KR100709554B1 - Catalyst binder for membrane electrode assembly using hydrocarbon-based sulfonated polymer, method for preparing the same, membrane electrode assembly using the catalyst binder polymer - Google Patents
Catalyst binder for membrane electrode assembly using hydrocarbon-based sulfonated polymer, method for preparing the same, membrane electrode assembly using the catalyst binder polymer Download PDFInfo
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Abstract
본 발명에서는 탄화수소계열 술폰화 고분자를 이용하여 제작된 멤브레인을 구비하는 MEA의 촉매 바인더로서, 탄화수소계열 술폰화 고분자를 포함하는 것을 특징으로 하는 MEA의 촉매 바인더, 그 제조 방법 및 상기 촉매 바인더를 이용하여 제조되는 MEA를 제공한다. 본 발명에 따르면 탄화수소계열 술폰화 고분자 멤브레인을 구비하는 MEA에 있어서, 멤브레인과 전극의 접착력을 높일 수 있고, 성능이 우수하게 되며, 이에 따라 탄화수소계열 술폰화 고분자 멤브레인을 구비하는 MEA의 상용화를 가능하게 할 수 있다.In the present invention, the catalyst binder of the MEA having a membrane produced using a hydrocarbon-based sulfonated polymer, the catalyst binder of the MEA, characterized in that it comprises a hydrocarbon-based sulfonated polymer, a method for producing the same and the catalyst binder It provides a MEA to be manufactured. According to the present invention, in the MEA having a hydrocarbon-based sulfonated polymer membrane, the adhesion between the membrane and the electrode can be improved, and the performance is excellent, thereby enabling the commercialization of the MEA having the hydrocarbon-based sulfonated polymer membrane. can do.
탄화수소계열술폰화고분자, 촉매바인더, 멤브레인, 막전극집합체 Hydrocarbon-based sulfonated polymer, catalyst binder, membrane, membrane electrode assembly
Description
도 1은 본 실험예에 있어서의 실시예와 비교예의 전류밀도에 대한 전압 특성을 나타내는 그래프이다. 1 is a graph showing the voltage characteristics with respect to the current density of the examples and comparative examples in the present experimental example.
본 발명은 탄화수소계열 술폰화 고분자를 이용한 막전극집합체의 촉매 바인더, 그 제조 방법 및 상기 촉매 바인더를 이용한 막전극집합체에 관한 것이다.The present invention relates to a catalyst binder of a membrane electrode assembly using a hydrocarbon-based sulfonated polymer, a method of manufacturing the same, and a membrane electrode assembly using the catalyst binder.
연료전지를 구성하는 여러 요소 중 멤브레인과 전극으로 이루어진 막전극집합체인 MEA(Membrane Electrode Assembly ; 이하, "MEA"라고 한다)는 가장 핵심 부품이다. 그리고, 그 중 전극은 촉매(Pt/C 또는 Pt)와 촉매 바인딩 고분자, 즉 촉매 바인더로 이루어져 있다. Among the various elements that make up a fuel cell, a membrane electrode assembly composed of a membrane and an electrode (MEA) is a core component. The electrode is composed of a catalyst (Pt / C or Pt) and a catalyst binding polymer, that is, a catalyst binder.
종래에는 통상적으로 나피온 타입(Nafion type) 퍼플루오르술폰화 고분자 (perfluorosulfonated polymer)가 MEA의 멤브레인으로 이용되었으며, 나피온 타입 퍼플루오르술폰화 고분자가 멤브레인으로 사용될 경우에, 촉매 바인더로서도 나피온 타입 고분자가 이용되었다. 상기 촉매 바인더로 사용되는 나피온 타입 고분자는 일반적으로 이소프로판올(isopropanol)에 용해된 용액 상태로 상업화되어 현재까지도 MEA 제조에 이용되고 있다.Conventionally, Nafion type perfluorosulfonated polymers have been used as membranes of MEA, and when Nafion type perfluorosulfonated polymers are used as membranes, Nafion type polymers are also used as catalyst binders. Was used. The Nafion type polymer used as the catalyst binder is generally commercialized in a solution state dissolved in isopropanol and is still used in the manufacture of MEA.
그러나, 기존의 나피온 타입 퍼플루오르술폰화 고분자는 고가일 뿐만 아니라, 메탄올 크로스 오버(methanol cross-over)의 문제점이 있고, 특히 페록사이드 라디칼(peroxide radical)에 의해 고분자가 깨지는 문제점이 있으며, 고온 저습 상태에서 쉽게 마르기 때문에 연료 전지가 고온 저습 상태에서 운전되는 경우에는 적합하지 않다.However, the conventional Nafion type perfluorosulfonated polymer is not only expensive, but also has a problem of methanol cross-over, in particular, a polymer is broken by a peroxide radical, and has a high temperature. It is not suitable when the fuel cell is operated at high temperature and low humidity because it dries easily in low humidity.
따라서, 기존의 나피온 타입 퍼플루오르술폰화 고분자를 대체할 수 있는 고분자의 개발이 요구되어 왔다.Therefore, the development of a polymer that can replace the existing Nafion type perfluorsulfonated polymer has been required.
이에 따라, 최근에는 탄화불소계열인 나피온 타입 고분자와 다른 구조를 지니는 저가의 탄화수소계열(hydrocarbon-based) 술폰화 고분자를 MEA의 멤브레인으로 이용하려는 시도가 많이 진행되었다. Accordingly, in recent years, many attempts have been made to use low-cost hydrocarbon-based sulfonated polymers having a structure different from that of fluorocarbon-based Nafion type polymers as membranes of MEA.
상기 탄화수소계열 술폰화 고분자로 제조되는 멤브레인은 실질적으로 프로톤 전도도가 높고 기계적 강도도 우수하다. The membrane made of the hydrocarbon-based sulfonated polymer has substantially high proton conductivity and excellent mechanical strength.
그런데, 탄화수소계열 술폰화 고분자를 멤브레인으로 이용하고자 하였던 기존의 연구에서는 MEA 제조시 촉매 바인더로 나피온 타입 고분자를 이용하였다. By the way, in the previous researches to use hydrocarbon-based sulfonated polymers as membranes, Nafion type polymers were used as catalyst binders in the preparation of MEA.
그러나, 이와 같이 촉매 바인더로 나피온 타입 고분자를 이용할 경우, 나피 온 용액이 고가라는 단점 이외에도 탄화수소와 탄화불소 간의 결합력이 매우 약하기 때문에 특히 장기적인 면에 있어서 전해질막과 전극이 분리되는 현상이 발생한다.However, in the case of using a Nafion type polymer as the catalyst binder as described above, in addition to the disadvantage that Nafion solution is expensive, the binding force between the hydrocarbon and the fluorine carbide is very weak, so that the electrolyte membrane and the electrode are separated in the long term.
요컨대, 탄화수소계열 술폰화 고분자 멤브레인을 이용하는 기존까지의 MEA 제조 방법은 전극 제조시 사용되는 촉매 바인더 고분자의 선정에 문제점이 있고, 이러한 문제점에 기인하여 기존의 탄화수소계열 술폰화 고분자 멤브레인을 이용하는 MEA는 아직까지 상업화되지 못하고 있는 실정이다. In short, the conventional MEA manufacturing method using a hydrocarbon-based sulfonated polymer membrane has a problem in selecting a catalyst binder polymer used in electrode production, and due to these problems, a MEA using a hydrocarbon-based sulfonated polymer membrane has not yet been developed. It has not been commercialized until now.
따라서, 본 발명은 상기와 같은 문제점을 해결하기 위하여 안출된 것으로, 본 발명의 목적은, 탄화수소계열 술폰화 고분자 멤브레인을 MEA에 이용할 경우 그 멤브레인과 전극의 접착력을 높일 수 있고, 이에 따라 성능이 우수하여, 탄화수소계열 술폰화 고분자 멤브레인을 구비하는 MEA의 상용화를 가능하게 할 수 있는, MEA의 촉매 바인더, 그 제조 방법 및 상기 촉매 바인더를 이용한 MEA를 제공하는 것이다.Accordingly, the present invention has been made to solve the above problems, an object of the present invention, when using a hydrocarbon-based sulfonated polymer membrane in the MEA can increase the adhesion between the membrane and the electrode, thereby excellent performance The present invention provides a catalyst binder of MEA, a method for producing the same, and a MEA using the catalyst binder capable of enabling commercialization of MEA having a hydrocarbon-based sulfonated polymer membrane.
상기와 같은 본 발명의 목적은, 탄화수소계열 술폰화 고분자를 이용하여 제작된 멤브레인을 구비하는 MEA의 촉매 바인더로서, 탄화수소계열 술폰화 고분자를 포함하는 것을 특징으로 하는 MEA의 촉매 바인더에 의하여 달성된다.The object of the present invention as described above is achieved by a catalyst binder of MEA comprising a hydrocarbon-based sulfonated polymer as a catalyst binder of the MEA having a membrane produced using a hydrocarbon-based sulfonated polymer.
그리고, 상기 촉매 바인더는, 탄화수소계열 술폰화 고분자가 이소프로판올(isopropanol), 1-프로판올(1-propanol), 물 및 유기용매에 용해된 탄화수소계열 술폰화 고분자 용액인 것이 바람직하다.The catalyst binder is preferably a hydrocarbon-based sulfonated polymer solution in which a hydrocarbon-based sulfonated polymer is dissolved in isopropanol, 1-propanol, water, and an organic solvent.
그리고, 상기 탄화수소계열 술폰화 고분자는 150 ~ 180℃의 온도 및 100 ~ 200 psi의 압력 조건에서 용해된 것이 바람직하다.In addition, the hydrocarbon-based sulfonated polymer is preferably dissolved at a temperature of 150 ~ 180 ℃ and pressure conditions of 100 ~ 200 psi.
상기와 같은 본 발명의 목적은, 탄화수소계열 술폰화 고분자를 이용하여 제작된 멤브레인을 구비하는 MEA의 촉매 바인더 제조 방법으로서, 탄화수소계열의 술폰화 고분자를 이소프로판올, 1-프로판올, 물 및 유기용매에 용해하는 단계를 포함하는 것을 특징으로 하는 MEA의 촉매 바인더 제조 방법에 의하여 달성된다.An object of the present invention as described above, MEA catalyst binder manufacturing method comprising a membrane prepared using a hydrocarbon-based sulfonated polymer, a hydrocarbon-based sulfonated polymer is dissolved in isopropanol, 1-propanol, water and organic solvents It is achieved by a method of producing a catalyst binder of the MEA comprising the step of.
그리고, 상기 용해는 150 ~ 180℃의 온도 및 100 ~ 200 psi의 압력 조건에서 수행되는 것이 바람직하다.And, the dissolution is preferably carried out at a temperature of 150 ~ 180 ℃ and pressure conditions of 100 ~ 200 psi.
상기와 같은 본 발명의 목적은, MEA에 있어서, 탄화수소계열 술폰화 고분자를 이용하여 제작된 멤브레인을 구비하고, 촉매 바인더가 탄화수소계열 술폰화 고분자를 포함하는 것을 특징으로 하는 MEA에 의하여 달성된다.The object of the present invention as described above is achieved by MEA, wherein in MEA, the membrane is prepared using a hydrocarbon-based sulfonated polymer, and the catalyst binder comprises a hydrocarbon-based sulfonated polymer.
그리고, 상기 탄화수소계열 술폰화 고분자는, 술폰화 폴리에테르술폰, s-폴리스티렌계, s-폴리카보네이트계, s-폴리이미드계 또는 s-폴리에테르에테르케톤계인 것이 바람직하다.The hydrocarbon sulfonated polymer is preferably sulfonated polyether sulfone, s-polystyrene, s-polycarbonate, s-polyimide or s-polyether ether ketone.
이하, 본 발명에 따른 탄화수소계열 술폰화 고분자를 이용한 MEA의 촉매 바인더, 그 제조 방법 및 상기 촉매 바인더를 이용한 MEA에 대하여 상술한다.Hereinafter, a catalyst binder of MEA using a hydrocarbon-based sulfonated polymer according to the present invention, a method for producing the same, and a MEA using the catalyst binder will be described in detail.
본 발명에서는 탄화수소계열 술폰화 고분자를 이용하여 제작된 멤브레인을 구비하는 MEA의 촉매 바인더를 제조함에 있어서, 기존의 나피온 타입 고분자의 사용을 배제하고 탄화수소계열 술폰화 고분자를 이용한다.In the present invention, in preparing a MEA catalyst binder having a membrane prepared using a hydrocarbon-based sulfonated polymer, a hydrocarbon-based sulfonated polymer is used without the use of a conventional Nafion type polymer.
이를 위해, 탄화수소계열의 술폰화 고분자를 이소프로판올(isopropanol), 1-프로판올(1-propanol), 물 및 미량의 유기용매(DMSO, DMAc, DMF 등)에 고온 가압 조건하에서 용해하여 전극 제조용 용액을 제조한다. To this end, a hydrocarbon sulfonated polymer is dissolved in isopropanol, 1-propanol, water and a small amount of an organic solvent (DMSO, DMAc, DMF, etc.) under high temperature pressurized conditions to prepare a solution for electrode production. do.
삭제delete
한편, 상기 탄화수소계열 술폰화 고분자 용액 제조에 이용되는 탄화수소계열 술폰화 고분자는, 나피온 타입의 탄화불소계열 고분자를 대체하여 연료전지용으로 사용될 수 있는 탄화수소계 고분자로서, 예를 들어, 술폰화 폴리에테르술폰(sulfonated polyethersulfone)을 사용할 수 있고, 그 외에도 s-폴리스티렌계(s-polystyrenes), s-폴리카보네이트계(s-polycarbonates), s-폴리이미드계(s-polyimides), s-폴리에테르에테르케톤계(s-polyetheretherketones)(s-PEEK) 등을 이용할 수 있다Meanwhile, the hydrocarbon-based sulfonated polymer used for preparing the hydrocarbon-based sulfonated polymer solution is a hydrocarbon-based polymer that can be used for a fuel cell by replacing Nafion-type fluorocarbon-based polymer, for example, sulfonated polyether Sulfonated polyethersulfone may be used, in addition to s-polystyrenes, s-polycarbonates, s-polyimides, s-polyetheretherketones S-polyetheretherketones (s-PEEK) and the like can be used.
또한, 아릴(aryl), 알킬(alkyl), 아릴에테르(aryl ether), 또는 알킬에테르(alkylether)기를 가지는 폴리에테르이미드(polyetherimide), 폴리술폰(polysulfone), 폴리페닐술폰(polyphenylsulfone), 폴리(헥사플루오르이소프로필리덴디앤하이드라이드/메타페닐렌디아민)[poly(hexafluoroisopropylidenedianhydride/meta phenylene diamine)], 폴리(트리페닐포스핀옥사이드설파이드-페닐술폰-설파이드)[poly(triphenylphosphine oxide sulfide-phenylsulfone-sulfide)], 폴리(2-페닐설파이드-1,4-페닐렌)[poly(2-phenylsulfide-1,4-phenylene)], 폴리(헥사플루오르이소프로필리덴디앤하이드라이드/디아미노페닐술폰)[poly(hexafluoroisopropyl idenedianhydride/diaminodiphenyl sulfone)], 폴리비닐술폰산[polyvinyl sufonic acid], 폴리(헥사플루오르이소프로필리덴디앤하이드라이드/디아미노페녹시벤젠[poly(hexafluoroisopropylidenedianhydride/diaminophenoxybenzene)], 폴리(4-페녹시벤조일-1,4-페닐렌)[poly(4-phenoxybenzoyl-1,4-phenylene)], 폴리(피롤멜리틱디이미드-1,3-페닐렌)[poly(pyrolmellitic diimide-1,3-phenylene)], 폴리(디프탈이미드-1,3-페닐렌)[poly(diphthalimide-1,3-phenylene)], 폴리(1,4-페닐렌옥사이드)[poly(1,4-phenylene oxide)], 폴리(2,6-디페닐-1,4-페닐렌옥사이드)[poly(2,6-diphenyl-1,4-phenylene oxide)], 폴리(벤조페논설파이드)[poly(benzophenone sulfide)], 폴리(벤조페논설파이드-페닐술폰-설파이드)[poly(benzophenone sulfide-phenylsulfone-sulfide)], 폴리(비닐카르복실산)[poly(vinyl carboxylic acid)], 폴리(트리플루오르스티렌술폰산)[poly(trifluorostyrene suflonic acid)], 폴리(비닐포스폰산)[poly(vinyl phosphonic acid)], 폴리(스티렌술폰산)[poly(styrene sulfonic acid)] 등의 탄화수소계 고분자들을 술폰화시켜서 사용할 수 있다.In addition, polyetherimide, polysulfone, polyphenylsulfone, polyphenylsulfone, poly (hexa) having an aryl, alkyl, aryl ether, or alkylether group Fluoroisopropylidenedihydride / metaphenylenediamine) [poly (hexafluoroisopropylidenedianhydride / meta phenylene diamine)], poly (triphenylphosphineoxide sulfide-phenylsulfone-sulfide) [poly (triphenylphosphine oxide sulfide-phenylsulfone-sulfide)] , Poly (2-phenylsulfide-1,4-phenylene) [poly (2-phenylsulfide-1,4-phenylene)], poly (hexafluoroisopropylidene dianhydride / diaminophenylsulfone) [poly (hexafluoroisopropyl idenedianhydride / diaminodiphenyl sulfone)], polyvinyl sufonic acid, poly (hexafluoroisopropylidenedianhydride / diaminophenoxybenzene), poly (4- Phenoxybenzoyl-1,4-phenylene) [poly (4-phenoxybenzoyl-1,4-phenylene)], poly (pyrolmeltic diimide-1,3-phenylene) [poly (pyrolmellitic diimide-1,3 -phenylene)], poly (diphthalimide-1,3-phenylene) [poly (diphthalimide-1,3-phenylene)], poly (1,4-phenylene oxide) [poly (1,4-phenylene oxide)], poly (2,6-diphenyl-1,4-phenylene oxide) [poly (2,6-diphenyl-1,4-phenylene oxide)], poly (benzophenonesulfide) [poly (benzophenone sulfide)], poly (benzophenone sulfide-phenylsulfone-sulfide), poly (vinyl carboxylic acid), poly (trifluorostyrenesulfonic acid) hydrocarbon-based polymers such as poly (trifluorostyrene suflonic acid), poly (vinyl phosphonic acid), and poly (styrene sulfonic acid) can be used by sulfonating. .
이 후, 상기 제조된 탄화수소계열 술폰화 고분자 용액과 촉매를 혼합하여 촉매 슬러리를 제조하여 전극을 제조한 후, 이 전극을 이용하여 MEA를 제조한다.Thereafter, the hydrocarbon-based sulfonated polymer solution prepared above is mixed with a catalyst to prepare a catalyst slurry, and then an electrode is manufactured using the electrode.
이하, 본 발명의 바람직한 실시예를 설명함으로써 본 발명을 더욱 상세하게 설명한다. 그러나 본 발명이 하기 실시예에 한정되는 것은 아니며 첨부된 특허청구범위내에서 다양한 형태의 실시예들이 구현될 수 있고, 단지 하기 실시예는 본 발명의 개시가 완전하도록 함과 동시에 당업계에서 통상의 지식을 가진 자에게 발명 의 실시를 용이하게 하고자 하는 것이다.Hereinafter, the present invention will be described in more detail by explaining preferred embodiments of the present invention. However, the present invention is not limited to the following examples, and various forms of embodiments can be implemented within the scope of the appended claims, and the following examples are only common in the art while making the disclosure of the present invention complete. It is intended to facilitate the implementation of the invention to those with knowledge.
<실시예><Example>
술폰화 폴리에테르술폰의 합성Synthesis of Sulfonated Polyethersulfone
4-플루오르페닐술폰(4-fluorophenyl sulfone)(5.11g), 비스페놀 A(bisphenol A)(2.3g), 하이드로퀴논 2-포타슘 술포네이트(hydroquinone 2-potassium sulfonate)(2.31g) 및 K2CO3(5.7g)을 톨루엔(toluene)(40mL)과 디메틸아세트아미드(dimethylacetamide)(25mL)의 혼합 용매에 분산시키고 질소 분위기 하에서 딘-스타크(Dean-Stark) 증류장치를 이용하여 4시간 동안 140℃에서 가열하였다.4-fluorophenyl sulfone (5.11 g), bisphenol A (2.3 g), hydroquinone 2-potassium sulfonate (2.31 g) and K 2 CO 3 (5.7 g) was dispersed in a mixed solvent of toluene (40 mL) and dimethylacetamide (25 mL), and the mixture was heated at 140 ° C. for 4 hours using a Dean-Stark distillation apparatus under a nitrogen atmosphere. Heated.
그 후, 톨루엔을 단순 증류 방법으로 제거하고, 나머지 반응 혼합물을 질소 분위기 하에서 20시간 동안 180℃의 온도에서 가열하였다.Thereafter, toluene was removed by a simple distillation method, and the remaining reaction mixture was heated at a temperature of 180 ° C. for 20 hours under a nitrogen atmosphere.
생성된 고분자 혼합물을 HCl(100mL) 및 메탄올(200mL)의 혼합 용매와 물로 여러 번 세척하고 진공오븐에서 60℃의 온도에서 24 시간 건조하여 하기 [화학식1]과 같은 반복단위를 가지는 술폰화 폴리에테르술폰을 얻었다.The resulting polymer mixture was washed several times with a mixed solvent of HCl (100 mL) and methanol (200 mL) and water, and dried in a vacuum oven at a temperature of 60 ° C. for 24 hours to sulfonated polyether having a repeating unit as shown in [Formula 1]. I got a sulfone.
(n : 반복단위수)(n: number of repeating units)
술폰화 폴리에테르술폰 멤브레인 제조Sulfonated Polyethersulfone Membrane Preparation
상기 술폰화 폴리에테르술폰(3g)을 디메틸설폭사이드(dimethylsulfoxide)(20mL)에 완전히 녹인 후 닥터 블래이드(Doctor blade)를 이용하여 유리판 위에 균일하게 도포하였다. The sulfonated polyether sulfone (3 g) was completely dissolved in dimethylsulfoxide (20 mL), and then uniformly coated on a glass plate using a doctor blade.
이것을 진공오븐에 위치시키고 60℃의 온도에서 48시간 건조하여 술폰화 폴리에테르술폰 멤브레인을 제조하였다.This was placed in a vacuum oven and dried for 48 hours at a temperature of 60 ℃ to prepare a sulfonated polyether sulfone membrane.
탄화수소계열 술폰화 고분자 용액의 제조Preparation of Hydrocarbon-Based Sulfonated Polymer Solution
탄화수소계열 술폰화 고분자 용액으로서 술폰화 폴리에테르술폰(Sulfonated Polyethersulfone) 용액을 제조하였다.A sulfonated polyethersulfone solution was prepared as a hydrocarbon-based sulfonated polymer solution.
이소프로판올(Isopropanol)(135mL), 1-프로판올(1-propanol)(135mL), 물(25mL) 및 DMSO(5mL)가 혼합되어 있는 용액에 0.03g의 상기 술폰화 폴리에테르술폰을 넣고, 150℃, 150psi에서 48시간 동안 교반시켜 술폰화 폴리에테르술폰 용액을 제조하였다. To a solution containing isopropanol (135 mL), 1-propanol (1-propanol) (135 mL), water (25 mL) and DMSO (5 mL) was added 0.03 g of the sulfonated polyethersulfone, 150 ° C, The sulfonated polyethersulfone solution was prepared by stirring at 150 psi for 48 hours.
촉매 슬러리 및 MEA 제조Catalyst Slurry and MEA Preparation
상기 제조된 술폰화 폴리에테르술폰 용액(0.3 g 폴리머/300 mL 용매)과 40 wt% Pt/C (E-TEK)(0.9 g)를 섞은 후, 초음파기에서 30분 동안 처리하여 균일한 슬러리를 얻었다.The prepared sulfonated polyethersulfone solution (0.3 g polymer / 300 mL solvent) and 40 wt% Pt / C (E-TEK) (0.9 g) were mixed and treated with an ultrasonicator for 30 minutes to obtain a uniform slurry. .
이와 같이 제조된 슬러리를 스프레이 코팅기(spray coater)를 이용하여 상기 제조된 술폰화 폴리에테르술폰 멤브레인위에 도포하였다. 이때, 촉매 로딩(loading) 양은 애노드(anode)와 캐소드(cathode) 모두 0.4 mg/cm2으로 하였고, 60℃의 온도에서 하루 동안 건조시켜 MEA를 제조하였다.The slurry thus prepared was applied onto the sulfonated polyethersulfone membrane prepared above using a spray coater. At this time, the amount of catalyst loading (anode) and cathode (cathode) was 0.4 mg / cm 2 , and dried for one day at a temperature of 60 ℃ to prepare a MEA.
이와 같이 제조된 MEA를 이용하여 단위 셀을 제조하고 아래 실험예와 같이 셀 성능을 측정하였다.The unit cell was prepared using the MEA thus prepared, and cell performance was measured as in the following experimental example.
<비교예>Comparative Example
일반적인 나피온 타입 퍼플루오르술폰화 고분자 용액(상용화되어 있는 5% Nafion solution 6g)과, 40wt% Pt/C (E-TEK)(0.9g)를 섞은 후, 초음파기에서 30분 동안 처리하여 균일한 슬러리를 얻었다. A mixture of a typical Nafion type perfluorosulfonated polymer solution (commercially available 5% Nafion solution 6g) and 40wt% Pt / C (E-TEK) (0.9g) was mixed in a sonicator for 30 minutes to give a uniform slurry. Got.
이와 같이 제조된 슬러리를 스프레이 코팅기(spray coater)를 이용하여 나피온 타입 퍼플루오르술폰화 고분자 위에 도포하였다. 이때, 촉매 로딩(loading) 양은 애노드(anode)와 캐소드(cathode) 모두 0.4 mg/cm2으로 하였고, 60℃의 온도에서 하루 동안 건조시켜 MEA를 제조하였다.The slurry thus prepared was applied onto a Nafion type perfluorosulfonated polymer using a spray coater. At this time, the amount of catalyst loading (anode) and cathode (cathode) was 0.4 mg / cm 2 , and dried for one day at a temperature of 60 ℃ to prepare a MEA.
이와 같이 제조된 MEA를 이용하여 단위 셀을 제조하고 아래 실험예와 같이 셀 성능을 측정하였다. The unit cell was prepared using the MEA thus prepared, and cell performance was measured as in the following experimental example.
<실험예>Experimental Example
표 1은 단위 셀 성능 테스트 조건을 나타낸 것이다.Table 1 shows the unit cell performance test conditions.
도 1은 80℃ 온도, 100% 상대 습도에서 측정한 각 촉매 바인더 고분자의 특성을 나타내는 그래프이다.1 is a graph showing the characteristics of each catalytic binder polymer measured at 80 ° C. temperature and 100% relative humidity.
도 1에 도시된 바와 같이, 탄화수소계열 술폰화 고분자를 이용하여 멤브레인을 제작한 경우, 그 촉매 바인더로서 탄화수소계열 술폰화 고분자를 이용하는 실시예가 비교예의 나피온 고분자를 이용하는 경우와 대비하여 성능이 보다 우수함을 알 수 있다. 이와 같이 촉매 바인더로서 탄화수소계열 술폰화 고분자를 이용하는 경우에는 전해질막과 전극의 접착력이 증대된다. As shown in FIG. 1, when the membrane is manufactured using a hydrocarbon-based sulfonated polymer, an embodiment using the hydrocarbon-based sulfonated polymer as the catalyst binder is superior to the case of using the Nafion polymer of the comparative example. It can be seen. Thus, when using a hydrocarbon type sulfonated polymer as a catalyst binder, the adhesive force of an electrolyte membrane and an electrode increases.
본 발명에 따르면 탄화수소계열 술폰화 고분자 멤브레인을 구비하는 MEA에 있어서, 멤브레인과 전극의 접착력을 높일 수 있고, 성능이 더 우수하게 되며, 이에 따라 탄화수소계열 술폰화 고분자 멤브레인을 구비하는 MEA의 상용화를 가능하게 할 수 있다.According to the present invention, in the MEA having a hydrocarbon-based sulfonated polymer membrane, the adhesion between the membrane and the electrode can be improved, and the performance is more excellent. Accordingly, the MEA having the hydrocarbon-based sulfonated polymer membrane can be commercialized. It can be done.
비록 본 발명이 상기 언급된 바람직한 실시예와 관련하여 설명되어졌지만, 발명의 요지와 범위로부터 벗어남이 없이 다양한 수정이나 변형을 하는 것이 가능하다. 따라서 첨부된 특허청구의 범위는 본 발명의 요지에서 속하는 이러한 수정이나 변형을 포함할 것이다. Although the present invention has been described in connection with the above-mentioned preferred embodiments, it is possible to make various modifications or variations without departing from the spirit and scope of the invention. Accordingly, the appended claims will cover such modifications and variations as fall within the spirit of the invention.
Claims (8)
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| US5677074A (en) | 1996-06-25 | 1997-10-14 | The Dais Corporation | Gas diffusion electrode |
| JPH1045913A (en) | 1996-04-18 | 1998-02-17 | Sumitomo Chem Co Ltd | High-molecular electrolyte, its production and fuel cell made by using the same |
| JP2004047244A (en) | 2002-07-11 | 2004-02-12 | Mitsui Chemicals Inc | Ion conductive binding agent for fuel cell, composition and varnish for forming electrode, and fuel cell |
| WO2004090015A1 (en) | 2003-04-07 | 2004-10-21 | Mitsui Chemicals, Inc. | Crosslinkable ionically conducting resin, and ionically conducting polymer membranes, binders and fuel cells, made by using the resin |
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| JPH1045913A (en) | 1996-04-18 | 1998-02-17 | Sumitomo Chem Co Ltd | High-molecular electrolyte, its production and fuel cell made by using the same |
| US5677074A (en) | 1996-06-25 | 1997-10-14 | The Dais Corporation | Gas diffusion electrode |
| JP2004047244A (en) | 2002-07-11 | 2004-02-12 | Mitsui Chemicals Inc | Ion conductive binding agent for fuel cell, composition and varnish for forming electrode, and fuel cell |
| WO2004090015A1 (en) | 2003-04-07 | 2004-10-21 | Mitsui Chemicals, Inc. | Crosslinkable ionically conducting resin, and ionically conducting polymer membranes, binders and fuel cells, made by using the resin |
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