WO2023106657A1 - Polycarbazole-based cation-exchange ion conductor and method for manufacturing same - Google Patents

Abstract

The present invention relates to a polycarbazole-based cation-exchange ion conductor, a method for manufacturing same, and use thereof and, more particularly, to: a cation-exchange ion conductor which not only can be used as an electrode binder, but can also be used as an ion-exchange material for water electrolysis, a redox flow cell, a fuel cell, carbon dioxide reduction, electrochemical ammonia production and decomposition, electrodialysis (D), reverse electrodialysis (RED) or a capacitive deionization (CDI) separator; and a method for manufacturing same.

Description

Polycarbazole-based cation exchange type ion conductor and its manufacturing method

The present invention relates to a polycarbazole-based cation exchange type ion conductor, a manufacturing method and use thereof.

More specifically, as an electrode binder, as well as water electrolysis, redox flow cell, fuel cell, carbon dioxide reduction, electrochemical ammonia production and decomposition, electrodialysis (ED), reverse electrodialysis (RED) or capacitive It relates to a cation exchange type ion conductor that can also be used as an ion exchange material for a capacitive deionization (CDI) separator and a method for manufacturing the same.

This application claims priority based on Korean Patent Application No. 10-2021-0175241 filed on December 08, 2021, and all contents disclosed in the specification and drawings of the application are incorporated into this application.

The use of petroleum energy in industries is becoming increasingly restricted due to depletion of petroleum resources, global warming problems such as carbon monoxide and carbon dioxide, and environmental destruction such as fine dust. Therefore, research is focused on the use of sustainable energy such as solar energy, water power, and wind energy as alternative energy, but it has limitations that are low in efficiency and applied only in special cases.

On the other hand, hydrogen energy is attracting attention worldwide as a future clean energy, and numerous countries and companies are investing and developing technologies to preoccupy related technologies. Recently, high interest in hydrogen energy is held per mass In line with the trend of practical use using fuel cells with high energy content, the field of hydrogen production is also attracting attention.

Representative hydrogen production and utilization technologies include water electrolysis and fuel cells. A fuel cell is an energy conversion device that directly converts the chemical energy of fuel into electrical energy, and is being researched and developed as a next-generation energy source due to its high energy efficiency and low pollutant emission. In particular, a polymer electrolyte fuel cell using a polymer electrolyte is a kind of DC power generation device that directly converts the chemical energy of the fuel into electrical energy by an electrochemical reaction, and is an electrode-membrane assembly (MEA, membrane) like the heart of a fuel cell. It consists of a continuous composite of an electrode assembly and a bipolar plate that collects and supplies the generated electricity. Here, the membrane-electrode assembly refers to an assembly of an electrode in which an electrochemical catalytic reaction between hydrogen and air occurs and a polymer membrane in which hydrogen ions are transferred. Meanwhile, all electrochemical reactions are composed of two separate reactions, an oxidation reaction occurring at the anode and a reduction reaction occurring at the cathode, and the anode and cathode are separated through an electrolyte. Electrolyte membranes generally used in polymer electrolyte fuel cells can be divided into perfluorinated polymer electrolytes and hydrocarbon polymer electrolytes. The fluorinated polymer electrolyte is chemically stable due to the strong bonding force between carbon-fluorine (C-F) and the shielding effect characteristic of the fluorine atom, excellent mechanical properties, and especially high conductivity as a hydrogen ion exchange membrane. It is being commercialized as a polymer membrane for electrolyte type fuel cells. Nafion (perfluorinated sulfonic acid polymer), a product of Du Pont, USA, is a representative example of a commercially available hydrogen ion exchange membrane, and is currently most widely used due to its excellent ionic conductivity, chemical stability, ion selectivity, etc. However, the fluorinated polymer electrolyte membrane has disadvantages such as low industrial use due to its high price, high hydrogen permeability (crossover), and reduced efficiency of the polymer membrane at temperatures above 80 ° C. Research on hydrocarbon ion exchange membranes and electrode binders is being actively conducted.

In addition, a representative hydrogen electrolysis system for producing hydrogen is attracting attention as a key system for producing green hydrogen. The process of generating hydrogen (H ₂ ) and oxygen (O ₂ ) from water (H ₂ O) by a water electrolysis device does not produce other substances other than hydrogen, oxygen, and water that may cause environmental pollution, so it is an eco-friendly alternative energy source. It has value, and the representative technologies of such water electrolysis can be divided into three major categories: water electrolysis using a proton exchange membrane (PEM), alkaline electrolysis (AE) using an alkaline electrolyte, and There is a high temperature electrolysis (HTE) method using a ceramic electrolyte under high temperature steam conditions.

Among them, the cation exchange membrane (PEM) water electrolysis consists of an anode mainly using Ir and Ru, a cathode mainly using Pt, and a cation exchange membrane, and the Amode catalyst decomposes H ₂ O to produce H+ and O ₂ (Oxygen Evolution Reaction; OER), and the generated H+ cation passes through the cation exchange membrane and moves to the cathode, generating H ₂ on the catalyst surface (hydrogen evolution reaction, HER), which has higher hydrogen ion conductivity than other water electrolysis It is characterized by having a high current density of 1 A/cm ² or more.

In the production and utilization technology of hydrogen, ion exchange materials are used as key materials for fuel cells and water electrolysis systems. Currently, perfluorinated cation exchange materials are used, but non-perfluorinated (hydrocarbon) materials are to be developed. In the case of the case, it is expected that not only price competitiveness but also fundamental improvement in performance will be possible, and in the case of separators, materials with performance comparable to perfluorine-based materials are being developed, but in the case of electrode binders, carbon-based materials have very low performance, There is an urgent need to develop materials.

On the other hand, among these ion exchange materials, as a prior art for an anion exchange material, particularly a carbazole-based anion exchange material, Korean Patent Registration No. 10-2284854 developed by the inventors of the present invention describes a main chain based on a carbazole-based material with excellent stability. By providing an anion exchange material in which all of the bonds between monomers constituting C-C bonds are provided, a separation membrane with improved physical and chemical stability and durability has been provided by dramatically improving molecular weight while having solubility in solvents, and also, Korean Registered Patent Publication No. 10-2168673 has provided a fuel cell membrane-electrode assembly with excellent physical properties and chemical resistance and easy control of ion exchange capacity, but the development of technology related to cation exchange materials is also required.

Therefore, in the present invention, a novel cation exchange type ion conductor having a polycarbazole-based main chain structure was developed, which can be used not only as an electrode binder but also as an ion exchange material for separators, and when applied as an electrode binder, compared to conventional materials The present invention was completed by confirming that it had superior performance of 50% or more.

The present invention was developed to solve the above problems, and an object of the present invention is to provide a non-perfluorine-based (hydrocarbon-based) cation exchange type ion conductor.

In addition, the present invention is to provide a cation exchange type ion conductor having a polycarbazole-based main chain that can be used as a binder for an electrode.

In addition, in the present invention, as an electrode binder, as well as water electrolysis, redox flow battery, fuel cell, carbon dioxide reduction, electrochemical ammonia production and decomposition, electrodialysis (ED), reverse electrodialysis (RED) or electricity storage It is an object of the present invention to provide a cation exchange type ion conductor that can also be used as an ion exchange material for a capacitive deionization (CDI) separation membrane.

In addition, the present invention intends to provide a Proton Exchange Membrane Fuel Cell (PEMFC) device or a Proton Exchange Membrane Water Electrolysis (PEMWE) device for water electrolysis of a carbazole-based polymer.

In the present invention, in order to solve the above problems, preparing at least one type of monomer from a monomer group consisting of a halogen-containing carbazole-based monomer and a carbazole-based monomer: Preparing a halogen-containing polycarbazole-based polymer in which all of the bonds between monomers constituting the main chain are C-C bonds; preparing a thioacetylated polycarbazole-based polymer by thioacetylating the halogen group of the halogen-containing polycarbazole-based polymer; and sulfonating the thioacetylated polycarbazole-based polymer.

In addition, in the present invention, as an electrode binder, as well as water electrolysis, redox flow battery, fuel cell, carbon dioxide reduction, electrochemical ammonia production and decomposition, electrodialysis (ED), reverse electrodialysis (RED) or electricity storage A cation exchange type ion conductor that can also be used as an ion exchange material for a capacitive deionization (CDI) separation membrane is provided.

In addition, the present invention provides a Proton Exchange Membrane Fuel Cell (PEMFC) device or a Proton Exchange Membrane Water Electrolysis (PEMWE) device.

The present invention provides a cation exchange type ion conductor based on a carbazole-based material in which the main chain does not include a linking group of electron donating characteristics such as -O- or -S-, and the main chain is all composed of C-C bonds, thereby providing physical properties In addition to excellent chemical resistance, it is easy to control the ion exchange capacity, and it is possible to introduce a side chain, thereby increasing solubility and improving phase separation characteristics.

In addition, the present invention is an electrode binder as well as water electrolysis, redox flow battery, fuel cell, carbon dioxide reduction, electrochemical ammonia production and decomposition, electrodialysis (ED), reverse electrodialysis (RED) or electrical storage It has a great advantage that it can also be used as an ion exchange material for capacitive deionization (CDI) membranes.

1 shows the results of ¹ H NMR and ¹ H- ¹ H COZY NMR spectrum analysis of a halogen-containing carbazole-based monomer (M1) according to an embodiment of the present invention.

2 is a halogen-containing polycarbazole-based polymer (PCTFP-br: P1), a thioacetylated polycarbazole-based polymer (PCTFP-TAc: P2), and a sulfonated polycarbazole-based polymer (sPCTFP: P3) shows the results of ¹ H-NMR spectrum analysis.

Figure 3 shows the results of ¹ H- ¹ H COZY NMR spectrum analysis of thioacetylated polycarbazole-based polymer (PCTFP-TAc: P2) and sulfonated polycarbazole-based polymer (sPCTFP: P3) according to an embodiment of the present invention. it is shown

4 shows a method for manufacturing an MEA using a polycarbazole-based cation exchange type conductor as a binder for an electrode according to an embodiment of the present invention.

5 shows evaluation results of a fuel cell unit cell using a polycarbazole-based cation exchange type conductor according to an embodiment of the present invention as a binder.

Hereinafter, the present invention will be described in detail. The terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventors may appropriately define the concept of terms in order to explain their invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

The present invention relates to a polycarbazole-based cation exchange ion conductor, its manufacturing method and use, more specifically, as an electrode binder as well as water electrolysis, redox flow battery, fuel cell, carbon dioxide reduction, electrochemical ammonia production and decomposition, electrodialysis (ED), reverse electrodialysis (RED) or capacitive deionization (CDI) provides a cation exchange type ion conductor that can also be used as an ion exchange material for separation membranes and a manufacturing method thereof do.

In the present invention, in order to solve the above problems, preparing at least one monomer from a monomer group consisting of a halogen-containing carbazole-based monomer and a carbazole-based monomer: using a polymerization reaction using a superacid catalyst for the monomer preparing a halogen-containing polycarbazole-based polymer in which all of the bonds between monomers constituting the main chain are composed of C-C bonds; preparing a thioacetylated polycarbazole-based polymer by thioacetylating the halogen group of the halogen-containing polycarbazole-based polymer; and sulfonating the thioacetylated polycarbazole-based polymer, thereby providing a method for producing a polycarbazole-based cation exchange-type ion conductor having a chemical structure of Formula A below.

<Formula A>

In Formula A,

W is a cation exchange group and is either a sulfonic acid group (-SO ₃ H), a phosphoric acid group (-PO ₃ H ₂ ), an acetic acid group (-COOH), or an alkali metal salt thereof, or a nitro group (-NO ₂ ),

Substituents represented by R ₁ to R ₄ are each independently any one of an alkylene group, an arylene group, and an allylene group;

Any one of an alkylene group, an arylene group, and an allylene group containing a fluorine atom;

a perfluoroalkylene group,

Any one of a perfluoroalkylene group, a perfluoroarylene group, and an -O-perfluoroarylene group, optionally containing one or more oxygen, nitrogen, or sulfur atoms in its chain,

m, the number of repeating units, is a positive integer of 100,000 or less, and n is 0 or a positive integer of 100,000 or less.

In the production method according to an embodiment of the present invention, the acetic acid catalyst is trifluoromethanesulfonic acid (TFSA, CF ₃ SO ₃ H) or fluorosulfonic acid (fluorosulfonic acid: HSO ₃ F). can be

In the production method according to one embodiment of the present invention, the halogen-containing carbazole-based monomers are the halogen-containing polycarbazole-based monomers in which all the bonds between monomers constituting the main chain are composed of C-C bonds by using a polymerization reaction using the acetic acid catalyst. It can be made of polymers. The polymerization reaction is by the C-C bond synthesis method by the acetic acid catalyst, and has a chemical structure of the following formula B consisting of all C-C bonds without including electron donating groups such as -O- and -S- in the main chain. A polycarbazole-based cation exchange type ion conductor can be prepared.

<Formula B>

In the above formula B,

X is any one of halogen atoms chlorine (Cl), bromine (Br), iodine (I),

Substituents represented by R ₁ to R ₄ are each independently any one of an alkylene group, an arylene group, and an allylene group;

Any one of an alkylene group, an arylene group, and an allylene group containing a fluorine atom;

a perfluoroalkylene group,

Any one of a perfluoroalkylene group, a perfluoroarylene group, and an -O-perfluoroarylene group, optionally containing one or more oxygen, nitrogen, or sulfur atoms in its chain,

m, the number of repeating units, is a positive integer of 100,000 or less, and n is 0 or a positive integer of 100,000 or less.

According to one embodiment of the present invention, the acetic acid catalyst may be used in an amount of 0.1 to 100 equivalents based on the total amount of carbazole-based monomers. Preferably, it may be used in an amount of 1 to 20 equivalents based on the total amount of the halogen-containing carbazole-based monomers.

According to one embodiment of the present invention, in the step of preparing the halogen-containing polycarbazole-based polymer, at least one monomer from the monomer group consisting of the halogen-containing carbazole-based monomer and the carbazole-based monomer and the acetic acid catalyst are dissolved in a solvent. It may include mixing and stirring, wherein the solvent is CCl ₄ , CHCl ₃ , CH ₂ Cl ₂ , C ₂ H ₂ Cl ₄ , or an organic solvent containing a halogen element such as iodine, bromine or fluorine may be used. there is.

According to one embodiment of the present invention, the step of preparing the thioacetylated polycarbazole-based polymer is to convert the halogen group of the halogen-containing polycarbazole-based polymer to thioacetic acid, ethylthioacetate, or thioacetate. It may be a reaction with any one of metal salts, and more preferably, it may be a reaction using sodium thioacetate or potassium thioacetate.

According to one embodiment of the present invention, the step of sulfonating the thioacetylated polycarbazole-based polymer with hydrogen peroxide, sulfuric acid, chlorosulfonic acid, sodium bisulfite, m-chloroperoxybenzoic acid ( m -chloroperoxybenzoic acid : mCPBA) may be reacted with any one of them.

In addition, the present invention provides a polycarbazole-based cation exchange type ion conductor characterized in that it has a chemical structure of the following formula (A).

<Formula A>

In Formula A,

W is a cation exchange group and is either a sulfonic acid group (-SO ₃ H), a phosphoric acid group (-PO ₃ H ₂ ), an acetic acid group (-COOH), or an alkali metal salt thereof, or a nitro group (-NO ₂ ),

Substituents represented by R ₁ to R ₄ are each independently any one of an alkylene group, an arylene group, and an allylene group;

Any one of an alkylene group, an arylene group, and an allylene group containing a fluorine atom;

a perfluoroalkylene group,

Any one of a perfluoroalkylene group, a perfluoroarylene group, and an -O-perfluoroarylene group, optionally containing one or more oxygen, nitrogen, or sulfur atoms in its chain,

m, the number of repeating units, is a positive integer of 100,000 or less, and n is 0 or a positive integer of 100,000 or less.

In addition, the present invention provides a binder for an electrode comprising a polycarbazole-based cation exchange ion conductor prepared according to the above manufacturing method.

According to one embodiment of the present invention, the polycarbazole-based cation exchange ion conductor prepared according to the manufacturing method is mixed with a catalyst during the manufacture of a membrane electrode assembly (MEA) or an electrode layer in a fuel cell or the like. Can be used as a binder.

In addition, the present invention provides a separation membrane comprising a polycarbazole-based cation exchange ion conductor prepared according to the above manufacturing method.

In this case, the separation membrane may be any one selected from the group consisting of a single membrane, a reinforced membrane, a composite membrane, and a reinforced composite membrane made of the corresponding cation exchange ion conductor, and specifically, the single membrane is a cationic membrane according to an embodiment of the present invention. It refers to a separator made of an exchange ion conductor as the main material, and a reinforced membrane is made of polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, polystyrene, polysulfone, and polyvinyl alcohol to improve the physical properties of the membrane. One embodiment of the present invention using a porous membrane based on polybenzimidazole, polyimide, polyamideimide, glass fiber, cellulose, or a mixture thereof or a porous membrane based on an organic or inorganic material having pores therein as a support It may be impregnated with a cation exchange ion conductor according to, and the composite membrane uses the cation exchange ion conductor according to an embodiment of the present invention as a main material to lower the crossover of fuel and active material or to improve performance It can be in the form of organic, inorganic or organic-inorganic hybrid nanoparticles and additives that can improve the strength of the composite membrane, and the reinforced composite membrane is a form in which the concept of the above-mentioned composite membrane and reinforced membrane is applied together, and the cation containing nanoparticles and additives It may be manufactured by impregnating a composite membrane of an exchange ion conductor into a porous support based on an organic or inorganic material.

According to one embodiment of the present invention, the separator may be for a Proton Exchange Membrane Fuel Cell (PEMFC).

In addition, the separation membrane according to one embodiment of the present invention is used for water electrolysis, redox flow battery, fuel cell, carbon dioxide reduction, electrochemical ammonia production and decomposition, It is for electrodialysis (ED), reverse electrodialysis (RED) or capacitive deionization (CDI), more preferably, the separator is a proton exchange membrane water electrolysis (PEMWE) can

In addition, a binder for an electrode comprising a polycarbazole-based cation exchange ion conductor according to an embodiment of the present invention; And the separation membrane may be used in a Proton Exchange Membrane Fuel Cell (PEMFC) device and a Proton Exchange Membrane Water Electrolysis (PEMWE) device.

Hereinafter, implementation examples and embodiments of the present invention will be described in detail so that those with general knowledge in the technical field to which the present application pertains can easily practice, as shown in the accompanying drawings, preferred embodiments of the present invention. In particular, the technical idea of the present invention and its core configuration and operation are not limited by this. In addition, the contents of the present invention can be implemented in various types of equipment, and is not limited to the implementation examples and examples described herein.

A polycarbazole-based cation exchange type ion conductor according to an embodiment of the present invention was prepared according to the method of Reaction Scheme 1 below.

<Scheme 1>

<Preparation Example 1> Preparation of halogen-containing carbazole-based monomer (BHC: M1)

A monomer synthesis process for synthesizing a polycarbazole-based polymer according to an embodiment of the present invention is as follows. First, prepare a dried three-necked flask, dissolve 10.0 g of carbazole and 43.8 g of dibromohexane in 200 ml of N,N-dimethylformamide, ^and KOH (3.4g) was added under C and Ar atmosphere and reacted for 24 h. After the reaction was completed, the mixture was precipitated in iced water and extracted with dichloromethane to obtain a mixture. The resulting mixture was subjected to column chromatography ) and recrystallized with ethanol to prepare a monomer.

1 shows the results of NMR spectrum analysis of a halogen-containing carbazole-based monomer (M1) according to an embodiment of the present invention.

<Preparation Example 2> Preparation of halogen-containing polycarbazole-based polymer (PCTFP-br: P1)

* A process for synthesizing a halogen-containing polycarbazole-based polymer according to an embodiment of the present invention is as follows. A completely dried flask was prepared and dissolved in 10 g of the halogen-containing carbazole-based monomer (M1) prepared in Preparation Example 1, 4.4 g of trifluoroacetone, and 24 ml of methylene chloride, and then dissolved in an Ar atmosphere at 0 ° C. 43.2 g of trifluoromethanesulfonic acid (TFSA, CF ₃ SO ₃ H) was added thereto, stirred for 2 h, raised to room temperature, and reacted for 48 h. After completion of the reaction, the mixture was washed with methanol, and the synthesized polymer was dried in a vacuum at 80 °C to obtain a halogen-containing polycarbazole-based polymer (P1). The prepared polymer P1 was analyzed by ¹ H-NMR spectroscopy to confirm the synthesis of the polymer.

<Preparation Example 3> Preparation of thioacetylated polycarbazole-based polymer (PCTFP-TAc: P2)

The manufacturing process of the thioacetylated polycarbazole-based polymer according to one embodiment of the present invention is as follows. Prepare a dried three-necked flask and add 10.0 g of the halogen-containing polycarbazole-based polymer (PCTFP-br: P1) prepared in Preparation Example 2 under an Ar atmosphere to 100 ml of N, N-dimethylformamide. After melting, 5.9 g of potassium thioacetate was added at room temperature and reacted at room temperature for 24 h. After the reaction was completed, it was precipitated in methanol, washed with methanol several times, filtered, and the prepared polymer was vacuum dried at 80 ° C to obtain a thioacetylated polycarbazole-based polymer (PCTFP-TAc: P2).

<Preparation Example 4> Preparation of sulfonated polycarbazole-based polymer (sPCTFP: P3)

A process for synthesizing a sulfonated polycarbazole-based polymer according to an embodiment of the present invention is as follows. A completely dried flask was prepared and 10 g of the thioacetylated polycarbazole-based polymer (PCTFP-TAc: P2) prepared in Preparation Example 3 was added to 200 ml of N, N-dimethylformamide under an Ar atmosphere. After melting and lowering the temperature to 0 °C, 8.013 g of m -chloroperoxybenzoic acid (mCPBA) was slowly added thereto, and then the temperature was raised to 10 °C and the reaction proceeded for 2 h. After the reaction was completed, it was precipitated in 1M NaCl solution, dissolved in dimethyl sulfoxide (DMSO), reprecipitated in acetone, filtered, and vacuum dried at 80 ° C to obtain a sulfonated polycarbazole-based polymer (sPCTFP: P3) polymer. got it

2 is a halogen-containing polycarbazole-based polymer (PCTFP-br: P1), a thioacetylated polycarbazole-based polymer (PCTFP-TAc: P2), and a sulfonated polycarbazole-based polymer (sPCTFP: P3) shows the results of ¹ H-NMR spectrum analysis.

Figure 3 shows the results of ¹ H- ¹ H COZY NMR spectrum analysis of thioacetylated polycarbazole-based polymer (PCTFP-TAc: P2) and sulfonated polycarbazole-based polymer (sPCTFP: P3) according to an embodiment of the present invention. it is shown

2, halogen-containing polycarbazole-based polymer (PCTFP-br: P1) as a main chain polymer, thioacetylated polycarbazole-based polymer (PCTFP-TAc: P2) synthesized through thioacetylation, and sulfonated It can be seen that all polycarbazole-based polymers (sPCTFP: P3) were successfully synthesized. In addition, in ^{the 1} H- ¹ H COZY NMR spectrum analysis of FIG. 3, a thioacetylated polycarbazole-based polymer (PCTFP-TAc: P2) synthesized through thioacetylation through resonance analysis between protons introduced into neighboring carbons And it can be more clearly confirmed that the sulfonated polycarbazole-based polymer (sPCTFP: P3), which is the final target material, was successfully synthesized.

<Analysis Example 1> Evaluation of characteristics of polycarbazole-based cation exchange type ion conductor

^{For 1} H NMR spectra, 500 and 700 MHz Bruker AVANCE instruments were used, and tetramethylsilane (TMS) was used as the standard. As solvents, DMF- d ₇ (δ = 2.75, 2.92, 8.03 ppm) and CDCl ₃ -d ₁ (δ = 7.28 ppm) was used.

The molecular weight of the prepared polymer was measured by dissolving the polymer in THF solution using HR 3,4 columns and gel permeation chromatograph (GPC) using Waters' 2414 model as a detector. It was measured in mL/min and the results are shown in Table 1.

	Mn(KDa)	Mw (KDa)
PCTFP-br	40	91
PCTFP-TAc	41	107
sPCTFP	43	124

The ion exchange capacity (IEC) of the prepared cation exchange membrane was prepared by preparing a sample in which the counter ion was replaced with Cl ^- , stirring the prepared cation exchange material in 0.01M HCl aqueous solution for 24 hours, and then adding 0.01M NaOH aqueous solution. It was measured through acid-base titration using

For the dimensional stability of the prepared membrane, the weight, length, thickness, and volume changes of the ion exchange membrane in the wet and dry state were measured at room temperature. Impedance was measured, and after the ion exchange membrane was immersed in 1.5 MH ₂ SO ₄ aqueous solution for 24 hours, the H ⁺ ion conductivity was measured at 25 ℃, 40 ℃, 60 ℃, 80 ℃ at 100% relative humidity, the results are shown in Table 2 described.

	IEC (meq/g)	Water uptake (%)	Proton conductivity (mS/cm)
			25℃	80℃
sPCTFP	2.1	55	59	115

As shown in Table 2, sPCTFP according to one embodiment of the present invention showed an appropriate moisture content of 55% at room temperature. In addition, it can be seen that it has an excellent cationic conductivity almost similar to that of Nafion 115, a commercial film.

<Analysis Example 2> Characteristic evaluation of electrode binder for fuel cell of cation exchange type ion conductor

4 shows a method for manufacturing an MEA using a polycarbazole-based cation exchange type conductor as a binder for an electrode according to an embodiment of the present invention.

A polymer binder solution was prepared by dissolving the sulfonated polycarbazole-based polymer (sPCTFP: P3) prepared according to Preparation Example 4 in n-propanol/NMP (Junsei chemical, GC) at 5 wt%, and the prepared polymer binder solution And Pt / C (50 wt% Pt, RTX ), balance (balance) solution using a ball-mill (ball-mill: PM-100, Retsch, Germany) to prepare a slurry (slurry), the prepared slurry A typical hydrocarbon-based cation exchange membrane, sPAES50, was coated on both sides with an active area of 5 cm ² using a spray coater (LSC-300, Lithotech., Korea) and dried to form a membrane-electrode assembly (MEA). The prepared MEA was immersed in an aqueous 1M sulfuric acid solution for 24 hours and then evaluated.

At this time, the unit cell characteristics of the cation exchange fuel cell were evaluated as follows. A membrane-electrode junction layer was prepared by overlapping the prepared electrode layer and the ion exchange membrane, and SGL-39BC was used as a gas diffusion layer material. The cell test station (Z010-100, SCITHEC KOREA) was evaluated under 0.2 V - 1.1 V / zero back pressure / 100% humidification condition and temperature condition of 80 ℃.

5 shows evaluation results of a fuel cell unit cell using a polycarbazole-based cation exchange type conductor according to an embodiment of the present invention as a binder.

As a result of the evaluation, the MEA using sPAES50, an existing hydrocarbon-based ion conductor, as a binder showed a current density of 250 mA/cm ² at 0.6V, whereas the MEA using the developed sPCTFP binder had a current density of 375 mA/cm ² at 0.6V. It was confirmed that the fuel cell performance was improved by 50% compared to the existing material by showing the density.

Claims (12)

1. Preparing at least one monomer from a monomer group consisting of a halogen-containing carbazole-based monomer and a carbazole-based monomer:

   preparing a halogen-containing polycarbazole-based polymer in which all the bonds between the monomers constituting the main chain are composed of C-C bonds by using a polymerization reaction of the monomers using a superacid catalyst;

   preparing a thioacetylated polycarbazole-based polymer by thioacetylating the halogen group of the halogen-containing polycarbazole-based polymer; and

   Including the step of sulfonating the thioacetylated polycarbazole-based polymer,

   A method for producing a polycarbazole-based cation exchange type ion conductor having the chemical structure of Formula A below:

   <Formula A>

   

   In Formula A,

   W is a cation exchange group and is either a sulfonic acid group (-SO ₃ H), a phosphoric acid group (-PO ₃ H ₂ ), an acetic acid group (-COOH), or an alkali metal salt thereof, or a nitro group (-NO ₂ ),

   Substituents represented by R ₁ to R ₄ are each independently any one of an alkylene group, an arylene group, and an allylene group;

   Any one of an alkylene group, an arylene group, and an allylene group containing a fluorine atom;

   a perfluoroalkylene group,

   Any one of a perfluoroalkylene group, a perfluoroarylene group, and an -O-perfluoroarylene group, optionally containing one or more oxygen, nitrogen, or sulfur atoms in its chain,

   m, the number of repeating units, is a positive integer of 100,000 or less, and n is 0 or a positive integer of 100,000 or less.
2. The method of claim 1,

   The acetic acid catalyst is a polycarbazole-based cation exchange type ion conductor, characterized in that any one of trifluoromethanesulfonic acid (TFSA, CF ₃ SO ₃ H) or fluorosulfonic acid (HSO ₃ F) Manufacturing method of.
3. The method of claim 1,

   Method for producing a polycarbazole-based cation exchange type ion conductor, characterized in that the halogen-containing polycarbazole-based polymer has a chemical structure of the following formula (B):

   <Formula B>

   

   In the above formula B,

   X is any one of halogen atoms chlorine (Cl), bromine (Br), iodine (I),

   Substituents represented by R ₁ to R ₄ are each independently any one of an alkylene group, an arylene group, and an allylene group;

   Any one of an alkylene group, an arylene group, and an allylene group containing a fluorine atom;

   a perfluoroalkylene group,

   Any one of a perfluoroalkylene group, a perfluoroarylene group, and an -O-perfluoroarylene group, optionally containing one or more oxygen, nitrogen, or sulfur atoms in its chain,

   m, the number of repeating units, is a positive integer of 100,000 or less, and n is 0 or a positive integer of 100,000 or less.
4. The method of claim 1,

   The step of preparing the thioacetylated polycarbazole-based polymer is a reaction of the halogen group of the halogen-containing polycarbazole-based polymer with any one of thioacetic acid, ethylthioacetate, and thioacetate metal salt. A method for producing a polycarbazole-based cation exchange type ion conductor.
5. The method of claim 1,

   The sulfonating step is a reaction of the thioacetylated polycarbazole-based polymer with any one of hydrogen peroxide, sulfuric acid, chlorosulfonic acid, sodium bisulfite, and m- chloroperoxybenzoic acid (mCPBA) Method for producing a polycarbazole-based cation exchange type ion conductor, characterized in that.
6. A polycarbazole-based cation exchange type ion conductor characterized in that it has the chemical structure of Formula A:

   <Formula A>

   

   In Formula A,

   W is a cation exchange group and is either a sulfonic acid group (-SO3H), a phosphoric acid group (-PO3H2), an acetic acid group (-COOH), or an alkali metal salt thereof, or a nitro group (-NO2),

   Substituents represented by R ₁ to R ₄ are each independently any one of an alkylene group, an arylene group, and an allylene group;

   Any one of an alkylene group, an arylene group, and an allylene group containing a fluorine atom;

   a perfluoroalkylene group,

   Any one of a perfluoroalkylene group, a perfluoroarylene group, and an -O-perfluoroarylene group, optionally containing one or more oxygen, nitrogen, or sulfur atoms in its chain,

   m, the number of repeating units, is a positive integer of 100,000 or less, and n is 0 or a positive integer of 100,000 or less.
7. An electrode binder comprising the polycarbazole-based cation exchange type ion conductor according to claim 6.
8. Separation membrane comprising the polycarbazole-based cation exchange type ion conductor according to claim 6.
9. The method of claim 8,

   The separator is a separator, characterized in that for a cation exchange membrane fuel cell (Proton Exchange Membrane Fuel Cell: PEMFC).
10. The method of claim 8,

    The separation membrane is used for water electrolysis, redox flow cell, fuel cell, carbon dioxide reduction, electrochemical ammonia production and decomposition, A separation membrane, characterized in that it is a membrane for electrodialysis (ED), reverse electrodialysis (RED) or capacitive deionization (CDI).
11. Binder for an electrode according to claim 6; and

    A cation exchange membrane fuel cell (Proton Exchange Membrane Fuel Cell: PEMFC) device comprising the separator according to claim 8.
12. Binder for an electrode according to claim 6; and

    A cation exchange membrane water electrolysis (PEMWE) apparatus comprising the separation membrane according to claim 8.

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