WO2018048134A1 - Couche d'adhérence d'interface membrane-électrode destinée à une pile à combustible, et ensemble membrane-électrode et pile à combustible utilisant une telle couche - Google Patents

Couche d'adhérence d'interface membrane-électrode destinée à une pile à combustible, et ensemble membrane-électrode et pile à combustible utilisant une telle couche Download PDF

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WO2018048134A1
WO2018048134A1 PCT/KR2017/009443 KR2017009443W WO2018048134A1 WO 2018048134 A1 WO2018048134 A1 WO 2018048134A1 KR 2017009443 W KR2017009443 W KR 2017009443W WO 2018048134 A1 WO2018048134 A1 WO 2018048134A1
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membrane
based polymer
electrode
fuel cell
hydrocarbon
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PCT/KR2017/009443
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English (en)
Korean (ko)
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김태호
이장용
홍영택
정환엽
김석제
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한국화학연구원
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Publication of WO2018048134A1 publication Critical patent/WO2018048134A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • H01M2300/0097—Composites in the form of layered products, e.g. coatings with adhesive layers
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention is a fuel cell comprising a mixture of a hydrocarbon-based polymer and a fluorine-based polymer for overcoming the problem that the interface detaches during operation of the fuel cell due to lack of compatibility between the hydrocarbon-based polymer electrolyte membrane and the catalyst layer containing the fluorine ionomer.
  • a membrane-electrode interface adhesive layer comprising a composition gradient of a hydrocarbon-based polymer and a fluorine-based polymer in a thickness direction, and a membrane-electrode interface adhesive layer for a fuel cell, and a membrane-electrode assembly using the same ) And fuel cells.
  • PEMFCs proton exchange membrane fuel cells
  • PEM polymer electrolyte membrane
  • Nafion among perfluorosulfonated PEMs is a commercialized material for proton exchange membrane fuel cells with high proton conductivity, good mechanical properties and excellent dimensional stability.
  • Nafion has the disadvantage of high unit cost and limited use at high temperatures.
  • hydrocarbon membranes cheaper than Nafion
  • the representative one of them is sulfonated poly (arylene ether sulfone) copolymer (SPAES).
  • SPAES sulfonated poly (arylene ether sulfone) copolymer
  • hydrocarbon-based copolymers containing such aromatic structures have been widely studied in the past because of their thermal stability due to the aromatic structure, excellent mechanical strength and elongation, and low gas cross-mixing ability between the anode and the cathode. to be.
  • the transfer of the electrode is not easily performed due to the decrease in miscibility with the electrode catalyst layer containing Nafion, a fluorine-based polymer, as a binder. Even when the membrane-electrode assembly is constructed, the bonding strength is weak, so that the resistance may increase due to the detachment between the interfaces or the driving may not be possible for a long time.
  • PVDF polyvinylidene fluoride
  • the electrolyte membrane was formed by adding PVDF lacking ion conductivity. There is a problem that the overall ion conductivity decreases.
  • perfluoro-based membranes which are electrolyte membranes, account for a large portion of the price increase of polymer electrolyte membrane fuel cells (PEMFC), and many kinds of hydrocarbon-based electrolyte membranes are under research and development. It is known to exhibit characteristics close to the perfluorine material in terms of performance and durability. However, hydrocarbon-based polymer electrolyte membranes have a problem in that desorption with the electrode layer is serious in use.
  • the ionomer of the electrode layer is perfluorinated, and unlike the electrolyte membrane, the ionomer of the electrode layer is very difficult to use as an ionomer because the gas permeability of the hydrocarbon-based material is very low, and even though the hydrocarbon-based polymer electrolyte membrane is applied, the ionomer of the electrode layer is perfluorinated.
  • the material is more realistic, in this case, performance is initially achieved in the fuel cell operating environment, but gradually the interface between the hydrocarbon-based polymer electrolyte membrane and the electrode layer containing the perfluorinated ionomer is exposed to repeated temperature and humidity changes. There is a disadvantage in that desorption occurs and the performance and durability are greatly reduced.
  • Japanese Patent Laid-Open Publication No. 5144023 and Korean Laid-Open Patent Publication No. 10-2016-0080778 use hydrocarbon-based and fluorine-based polymers to improve the bonding strength of the membrane-electrode assembly or to maintain water retention, drainage, and Although a technique for maintaining water repellency has been disclosed, there is still no sufficient improvement in the adhesion of the membrane-electrode interface.
  • the present invention was developed to solve the above problems, the interface between the hydrocarbon-based polymer electrolyte membrane and the catalyst layer containing the perfluorinated ionomer (eg, Nafion), the interface is detached during operation of the fuel cell due to lack of compatibility (compatability) It aims to overcome the problem.
  • the perfluorinated ionomer eg, Nafion
  • MEA membrane-electrode assembly
  • PEMFC polymer electrolyte membrane fuel cell
  • DMFC direct methanol fuel cell
  • the membrane-electrode interface adhesive layer composed of a mixture of a hydrocarbon-based polymer and a fluorine-based polymer
  • the membrane-electrode interface adhesive layer is a composition gradient of the hydrocarbon-based polymer and the fluorine-based polymer in the thickness direction ( A film-electrode interfacial adhesive layer having a composition gradient is provided.
  • an ion conductive membrane containing a hydrocarbon-based polymer containing a hydrocarbon-based polymer
  • a membrane-electrode interface adhesive layer for a fuel cell having a composition gradient of a hydrocarbon-based polymer and a fluorine-based polymer in a thickness direction formed on both sides of the ion conductive membrane
  • MEA membrane-electrode assembly
  • the catalyst layer transfer can be easily performed at a lower temperature and pressure by making the surface of the hydrocarbon-based electrolyte membrane more flexible during the decal process for manufacturing the membrane-electrode assembly (MEA).
  • the membrane-electrode assembly according to the present invention prevents an increase in interfacial resistance and desorption due to a decrease in bonding strength due to poor compatibility with a fluorine-based polymer binder when an electrolyte membrane formed of an ion conductive hydrocarbon-based polymer is used.
  • Membrane-electrode assembly with improved durability can be usefully used in fuel cells.
  • the performance of the MEA can be further improved when driving the fuel cell.
  • FIG. 1 is a process chart showing a film manufacturing process using a bonding layer having a composition gradient according to an embodiment of the present invention.
  • FIG. 2 is an optical camera photograph of a film having a compositional gradient in accordance with one embodiment of the present invention.
  • SEM scanning electron microscope
  • FIG. 4 shows a polarization curve of a film having a composition gradient according to an embodiment of the present invention.
  • Figure 5 illustrates the results of the boiling water acceleration experiment of the membrane having a composition gradient according to an embodiment of the present invention.
  • the present invention blocks the increase in interfacial resistance and desorption phenomena due to a decrease in bonding strength due to poor miscibility with the fluorine-based polymer binder in the case of using an electrolyte membrane formed of an ion conductive hydrocarbon-based polymer in a conventional membrane-electrode assembly. It is for improving durability.
  • the membrane-electrode interfacial adhesion layer for a fuel cell composed of a mixture of a hydrocarbon-based polymer and a fluorine-based polymer
  • the membrane-electrode interfacial adhesion layer is a fuel having a composition gradient of the hydrocarbon-based polymer and the fluorine-based polymer in the thickness direction
  • a battery film-electrode interface adhesive layer is provided.
  • the membrane-electrode interface adhesive layer has a composition gradient by stacking a composition having different mixing ratios of hydrocarbon-based polymers and fluorine-based polymers in multiple layers. You can do that.
  • the membrane-electrode interfacial adhesive layer having a composition gradient by laminating in multiple layers is prepared by n-type compositions having different mixing ratios, and then sequentially laminated so as to have a desired composition gradient, and then compressed by film-compression or the like.
  • the electrode interface adhesive layer may be prepared or compositions having different mixing ratios may be sequentially sprayed to have a membrane-electrode interface adhesive layer having a multi-layer composition gradient.
  • n kinds of compositions having different mixing ratios may be prepared to have various composition gradients through the composition ratio combination of the mixtures selected from them.
  • n which is a mixing ratio of different compositions
  • a mixing ratio of a hydrocarbon polymer and a fluorine polymer is 9: 1 and 1: 9, 2: 8 and 8: 2, 3: 7 and 7: 3, 4: 9: 1/1: 9, 2: 8/8: 2, 3: 7/7: 3, 4: 6/6: 4 prepared from various compositions having different mixing ratios of 6 and 6: 4
  • Two layers of the film-electrode interface adhesive layer having a composition gradient of two levels of phosphorus may be configured in four forms.
  • n which is a different mixing ratio
  • the mixing ratio of the hydrocarbon-based polymer and the fluorine-based polymer is 3: 5, 5: 5, 7: 3.
  • a fluorine-based polymer may form a three-layer film-electrode interface adhesive layer having a three-step compositional gradient of 3: 5/5: 5/7: 3.
  • the mixing ratio of the hydrocarbon polymer and the fluorine polymer is 9: 1, 2: 8, 3: 7 and 3: 7, 8: 2, 1: 9 or
  • the mixing ratio of hydrocarbon polymer and fluorine polymer is 9: 1/2: 8 using various compositions having different mixing ratios of 9: 1, 3: 7, 4: 6 and 6: 4, 7: 3, 1: 9.
  • a film-electrode interface adhesive layer can be formed.
  • the membrane-electrode interfacial adhesive layer for a fuel cell is laminated in a multi-layer after film forming a composition having a different mixing ratio of hydrocarbon-based polymer and fluorine-based polymer or different mixing ratio
  • the composition may be coated in multiple layers by a spray coating method.
  • the thickness may be even thicker. Therefore, in the case of manufacturing a thin adhesive layer, a spray coating method is more preferable, and the adhesive layer has a fluorine-based hydrocarbon polymer having no ion conductivity other than the ion conductive polymer constituting the electrolyte membrane. Since the thickness of the bonding layer is formed to increase the ion conductivity of the entire membrane can be reduced. Therefore, the adhesive layer is preferably formed as thin as possible. However, when the thickness of the bonding layer is less than 50 nm, it may be difficult to achieve the desired improvement in adhesion between the membrane and the electrode catalyst layer, and when the thickness exceeds 1,000 nm, the battery manufactured by reducing the ion conductivity in the membrane. Can cause a decrease in performance.
  • a solution obtained by dissolving a hydrocarbon-based polymer and a fluorine-based polymer in a solvent may be formed by applying a spray.
  • the bonding layer is thin and uniformly formed at a constant thickness over the entire interface between the electrolyte membrane and the electrode layer. Therefore, a mixed solution of a hydrocarbon-based polymer and a fluorine-based polymer may be prepared and evenly applied to the entire surface of the electrolyte membrane with a spray.
  • the solvent may be used without limitation as long as it is a solvent capable of dissolving both the hydrocarbon-based polymer and the fluorine-based polymer.
  • a predetermined mixing ratio is prepared, and then a film is formed using the prepared composition and laminated after film forming, or the composition is coated in a multilayer by spray method.
  • the electrode interfacial adhesive layer may be formed, a more effective compositional gradient may be achieved by using a mixing nozzle capable of simultaneously controlling the amount of electrolyte supply and mixing them through a nozzle having a hydrocarbon polymer and a fluorine polymer separately. It is also possible to use a method of supplying a mixed composition having a composition gradient to form it in the form of a film or coating in multiple layers by a spray method.
  • the membrane-electrode assembly first laminates films of different compositions to increase the adhesive strength of the interface between the films to increase the crimping temperature during a process such as pressing.
  • the predetermined nonflammable and stepwise gradient initially set by diffusion of the polymer between layers of different compositions gradually changes to a gradient of continuous composition.
  • the predetermined compositional gradient of the first sprayed layer is more prone to a subsequent compositional gradient with the compositional gradient of the later sprayed layer.
  • a method of coating compositions having different compositions with a spray method rather than constructing a film having a predetermined composition in multiple layers to have a compositional gradient is more continuous. It is more preferable for the adhesive force improvement.
  • the membrane-electrode interfacial adhesive layer for a fuel cell according to an embodiment of the present invention, has a high content of a hydrocarbon-based electrolyte in contact with the hydrocarbon-based polymer in the thickness direction, and the contact portion with the electrode is a fluorine-based polymer.
  • the content of is high, and the middle portion between them may have a composition gradient gradually changing.
  • the hydrocarbon-based polymer and the contact portion are composed of a hydrocarbon-based polymer and a fluorine-based polymer in a weight ratio of 9: 1 to 7: 3, and the contact portion with the electrode
  • the composition of the silver hydrocarbon-based polymer and the fluorine-based polymer is 1: 9 to 3: 7 by weight, and the middle portion may have a composition gradient gradually changing.
  • the hydrocarbon-based polymer and the contacting part are prepared in a weight ratio of 9: 1 hydrocarbon-based polymer and the fluorine-based polymer in a weight ratio
  • the electrode and the contact part are the mixed solution of the hydrocarbon-based polymer and fluorine-based polymer in a weight ratio of 1: 9.
  • the middle portion is a gradually changing composition by sequentially spray coating the mixed solution mixed in a different weight ratio on the hydrocarbon-based polymer using a mixed solution mixed in a weight ratio of 7: 3, 5: 5, 3: 7
  • a film-electrode interface adhesive layer having a composition gradient can be prepared.
  • the hydrocarbon-based polymer is a sulfonated poly (arylene ether sulfone) copolymer (SPAES), sulfonated Sulfonated poly (ether ketone) copolymers (SPEK), sulfonated polyimide copolymers (SPI), sulfonated polysulfone copolymers (SPS), Sulfonated polyphenylene copolymer (SPP), sulfonated poly (arylene sulfide sulfone) copolymer (SPASS), sulfonated poly (benzimidazole ( and block copolymers including sulfonated Polybenzimidazole (SPBI), sulfonated Poly (benzoxazole); SPBO, and combinations thereof.
  • SPAES sulfonated poly (arylene ether sulfone) copolymer
  • SPEK sulfonated Sulfonated poly (ether ketone) cop
  • the fluorine-based polymer is polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene ( polytetrafluoroethylene (PTFE), fluorinated ethylene-propylene (FEP), polyvinylidene fluoride hexafluoropropylene copolymer (Poly (vinylidene fluoride-co-hexafluoropropylene; PVDF-HFP), perfluorinated ionomer (perfluorinated ionomers), or mixtures thereof.
  • PVDF polyvinylidene fluoride
  • PVDF polyvinyl fluoride
  • PVFE polytetrafluoroethylene
  • FEP fluorinated ethylene-propylene
  • PVDF-HFP polyvinylidene fluoride hexafluoropropylene copolymer
  • perfluorinated ionomer perfluorinated ionomers
  • the present invention is an ion conductive membrane containing a hydrocarbon-based polymer;
  • a fluorine-based binder is transferred through a membrane-electrode interface adhesive layer for fuel cells having a composition gradient of a hydrocarbon-based polymer and a fluorine-based polymer in a thickness direction formed on both sides of the ion conductive membrane and the membrane-electrode interface adhesive layer for the fuel cell.
  • a membrane-electrode assembly (MEA) having an electrode layer comprising a polymer is provided.
  • the present invention is a membrane-electrode assembly (MEA) having a membrane-electrode interfacial adhesive layer for a fuel cell having the composition gradient (composition gradient) and a polymer electrolyte membrane fuel cell having the same; PEMFC) or direct methanol fuel cell (DMFC).
  • MEA membrane-electrode assembly
  • PEMFC polymer electrolyte membrane fuel cell having the same
  • DMFC direct methanol fuel cell
  • gradient bonding layer used synthetic SPAES synthesized 40% sulfonated, Nafion-dispersion solution D1021 purchased from Du Pont using a spray-dryer It was used to dry again, and NMP was used as a solvent.
  • Materials for preparing the catalyst include Tanaka's Pt / C (Pt 37.7%), deionized water (DIwater, ELGA Pure Lab Classic), isopropyl alcohol (IPA, Samchun Chemical) and 5 wt% Nafion dispersion solution (Dupont Inc) was used.
  • SPAES Sulfonated poly (arylene ether sulfone): SPAES was prepared according to Scheme 1 below.
  • Sulfonated poly (arylene ether sulfone) is a monomer that contains biphenol (BP, TCI) and dichloro diphenyl sulfone (DCDPS, Solvay Advanced Polymers).
  • DCDPS was prepared by using sulfonated dichloro diphenyl sulfone (SDCDPS) using 65% fuming sulfuric acid (Merck). Each monomer was used after recrystallization in isopropyl alcohol (IPA, Samchun Chemical). N-methyl-2-pyrrolidone (NMP, Junsei), anhydrous toluene (Aldrich) was used as a solvent, and anhydrous potassium carbonate (K2CO3, Aldrich) was used. Synthesis was carried out using as a catalyst.
  • More detailed manufacturing method is as follows. In a four-necked round flask, a gas sparge tube, Dean-stark trap condenser and stirrer are installed to create an Ar atmosphere. Then, biphenol and K 2 CO 3 were put, NMP and toluene were heated and stirred at 150 ° C. for 2 hours, and then heated up to 160 ° C. to toluene was refluxed for 4 hours to remove water. After the addition of SDCDPS and DCDPS, the reaction proceeds while stirring at 175 °C for 25 hours.
  • SPAES 40 (sulfonation degree 40%) to prepare a 16wt% polymer solution in the solvent NMP, using a doctor blade (doctor blade) to make a film on a glass plate and dried in an oven at 80 °C 3 hours to complete the film.
  • Figure 1 is a process chart showing a film manufacturing process using a bonding layer having a composition gradient according to an embodiment of the present invention
  • Figure 2 is an optical camera photograph of a film having a composition gradient according to an embodiment of the present invention.
  • T-peel strength was measured by using a universal testing machine (LR5K, LLOYD instrument) to indirectly determine the bonding strength of the membrane and the fluorine-based electrode layer prepared in Preparation Example 3. Cut the G-layer membrane and Nafion 212 membrane into 1cm x 5cm size, overlap the two membranes, and add 1cm x 4cm polyimide. Thereafter, the two membranes are bonded by hot pressing under the same conditions as in the preparation of the MEA of Preparation Example 5, and then the upper and lower ends of the two membranes are grasped by the UTM apparatus, and the binding force is measured.
  • LR5K universal testing machine
  • Hydrogen ion conductivity measurement was performed according to the change in temperature and humidity, and the conductivity was measured while raising the temperature at 100 ° C and 25 ° C and 40 ° C and 55 ° C and 70 ° C.
  • the electrolyte membrane was prepared in a dried state and measured using an Impedence / Gain-phase analyzer (solartron-1280, Solartron).
  • SEM VEGA3, TESCAN
  • MIRA3, TESCAN SEM
  • FIG. 3 is a SEM photograph showing a cross-sectional structure of a film having a composition gradient and a film-electrode assembly using the same according to an embodiment of the present invention.
  • (a) is a cross-sectional structure of a gradient membrane having a composition gradient of Preparation Example 3 and
  • (b) shows a cross-sectional structure of a membrane-electrode assembly (MEA) in SEM.
  • MEA membrane-electrode assembly
  • the SEM image measured with Preparation Example 5 showed a binding picture of the MEA bonded to the cross section of the composition gradient membrane (gradient membrane).
  • gradient membrane composition gradient membrane
  • Figure 4 shows the polarization curve of the composition gradient membrane (gradient membrane) according to an embodiment of the present invention.
  • 850mA / cm 2 was obtained as a result of Pristine BPSH-40 at 0.6V, and 964mA / cm 2 was obtained for a gradient membrane having a composition gradient. This indicates that the bonding layer fills the void space between the film and the interface, which helps to improve performance.
  • the resistance of the membrane using the EIS was measured to be 73 ohm / cm 2 for the SPAES-40 and 111 ohm / cm 2 for the gradient film.
  • Figure 5 illustrates the results of the boiling water acceleration experiment of the membrane having a composition gradient according to an embodiment of the present invention.
  • the existing SPAES-40 shows that the electrode layer is detached after 1 hour, but the gradient membrane of the composition shows that the electrode is maintained even after 3 hours. have. And, considering the amount of catalyst remaining on the transfer paper, it can be seen that a gradient membrane having a composition gradient is better transferred under the same conditions.

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Abstract

La présente invention porte sur une couche d'adhérence d'interface membrane-électrode destinée à une pile à combustible, et sur un ensemble membrane-électrode (MEA) et une pile à combustible utilisant une telle couche, la couche d'adhérence d'interface membrane-électrode permettant de pallier le problème de séparation interfaciale pendant le fonctionnement de piles à combustible due à une compatibilité insuffisante entre une membrane d'électrolyte à base d'hydrocarbure et une couche de catalyseur qui contient un ionomère à base de fluorure, et présentant une force d'adhérence améliorée grâce à un gradient de composition d'un polymère électrolytique à base d'hydrocarbure et d'un polymère de nafion.
PCT/KR2017/009443 2016-09-12 2017-08-29 Couche d'adhérence d'interface membrane-électrode destinée à une pile à combustible, et ensemble membrane-électrode et pile à combustible utilisant une telle couche WO2018048134A1 (fr)

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US20220216494A1 (en) * 2019-03-28 2022-07-07 Toray Industries, Inc. Multilayer electrolyte membrane, membrane electrode assembly, water electrolysis-type hydrogen generator and method of producing multilayer electrolyte membrane

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EP3832766B1 (fr) 2018-08-01 2024-02-28 Toray Industries, Inc. Procédé et dispositif de fabrication d'un ensemble membrane-catalyseur
KR102525692B1 (ko) 2020-11-27 2023-04-24 한국화학연구원 탄소계 물질과 과불소계 이오노머의 혼합물층을 포함하여 구성되는 막-전극 계면 접합층, 이를 이용한 탄화수소계 막-전극 접합체 및 연료전지
KR20230078426A (ko) 2021-11-26 2023-06-02 한국화학연구원 향상된 계면 접착력을 가지는 탄화수소계 고분자 전해질 막-전극 접합체의 제조방법
KR20230141332A (ko) * 2022-03-31 2023-10-10 코오롱인더스트리 주식회사 불소 함유 촉매층을 포함하는 막-전극 어셈블리 및 이를 포함하는 연료 전지

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050117583A (ko) * 2003-04-09 2005-12-14 미쓰이 가가쿠 가부시키가이샤 연료전지 및 그 제조방법
JP2008053011A (ja) * 2006-08-23 2008-03-06 Toyota Motor Corp 固体高分子電解質型燃料電池の製造方法
JP2009021224A (ja) * 2007-06-12 2009-01-29 Toshiba Corp 燃料電池用膜電極接合体および燃料電池
JP5458774B2 (ja) * 2009-09-25 2014-04-02 日産自動車株式会社 電解質膜−電極接合体
KR20160080778A (ko) * 2014-12-30 2016-07-08 한국화학연구원 불소계 탄화수소 고분자를 함유하는 접합층을 포함하는 탄화수소계 막-전극 접합체 및 이의 제조방법

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5153579A (en) 1974-11-06 1976-05-12 Akira Nakajima Purasuchitsukuno bo mataha kanomochiita uzumakijo mataha rasenjoseikeihinno seizosochi

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050117583A (ko) * 2003-04-09 2005-12-14 미쓰이 가가쿠 가부시키가이샤 연료전지 및 그 제조방법
JP2008053011A (ja) * 2006-08-23 2008-03-06 Toyota Motor Corp 固体高分子電解質型燃料電池の製造方法
JP2009021224A (ja) * 2007-06-12 2009-01-29 Toshiba Corp 燃料電池用膜電極接合体および燃料電池
JP5458774B2 (ja) * 2009-09-25 2014-04-02 日産自動車株式会社 電解質膜−電極接合体
KR20160080778A (ko) * 2014-12-30 2016-07-08 한국화학연구원 불소계 탄화수소 고분자를 함유하는 접합층을 포함하는 탄화수소계 막-전극 접합체 및 이의 제조방법

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109671965A (zh) * 2018-12-21 2019-04-23 清华大学 一种高耐久性燃料电池膜电极及其制备方法
US20220216494A1 (en) * 2019-03-28 2022-07-07 Toray Industries, Inc. Multilayer electrolyte membrane, membrane electrode assembly, water electrolysis-type hydrogen generator and method of producing multilayer electrolyte membrane
US11973252B2 (en) * 2019-03-28 2024-04-30 Toray Industries, Inc. Multilayer electrolyte membrane, membrane electrode assembly, water electrolysis-type hydrogen generator and method of producing multilayer electrolyte membrane
EP3951017A4 (fr) * 2019-03-28 2024-07-24 Toray Industries Membrane électrolytique multicouche, ensemble membrane-électrode, générateur d'hydrogène de type électrolyse de l'eau et procédé de production d'une membrane électrolytique multicouche

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