KR20190071965A - Electrode composition for fuel cell comprising anion conducting hydrocarbonaceous binder, membrane/electrode assembly comprising said composition and preparation method thereof - Google Patents

Abstract

The present invention relates to a positive electrode composition for a fuel cell comprising a hydrocarbon-based anion conductive binder, a membrane-electrode assembly comprising the same, and a method for manufacturing the same. More specifically, the present invention relates to a positive electrode composition for a fuel cell in a slurry state comprising a hydrocarbon-based anion conductive binder and a catalyst metal, a membrane-electrode assembly comprising a catalyst layer formed using the positive electrode composition and an anion conductive electrolyte membrane, and a method for manufacturing the same. According to the present invention, by providing an anion exchange material binder based on a low-cost hydrocarbon-based material, a membrane-electrode assembly for a fuel cell having excellent economic efficiency and excellent performance and durability can be manufactured.

Description

[0001] The present invention relates to a positive electrode composition for a fuel cell including a hydrocarbon-based anionic conductive binder, a membrane-electrode assembly comprising the same, and a membrane-

The present invention relates to a positive electrode composition for a fuel cell comprising a hydrocarbon-based anionic conductive binder, a membrane-electrode assembly comprising the same, and a process for producing the same.

More particularly, the present invention relates to a membrane-electrode assembly for a fuel cell comprising a cathode composition for a fuel cell in a slurry state containing a hydrocarbon-based anionic conductive binder and a catalyst metal, and a catalyst layer formed using such a cathode composition and an anionic conductive electrolyte membrane, It is about.

Increasing demand for fossil fuel depletion, pollution and electrical energy due to recent population growth necessitates the development of alternative energy sources. Therefore, many researchers are attempting to invent a new system capable of producing electrical energy. Among them, proton exchange membrane fuel cells (PEMFCs) using polymer electrolyte can directly convert chemical energy into electrical energy and discharge non-toxic substances such as water. Therefore, alternative energy for automobiles and portable household appliances System. An important element of the PEMFC is a polymer electrolyte membrane (PEM) that determines the performance and durability of the PEMFC and separates both electrodes. Therefore, high proton conductivity, strong mechanical properties, stable dimensions in water and low unit cost are essential in the choice of PEM.

In general, an electrolyte membrane used in a polymer electrolyte fuel cell can be divided into a perfluorinated polymer electrolyte and a hydrocarbon polymer electrolyte. The fluorinated polyelectrolyte is chemically stable due to strong binding force between carbon-fluorine (CF) and shielding effect of fluorine atom, and has excellent mechanical properties. In particular, since it is a hydrogen ion exchange membrane and has high conductivity, Has been commercialized as a polymer membrane of an electrolyte type fuel cell. Nafion (perfluorinated sulfonic acid polymer), a product of Du Pont, USA, is a typical example of a commercially available hydrogen ion exchange membrane and has been widely used since it has excellent ion conductivity, chemical stability and ion selectivity. However, the fluorinated polymer electrolyte membranes have a disadvantage in that they are low in industrial availability due to their high cost, high methanol crossover through the polymer membrane, and decrease in the efficiency of the polymer membrane at a temperature of 80 ° C or higher Therefore, studies on competitive hydrocarbon ion exchange membranes have been actively conducted.

Since the polymer electrolyte membrane used in the fuel cell must be stable under the conditions required for operation of the fuel cell, sufficiently high mechanical properties are required. On the other hand, the increase of the film thickness for the increase of the mechanical property has a disadvantage that the ion resistance of the film is lowered and the ion conductivity of the film is lowered. The membrane with weak strength causes decomposition reaction of the polymer membrane due to electrochemical stress such as hydrolysis, oxidation and reduction reaction when the fuel cell is driven, thereby deteriorating the performance of the fuel cell.

 Therefore, in the prior art Japanese Patent Laid-Open No. 2006-019271 related to an electrode binder for a fuel cell, polyvinylidene fluoride (PVDF), polybenzimidazole (PBI) having stability to phosphoric acid which is an electrolyte for the catalyst Pt / C, Is used. However, when PVDF is used as a binder, the distribution and flow control ability of phosphoric acid is not sufficient. When PBI is used as a binder, the electrode is partially damaged due to the phosphoric acid solubility of PBI itself and the electrode microstructure is changed due to swelling of the electrode And the like.

On the other hand, in order to improve the disadvantage of poor compatibility with the fluorine-based polymer Nafion when the fluorochemical naphion is used as the binder in the electrode catalyst of the membrane-electrode assembly having the hydrocarbon-based ion conductive polymer membrane, Korean Patent Publication No. 2016-0143103 Discloses a technique capable of improving the durability by producing a membrane-electrode assembly in combination with an electrolyte membrane having excellent durability, which is produced from a partially branched block copolymer. In the case of using such a branched hydrocarbon-based ion conductive polymer membrane It is possible to provide an electrolyte membrane having an increased strength. However, since the durability of the electrode catalyst layer is low, the performance of the membrane-electrode assembly produced therefrom may rapidly decrease in a short time.

Particularly, a fuel cell incorporating an anion exchange membrane as compared with a conventional PEMFC in which a cation exchange membrane is introduced has attracted much attention because it can use a low-cost catalyst and has a smooth oxygen reduction reaction. However, The material has not been developed sufficiently.

Japanese Patent Laid-Open No. 2006-019271 Korean Patent Publication No. 2016-0143103

The present invention has been developed in order to solve the above problems, and it is an object of the present invention to provide a slurry-type cathode composition for a fuel cell using a hydrocarbon-based polymer which does not use a fluorine-based polymer as a binder.

Also, the present invention provides a membrane-electrode assembly for a fuel cell comprising a catalyst layer formed using a positive electrode composition containing a hydrocarbon-based polymer as a binder and an anionic conductive electrolyte membrane.

In order to solve the above problems, the present invention provides a method for producing a hydrocarbon-based polymer, Preparing a halogenated polymer by halogenating the hydrocarbon-based polymer; A step of preparing a binder polymer having an anionic conductive group through quaternization of the halogenated polymer; And an electrode slurry preparation step of mixing the binder polymer, the catalyst metal, and the solvent to prepare a slurry, wherein the binder slurry is prepared by mixing the binder polymer, the catalyst metal, and the solvent.

Also, in the present invention, a hydrocarbon-based anion-conducting binder; Catalytic metal; And an organic solvent, wherein the organic solvent contains a hydrocarbon-based anion conductive binder and a catalyst metal in an amount of 2 to 50% by weight and is in a slurry state.

According to another aspect of the present invention, there is provided a method for preparing an anion-conducting electrolyte membrane, comprising: forming a catalyst layer using a cathode composition for a fuel cell; Drying the catalyst layer; And heating / pressing the catalyst layer. The present invention also provides a method for manufacturing a membrane-electrode assembly for a fuel cell.

In the present invention, an anionic conductive electrolyte membrane, which is produced according to the above-described production method, And a hydrocarbon-based anionic conductive binder; And a cathode for a fuel cell made of a catalytic metal.

INDUSTRIAL APPLICABILITY As described above, the present invention provides a fuel cell membrane-electrode assembly having excellent performance and durability by providing an anion-exchange material binder based on a low-cost hydrocarbon-based material.

The present invention has an effect of improving the adhesion compatibility between an electrolyte membrane and an electrode by using an anionic conductive binder, maintaining a binding force between electrode catalyst particles, and forming a three-dimensional structure constituting a three-phase interface. In addition, the performance of the AEMFC can be maximized.

In particular, anion-exchange material binders in the anion exchange membrane fuel cell, which have recently attracted much attention compared to conventional cation exchange membrane fuel cells due to their ability to use low-cost catalysts and smooth oxygen reduction reactions, .

1 shows the solubility of a halogenated polymer in a solvent according to an embodiment of the present invention.
2 shows a process for manufacturing a membrane-electrode assembly according to an embodiment of the present invention.
FIG. 3 is a graph showing the results of single cell performance evaluation of a fuel cell of a membrane-electrode assembly according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The present invention relates to a polymer electrolyte membrane for a fuel cell, a membrane-electrode assembly for a fuel cell comprising the same, and a fuel cell system, and more particularly, to an anion exchange material for an AEMFC binder.

 In a polymer electrolyte fuel cell, a catalyst layer including a metal catalyst supported on a carbon powder and an ion-conductive binder including a polymer electrolyte is formed on both sides of a polymer electrolyte membrane having ion conductivity. In addition, the integrated combination of the catalyst layer and the gas diffusion layer is referred to as a gas diffusion electrode, and a structure in which a pair of gas diffusion electrodes are respectively bonded to an electrolyte membrane so that the catalyst layer faces the electrolyte membrane is referred to as a membrane-electrode assembly.

The catalytic metal may be at least one selected from the group consisting of platinum (Pt), palladium (Pd), ruthenium (Ru), iridium (Ir), osmium (Os), platinum (Pt) V, Cr, Mo, W, Mn, Fe, Co, Rh) alloy, platinum (Pt) - iridium (Ir) alloy, platinum (Pt) - osmium alloy, platinum , Ni, Cu, Ag, Au, Zn, Ga, and Sn), or a combination thereof. However, the present invention is not limited thereto.

The ion-conductive binder is also used for enhancing the utilization efficiency of the catalyst by binding the catalyst and mediating the transfer of proton or hydroxide ions from the catalyst layer to the electrolyte membrane.

According to an embodiment of the present invention, there is provided a positive electrode composition for a polymer electrolyte membrane fuel cell comprising a platinum catalyst as a positive electrode active material and a positive electrode binder, wherein the positive electrode binder comprises a hydrocarbon polymer having an anion- A positive electrode composition for a membrane fuel cell is provided.

In order to solve the above-described problems, the present invention provides a process for producing a hydrocarbon-based polymer, which comprises polymerizing a polymer having a chemical structure represented by Chemical Formula 1 as a main chain; Preparing a halogenated polymer by halogenating the hydrocarbon-based polymer; A step of preparing a binder polymer having an anionic conductive group through quaternization of the halogenated polymer; And an electrode slurry preparation step of mixing the binder polymer, the catalyst metal, and the solvent to prepare a slurry, wherein the binder slurry is prepared by mixing the binder polymer, the catalyst metal, and the solvent.

≪ Formula 1 >

Wherein M and M 'are a single bond or an electron donor group, -O-, -S-, -NH- or NR _a -, wherein R _a is a C ₁ to C ₁₂ alkyl group, R ₁ to R The substituents represented by R < ₈ > each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen, an allyl group, a cyano group, an aryl group, a nitro group, a perfluoroalkyl group, Or a perfluoroalkylaryl group containing a sulfur atom, a perfluoroaryl group or an -O-perfluoroaryl group.

E is a single bond or an electron donating group _{-O-, -S-, -C 34 R 34} '- (R 34 and R _34' is a hydrogen atom, an alkyl group, an aryl group, each independently), -NH-, or NR ₃₅ -, wherein R ₃₅ may be a C ₁ to C ₁₂ alkyl group.

X, which is the number of repeating units, may be an integer of 1 or more and 10,000 or less, and more preferably an integer of 5 or more and 500 or less.

In the above formula (1), Ar is as shown in the following formula (2).

(2)

In the formula 2, Q is a single bond or - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or - include _{- (C (CF 3) 2} ) Lt; / RTI >

The substituents represented by R ₉ to R ₂₀ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen, an allyl group, a cyano group, an aryl group, a nitro group, a perfluoroalkyl group, A perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group or a perfluoroaryl group.

The halogenated polymer may be prepared by a chloromethylation reaction, a bromination reaction, or an iodination reaction according to an embodiment of the present invention.

(3)

M, M ', Ar and E in Formula 3 are the same as those in Formula 1, W ₁ and W ₂ are each independently a hydrogen atom or an alkyl group, represented by (CH ₂ ) _h X (1 ≦ _h ≦ 12) A brominated alkyl group, or an iodinated alkyl group containing an ether group and an ester group, and the substituents represented by R ₂₁ to R ₂₆ are each independently a hydrogen atom, a halogen atom, an alkyl group, a halogen A nitro group, a perfluoroalkyl group, a perfluoroalkyl group optionally containing at least one oxygen atom, a nitrogen or sulfur atom, a perfluoroaryl group or a perfluoroalkyl group, -O-perfluoroaryl group, and the present substituents may be the same or different in each repeating unit or repeating unit, and x, which is the number of repeating units, may be an integer of 1 or more and 10,000 or less. And more preferably an integer of 5 or more and 500 or less.

In the preparation method according to one embodiment of the present invention, the binder polymer having an anionic conductive group may have a chemical structure represented by the following chemical formula (4).

≪ Formula 4 >

Z _1, Z ₂ of the formula 4 are either each independently a hydrogen atom (CH ₂₎ comprising a _h M (1≤h≤12) or an ether group and an ester (CH _{2) h} M (1≤h≤12) and, M is a ion-exchange functional groups amine group, an ammonium group, an amino group, imine group, sulfonyl nyumgi, phosphorylation nyumgi, a pyridyl group, a carbazolyl group and an imidazole anion exchange functional group selected from thiazolyl group Or an anion exchange functional group in their salt state; An amphoteric ion exchange functional group selected from betaines and sulfobetaines, and combinations thereof, or an anion exchange functional group in the salt form thereof. More specifically, depending on the form of the anion exchange functional group, there may be mentioned, for example, triethylamine, dimethylamine, diethanolamine, aminoalkylphosphonated compounds, iminodiacetate or N-methylglucamine, Or more.

According to one embodiment of the present invention, examples of usable examples of the binder polymer having an anionic conductive group include a mixture of two or more kinds selected from the group consisting of polyether ether ketone, polyether ketone, polysulfone, polyphenyl sulfone, But it is not limited thereto. Here, the hydrocarbon-based polymer having an anion exchange functional group preferably has a number average molecular weight of 1,000 to 100,000 and a mass average molecular weight of 20,000 to 1,000,000.

According to one embodiment of the present invention, the binder polymer having an anionic conductive group can be obtained by ion-exchanging a hydroxide ion with a solution of a reagent capable of releasing hydroxide ions such as NaOH, KOH, and then drying.

The catalyst metal may be at least one selected from the group consisting of platinum (Pt), palladium (Pd), ruthenium (Ru), iridium (Ir), osmium (Os), platinum ) Alloy, platinum (Pt) -ruthenium (Ru) alloy, platinum-iridium (Ir) alloy, platinum-osmium alloy, platinum- At least one selected from the group consisting of Mo, W, Mn, Fe, Co, Rh, Ni, Cu, Ag, Au, Zn, Ga and Sn) . According to one embodiment of the present invention, a platinum catalyst supported on carbon at 60% or less can be used.

In the preparation method according to one embodiment of the present invention, the solvent may be selected from water, an alcohol and an organic solvent containing two or more alcohol groups, and the total amount of the binder polymer and the catalyst metal is in the range of 2 To 50% by weight.

Also, according to one embodiment, the binder polymer is preferably added at a weight ratio of 10 to 50% of the hydrocarbon polymer having an anion exchange functional group to the total cathode composition, but the present invention is not limited thereto. If it is added in an amount of less than 10%, the support and dispersion of the positive electrode active catalyst and the conductive role of the hydroxide ion are insignificant and can not serve as a binder.

More specifically, the binder slurry for a membrane-electrode assembly (MEA) according to an embodiment of the present invention can be prepared by dissolving an anionic conductive polymeric binder material in a water or alcohol solvent. The ion conductive binder material is the same as the above general formula wherein the solvent is selected from the group consisting of DI water, methanol, ethanol, 1-propanol, isopropanol, And an organic solvent containing an alcohol group. The amount of the polymer binder to be used may be 1 to 50 wt%, preferably 2 to 20 wt%, based on the solvent. The mixing of the polymer binder and the solvent is carried out through a pressure reactor, and the reaction pressure can be set to 1 to 1000 a tm, preferably 1 to 300 atm. The temperature can be set to 25 to 300 ° C, preferably 100 to 250 ° C. The reaction time can be set from 1 to 72 hours, preferably from 12 to 48 hours.

The slurry was prepared by the above-described method, and sonication and stirring were performed to bind the catalyst and the ion conductive binder, and the time for the binding step was limited I do not.

The present invention also provides a hydrocarbon-based anionic conductive binder having a chemical structure represented by the following Chemical Formula 4: (Pt), palladium (Pt), ruthenium (Ru), iridium (Ir), osmium (Os), platinum (M is at least one element selected from the group consisting of Ti, V, Cr, Mo, W, Mn, Fe, Co, Rh, Ni, Cu, At least one selected from the group consisting of Ag, Au, Zn, Ga and Sn) or a mixture thereof; And an organic solvent containing water, an alcohol and two or more alcohol groups, wherein the organic solvent contains a hydrocarbon-based anion conductive binder and a catalyst metal in an amount of 2 to 50% by weight in a slurry state do.

≪ Formula 4 >

Z _1, Z ₂ of the formula 4 are either each independently a hydrogen atom (CH ₂₎ comprising a _h M (1≤h≤12) or an ether group and an ester (CH _{2) h} M (1≤h≤12) and, M is a ion-exchange functional groups amine group, an ammonium group, an amino group, imine group, sulfonyl nyumgi, phosphorylation nyumgi, a pyridyl group, a carbazolyl group and an imidazole anion exchange functional group selected from thiazolyl group Or an anion exchange functional group in their salt state; An amphoteric ion exchange functional group selected from betaines and sulfobetaines, and combinations thereof, or an anion exchange functional group in the salt form thereof.

Ar is as shown in the following formula (2)

(2)

In the formula 2, Q is a single bond or - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or - include _{- (C (CF 3) 2} ) Lt; / RTI >

The substituents represented by R ₉ to R ₂₀ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen, an allyl group, a cyano group, an aryl group, a nitro group, a perfluoroalkyl group, A perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group or a perfluoroaryl group.

According to another aspect of the present invention, there is provided a process for preparing an anionic conductive electrolyte membrane, comprising: forming a catalyst layer on the anionic conductive electrolyte membrane using the cathode composition for a fuel cell according to any one of claims 1 to 6; Drying the catalyst layer; And heating / pressing the catalyst layer. The present invention also provides a method for manufacturing a membrane-electrode assembly for a fuel cell.

In the manufacturing method according to an embodiment of the present invention, the forming of the catalyst layer may be performed using a catalyst coated membrane (CCM) or a catalyst coated gas diffusion layer (CCG) A decal method, a spray method, a brush method, and the like, but there is no limitation on the production method. At this time, the drying of the catalyst layer is performed at a temperature of 80 ° C or higher, and the time is not limited. In addition, in the heat-pressing step, the membrane-electrode assembly manufacturing conditions can be a temperature of 100 ° C or higher, a pressure of 10 kgf / cm 2 or higher can be used, and anion conductive binder is limited to a temperature and a pressure that are not degraded do.

In addition, according to one embodiment of the present invention, the cathode composition for a fuel cell includes a platinum catalyst, which is a cathode active material, and a cathode binder, and the prepared slurry is coated on a gas diffusion layer with a spray coater to produce a catalyst layer .

In the present invention, an anionic conductive electrolyte membrane, which is produced according to the above-described production method, And a hydrocarbon-based anion conductive binder having a chemical structure represented by the following formula (4); And a cathode for a fuel cell made of a catalytic metal.

≪ Formula 4 >

Z _1, Z ₂ of the formula 4 are either each independently a hydrogen atom (CH ₂₎ comprising a _h M (1≤h≤12) or an ether group and an ester (CH _{2) h} M (1≤h≤12) and, M is a ion-exchange functional groups amine group, an ammonium group, an amino group, imine group, sulfonyl nyumgi, phosphorylation nyumgi, a pyridyl group, a carbazolyl group and an imidazole anion exchange functional group selected from thiazolyl group Or an anion exchange functional group in their salt state; An amphoteric ion exchange functional group selected from betaines and sulfobetaines, and combinations thereof, or an anion exchange functional group in the salt form thereof.

Ar is as shown in the following formula (2)

(2)

In the formula 2, Q is a single bond or - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or - include _{- (C (CF 3) 2} ) Lt; / RTI >

The substituents represented by R ₉ to R ₂₀ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen, an allyl group, a cyano group, an aryl group, a nitro group, a perfluoroalkyl group, A perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group or a perfluoroaryl group.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. In particular, the technical idea of the present invention and its core structure and action are not limited by this. In addition, the content of the present invention can be implemented by various other types of equipment, and is not limited to the embodiments and examples described herein.

1. Preparation of Hydrocarbon Type Anionic Conductive Binder

The hydrocarbon-based anionic conductive binder according to one embodiment of the present invention was prepared by the following method.

First, radlets (9.0 g) are dissolved in 180 mL of 1,1,2,2-tetrachloroethane in a flask substituted with argon atmosphere. The flask in the dissolved solution is adjusted to 0 ° C with ice bath and zinc chloride is added. After about 30 minutes, add chloromethyl methyl ether slowly to the solution in which the radel melts. The reaction proceeds under an argon atmosphere at 60 ° C for 24 hours. After the reaction, the reaction mixture was cooled to room temperature and then precipitated in 1 L of methanol and filtered. The polymer is washed in 1.5 L of methanol for 12 hours and then dried in a 60 degree vacuum oven. Through this process, a chloromethylated Radel of formula (5) with a degree of functionalization (DF) of 0.89 was finally obtained.

≪ Formula 5 >

The solubility of 0.5 g of the prepared methyl rradle in 10 mL of N-methylpyrrolidone (NMP) and dimethylacetamide (DMAc) was tested. The results are shown in Table 1 and FIG. As shown in Table 1 and FIG. 1, the methyl chloride rradle was completely dissolved in N-methylpyrrolidone (NMP) and dimethylacetamide (DMAc) solvent.

Sample Functionalization (DF) NMP DMAc Methyl rudel chloride 0.89 Completely dissolved Completely dissolved

Then, methyl chloride (DF = 0.89) was dissolved in dimethylacetamide (DMAc) at 5 wt%. In a round flask, a trimethylamine solution was slowly added dropwise to 3 equivalents of a methyl chloride ladle and reacted for 24 hours at room temperature under an argon atmosphere with mechanical stirring. Then, the solution is precipitated in 10 times 0.5 M NaOH relative to the solution. In the precipitation process, after stirring for the first 30 minutes, the polymer is obtained by filtration under reduced pressure, and the obtained polymer is stirred for one day in an excessive amount of distilled water. After the filter was dried at 80 degrees in a vacuum oven, a hydrocarbon-based anionic conductive binder represented by the following Formula 6 was prepared.

(6)

2. Preparation of Hydrocarbon-Based Anionic Conductive Binder Solution

The hydrocarbon-based anionic conductive binder prepared according to the above-described production method was heated at 190 DEG C for 15 hours using a pressure reactor, and dispersed in isopropanol (IPA) and filtered to obtain a hydrocarbon-based anionic conductive binder, which was added to isopropanol The dissolved final solution was prepared.

3. Preparation of membrane-electrode assembly

The membrane-electrode assembly according to one embodiment of the present invention was produced according to the procedure shown in Fig. 2 in the composition shown in Table 2.

First, 0.3 g of Pt / C catalyst and deionized water were mixed and stirred, and 1-propanol was added thereto. Thereafter, the hydrocarbon-based anionic conductive binder prepared according to the above-mentioned preparation method was charged and stirred for 1 hour by using a magnetic stirrer at 500 rpm, for 1 hour by ultrasonic irradiation and at 500 rpm for 2 hours by magnetic stirring to prepare a catalyst slurry.

The prepared catalyst slurry was sprayed using a catalyst coated gas diffusion layer (CCG) using a spray coater. Then, a membrane-electrode assembly (MEA) was prepared by a catalyst coated GDL method.

Pt / C (g) H2O (g) 1-Propanol (g) Binder (g) Example 0.3 1.1357 2.1357 2.5714 Comparative Example 0.3 1.1357 2.1357 2.5714

Comparative Example: Use of Conventional Binder AS-4 (anion exchange ionomer from Tokuyama corporation)

4. Fuel cell single cell performance evaluation of membrane-electrode assembly

In order to measure the cell performance of the membrane-electrode assemblies of the examples and comparative examples prepared by the above-mentioned production method, a change in the voltage according to the current density was measured by discharging with an electric load. The cell operating conditions are the same as those of the comparative example and the example. The thickness of the ion exchange membrane is 25 μm and the size is 30 mm × 60 mm. The temperature is 60 ° C. The hydrogen supply amount is 600 cc / min. And the active area was 5 cm < 2 >. The ion exchange membranes used in the Examples and Comparative Examples were subjected to ion exchange in 1 M NaOH for 1 day as a pretreatment, and the measurement was carried out in a dried state. The results are shown in FIG.

In the embodiment of the present invention, the voltage for the current density is not different from the comparative example, but the power density with respect to the current density is superior to the comparative example.

Claims (10)

A step of preparing a hydrocarbon-based polymer to produce a polymer having a chemical structure of the following formula (1) as a main chain;
Preparing a halogenated polymer by halogenating the hydrocarbon-based polymer;
A step of preparing a binder polymer having an anionic conductive group through quaternization of the halogenated polymer; And
A binder metal, a catalyst metal, and a solvent to prepare a slurry. The method for producing a cathode composition for a fuel cell according to claim 1,
≪ Formula 1 >

Wherein M and M 'are a single bond or an electron donor group, -O-, -S-, -NH- or NR _a -, wherein R _a is a C ₁ to C ₁₂ alkyl group, R ₁ to R The substituents represented by R < ₈ > each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen, an allyl group, a cyano group, an aryl group, a nitro group, a perfluoroalkyl group, Or a perfluoroalkylaryl group containing a sulfur atom, a perfluoroaryl group or an -O-perfluoroaryl group,
E is a single bond or an electron donating group _{-O-, -S-, -C 34 R 34} '- (R 34 and R _34' is a hydrogen atom, an alkyl group, an aryl group, each independently), -NH-, or NR ₃₅ -, wherein R ₃₅ is a C ₁ to C ₁₂ alkyl group,
X, which is the number of repeating units, is an integer of 1 or more and 10,000 or less,
Ar is as shown in the following formula (2)
(2)

In the formula 2, Q is a single bond or - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or - include _{- (C (CF 3) 2} ) Lt; / RTI >
The substituents represented by R ₉ to R ₂₀ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen, an allyl group, a cyano group, an aryl group, a nitro group, a perfluoroalkyl group, A perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group or a perfluoroaryl group. The method according to claim 1,
Wherein the step of preparing the halogenated polymer comprises preparing a halogenated polymer having a chemical structure represented by Chemical Formula 3 through a chloromethylation reaction, a bromination reaction, or an iodination reaction.
(3)

M, M ', Ar and E in Formula 3 are the same as those in Formula 1, W ₁ and W ₂ are each independently a hydrogen atom or an alkyl group, represented by (CH ₂ ) _h X (1 ≦ _h ≦ 12) A brominated alkyl group, or an iodinated alkyl group containing an ether group and an ester group, and the substituents represented by R ₂₁ to R ₂₆ are each independently a hydrogen atom, a halogen atom, an alkyl group, a halogen A nitro group, a perfluoroalkyl group, a perfluoroalkyl group optionally containing at least one oxygen atom, a nitrogen or sulfur atom, a perfluoroaryl group or a perfluoroalkyl group, -O-perfluoroaryl group, and the present substituents may be the same or different in each repeating unit or repeating unit, and x, which is the number of repeating units, is an integer of 1 or more and 10,000 or less. The method according to claim 1,
Wherein the binder polymer having an anionic conductive group has a chemical structure represented by the following formula (4): < EMI ID =
&Lt; Formula 4 &gt;

Z _1, Z ₂ of the formula 4 are either each independently a hydrogen atom (CH ₂₎ comprising a _h M (1≤h≤12) or an ether group and an ester (CH _{2) h} M (1≤h≤12) and, M is a ion-exchange functional groups amine group, an ammonium group, an amino group, imine group, sulfonyl nyumgi, phosphorylation nyumgi, a pyridyl group, a carbazolyl group and an imidazole anion exchange functional group selected from thiazolyl group Or an anion exchange functional group in their salt state; An amphoteric ion exchange functional group selected from betaines and sulphobetaines, and combinations thereof, or anion exchange functional groups in their salt form. The method according to claim 1,
The catalyst metal may be at least one selected from the group consisting of Pt, Pd, Ru, Ir, Os, Pt-Pd, V, Cr, Mo, W, Mn, Fe, Co, Rh, Pt, and the like), platinum (Pt), iridium (Ir) At least one selected from the group consisting of Ni, Cu, Ag, Au, Zn, Ga and Sn) or a mixture thereof. &Lt; / RTI &gt; The method according to claim 1,
Wherein the solvent is selected from water, an alcohol, and an organic solvent containing at least two alcohol groups. The method according to claim 1,
Wherein the total amount of the binder polymer and the catalyst metal in the slurry is 2 to 50 wt% based on the total amount of the slurry. A hydrocarbon-based anionic conductive binder having a chemical structure represented by the following Chemical Formula 4;
(Pt), palladium (Pt), ruthenium (Ru), iridium (Ir), osmium (Os), platinum (M is at least one element selected from the group consisting of Ti, V, Cr, Mo, W, Mn, Fe, Co, Rh, Ni, Cu, At least one selected from the group consisting of Ag, Au, Zn, Ga and Sn) or a mixture thereof; And
Wherein the organic solvent comprises water, an alcohol and at least two alcohol groups, and the hydrocarbon-based anion conductive binder and the catalyst metal are contained in an organic solvent in a slurry state in an amount of 2 to 50% by weight.
&Lt; Formula 4 >

Z _1, Z ₂ of the formula 4 are either each independently a hydrogen atom (CH ₂₎ comprising a _h M (1≤h≤12) or an ether group and an ester (CH _{2) h} M (1≤h≤12) and, M is a ion-exchange functional groups amine group, an ammonium group, an amino group, imine group, sulfonyl nyumgi, phosphorylation nyumgi, a pyridyl group, a carbazolyl group and an imidazole anion exchange functional group selected from thiazolyl group Or an anion exchange functional group in their salt state; An anion exchange functional group selected from an amphoteric ion exchange functional group selected from betaines and sulfobetaines, and a combination thereof, or an anion exchange functional group in a salt form thereof,
Ar is as shown in the following formula (2)
(2)

In the formula 2, Q is a single bond or - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or - include _{- (C (CF 3) 2} ) Lt; / RTI &gt;
The substituents represented by R ₉ to R ₂₀ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen, an allyl group, a cyano group, an aryl group, a nitro group, a perfluoroalkyl group, A perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group or a perfluoroaryl group. Preparing an anionic conductive electrolyte membrane;
Forming a catalyst layer on the anionically conductive electrolyte membrane by using the cathode composition for a fuel cell produced according to any one of claims 1 to 6;
Drying the catalyst layer; And
And heating / pressing the catalyst layer. The method of manufacturing a membrane-electrode assembly for a fuel cell according to claim 1, The method of claim 8,
Wherein the step of forming the catalyst layer comprises using either a CCM method or a CCG method. The process according to claim 8,
Anionic conductive electrolyte membrane; And
A hydrocarbon-based anionic conductive binder having a chemical structure represented by the following Chemical Formula 4; And a cathode for a fuel cell made of a catalytic metal. The membrane-electrode assembly for a fuel cell according to claim 1,
&Lt; Formula 4 >

Z _1, Z ₂ of the formula 4 are either each independently a hydrogen atom (CH ₂₎ comprising a _h M (1≤h≤12) or an ether group and an ester (CH _{2) h} M (1≤h≤12) and, M is a ion-exchange functional groups amine group, an ammonium group, an amino group, imine group, sulfonyl nyumgi, phosphorylation nyumgi, a pyridyl group, a carbazolyl group and an imidazole anion exchange functional group selected from thiazolyl group Or an anion exchange functional group in their salt state; An anion exchange functional group selected from an amphoteric ion exchange functional group selected from betaines and sulfobetaines, and a combination thereof, or an anion exchange functional group in a salt form thereof,
Ar is as shown in the following formula (2)
(2)

In the formula 2, Q is a single bond or - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or - include _{- (C (CF 3) 2} ) Lt; / RTI &gt;
The substituents represented by R ₉ to R ₂₀ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyl group substituted with a halogen, an allyl group, a cyano group, an aryl group, a nitro group, a perfluoroalkyl group, A perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group, a perfluoroalkyl group or a perfluoroaryl group.

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