 1-2, the compound represented by the following formula 2-1 is in a weight ratio of 0.47 to 1.21, preferably 0.6 to 1.1, more preferably 0.75 to 0.92, even more preferably may be added in a weight ratio of 0.75 to 0.82.

[Formula 1-2]

In Formula 1-2, n is 5.

[Formula 2-1]

In Formula 2-1, m is 4.

In addition, with respect to 1 weight of the compound represented by the following formula 1-2, 0.64 to 1.36 weight ratio of the compound represented by the following formula 2-2, preferably 0.8 to 1.2 weight ratio, more preferably 0.91 to 1.1 weight ratio, even more preferably may be added in a weight ratio of 0.91 to 0.98.

[Formula 1-2]

In Formula 1-2, n is 5.

[Formula 2-2]

In Formula 2-2, m is 5.

In addition, with respect to 1 weight of the compound represented by the following formula 1-2, 0.64 to 1.30 weight ratio of the compound represented by the following formula 2-3, preferably 0.8 to 1.2 weight ratio, more preferably 0.9 to 1.04 weight ratio, even more preferably may be added in a weight ratio of 0.9 to 0.95.

[Formula 1-2]

In Formula 1-2, n is 5.

[Formula 2-3]

In Formula 2-3, m is 6.

_{On the other hand, when preparing a compound containing a -SO 2} F group through the fourth step of the method for producing a perfluorinated sulfonated ionomer of the present invention, the inside of the reactor is 0.4 to 1.2 MPa, preferably 0.6 to 1.0 MPa, more preferably preferably at a pressure of 0.7 to 0.9 MPa, 40 to 60 ° C, preferably at a temperature of 45 to 55 ° C, 150 to 450 rpm, preferably 200 to 400 rpm, more preferably at a stirring rate of 250 to 350 rpm. It may be carried out for 5 hours, preferably 2 to 4 hours.

Finally, as the fifth step of the method for preparing the perfluorinated sulfonated ionomer of the present invention, the _{compound containing the -SO 2} F group prepared in the fourth step is immersed in a solution containing a hydrolyzing agent to include a sulfonate group A compound is prepared, and the compound containing the sulfonate group is immersed in a solution containing an acid-forming agent to include a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4, and a repeating unit represented by the following Chemical Formula 5 A polymer can be prepared, and preferably a polymer including a repeating unit represented by the following formula (6) can be prepared.

[Formula 3]

[Formula 4]

In Formula 4, n is 4 or 5.

[Formula 5]

In Formula 5, m is 4, 5 or 6.

[Formula 6]

In Formula 6, n is 4 or 5, m is 4, 5 or 6, and x, y and z are molar ratios, and a rational number of 1: 0.01 to 1: 0.01 to 1, preferably 1: 0.05 to 0.5: a rational number of 0.05 to 0.5, more preferably 1: 0.1 to 0.4: a rational number of 0.1 to 0.4, still more preferably 1: 0.12 to 0.3: a rational number of 0.12 to 0.3, even more preferably 1: 0.15 to 0.25 : It may be a rational number of 0.15 to 0.25, and the order of bonding of each constituent unit according to x, y, and z may be randomly modified.

In addition, the polymer has a weight average molecular weight of 20,000 to 10,000,000, preferably a weight average molecular weight of 50,000 to 5,000,000, more preferably a weight average molecular weight of 80,000 to 1,000,000, still more preferably a weight average molecular weight of 100,000 to 500,000, even more preferably a weight average The molecular weight may be 140,000 to 160,000.

Specifically, in the fifth step of the method for producing a perfluorinated sulfonated ionomer of the present invention, _{the compound containing the -SO 2} F group prepared in the fourth step is hydrolyzed through a hydrolyzing agent to convert the -SO ₂ F group into a sulfonate group. It is a process of substituting a _{sulfonate group with a -SO 3} H group through an acid-forming agent.

A solution containing a hydrolyzing agent is a material in which the aforementioned hydrolyzing agent is mixed with a solvent, and a solution containing an acid-forming agent is a material in which the aforementioned acid-forming agent is mixed in a solvent, and the solvent is water or a mixture of water and a polar solvent. It may be a mixed solvent. As the polar solvent, alcohols (methanol, ethanol, etc.) or dimethyl sulfoxide may be used.

On the other hand, referring to Figure 1, the PEMFC (Polymer Electrolyte Membrane Fuel Cell) composite electrolyte membrane of the present invention is a support layer 10, the first electrolyte layer formed on one surface of the support layer 10, 20 and the support layer ( 10) It may include a second electrolyte layer 30 formed on the other surface.

Specifically, the first electrolyte layer 20 may be disposed in an anode direction, and the second electrolyte layer 30 may be disposed in a cathode direction.

At this time, at least one of the first electrolyte layer 20 and the second electrolyte layer 30 may include the above-mentioned perfluorinated sulfonated ionomer of the present invention. Specifically, the first electrolyte layer 20 or the second electrolyte layer 30 includes the perfluorinated sulfonated ionomer of the present invention, or the first electrolyte layer 20 and the second electrolyte layer 30 The above-mentioned perfluorinated sulfonated ionomer of the present invention may be included.

In addition, the perfluorinated sulfonated ionomer of the present invention may be included in the pores of the support layer 10 as well as constituting the first electrolyte layer 20 and/or the second electrolyte layer 30 .

Meanwhile, the first electrolyte layer 20 and/or the second electrolyte layer 30 of the present invention may further include a radical scavenger for PEMFC in addition to the perfluorinated sulfonated ionomer of the present invention.

The radical scavenger for PEMFC of the present invention is a CeZnO metal oxide having a cerium ion-doped ZnO crystal structure by mixing and reducing a Ce precursor aqueous solution in a _{[Zn(OH) 4} ] ^{2-containing solution.} It can be prepared by forming particles. Here, the "Ce ion-doped ZnO crystal structure" means that a crystal structure in which some of Zn atoms are substituted with Ce atoms in a ZnO crystal structure having a crystal structure such as wurtzite is newly formed.

To explain this in more detail, a first step of dissolving a Zn precursor in alcohol to prepare a Zn precursor solution, and then heating the Zn precursor solution; [Zn(OH) ₄ ] A second step of preparing a ^{2-containing solution;} [Zn(OH) ₄ ] A third step of forming CeZnO metal oxide particles having a ZnO crystal structure doped with Ce ions by mixing and reducing a Ce precursor aqueous solution in a ^{2-containing solution;} a fourth step of recovering and washing the CeZnO metal oxide particles; and a fifth step of drying the washed CeZnO metal oxide particles; a radical scavenger for PEMFC can be manufactured. For a more detailed description of this, Korean Patent Registration No. 10-1860870 by the same applicant may be inserted as a reference.

The radical scavenger for PEMFC of the present invention is a metal oxide particle having a crystal structure composed of a cerium (Ce) atom, a zinc (Zn) atom and an oxygen (O) atom. In a ZnO crystal structure having a structure, it may have a crystal structure in which some of Zn atoms are substituted with Ce atoms.

In addition, the radical scavenger for PEMFC of the present invention may contain 12 to 91% by weight of Ce, 7 to 84.5% by weight of Zn, and the remaining amount of O, preferably 13.40 to 89.20% by weight of Ce, 7.55 to 88.20% by weight of Zn % and the balance O. And, it may further include other unavoidable impurities.

In addition, the radical scavenger of the present invention may be 200 nm or less, preferably 160 nm or less, more preferably 45 to 160 nm when the particle size (D50) is analyzed with a DLS (Dynamic Light Scattering) type nano particle size analyzer. have.

Furthermore, the first electrolyte layer 20 and/or the second electrolyte layer 30 of the present invention are each independently 0.5 to 1.5 parts by weight of the radical scavenger for PEMFC based on 100 parts by weight of the perfluorinated sulfonated ionomer, preferably may include 0.7 to 1.3 parts by weight, more preferably 0.9 to 1.1 parts by weight, and if it contains less than 0.5 parts by weight, there may be a problem of poor durability, and if it exceeds 1.5 parts by weight, the durability is improved, There may be a problem in that the conductivity of the composite electrolyte membrane of the present invention is deteriorated due to a decrease in conductivity.

In addition, the first electrolyte layer 20 and/or the second electrolyte layer 30 may each independently further include hollow silica.

The hollow silica is spherical, and may have an average particle diameter of 10 to 300 nm, more preferably 10 to 100 nm. Here, the particle size means the diameter when the shape of the hollow silica is spherical, and when the shape of the hollow silica is not spherical, it means the maximum distance among the linear distances from any one point on the surface of the hollow silica to another point.

In addition, the first electrolyte layer 20 and/or the second electrolyte layer 30 may each independently further include one or more moisture absorbents selected from zeolite, titania, zirconia, and montmorillonite.

In addition, the support layer 10 and the first electrolyte layer 20 of the present invention may have a thickness ratio of 1:0.8 to 1.2, preferably 1:0.9 to 1.1.

On the other hand, the support layer 10 of the present invention may use a general porous support used in the art, and preferably may include a PTFE (Polytetrafluoroethylene) porous support prepared by the following manufacturing method having specific physical properties.

The PTFE porous support of the present invention is prepared by mixing and stirring PTFE powder and a lubricant in step 1-1 to prepare a paste; Step 1-2 of aging the paste; Steps 1-3 of extruding and rolling the aged paste to prepare an unfired tape; After drying the unbaked tape, steps 1-4 of removing the liquid lubricant; Steps 1-5 of uniaxially stretching the unbaked tape from which the lubricant has been removed; Steps 1-6 of biaxially stretching the uniaxially stretched unbaked tape; and steps 1-7 of calcining.

In step 1-1, the paste may contain 15 to 35 parts by weight of a lubricant, preferably 15 to 30 parts by weight, and more preferably 15 to 25 parts by weight based on 100 parts by weight of the PTFE powder. When the lubricant is less than 15 parts by weight based on 100 parts by weight of the PTFE powder, the porosity may be lowered when the PTFE porous support is formed by the biaxial stretching process to be described later, and when it exceeds 35 parts by weight, the size of the pores when the PTFE porous support is formed It may become large and the strength of the support may be weakened.

The average particle diameter of the PTFE powder is 300㎛ ~ 800㎛. Preferably, it may be 450 μm to 700 μm, but is not limited thereto. The lubricant is a liquid lubricant, and in addition to hydrocarbon oils such as liquid paraffin, naphtha, white oil, toluene, and xylene, various alcohols, ketones, esters, etc. may be used, and preferably liquid paraffin, naphtha and white oil. One or more types may be used.

Next, the aging of step 1-2 is a preforming process, and the paste may be aged for 12 to 24 hours at a temperature of 30° C. to 70° C., preferably 16 to at a temperature of 35° C. to 60° C. It can be aged for 20 hours. When the aging temperature is less than 30° C. or the aging time is less than 12 hours, the lubricant coating becomes non-uniform on the surface of the PTFE powder, so that the stretching uniformity of the PTFE porous support may be limited during biaxial stretching, which will be described later.

In addition, when the aging temperature exceeds 70° C. or the aging time exceeds 24 hours, there may be a problem in that the pore size of the PTFE porous support after the biaxial stretching process is too small due to evaporation of the lubricant.

Next, in the extrusion of steps 1-3, a PTFE block is prepared by compressing the aged paste in a compressor, and then the PTFE block is ^{pressed at a pressure of 0.069 to 0.200 Ton/cm 2} , preferably 0.090 to 0.175 Ton/cm It can be carried out by pressure extrusion at a pressure of ^2.

At this time, when the pressure-extrusion pressure is ^{less than 0.069 Ton/cm 2} , the pore size of the porous support increases and the strength of the porous support may be weakened, and ^{when it exceeds 0.200 Ton/cm 2} , the pore size of the porous support after the biaxial stretching process There may be a problem with the .

In addition, the rolling of steps 1-3 may be performed by a calendering process at 50 to 100° C. with a hydraulic pressure of 5 to 10 MPa. At this time, when the hydraulic pressure is less than 5 MPa, the pore size of the porous support may be increased, and thus the strength of the porous support may be weakened.

Next, the drying of steps 1-4 can be performed through a general drying method used in the art, and for example, an unbaked tape prepared by rolling is 1 to 5M at a temperature of 100°C to 200°C. While conveying to the conveyor belt at a speed of /min, it may be carried out while conveying preferably at a temperature of 140 ° C. to 190 ° C. at a speed of 2 to 4 M / min. At this time, when the drying temperature is less than 100°C or the drying rate exceeds 5M/min, bubbles may occur during the stretching process due to non-evaporation of the lubricant, and the drying temperature exceeds 200°C or the drying rate is 1M When the value is less than /min, the stiffness of the dried tape may increase and slip may occur during the stretching process.

Next, the uniaxial stretching of steps 1-5 is a process of stretching the unbaked tape from which the lubricant has been removed in the longitudinal direction. When transported through the rollers, the uniaxial stretching is performed using the speed difference between the rollers. . And, the uniaxial stretching is 3 to 10 times, preferably 6 to 9.5 times, more preferably 6.2 to 9 times, even more preferably 6.3 to 8.2 times the stretching of the unbaked tape from which the lubricant is removed in the longitudinal direction. It is good to do At this time, if the uniaxial stretching ratio is less than 3 times, sufficient mechanical properties cannot be secured, and if the uniaxial stretching ratio exceeds 10 times, the mechanical properties are rather decreased, and there may be a problem in that the pores of the support become too large.

In addition, uniaxial stretching is performed at a stretching temperature of 260 ° C. to 350 ° C. and a stretching rate of 6 to 12 M / min, preferably a stretching temperature of 270 ° C. to 330 ° C. and a stretching rate of 8 to 11.5 M / min. Preferably, if the stretching temperature is less than 260°C during uniaxial stretching or if the stretching speed is less than 6 M/min, there may be a problem that a firing section occurs due to a large amount of heat applied to the dry sheet, and the stretching temperature during uniaxial stretching When the temperature exceeds 350°C or the stretching speed exceeds 12 M/min, there may be a problem in that the thickness uniformity is deteriorated due to slip occurring during the uniaxial stretching process.

Next, in the biaxial stretching of steps 1-6, stretching is performed in the width direction (direction perpendicular to the uniaxial stretching) of the uniaxially stretched unbaked tape, and the width is widened in the lateral direction while the end is fixed. can be stretched However, the present invention is not limited thereto, and may be stretched according to a stretching method commonly used in the art. In the present invention, the biaxial stretching may be performed at 15 to 50 times in the width direction, preferably 25 to 45 times, more preferably 28 to 45 times, still more preferably 29 to 42 times. In this case, if the biaxial stretching ratio is 15 times or less, sufficient mechanical properties may not be secured, and even if it exceeds 50 times, there is no improvement in mechanical properties, and the uniformity of physical properties in the longitudinal direction and/or the width direction is lowered. Since there may be, it is preferable to perform stretching within the above range.

In addition, the biaxial stretching is carried out at a stretching rate of 10 to 20 M/min under a stretching temperature of 150° C. to 260° C., preferably at a stretching rate of 11 to 18 M/min under a stretching temperature of 200° C. to 250° C. If the biaxial stretching temperature is less than 150 ℃ or the stretching speed is less than 10 M/min, there may be a problem that the stretching uniformity in the transverse direction is lowered, and the biaxial stretching temperature exceeds 260 ℃, or When the stretching speed exceeds 20 M/min, there may be a problem in that an unbaked section occurs and the physical properties are deteriorated.

Finally, the firing of steps 1-7 moves the stretched porous support on a conveyor belt at a speed of 10 to 18 M/min, preferably at a speed of 13 to 17 M/min, at 350° C. to 450° C., Preferably, a temperature of 380 ° C. to 440 ° C., and more preferably a temperature of 400 ° C. to 435 ° C. may be applied, thereby fixing the draw ratio and improving the strength. During calcination, if the calcination temperature is less than 350 ° C., the strength of the porous support may be lowered, and if it exceeds 450 ° C., there may be a problem in that the physical properties of the support are lowered due to a decrease in the number of fibrils due to underfiring.

In addition, the PTFE porous support prepared by performing the process of steps 1-7 has a draw ratio (or aspect ratio) in the uniaxial direction (length direction) and biaxial direction (width direction) of 1:3.00 to 8.5, preferably 1 : 4.0 to 7.0, more preferably 1: 4.00 to 5.50, even more preferably 1: 4.20 to 5.00, and the uniaxial and biaxial stretching ratios (or aspect ratios) are high in the above ranges. It is preferable in terms of mechanical properties, securing an appropriate pore size of the support, and securing an appropriate current flow.

The prepared PTFE porous support of the present invention may have an average pore size of 0.080 μm to 0.200 μm, preferably 0.090 μm to 0.180 μm, more preferably 0.095 μm to 0.150 μm, even more preferably 0.100 to 0.140 μm. . In addition, the PTFE porous support of the present invention may have an average porosity of 60% to 90%, more preferably 60% to 79.6%.

If the average pore size of the PTFE porous support of the present invention is less than 0.080 μm or the porosity is less than 60%, the degree of impregnation of the electrolyte in the PTFE porous support is limited when impregnated with the electrolyte to prepare an electrolyte membrane using the PTFE porous support. can In addition, when the average pore size exceeds 0.200 μm or the porosity exceeds 90%, the PTFE porous support structure is deformed when impregnated with an electrolyte, and there may be a problem in that the product life is reduced due to a decrease in dimensional stability.

Meanwhile, in the PTFE porous support of the present invention, when measured according to ASTM D 882, uniaxial modulus and biaxial modulus values may satisfy Equation 1 below.

[Equation 1]

0 ≤ │(uniaxial modulus - biaxial modulus)/(uniaxial modulus)×100%│ ≤ 54%, preferably 0 ≤ │(uniaxial modulus - biaxial modulus)/(uniaxial modulus) directional modulus)×100%│ ≤ 40%, more preferably 1 ≤ │(uniaxial modulus - biaxial modulus)/(uniaxial modulus)×100%│ ≤ 26%

In addition, the PTFE porous support of the present invention may have a uniaxial (lengthwise) modulus of 40 MPa or more, preferably a uniaxial direction modulus of 50 MPa or more, more Preferably, the uniaxial modulus may be 48 to 75 Mpa, more preferably 65 to 75 Mpa. In addition, the modulus in the biaxial direction (width direction) is 40 MPa or more, preferably the modulus in the biaxial direction (width direction) is 55 Mpa or more, more preferably 46 to 75 Mpa, even more preferably 55 to 75 Mpa. can

In addition, the PTFE porous support of the present invention may have a uniaxial (length direction) tensile strength of 40 MPa or more and a biaxial direction (width direction) tensile strength of 40 MPa or more, preferably 1 The tensile strength in the axial direction may be 50 MPa or more, and more preferably, the tensile strength in the uniaxial direction may be 54 to 65 Mpa. Also, preferably, the tensile strength in the biaxial direction may be 52 Mpa or more, and more preferably, the tensile strength in the biaxial direction may be 52 to 70 Mpa.

Furthermore, the method for manufacturing a composite electrolyte membrane for PEMFC of the present invention includes first to fourth steps.

First, in the first step of the method for manufacturing a composite electrolyte membrane for PEMFC of the present invention, a poly tetra fluoro ethylene (PTFE) porous support may be prepared.

The PTFE porous support prepared in the first step may be the same as the above-described PTFE porous support and manufacturing method.

Next, in the second step of the method for manufacturing a composite electrolyte membrane for PEMFC of the present invention, a first electrolyte layer may be formed on one surface of the PTFE porous support prepared in the first step.

Specifically, the second step is a process of forming a first electrolyte layer on one surface of the PTFE porous support. It is applied to a solution containing the perfluorinated sulfonated ionomer of the present invention on one surface of the PTFE porous support, or one surface of the PTFE porous support. is impregnated in a solution containing the perfluorinated sulfonated ionomer of the present invention, and then dried to form a first electrolyte layer.

The drying of the second step may be performed by applying heat of 60°C to 100°C for 1 minute to 30 minutes, or preferably by applying heat of 70°C to 90°C for 5 minutes to 15 minutes. At this time, if the drying temperature is less than 60 ℃, the liquid retention of the solution containing the perfluorinated sulfonated ionomer of the present invention impregnated in the porous support may be reduced, and if it exceeds 100 ℃, the electrolyte membrane and/or membrane-electrode assembly During manufacture, adhesion with the electrode may be deteriorated.

Next, in the third step of the method for manufacturing a composite electrolyte membrane for PEMFC of the present invention, a second electrolyte layer may be formed on the other surface of the PTFE porous support prepared in the first step.

Specifically, the third step is a process of forming a second electrolyte layer on the other surface of the porous PTFE support on which the first electrolyte layer is formed. , After impregnating the other surface of the PTFE porous support in the solution containing the perfluorinated sulfonated ionomer of the present invention, it may be dried to form a second electrolyte layer.

Drying in the third step may be performed by applying heat of 60°C to 100°C for 1 minute to 30 minutes, or preferably by applying heat of 70°C to 90°C for 5 minutes to 15 minutes. At this time, if the drying temperature is less than 60 ℃, the liquid retention of the solution containing the first perfluorinated sulfonated ionomer impregnated in the porous support may be reduced, and if it exceeds 100 ℃, the electrolyte membrane and / or membrane-electrode assembly manufacturing Bondability with the electrode may be deteriorated.

On the other hand, the solution containing the perfluorinated sulfonated ionomer of the present invention used to form the first electrolyte layer and/or the second electrolyte layer in the second and third steps is a radical scavenger for PEMFC, hollow silica or a desiccant. may be additionally mixed, and each of the perfluorinated sulfonated ionomer, the radical scavenger for PEMFC, the hollow silica and the moisture absorbent of the present invention is the perfluorinated sulfonated ionomer of the present invention, the radical scavenger for PEMFC, and the hollow type silica and desiccant.

Finally, in the fourth step of the method for manufacturing the composite electrolyte membrane for PEMFC of the present invention, the composite electrolyte membrane for PEMFC of the present invention may be manufactured by heat-treating the PTFE porous support on which the first electrolyte layer and the second electrolyte layer are formed.

The heat treatment of the fourth step may be performed at 100° C. to 200° C. for 1 minute to 5 minutes, preferably at 140° C. to 180° C. for 1 minute to 5 minutes, and the heat treatment temperature is less than 100° C. or the heat treatment time is less than 1 minute. On the other hand, the liquid retention of the first and/or second electrolyte layers may be reduced, and when the heat treatment temperature exceeds 200° C., the adhesion (bonding) between the first and second electrolyte layers and the porous support may be reduced. have.

In the PTFE porous support of the composite electrolyte membrane subjected to the heat treatment of the fourth step, the volume of the blocked pores may be 85% by volume or more, preferably 90% by volume or more with respect to the total pore volume.

Furthermore, the composite electrolyte membrane for PEMFC of the present invention may have a durability of 1.5 to 10 μmol/hr·g, preferably 1.5 to 5 μmol/hr·g, and more preferably 1.7 to 2.4 μmol/hr·g.

In addition, the composite electrolyte membrane for PEMFC of the present invention may have an ionic conductivity of 0.07 ~ 0.2 S / cm, 0.1 ~ 0.19 S / cm, preferably 0.12 ~ 0.18 S / cm, more preferably 0.14 ~ 0.17 S / cm .

On the other hand, referring to Figure 2, the PEMFC membrane-electrode assembly of the present invention is an anode (oxide electrode) 200, the composite electrolyte membrane 100 for PEMFC of the present invention mentioned above and a cathode (reducing electrode) (300) includes

In other words, the membrane-electrode assembly according to an embodiment of the present invention has an anode (anode, anode, 200) and a cathode (cathode, a cathode, 300) positioned opposite to each other with the composite electrolyte membrane 100 interposed therebetween. to provide At this time, the anode 200 includes an anode gas diffusion layer 3, an anode catalyst layer 2, and an anode electrode substrate 1, and the cathode 300 is a cathode gas diffusion layer 4, a cathode catalyst layer 5 and a cathode An electrode substrate 6 may be included.

Specifically, the anode 200 may be formed by sequentially stacking the anode gas diffusion layer 3, the anode catalyst layer 2 and the anode electrode substrate 1, and the anode gas diffusion layer 3 is a composite electrolyte membrane 200. may be bonded to one side of In addition, the cathode 300 may be formed by sequentially stacking the cathode gas diffusion layer 4 , the cathode catalyst layer 5 and the cathode electrode substrate 6 , and the cathode gas diffusion layer 4 is the composite electrolyte membrane 200 . It may be bonded to the other surface.

The membrane-electrode assembly of the present invention may be formed by disposing the anode 200, the composite electrolyte membrane 100, and the cathode 300, respectively, and then fastening them, or may be formed by pressing them at high temperature and high pressure.

The anode gas diffusion layer 3 may be formed by coating a gas diffusion layer forming material on one surface of the composite electrolyte membrane 100 .

The anode gas diffusion layer 3 may be provided to prevent rapid diffusion of fuel injected into the fuel cell and to prevent a decrease in ion conductivity. In addition, the anode gas diffusion layer 3 may control the diffusion rate of fuel through heat treatment or electrochemical treatment. In addition, the anode gas diffusion layer 3 serves as a current conductor between the composite electrolyte membrane 100 for PEMFC and the anode catalyst layer 2 , and serves as a passage for a gas as a reactant and water as a product. Accordingly, the anode gas diffusion layer 3 may have a porous structure having a porosity of 20% to 90% so that the gas can pass therethrough. The thickness of the anode gas diffusion layer 3 may be appropriately adopted as needed, and may be, for example, 100 to 400 μm. When the thickness of the anode gas diffusion layer 3 is less than 100 μm, the electrical contact resistance between the anode catalyst layer 2 and the anode electrode substrate 1 increases, and the structure may become unstable due to compression. In addition, when the thickness of the anode gas diffusion layer 3 exceeds 400 μm, it may be difficult to move the reactant gas.

In addition, the anode gas diffusion layer 3 may be formed to include a carbon-based material and a fluorine-based resin. Carbon-based materials include graphite, carbon black, acetylene black, denka black, kecheon black, activated carbon, mesoporous carbon, carbon nanotube, carbon nanofiber, carbon nanohorn, carbon nanoring, carbon nanowire, fullerene (C60) And it may include one or more selected from the group consisting of super P, but is not limited thereto. In addition, as the fluorine-based resin, polytetrafluoroethylene, polyvinylidene fluoride (PVdF), polyvinyl alcohol, cellulose acetate, polyvinylidene fluoride-hexafluoropropylene copolymer, or styrene-butadiene fluoride (SBR) It may include one or more selected from the group consisting of. In addition, the fuel may be a liquid fuel such as formic acid solution, methanol, formaldehyde, or ethanol.

The anode catalyst layer 2 is a layer into which an oxidation catalyst is introduced, and the anode catalyst layer 2 may be formed by coating a catalyst layer forming material on the anode gas diffusion layer 3 .

The catalyst layer forming material may be a metal catalyst or a metal catalyst supported on a carbon-based support. As the metal catalyst, one or more selected from the group consisting of platinum, ruthenium, a platinum-ruthenium alloy, a platinum-osmium alloy, a platinum-palladium alloy, and a platinum-transition metal alloy may be used typically. In addition, as the carbon-based support, graphite (graphite), carbon black, acetylene black, denka black, ketchen black, activated carbon, mesoporous carbon, carbon nanotube, carbon nanofiber, carbon nanohorn, carbon nanoring, carbon nano It may include at least one selected from the group consisting of wire, fullerene, and super P.

In addition, the anode catalyst layer 2 may include a conductive support and an ion conductive binder (not shown). In addition, the anode catalyst layer 2 may include a main catalyst attached to a conductive support. The conductive support may be carbon black, and the ion conductive binder may be a Nafion ionomer or a sulfonated polymer. In addition, the main catalyst may be a metal catalyst, for example, may be platinum (Pt). The anode catalyst layer 2 may be formed using an electroplating method, a spray method, a painting method, a doctor blade method, or a transfer method.

The anode electrode substrate 1 may use a conductive substrate selected from the group consisting of carbon paper, carbon cloth, and carbon felt, but is not limited thereto, and any anode electrode material applicable to a polymer electrolyte fuel cell may be used. possible. The anode electrode substrate 1 may be formed on one surface of the anode catalyst layer 2 through a conventional deposition method, and after forming the anode catalyst layer 2 on the anode electrode substrate 1, the anode gas diffusion layer 3 ) may be formed by disposing the anode catalyst layer 2 and the anode electrode substrate 1 in contact thereon.

The cathode gas diffusion layer 4 may be formed by applying a gas diffusion layer forming material to the other surface of the composite electrolyte membrane 100 .

The cathode gas diffusion layer 4 may be provided to prevent rapid diffusion of the gas injected into the cathode 300 and to uniformly disperse the gas injected into the cathode 300 . In addition, the cathode gas diffusion layer 4 serves as a current conductor between the composite electrolyte membrane 100 for PEMFC and the cathode catalyst layer 5, and serves as a passage for the reactant gas and the product water. Accordingly, the cathode gas diffusion layer 4 may have a porous structure having a porosity of 20% to 90% so that gas can pass therethrough. The thickness of the cathode gas diffusion layer 4 may be appropriately adopted as needed, and may be, for example, 100 to 400 μm. When the thickness of the cathode gas diffusion layer 4 is less than 100 μm, the electrical contact resistance between the cathode catalyst layer 5 and the cathode electrode substrate 6 increases, and the structure may become unstable due to compression. In addition, when the thickness of the cathode gas diffusion layer 4 exceeds 400 μm, it may be difficult to move the reactant gas.

In addition, the cathode gas diffusion layer 4 may be formed to include a carbon-based material and a fluorine-based resin. Carbon-based materials include graphite, carbon black, acetylene black, denka black, kecheon black, activated carbon, mesoporous carbon, carbon nanotube, carbon nanofiber, carbon nanohorn, carbon nanoring, carbon nanowire, fullerene (C60) And it may include one or more selected from the group consisting of super P, but is not limited thereto. In addition, as the fluorine-based resin, polytetrafluoroethylene, polyvinylidene fluoride (PVdF), polyvinyl alcohol, cellulose acetate, polyvinylidene fluoride-hexafluoropropylene copolymer, or styrene-butadiene fluoride (SBR) It may include one or more selected from the group consisting of. In addition, the fuel may be a liquid fuel such as formic acid solution, methanol, formaldehyde, or ethanol.

The cathode catalyst layer 5 is a layer into which a reduction catalyst is introduced, and the cathode catalyst layer 5 may be formed by coating a catalyst layer forming material on the cathode gas diffusion layer 4 .

The catalyst layer forming material may be a metal catalyst or a metal catalyst supported on a carbon-based support. As the metal catalyst, one or more selected from the group consisting of platinum, ruthenium, a platinum-ruthenium alloy, a platinum-osmium alloy, a platinum-palladium alloy, and a platinum-transition metal alloy may be used typically. In addition, as the carbon-based support, graphite (graphite), carbon black, acetylene black, denka black, ketchen black, activated carbon, mesoporous carbon, carbon nanotube, carbon nanofiber, carbon nanohorn, carbon nanoring, carbon nano It may include at least one selected from the group consisting of wire, fullerene, and super P.

In addition, the cathode catalyst layer 5 may include a conductive support and an ion conductive binder (not shown). In addition, the cathode catalyst layer 5 may include a main catalyst attached to the conductive support. The conductive support may be carbon black, and the ion conductive binder may be a Nafion ionomer or a sulfonated polymer. In addition, the main catalyst may be a metal catalyst, for example, may be platinum (Pt). The cathode catalyst layer 5 may be formed using an electroplating method, a spray method, a painting method, a doctor blade method, or a transfer method.

The cathode electrode substrate 6 may use a conductive substrate selected from the group consisting of carbon paper, carbon cloth, and carbon felt, but is not limited thereto, and any cathode electrode material applicable to a polymer electrolyte fuel cell may be used. possible. The cathode electrode substrate 6 may be formed on one surface of the cathode catalyst layer 5 through a conventional deposition method, and after forming the cathode catalyst layer 5 on the cathode electrode substrate 6, the cathode gas diffusion layer 4 ) on the cathode catalyst layer 5 and the cathode electrode substrate 6 may be formed by disposing in contact.

Furthermore, the membrane-electrode assembly for PEMFC of the present invention may have a hydrogen permeability of 1.0 to 2.6 mA/cm², preferably a hydrogen permeability of 1.5 to 2.5 mA/cm², more preferably a hydrogen permeability of 2.0 to 2.3 mA/cm² have.

On the other hand, the polymer electrolyte membrane fuel cell according to an embodiment of the present invention includes at least one electricity generator that generates electrical energy through an oxidation reaction of fuel and a reduction reaction of an oxidizing agent, and supplies the above-described fuel to the electricity generator. It is configured to include a fuel supply unit and an oxidizer air gap for supplying the oxidizer to the electricity generating unit.

The membrane-electrode assembly of the present invention includes one or more, and separators for supplying fuel and an oxidizing agent are disposed at both ends of the membrane-electrode assembly of the present invention to constitute an electricity generating unit. At least one of these electricity generators may be gathered to form a stack.

In this case, the arrangement form or method of manufacturing the polymer electrolyte membrane fuel cell of the present invention can be formed without limitation as long as it is a form applicable to the polymer electrolyte fuel cell, and thus can be variously applied with reference to the prior art.

In the above, the present invention has been mainly described with respect to the embodiment, but this is only an example and does not limit the embodiment of the present invention. It can be seen that various modifications and applications not exemplified above are possible without departing from the scope. For example, each component specifically shown in the embodiment of the present invention can be implemented by modification. And differences related to such modifications and applications should be construed as being included in the scope of the present invention defined in the appended claims.

[Example]

Example 1: Preparation of perfluorinated sulfonated ionomer

(1) 500 ml of deionized water, 77.83 g of a compound represented by the following Chemical Formula 1-1 and 61 g of a compound represented by the following Chemical Formula 2-1 were put in a 1L stainless steel autoclave, and the speed of 300 rpm for 30 minutes stirred.

[Formula 1-1]

In Formula 1-1, n is 4.

[Formula 2-1]

In Formula 2-1, m is 4.

After stirring, the inside of the autoclave can be vacuumed to remove moisture, and the process of purging with nitrogen gas was performed three times.

(2) Tetrafluoroethylene (TFE) gas was introduced into the autoclave, and the inside of the autoclave was replaced with a TFE gas atmosphere having a pressure of 0.01 MPa. After substitution, the inside of the autoclave was vacuumed to remove moisture, and TFE gas was introduced into the autoclave until the pressure inside the autoclave reached 0.8 MPa. Thereafter, heat was applied to the inside of the autoclave at a rate of 5°C/min, and the temperature was raised until the autoclave internal temperature reached 35°C.

(3) A solution containing a radical initiator (a solution containing 1% by weight of potassium persulfate (KPS) as a radical initiator in deionized water) was divided into 7 times for 30 minutes and 500 ppm was added inside the autoclave. Thereafter, heat was applied to the inside of the autoclave at a rate of 5° C./min, and the temperature inside the reactor was raised to 50° C., and the reaction was performed for 3 hours to prepare a compound containing _{-SO 2 F group.} . The prepared _{compound containing the -SO 2} F group was washed with water 3 times using 5L of distilled water.

(4) _{hydrolysis is performed by immersing the compound containing the washed -SO 2} F group in a solution containing a hydrolytic agent (aqueous solution containing potassium hydroxide), and a solution containing an acid-forming agent (aqueous solution containing hydrochloric acid) ) to prepare a perfluorinated sulfonated ionomer including a polymer represented by a repeating unit represented by the following Chemical Formula 6-1. The weight average molecular weight of the prepared perfluorinated sulfonated ionomer and _{the chemical equivalent of the -SO 3} H group are shown in Table 1 below.

[Formula 6-1]

In Formula 6-1, n is 4, m is 4, and x, y, and z are molar ratios, which are rational numbers of 1:0.181:0.16.

Examples 2 to 7

In the same manner as in Example 1 A perfluorinated sulfonated ionomer was prepared. However, the perfluorinated sulfonated ionomers of Examples 2 to 7 were prepared by varying the content of the components used as shown in Table 1 below.

Example 8

In the same manner as in Example 1 A perfluorinated sulfonated ionomer was prepared. However, a perfluorinated sulfonated ionomer including a polymer represented by a repeating unit represented by the following Chemical Formula 6-2 was prepared by using the compound represented by the following Chemical Formula 2-2 instead of the compound represented by the Chemical Formula 2-1. The weight average molecular weight of the prepared perfluorinated sulfonated ionomer _{, the chemical equivalent of -SO 3} H group, and the content of the components used are shown in Table 2 below.

[Formula 2-2]

In Formula 2-2, m is 5.

[Formula 6-2]

In Formula 6-2, n is 4, m is 5, and x, y and z are a molar ratio, which is a rational number of 1:0.19:0.18.

Examples 9 to 14

In the same manner as in Example 8 A perfluorinated sulfonated ionomer was prepared. However, the perfluorinated sulfonated ionomers of Examples 9 to 14 were prepared by varying the content of the components used as shown in Table 2 below.

Example 15

In the same manner as in Example 1 A perfluorinated sulfonated ionomer was prepared. However, a perfluorinated sulfonated ionomer including a polymer represented by a repeating unit represented by the following Formula 6-3 was prepared by using the compound represented by the following Formula 2-3 instead of the compound represented by the Formula 2-1. The weight average molecular weight of the prepared perfluorinated sulfonated ionomer _{, the chemical equivalent of -SO 3} H group, and the content of the components used are shown in Table 3 below.

[Formula 2-3]

In Formula 2-3, m is 6.

[Formula 6-3]

In Formula 6-3, n is 4, m is 6, and x, y and z are molar ratios, which are rational numbers of 1:0.2:0.21.

Example 16-Example 21

In the same manner as in Example 15 A perfluorinated sulfonated ionomer was prepared. However, the perfluorinated sulfonated ionomers of Examples 16 to 21 were prepared by varying the content of the components used as shown in Table 3 below.

Example 22

In the same manner as in Example 1 A perfluorinated sulfonated ionomer was prepared. However, a perfluorinated sulfonated ionomer including a polymer represented by a repeating unit represented by the following formula 6-4 was prepared by using a compound represented by the following formula 1-2 instead of the compound represented by the formula 1-1. The weight average molecular weight of the prepared perfluorinated sulfonated ionomer _{, the chemical equivalent of -SO 3} H group, and the content of the components used are shown in Table 4 below.

[Formula 1-2]

In Formula 1-2, n is 5.

[Formula 6-4]

In Formula 6-4, n is 5, m is 4, and x, y and z are molar ratios, which are rational numbers of 1:0.185:0.185.

Example 23-Example 28

In the same manner as in Example 22 A perfluorinated sulfonated ionomer was prepared. However, the perfluorinated sulfonated ionomers of Examples 23 to 28 were prepared by varying the content of the components used as shown in Table 4 below.

Example 29

In the same manner as in Example 22 A perfluorinated sulfonated ionomer was prepared. However, a perfluorinated sulfonated ionomer including a polymer represented by a repeating unit represented by the following Chemical Formula 6-5 was prepared by using the compound represented by the following Chemical Formula 2-2 instead of the compound represented by the Chemical Formula 2-1. The weight average molecular weight of the prepared perfluorinated sulfonated ionomer _{, the chemical equivalent of -SO 3} H group, and the content of the components used are shown in Table 5 below.

[Formula 2-2]

In Formula 2-2, m is 5.

[Formula 6-5]

In Formula 6-5, n is 5, m is 5, and x, y and z are molar ratios, which are rational numbers of 1:0.197:0.21.

Examples 30 to 35

In the same manner as in Example 29 A perfluorinated sulfonated ionomer was prepared. However, the perfluorinated sulfonated ionomers of Examples 30 to 35 were prepared by varying the content of the components used as shown in Table 5 below.

Example 36

In the same manner as in Example 22 A perfluorinated sulfonated ionomer was prepared. However, a perfluorinated sulfonated ionomer including a polymer represented by a repeating unit represented by the following Formula 6-6 was prepared by using the compound represented by the following Formula 2-3 instead of the compound represented by the Formula 2-1. The weight average molecular weight of the prepared perfluorinated sulfonated ionomer _{, the chemical equivalent of -SO 3} H group, and the content of the components used are shown in Table 6 below.

[Formula 2-3]

In Formula 2-3, m is 6.

[Formula 6-6]

In Formula 6-6, n is 5, m is 6, and x, y, and z are molar ratios, which are rational numbers of 1:0.235:0.219.

Example 37-Example 42

In the same manner as in Example 36 A perfluorinated sulfonated ionomer was prepared. However, the perfluorinated sulfonated ionomers of Examples 37 to 42 were prepared by varying the content of the components used as shown in Table 6 below.

Comparative Example 1: Preparation of perfluorinated sulfonated ionomers

(1) 500 ml of deionized water and 159.1 g of a compound represented by the following Chemical Formula 1-1 were added to a 1L stainless steel autoclave, and the mixture was stirred at a speed of 300 rpm for 30 minutes.

[Formula 1-1]

In Formula 1-1, n is 4.

After stirring, the inside of the autoclave can be vacuumed to remove moisture, and the process of purging with nitrogen gas was performed three times.

(2) Tetrafluoroethylene (TFE) gas was introduced into the autoclave, and the inside of the autoclave was replaced with a TFE gas atmosphere having a pressure of 0.01 MPa. After substitution, the inside of the autoclave was vacuumed to remove moisture, and TFE gas was introduced into the autoclave until the pressure inside the autoclave reached 0.8 MPa. Thereafter, heat was applied to the inside of the autoclave at a rate of 5°C/min, and the temperature was raised until the autoclave internal temperature reached 35°C.

(3) A solution containing a radical initiator (a solution containing 1% by weight of potassium persulfate (KPS) as a radical initiator in deionized water) was divided into 7 times for 30 minutes and 500 ppm was added inside the autoclave. Thereafter, heat was applied to the inside of the autoclave at a rate of 5° C./min, and the temperature inside the reactor was raised to 50° C., and the reaction was performed for 3 hours to prepare a compound containing _{-SO 2 F group.} . The prepared _{compound containing the -SO 2} F group was washed with water 3 times using 5L of distilled water.

(4) _{hydrolysis is performed by immersing the compound containing the washed -SO 2} F group in a solution containing a hydrolytic agent (aqueous solution containing potassium hydroxide), and a solution containing an acid-forming agent (aqueous solution containing hydrochloric acid) ) to prepare a perfluorinated sulfonated ionomer. The weight average molecular weight of the prepared perfluorinated sulfonated ionomer is 112,700, and the chemical equivalent of _{-SO 3 H group is 700.}

Comparative Example 2

In the same manner as in Comparative Example 1 A perfluorinated sulfonated ionomer was prepared. However, a perfluorinated sulfonated ionomer was prepared by using 218.4 g of a compound represented by the following formula 1-2 instead of the compound represented by the formula 1-1. The weight average molecular weight of the prepared perfluorinated sulfonated ionomer is 115,600, and the chemical equivalent of _{-SO 3 H group is 700.}

[Formula 1-2]

In Formula 1-2, n is 5.

Comparative Example 3: Preparation of perfluorinated sulfonated ionomers

(1) 500 ml of deionized water and 118.56 g of a compound represented by the following Chemical Formula 2-1 were added to a 1L stainless steel autoclave, and the mixture was stirred at a speed of 300 rpm for 30 minutes.

[Formula 2-1]

In Formula 2-1, m is 4.

After stirring, the inside of the autoclave can be vacuumed to remove moisture, and the process of purging with nitrogen gas was performed three times.

(2) Tetrafluoroethylene (TFE) gas was introduced into the autoclave, and the inside of the autoclave was replaced with a TFE gas atmosphere having a pressure of 0.01 MPa. After substitution, the inside of the autoclave was vacuumed to remove moisture, and TFE gas was introduced into the autoclave until the pressure inside the autoclave reached 0.8 MPa. Thereafter, heat was applied to the inside of the autoclave at a rate of 5°C/min, and the temperature was raised until the autoclave internal temperature reached 35°C.

(3) A solution containing a radical initiator (a solution containing 1% by weight of potassium persulfate (KPS) as a radical initiator in deionized water) was divided into 7 times for 30 minutes and 500 ppm was added inside the autoclave. Thereafter, heat was applied to the inside of the autoclave at a rate of 5° C./min, and the temperature inside the reactor was raised to 50° C., and the reaction was performed for 3 hours to prepare a compound containing _{-SO 2 F group.} . The prepared _{compound containing the -SO 2} F group was washed with water 3 times using 5L of distilled water.

(4) _{hydrolysis is performed by immersing the compound containing the washed -SO 2} F group in a solution containing a hydrolytic agent (aqueous solution containing potassium hydroxide), and a solution containing an acid-forming agent (aqueous solution containing hydrochloric acid) ) to prepare a perfluorinated sulfonated ionomer. The weight average molecular weight of the prepared perfluorinated sulfonated ionomer is 121,100, and the chemical equivalent of _{-SO 3 H group is 701.}

Comparative Example 4

In the same manner as in Comparative Example 3 A perfluorinated sulfonated ionomer was prepared. However, a perfluorinated sulfonated ionomer was prepared by using 159.1 g of a compound represented by the following formula 2-2 instead of the compound represented by the formula 2-1. The weight average molecular weight of the prepared perfluorinated sulfonated ionomer is 114,200, and the chemical equivalent of _{-SO 3 H group is 700.}

[Formula 2-2]

In Formula 2-2, m is 5.

Comparative Example 5

In the same manner as in Comparative Example 3 A perfluorinated sulfonated ionomer was prepared. However, a perfluorinated sulfonated ionomer was prepared by using 217.92 g of a compound represented by the following formula 2-3 instead of the compound represented by the formula 2-1. The weight average molecular weight of the prepared perfluorinated sulfonated ionomer is 117,300, and the chemical equivalent of the _{-SO 3 H group is 700.}

[Formula 2-3]

In Formula 2-3, m is 6.

Preparation Example 1: Preparation of PTFE porous support

A paste was prepared by mixing and stirring 23 parts by weight of naphtha, a liquid lubricant, to 100 parts by weight of PTFE fine powder having an average particle diameter of 570 μm to uniformly disperse it.

Next, the paste was aged at 50° C. for 18 hours, and then compressed using a molding jig to prepare a PTFE block.

Next, after putting the PTFE block into the extrusion mold, pressure extrusion was performed under a pressure of ^{about 0.10 Ton/cm 2 .}

Next, it was rolled using a rolling roll to prepare an unbaked tape having an average thickness of 850 µm.

Next, while the unbaked tape was transferred to a conveyor belt at a speed of 3 M/min, heat of 180° C. was applied and dried to remove the lubricant.

Next, uniaxial stretching (lengthwise stretching) was performed on the unbaked tape from which the lubricant was removed at a stretching temperature of 280° C. and a stretching speed of 10 M/min at 6.5 times.

Next, the uniaxially stretched unbaked tape was biaxially stretched 30 times (width direction stretching) under the conditions of a stretching temperature of 250° C. and a stretching speed of 10 M/min to prepare a porous support.

Next, the uniaxially and biaxially stretched porous support was fired by applying a temperature of 420° C. at a rate of 15 M/min on a conveyor belt to prepare a PTFE porous support having an average thickness of 5 μm and an average pore size of 0.114 μm.

Preparation Example 1: Preparation of composite electrolyte membrane for PEMFC

(1) The PTFE porous support prepared in Preparation Example 1 was prepared.

(2) 1 part by weight of a radical scavenger for PEMFC (Sangafrontech, CeZnO metal oxide) was mixed with 100 parts by weight of the perfluorinated sulfonated ionomer prepared in Example 1 to prepare a perfluorinated sulfonated ionomer solution.

(3) The PTFE porous support prepared in Preparation Example 1 was fixed to a glass substrate, and one surface of the PTFE porous support was impregnated with a perfluorinated sulfonated ionomer solution using an applicator. Next, the PTFE porous support impregnated with the perfluorinated sulfonated ionomer solution was put into a vacuum oven at 80° C. and dried for 10 minutes to form a first electrolyte layer on one surface of the PTFE porous support.

The first electrolyte layer is a layer formed by a perfluorinated sulfonated ionomer solution.

(4) Using an applicator, the other surface of the porous PTFE support on which the first electrolyte layer was formed was impregnated with the perfluorinated sulfonated ionomer solution. Next, the PTFE porous support impregnated with the perfluorinated sulfonated ionomer solution was put into a vacuum oven at 80° C. and dried for 10 minutes to form a second electrolyte layer on the other surface of the PTFE porous support. The second electrolyte layer is a layer formed by a perfluorinated sulfonated ionomer solution.

(5) A composite electrolyte membrane for PEMFC was prepared by heat-treating the PTFE porous support on which the first electrolyte layer and the second electrolyte layer were formed at 160° C. for 3 minutes. The first electrolyte layer had an average thickness of 5 μm, and the second electrolyte layer was The average thickness was formed to 5㎛.

Preparation Examples 2 to 42 and Comparative Preparation Examples 1 to 5

A composite electrolyte membrane for PEMFC was prepared in the same manner as in Preparation Example 1, except that Preparation Example 2 used the perfluorinated sulfonated ionomer prepared in Example 2 instead of the perfluorinated sulfonated ionomer prepared in Example 1 to produce a composite electrolyte for PEMFC. Membrane was prepared, and in Preparation Example 3, a composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 3 instead of the perfluorinated sulfonated ionomer prepared in Example 1, and Preparation Example 4 was prepared in Example 1 A composite electrolyte membrane for PEMFC was prepared by using the perfluorinated sulfonated ionomer prepared in Example 4 instead of the prepared perfluorinated sulfonated ionomer, and Preparation Example 5 was prepared in Example 5 instead of the perfluorinated sulfonated ionomer prepared in Example 1. A composite electrolyte membrane for PEMFC was prepared using the prepared perfluorinated sulfonated ionomer, and in Preparation Example 6, the perfluorinated sulfonated ionomer prepared in Example 6 was used instead of the perfluorinated sulfonated ionomer prepared in Example 1 for PEMFC. A composite electrolyte membrane was prepared, and in Preparation Example 7, a composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 7 instead of the perfluorinated sulfonated ionomer prepared in Example 1, and Preparation Example 8 was Example A composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 8 instead of the perfluorinated sulfonated ionomer prepared in Example 1, and Preparation Example 9 was prepared in Example instead of the perfluorinated sulfonated ionomer prepared in Example 1. A composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in 9, and in Preparation Example 10, the perfluorinated sulfonated ionomer prepared in Example 10 was used instead of the perfluorinated sulfonated ionomer prepared in Example 1. A composite electrolyte membrane for PEMFC was prepared, and in Preparation Example 11, a composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 11 instead of the perfluorinated sulfonated ionomer prepared in Example 1, and Preparation Example 12 was Example instead of the perfluorinated sulfonated ionomer prepared in Example 1 A composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 12, and in Preparation Example 13, the perfluorinated sulfonated ionomer prepared in Example 13 was used instead of the perfluorinated sulfonated ionomer prepared in Example 1. A composite electrolyte membrane for PEMFC was prepared, and in Preparation Example 14, a composite electrolyte membrane for PEMFC was prepared by using the perfluorinated sulfonated ionomer prepared in Example 14 instead of the perfluorinated sulfonated ionomer prepared in Example 1, and Preparation Example 15 was A composite electrolyte membrane for PEMFC was prepared by using the perfluorinated sulfonated ionomer prepared in Example 15 instead of the perfluorinated sulfonated ionomer prepared in Example 1, and Preparation Example 16 was used instead of the perfluorinated sulfonated ionomer prepared in Example 1 A composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 16. In Preparation Example 17, the perfluorinated sulfonated ionomer prepared in Example 17 was used instead of the perfluorinated sulfonated ionomer prepared in Example 1. A composite electrolyte membrane for PEMFC was prepared using the In Example 19, a composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 19 instead of the perfluorinated sulfonated ionomer prepared in Example 1, and in Preparation Example 20, the perfluorinated sulfonated ionomer prepared in Example 1 was prepared. A composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 20 instead of the ionomer, and in Preparation Example 21, the perfluorinated sulfonated ionomer prepared in Example 21 was replaced with the perfluorinated sulfonated ionomer prepared in Example 1 A composite electrolyte membrane for PEMFC was prepared using the ionomer, and in Preparation Example 22, a composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 22 instead of the perfluorinated sulfonated ionomer prepared in Example 1, Preparation 23 is an example A composite electrolyte membrane for PEMFC was prepared by using the perfluorinated sulfonated ionomer prepared in Example 23 instead of the perfluorinated sulfonated ionomer prepared in Example 1, and Preparation Example 24 was prepared in Example 24 instead of the perfluorinated sulfonated ionomer prepared in Example 1. A composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 24. In Preparation 25, the perfluorinated sulfonated ionomer prepared in Example 25 was used instead of the perfluorinated sulfonated ionomer prepared in Example 1. A composite electrolyte membrane for PEMFC was prepared, and in Preparation Example 26, a composite electrolyte membrane for PEMFC was prepared by using the perfluorinated sulfonated ionomer prepared in Example 26 instead of the perfluorinated sulfonated ionomer prepared in Example 1. A composite electrolyte membrane for PEMFC was prepared by using the perfluorinated sulfonated ionomer prepared in Example 27 instead of the perfluorinated sulfonated ionomer prepared in Example 1, and Preparation Example 28 was used instead of the perfluorinated sulfonated ionomer prepared in Example 1 A composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 28. In Preparation Example 29, the perfluorinated sulfonated ionomer prepared in Example 29 was used instead of the perfluorinated sulfonated ionomer prepared in Example 1. A composite electrolyte membrane for PEMFC was prepared using In Example 31, a composite electrolyte membrane for PEMFC was prepared by using the perfluorinated sulfonated ionomer prepared in Example 31 instead of the perfluorinated sulfonated ionomer prepared in Example 1, and in Preparation Example 32, the perfluorinated sulfonated ionomer prepared in Example 1 was prepared. A composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 32 instead of the ionomer, and in Preparation Example 33, the perfluorinated sulfonated ionomer prepared in Example 33 was replaced with the perfluorinated sulfonated ionomer prepared in Example 1. For PEMFCs using ionomers A composite electrolyte membrane was prepared, and in Preparation Example 34, a composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 34 instead of the perfluorinated sulfonated ionomer prepared in Example 1, and Preparation 35 was Example A composite electrolyte membrane for PEMFC was prepared by using the perfluorinated sulfonated ionomer prepared in Example 35 instead of the perfluorinated sulfonated ionomer prepared in Example 1, and Preparation 36 was prepared in Example instead of the perfluorinated sulfonated ionomer prepared in Example 1 A composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 36, and in Preparation Example 37, the perfluorinated sulfonated ionomer prepared in Example 37 was used instead of the perfluorinated sulfonated ionomer prepared in Example 1. A composite electrolyte membrane for PEMFC was prepared, and in Preparation Example 38, a composite electrolyte membrane for PEMFC was prepared by using the perfluorinated sulfonated ionomer prepared in Example 38 instead of the perfluorinated sulfonated ionomer prepared in Example 1. A composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 39 instead of the perfluorinated sulfonated ionomer prepared in Example 1, and Preparation 40 was prepared in place of the perfluorinated sulfonated ionomer prepared in Example 1 A composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Example 40. In Preparation Example 41, the perfluorinated sulfonated ionomer prepared in Example 41 was used instead of the perfluorinated sulfonated ionomer prepared in Example 1. A composite electrolyte membrane for PEMFC was prepared using In Example 1, a composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer prepared in Comparative Example 1 instead of the perfluorinated sulfonated ionomer prepared in Example 1, and Comparative Preparation Example 2 was prepared in Example 1 Prepared in Comparative Example 2 instead of the sulfonated ionomer A composite electrolyte membrane for PEMFC was prepared using the perfluorinated sulfonated ionomer, and Comparative Preparation Example 3 used the perfluorinated sulfonated ionomer prepared in Comparative Example 3 instead of the perfluorinated sulfonated ionomer prepared in Example 1 for PEMFC. A composite electrolyte membrane was prepared, and in Comparative Preparation Example 4, a composite electrolyte membrane for PEMFC was prepared by using the perfluorinated sulfonated ionomer prepared in Comparative Example 4 instead of the perfluorinated sulfonated ionomer prepared in Example 1, and Comparative Preparation Example 5 was A composite electrolyte membrane for PEMFC was prepared by using the perfluorinated sulfonated ionomer prepared in Comparative Example 5 instead of the perfluorinated sulfonated ionomer prepared in Example 1.

Experimental Example 1: Measurement of durability and ionic conductivity of composite electrolyte membrane for PEMFC

1) Fenton test

Prepare a test piece of each of the composite electrolyte membranes for PEMFC prepared in Preparation Examples 1 to 42 and Comparative Preparation Examples 1 to 5 in a size of 5 cm × 5 cm (width × length), and after drying at 80° C. in an oven for 5 hours or more, the mass measure The prepared specimen is immersed in 200 g of a solution prepared by adding ^{3 ppm Fe 2+} to 2% hydrogen peroxide, and then left at 80° C. for 120 hours. The fluoride ion concentration eluted from the test piece was measured using a fluorine ion selective electrode, and the results are shown in Tables 7 to 12 below. In the Fenton test, the lower the measured value, the lower the elution of fluoride ions, that is, the superior durability of the electrolyte membrane.

2) Ion conductivity measurement

Prepare a test piece of each of the composite electrolyte membrane for PEMFC prepared in Preparation Examples 1 to 42 and Comparative Preparation Examples 1 to 5 in a size of 1 cm × 5 cm (width × length), immersed in distilled water, and immersed in an oven at 80° C. for 5 hours After the fastened cell was immersed in distilled water, the impedance was measured after setting the temperature at 25°C, the ionic conductivity was calculated, and the results are shown in Tables 7 to 12 below.

Experimental Example 2: Moisture content measurement experiment of composite electrolyte membrane for PEMFC

After the composite electrolyte membrane for PEMFC prepared in Preparation Examples 1 to 42 and Comparative Preparation Examples 1 to 5 was completely dried at 120° C. for 1 hour, the weight (W _d ) was measured. This was again immersed in deionized water, left at 60 ~ 120 °C for 5 hours, and then the sample was taken out, the water was removed from the surface, and the weight (W _w ) was measured.

Thereafter, the moisture content was measured according to Equation 1 below, and the results are shown in Tables 7 to 12 below.

[Equation 1]

Moisture content (%) = ((W _w -W _d )/W _w ))*100

Experimental Example 3: Hydrogen permeability measurement experiment of composite electrolyte membrane for PEMFC

^{Membrane-electrode assemblies for PEMFCs having an electrode active area of 25 cm 2} including the composite electrolyte membranes for PEMFCs prepared in Preparation Examples 1 to 42 and Comparative Preparation Examples 1 to 5, respectively, were prepared and measured in a cell station under RH 100% conditions, Initial activation was performed to activate the performance of the PEMFC membrane-electrode assembly to realize optimal performance. Thereafter, in order to check the performance of the PEMFC membrane-electrode assembly, the performance of the PEMFC membrane-electrode assembly was measured under the condition of waiting for OCV for 1 minute in CC (Constant Current) mode and repeating each section from 0A to 45A for 1 minute. measured. Finally, to measure the hydrogen permeability, the temperature was set to 80°C and the RH value was 100%, and H ₂ to the anode and N ₂ gas to the cathode were flowed to plot the 0.4V ~ 0.5V section. It was measured by plotting, and the results are shown in Tables 7 to 12 below.

As can be seen in Table 7, the composite electrolyte membrane for PEMFC prepared in Preparation Examples 1 to 3 has superior durability than the composite electrolyte membrane for PEMFC prepared in Preparation Examples 4 to 7 and Comparative Preparation Examples 1 and 3, as well as ion It was confirmed that the conductivity was high and the hydrogen permeability was low.

As can be seen in Table 8, the composite electrolyte membrane for PEMFC prepared in Preparation Examples 8 to 10 has superior durability than the composite electrolyte membrane for PEMFC prepared in Preparation Examples 11 to 14 and Comparative Preparation Examples 1 and 4, as well as ion It was confirmed that the conductivity was high and the hydrogen permeability was low.

As can be seen in Table 9, the composite electrolyte membrane for PEMFC prepared in Preparation Examples 15 to 17 has superior durability than the composite electrolyte membrane for PEMFC prepared in Preparation Examples 18 to 21 and Comparative Preparation Examples 1 and 5, as well as ion It was confirmed that the conductivity was high and the hydrogen permeability was low.

As can be seen in Table 10, the composite electrolyte membrane for PEMFC prepared in Preparation Examples 22 to 24 has superior durability than the composite electrolyte membrane for PEMFC prepared in Preparation Examples 25 to 28 and Comparative Preparation Examples 2 and 3, It was confirmed that the conductivity was high and the hydrogen permeability was low.

As can be seen in Table 11, the composite electrolyte membrane for PEMFC prepared in Preparation Examples 29 to 31 has superior durability than the composite electrolyte membrane for PEMFC prepared in Preparation Examples 32 to 35 and Comparative Preparation Examples 2 and 4, as well as ion It was confirmed that the conductivity was high and the hydrogen permeability was low.

As can be seen in Table 12, the composite electrolyte membrane for PEMFC prepared in Preparation Examples 36 to 38 has superior durability than the composite electrolyte membrane for PEMFC prepared in Preparation Examples 39 to 42 and Comparative Preparation Examples 2 and 5, as well as ion It was confirmed that the conductivity was high and the hydrogen permeability was low.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (25)

tetrafluoroethylene (TFE); a compound represented by the following formula 1-1; a compound represented by the following formula 2-1; and radical initiators; including,
A composition for preparing a perfluorinated sulfonated ionomer comprising the compound represented by the following Chemical Formula 1-1 and the compound represented by the following Chemical Formula 2-1 in a weight ratio of 1: 0.75 to 0.95.
[Formula 1-1]

In Formula 1-1, n is 4.
[Formula 2-1]

In Formula 2-1, m is 4.
According to claim 1,
The radical initiator is a bis (fluoroacyl) peroxide compound, a bis (chlorofluoroacyl) peroxide compound, a dialkyl peroxydicarbonate compound, a diacyl peroxide compound, a peroxyester compound, an azo compound And a composition for preparing a perfluorinated sulfonated ionomer comprising at least one selected from the group consisting of persulfate-based compounds.
According to claim 1,
The composition comprises a hydrolyzing agent; and acid-forming agents; A composition for preparing a perfluorinated sulfonated ionomer further comprising a.
delete tetrafluoroethylene (TFE); a compound represented by the following formula 1-1; a compound represented by the following formula 2-2; and radical initiators; including,
A composition for preparing a perfluorinated sulfonated ionomer comprising the compound represented by the following Chemical Formula 1-1 and the compound represented by the following Chemical Formula 2-2 in a weight ratio of 1:0.9 to 1.1.
[Formula 1-1]

In Formula 1-1, n is 4.
[Formula 2-2]

In Formula 2-2, m is 5.
tetrafluoroethylene (TFE); a compound represented by the following formula 1-1; a compound represented by the following formula 2-3; and radical initiators; including,
A composition for preparing a perfluorinated sulfonated ionomer comprising the compound represented by the following Chemical Formula 1-1 and the compound represented by the following Chemical Formula 2-3 in a weight ratio of 1:15 to 1.32.
[Formula 1-1]

In Formula 1-1, n is 4.
[Formula 2-3]

In Formula 2-3, m is 6.
tetrafluoroethylene (TFE); a compound represented by the following formula 1-2; a compound represented by the following formula 2-1; and radical initiators; including,
A composition for preparing a perfluorinated sulfonated ionomer comprising the compound represented by the following Chemical Formula 1-2 and the compound represented by the following Chemical Formula 2-1 in a weight ratio of 1: 0.75 to 0.92.
[Formula 1-2]

In Formula 1-2, n is 5.
[Formula 2-1]

In Formula 2-1, m is 4.
tetrafluoroethylene (TFE); a compound represented by the following formula 1-2; a compound represented by the following formula 2-2; and radical initiators; including,
A composition for preparing a perfluorinated sulfonated ionomer comprising the compound represented by the following Chemical Formula 1-2 and the compound represented by the following Chemical Formula 2-2 in a weight ratio of 1: 0.91 to 1.1.
[Formula 1-2]

In Formula 1-2, n is 5.
[Formula 2-2]

In Formula 2-2, m is 5.
tetrafluoroethylene (TFE); a compound represented by the following formula 1-2; a compound represented by the following formula 2-3; and radical initiators; including,
A composition for preparing a perfluorinated sulfonated ionomer comprising the compound represented by the following Chemical Formula 1-2 and the compound represented by the following Chemical Formula 2-3 in a weight ratio of 1: 0.9 to 1.04.
[Formula 1-2]

In Formula 1-2, n is 5.
[Formula 2-3]

In Formula 2-3, m is 6.
A polymer comprising a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit represented by the following formula (5),
The polymer includes a repeating unit represented by the following Chemical Formula 6-1, and the polymer has a weight average molecular weight of 80,000 to 1,000,000;
[Formula 3]

[Formula 4]

In Formula 4, n is 4.
[Formula 5]

In Formula 5, m is 4.
[Formula 6-1]

In Formula 6-1, n is 4, m is 4, x, y, and z are a molar ratio, 1: 0.05 to 0.5: a rational number of 0.15 to 0.19, and each structural unit according to x, y and z The order of combinations of can be randomly modified.
A polymer comprising a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit represented by the following formula (5),
The polymer includes a repeating unit represented by the following Chemical Formula 6-2, and the polymer has a weight average molecular weight of 80,000 to 1,000,000;
[Formula 3]

[Formula 4]

In Formula 4, n is 4.
[Formula 5]

In Formula 5, m is 5.
[Formula 6-2]

In Formula 6-2, n is 4, m is 5, x, y, and z are a molar ratio, 1: 0.05 to 0.5: a rational number of 0.17 to 0.21, and each structural unit according to x, y and z The order of combinations of can be randomly modified.
11. The method of claim 10,
The polymer is _{a perfluorinated sulfonated ionomer, characterized in that the -SO 3} H group has an equivalent weight (EW) of 500 to 1200.
support layer;
a first electrolyte layer formed on one surface of the support layer; and
a second electrolyte layer formed on the other surface of the support layer; including,
13. A composite electrolyte membrane for PEMFC, characterized in that at least one of the first electrolyte layer and the second electrolyte layer comprises the perfluorinated sulfonated ionomer of claim 10.
14. The method of claim 13,
The composite electrolyte membrane is a composite electrolyte membrane for PEMFC, characterized in that the durability measured by the Fenton test is 1.5 to 10 μmol/hr·g, and the ionic conductivity is 0.07 to 0.2 S/cm.
anode (oxidation electrode); The composite electrolyte membrane for PEMFC of claim 13; and a cathode (reducing electrode); Membrane-electrode assembly for PEMFC comprising a.
16. The method of claim 15,
The membrane-electrode assembly is a membrane-electrode assembly for PEMFC, characterized in that the hydrogen permeability is 1.0 to 2.6 mA/cm².
The membrane-electrode assembly for PEMFC of claim 15 and a separator, comprising: an electricity generator generating electricity through an electrochemical reaction of a fuel and an oxidizing agent;
a fuel supply unit for supplying fuel to the electricity generating unit; and
an oxidizing agent supply unit for supplying an oxidizing agent to the electricity generating unit; A polymer electrolyte membrane fuel cell comprising a.
A first step of adding and stirring deionized water, a compound represented by the following Chemical Formula 1-1 and a compound represented by the following Chemical Formula 2-1 into the reactor;
a second step of injecting tetrafluoroethylene (TFE) gas into the reactor to replace the internal atmosphere of the reactor with a TFE gas atmosphere;
A third step of preparing a compound containing a _{-SO 2} F group by introducing a radical initiator into the reactor; and
The compound containing the -SO ₂ F group is immersed in a solution containing a hydrolyzing agent to prepare a compound containing a sulfonate group, and the compound containing the sulfonate group is immersed in a solution containing an acid-forming agent to Formula 3 a fourth step of preparing a polymer comprising a repeating unit represented by including,
The polymer comprises a repeating unit represented by the following Chemical Formula 6-1, and the polymer has a weight average molecular weight of 80,000 to 1,000,000. A method for producing a perfluorinated sulfonated ionomer;
[Formula 1-1]

In Formula 1-1, n is 4.
[Formula 2-1]

In Formula 2-1, m is 4.
[Formula 3]

[Formula 4]

In Formula 4, n is 4.
[Formula 5]

In Formula 5, m is 4.
[Formula 6-1]

In Formula 6-1, n is 4, m is 4, x, y and z are a molar ratio, 1: 0.05 to 0.5: a rational number of 0.15 to 0.19, and each structural unit according to x, y and z The order of combinations of can be randomly modified.
A first step of adding and stirring deionized water, a compound represented by the following Chemical Formula 1-1 and a compound represented by the following Chemical Formula 2-2 into the reactor;
a second step of injecting tetrafluoroethylene (TFE) gas into the reactor to replace the internal atmosphere of the reactor with a TFE gas atmosphere;
A third step of preparing a compound containing a _{-SO 2} F group by introducing a radical initiator into the reactor; and
The compound containing the -SO ₂ F group is immersed in a solution containing a hydrolyzing agent to prepare a compound containing a sulfonate group, and the compound containing the sulfonate group is immersed in a solution containing an acid-forming agent to Formula 3 a fourth step of preparing a polymer comprising a repeating unit represented by including,
wherein the polymer includes a repeating unit represented by the following Chemical Formula 6-2, and the polymer has a weight average molecular weight of 80,000 to 1,000,000;
[Formula 1-1]

In Formula 1-1, n is 4.
[Formula 2-2]

In Formula 2-2, m is 5.
[Formula 3]

[Formula 4]

In Formula 4, n is 4.
[Formula 5]

In Formula 5, m is 5.
[Formula 6-2]

In Formula 6-2, n is 4, m is 5, x, y, and z are a molar ratio, 1: 0.05 to 0.5: a rational number of 0.17 to 0.21, and each structural unit according to x, y and z The order of combinations of can be randomly modified.
A first step of adding and stirring deionized water and a compound represented by the following Chemical Formula 1-1 into the reactor;
a second step of injecting tetrafluoroethylene (TFE) gas into the reactor to replace the internal atmosphere of the reactor with a TFE gas atmosphere;
a third step of introducing a radical initiator into the reactor;
A fourth step of preparing a compound containing a _{-SO 2} F group by adding and stirring a compound represented by the following Chemical Formula 2-1 in the reactor; and
The compound containing the -SO ₂ F group is immersed in a solution containing a hydrolyzing agent to prepare a compound containing a sulfonate group, and the compound containing the sulfonate group is immersed in a solution containing an acid-forming agent to Formula 3 a fifth step of preparing a polymer including a repeating unit represented by including,
The polymer comprises a repeating unit represented by the following Chemical Formula 6-1, and the polymer has a weight average molecular weight of 80,000 to 1,000,000. A method for producing a perfluorinated sulfonated ionomer;
[Formula 1-1]

In Formula 1-1, n is 4.
[Formula 2-1]

In Formula 2-1, m is 4.
[Formula 3]

[Formula 4]

In Formula 4, n is 4.
[Formula 5]

In Formula 5, m is 4.
[Formula 6-1]

In Formula 6-1, n is 4, m is 4, x, y and z are a molar ratio, 1: 0.05 to 0.5: a rational number of 0.15 to 0.19, and each structural unit according to x, y and z The order of combinations of can be randomly modified.
A first step of adding and stirring deionized water and a compound represented by the following Chemical Formula 1-1 into the reactor;
a second step of injecting tetrafluoroethylene (TFE) gas into the reactor to replace the internal atmosphere of the reactor with a TFE gas atmosphere;
a third step of introducing a radical initiator into the reactor;
A fourth step of preparing a compound including a _{-SO 2} F group by adding and stirring a compound represented by the following Chemical Formula 2-2 into the reactor; and
The compound containing the -SO ₂ F group is immersed in a solution containing a hydrolyzing agent to prepare a compound containing a sulfonate group, and the compound containing the sulfonate group is immersed in a solution containing an acid-forming agent to Formula 3 a fifth step of preparing a polymer including a repeating unit represented by including,
wherein the polymer includes a repeating unit represented by the following Chemical Formula 6-2, and the polymer has a weight average molecular weight of 80,000 to 1,000,000;
[Formula 1-1]

In Formula 1-1, n is 4.
[Formula 2-2]

In Formula 2-2, m is 5.
[Formula 3]

[Formula 4]

In Formula 4, n is 4.
[Formula 5]

In Formula 5, m is 5.
[Formula 6-2]

In Formula 6-2, n is 4, m is 5, x, y, and z are a molar ratio, 1: 0.05 to 0.5: a rational number of 0.17 to 0.21, and each structural unit according to x, y and z The order of combinations of can be randomly modified.
A polymer comprising a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit represented by the following formula (5),
The polymer includes a repeating unit represented by the following Chemical Formula 6-3, and the polymer has a weight average molecular weight of 80,000 to 1,000,000;
[Formula 3]

[Formula 4]

In Formula 4, n is 4.
[Formula 5]

In Formula 5, m is 6.
[Formula 6-3]

In Formula 6-3, n is 4, m is 6, x, y, and z are a molar ratio, 1: 0.05 to 0.5: a rational number of 0.21 to 0.24, and each structural unit according to x, y and z The order of combinations of can be randomly modified.
A polymer comprising a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit represented by the following formula (5),
The polymer includes a repeating unit represented by the following Chemical Formula 6-4, and the polymer has a weight average molecular weight of 80,000 to 1,000,000; a perfluorinated sulfonated ionomer;
[Formula 3]

[Formula 4]

In Formula 4, n is 5.
[Formula 5]

In Formula 5, m is 4.
[Formula 6-4]

In Formula 6-4, n is 5, m is 4, x, y, and z are a molar ratio, 1: 0.05 to 0.5: a rational number of 0.18 to 0.22, and each structural unit according to x, y and z The order of combinations of can be randomly modified.
A polymer comprising a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit represented by the following formula (5),
The polymer includes a repeating unit represented by the following Chemical Formula 6-5, and the polymer has a weight average molecular weight of 80,000 to 1,000,000;
[Formula 3]

[Formula 4]

In Formula 4, n is 5.
[Formula 5]

In Formula 5, m is 5.
[Formula 6-5]

In Formula 6-5, n is 5, m is 5, x, y and z are molar ratios, 1: 0.05 to 0.5: a rational number of 0.20 to 0.24, and each structural unit according to x, y and z The order of combinations of can be randomly modified.
A polymer comprising a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit represented by the following formula (5),
The polymer includes a repeating unit represented by the following Chemical Formula 6-6, and the polymer has a weight average molecular weight of 80,000 to 1,000,000;
[Formula 3]

[Formula 4]

In Formula 4, n is 5.
[Formula 5]

In Formula 5, m is 6.
[Formula 6-6]

In Formula 6-6, n is 5, m is 6, x, y, and z are a molar ratio, 1: 0.05 to 0.5: a rational number of 0.21 to 0.24, and each structural unit according to x, y and z The order of combinations of can be randomly modified.

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