WO2023106657A1 - Conducteur ionique à échange cationique à base de polycarbazole et son procédé de fabrication - Google Patents

Conducteur ionique à échange cationique à base de polycarbazole et son procédé de fabrication Download PDF

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WO2023106657A1
WO2023106657A1 PCT/KR2022/017650 KR2022017650W WO2023106657A1 WO 2023106657 A1 WO2023106657 A1 WO 2023106657A1 KR 2022017650 W KR2022017650 W KR 2022017650W WO 2023106657 A1 WO2023106657 A1 WO 2023106657A1
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group
polycarbazole
cation exchange
ion conductor
halogen
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Korean (ko)
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이장용
유덕만
정환엽
신상훈
차민석
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한국화학연구원
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a polycarbazole-based cation exchange type ion conductor, a manufacturing method and use thereof.
  • 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.
  • ED electrodialysis
  • RED reverse electrodialysis
  • capacitive capacitive deionization
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • PEM proton exchange membrane
  • AE alkaline electrolysis
  • HTE high temperature electrolysis
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • ED electrodialysis
  • RED reverse electrodialysis
  • CDI capacitive deionization
  • 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.
  • PEMFC Proton Exchange Membrane Fuel Cell
  • PEMWE Proton Exchange Membrane Water Electrolysis
  • 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.
  • 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
  • ED electrodialysis
  • RED reverse electrodialysis
  • 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.
  • the present invention provides a Proton Exchange Membrane Fuel Cell (PEMFC) device or a Proton Exchange Membrane Water Electrolysis (PEMWE) device.
  • PEMFC Proton Exchange Membrane Fuel Cell
  • PEMWE Proton Exchange Membrane Water Electrolysis
  • 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
  • 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
  • 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.
  • 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.
  • ED electrodialysis
  • RED reverse electrodialysis
  • CDI capacitive deionization
  • PCTFP-br a halogen-containing polycarbazole-based polymer
  • PCTFP-TAc a thioacetylated polycarbazole-based polymer
  • sPCTFP a sulfonated polycarbazole-based polymer
  • FIG. 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
  • FIG. 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.
  • FIG. 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.
  • 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.
  • ED electrodialysis
  • RED reverse electrodialysis
  • CDI capacitive deionization
  • 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.
  • 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;
  • n 0 or a positive integer of 100,000 or less.
  • the acetic acid catalyst is trifluoromethanesulfonic acid (TFSA, CF 3 SO 3 H) or fluorosulfonic acid (fluorosulfonic acid: HSO 3 F).
  • TFSA trifluoromethanesulfonic acid
  • fluorosulfonic acid fluorosulfonic acid: HSO 3 F
  • 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.
  • 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;
  • n 0 or a positive integer of 100,000 or less.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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;
  • n 0 or a positive integer of 100,000 or less.
  • the present invention provides a binder for an electrode comprising a polycarbazole-based cation exchange ion conductor prepared according to the above manufacturing method.
  • 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.
  • MEA membrane electrode assembly
  • the present invention provides a separation membrane comprising a polycarbazole-based cation exchange ion conductor prepared according to the above manufacturing method.
  • 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.
  • the separator may be for a Proton Exchange Membrane Fuel Cell (PEMFC).
  • PEMFC Proton Exchange Membrane Fuel Cell
  • 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
  • a binder for an electrode comprising a polycarbazole-based cation exchange ion conductor according to an embodiment of the present invention
  • the separation membrane may be used in a Proton Exchange Membrane Fuel Cell (PEMFC) device and a Proton Exchange Membrane Water Electrolysis (PEMWE) device.
  • PEMFC Proton Exchange Membrane Fuel Cell
  • PEMWE Proton Exchange Membrane Water Electrolysis
  • 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.
  • 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.
  • 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.
  • M1 halogen-containing carbazole-based monomer
  • TFSA trifluoromethanesulfonic acid
  • 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.
  • PCTFP-br halogen-containing polycarbazole-based polymer
  • 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.
  • PCTFP-TAc: P2 thioacetylated polycarbazole-based polymer
  • Preparation Example 3 was added to 200 ml of N, N-dimethylformamide under an Ar atmosphere.
  • 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.
  • PCTFP-br a halogen-containing polycarbazole-based polymer
  • PCTFP-TAc a thioacetylated polycarbazole-based polymer
  • sPCTFP a sulfonated polycarbazole-based polymer
  • FIG. 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
  • PCTFP-br halogen-containing polycarbazole-based polymer
  • PCTFP-TAc thioacetylated polycarbazole-based polymer
  • sPCTFP polycarbazole-based polymers
  • PCTFP-TAc a thioacetylated polycarbazole-based polymer synthesized through thioacetylation through resonance analysis between protons introduced into neighboring carbons
  • sPCTFP sulfonated polycarbazole-based polymer
  • 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.
  • 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
  • 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 °C, 40 °C, 60 °C, 80 °C at 100% relative humidity, the results are shown in Table 2 described.
  • sPCTFP according to one embodiment of the present invention showed an appropriate moisture content of 55% at room temperature.
  • FIG. 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.
  • 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 °C.
  • FIG. 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.
  • 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.

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Abstract

La présente invention se rapporte à un conducteur d'ions à échange de cations à base de polycarbazole, à un procédé de fabrication de ce dernier, et à son utilisation et, plus particulièrement, à un conducteur d'ions à échange de cations qui non seulement peut être utilisé comme liant d'électrode, mais peut également être utilisé comme matériau échangeur d'ions pour l'électrolyse de l'eau, cellule à flux redox, pile à combustible, pour la réduction de dioxyde de carbone, pour la production et la décomposition d'ammoniac électrochimique, pour une électrodialyse (D), pour une électrodialyse inverse (RED) ou pour un séparateur de désionisation capacitive (CDI) ; et à son procédé de fabrication.
PCT/KR2022/017650 2021-12-08 2022-11-10 Conducteur ionique à échange cationique à base de polycarbazole et son procédé de fabrication WO2023106657A1 (fr)

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Cited By (1)

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WO2024094024A1 (fr) * 2022-11-01 2024-05-10 中国石油天然气股份有限公司 Polymère, et son procédé de préparation et son utilisation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050071570A (ko) * 2002-10-15 2005-07-07 니폰 가야꾸 가부시끼가이샤 설포알킬기 함유 고분자의 제조 방법
JP2009277532A (ja) * 2008-05-15 2009-11-26 Nippon Kayaku Co Ltd ポリエーテルスルホン系高分子電解質、固体高分子電解質膜、燃料電池、およびその製造方法
JP2013209500A (ja) * 2012-03-30 2013-10-10 Toyobo Co Ltd プロトン伝導性化合物、成型物、燃料電池用プロトン交換膜及び燃料電池
KR20160066485A (ko) * 2015-05-26 2016-06-10 성균관대학교산학협력단 연료전지의 멤브레인 제조용 공중합체 및 연료전지용 멤브레인
KR102168673B1 (ko) * 2019-04-29 2020-10-21 한국화학연구원 카바졸계 음이온 교환 소재 및 이를 바인더로 포함하는 연료전지용 전극, 막-전극 접합체

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102284854B1 (ko) 2020-02-28 2021-07-30 한국화학연구원 카바졸계 음이온 교환 소재, 그의 제조방법 및 용도

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050071570A (ko) * 2002-10-15 2005-07-07 니폰 가야꾸 가부시끼가이샤 설포알킬기 함유 고분자의 제조 방법
JP2009277532A (ja) * 2008-05-15 2009-11-26 Nippon Kayaku Co Ltd ポリエーテルスルホン系高分子電解質、固体高分子電解質膜、燃料電池、およびその製造方法
JP2013209500A (ja) * 2012-03-30 2013-10-10 Toyobo Co Ltd プロトン伝導性化合物、成型物、燃料電池用プロトン交換膜及び燃料電池
KR20160066485A (ko) * 2015-05-26 2016-06-10 성균관대학교산학협력단 연료전지의 멤브레인 제조용 공중합체 및 연료전지용 멤브레인
KR102168673B1 (ko) * 2019-04-29 2020-10-21 한국화학연구원 카바졸계 음이온 교환 소재 및 이를 바인더로 포함하는 연료전지용 전극, 막-전극 접합체

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024094024A1 (fr) * 2022-11-01 2024-05-10 中国石油天然气股份有限公司 Polymère, et son procédé de préparation et son utilisation

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