WO2018062877A1 - Fuel cell electrolyte film comprising porous carbonaceous film layer - Google Patents

Fuel cell electrolyte film comprising porous carbonaceous film layer Download PDF

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Publication number
WO2018062877A1
WO2018062877A1 PCT/KR2017/010768 KR2017010768W WO2018062877A1 WO 2018062877 A1 WO2018062877 A1 WO 2018062877A1 KR 2017010768 W KR2017010768 W KR 2017010768W WO 2018062877 A1 WO2018062877 A1 WO 2018062877A1
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WIPO (PCT)
Prior art keywords
electrolyte membrane
fuel cell
layer
film layer
porous carbonaceous
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PCT/KR2017/010768
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French (fr)
Korean (ko)
Inventor
박기호
김부곤
류정욱
Original Assignee
가드넥 주식회사
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Publication of WO2018062877A1 publication Critical patent/WO2018062877A1/en

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Classifications

    • 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
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1055—Inorganic layers on the polymer electrolytes, e.g. inorganic coatings
    • 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
    • H01M8/1016—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
    • H01M8/1039—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
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • 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
    • 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 fuel cell electrolyte membrane comprising a porous carbonaceous film layer.
  • It includes a membrane-electrode assembly and a fuel cell comprising the same.
  • Fuel cell is a cell that converts chemical energy into direct electric energy due to oxidation of fuel, and overcomes problems such as depletion of fossil fuel, greenhouse effect due to carbon dioxide generation and global warming. A lot of research is being done with solar cells.
  • [4] fuel cells generally utilize oxidation and reduction reactions of hydrogen and oxygen
  • the electrolyte membrane is located between the cathode and the anode to serve as a carrier of hydrogen ions and to prevent contact between oxygen gas and hydrogen gas. Therefore, the electrolyte membrane of a fuel cell must have high hydrogen ion conductivity and mechanical properties. And high chemical stability.
  • electrolyte separation membrane coated with a sulfone polymer membrane or a hydrocarbon-based polymer membrane with a fluorine ionomer was used as the electrolyte separation membrane.
  • the present invention has a uniform pore distribution and high porosity and high heat transfer efficiency.
  • the present invention provides a fuel cell electrolyte membrane, a membrane-electrode assembly including the same, and a fuel cell including the same, which exhibit excellent power generation efficiency.
  • the present invention has a uniform pore distribution and high porosity, but also high heat transfer efficiency.
  • Electrolyte membranes for fuel cells exhibiting excellent power generation efficiency which includes A membrane-electrode assembly and a fuel cell comprising the same are provided. Effects of the Invention
  • the electrolyte membrane according to the present invention has a high porosity and a uniform pore distribution, so that the heat transfer efficiency is excellent, thereby maintaining the water content of the electrolyte separator for fuel cells at a suitable level, and the membrane-electrode assembly and the fuel cell including the same have excellent excellent power generation. Indicates efficiency.
  • the electrolyte membrane according to the present invention has excellent mechanical and chemical stability due to the porous carbonaceous film layer.
  • Example 1 shows a current-voltage curve by measuring current-voltage values of a unit cell according to Example 5-2, Comparative Example 1-2, and Comparative Example 2-2 according to Test Example 1 below. .
  • FIG. 2 illustrates a current-voltage curve by measuring current-voltage values of unit cells according to Examples 3-2 to 7-2 according to Test Example 1 below.
  • FIG. 5 shows measurement results of chemical durability according to Example 5-2, Comparative Example 1-2, and Comparative Example 2-2, according to Test Example 3 below.
  • the fuel cell electrolyte membrane according to the present invention includes a porous carbonaceous film layer.
  • the average diameter of the pores of the carbonaceous film layer is 0.1 to 100 zm.
  • Area ratio is 10% to 90%, preferably 50% to 90%, more
  • the average pore area ratio of the porous carbonaceous film layer is less than 10%, the ionomer content impregnated between the carbonaceous film layers is excessively reduced, so that proton ions move during fuel cell operation. Due to the difficulty of water channel formation, the performance characteristics of the fuel cell are drastically reduced, and when exceeding 90%, the ionomer impregnated between carbonaceous materials is excessively increased, so that the expansion coefficient of the electrolyte membrane during fuel cell performance is excessively increased. As the carbonaceous film is destroyed, the bonding force between the carbonaceous film layer and the ionomer is weakened, which reduces the performance characteristics of the fuel cell.
  • the average pore area ratio means a percentage of the ratio of the average pore area per unit area of the porous carbonaceous film layer.
  • the porosity of the porous carbonaceous film layer is 20% to 90%.
  • the unit area of the porous carbonaceous film layer is 100. mm 2
  • the current maneuver is between 63000 and 64000.
  • the thickness of the porous carbonaceous film layer is 1 / -200.
  • the porous carbonaceous film layer is made of polyimide
  • the film is carbonized by heat treatment.
  • the porous carbonaceous film layer is porous
  • the carbon content of the porous graphite layer is 20 weights ⁇ 3 ⁇ 4 or more, based on the total increase of the porous graphite layer.
  • the heat treatment is a method comprising a carbonization step and a graphite step.
  • the carbonizing step includes carbonizing the polymer film and converting the polymer film into a carbonaceous film by introducing a polyimide film into a first heater having a first temperature section.
  • the first temperature range is 500 ⁇ 50 ° C.
  • the graphite step includes converting the carbonaceous film into a graphite film into a second heater having a second temperature section, which is a section where the temperature rises linearly.
  • the second heater has a length of 4000 mm to 6000 mm.
  • the second temperature interval range sequentially raised to 1000 ° C to 2800 o C.
  • the second temperature section is a temperature range of 1000 ° C. to 1500 ° C., 2-1 temperature range, 1500 ° C. to 2200 ° C., 2-2 temperature range, and 2200 ° C. C to
  • the graphite step is the second to 1-1.
  • the porous carbonaceous film layer forms pores by pressing a pin or irradiating a laser.
  • the pin has an average diameter of 1 ⁇ to 100
  • the pins are one or more, and the spacing of the pins is, on average, 10 ⁇ or more.
  • the pins are one or more, and the pins are To form a pattern that is a rectangle, a circle, an ellipse, a diamond, or a combination of these.
  • the pressing direction of the pin is a vertical direction of one surface of the porous carbonaceous film layer or a vertical direction of the rear surface thereof.
  • the pressing method of the pin is to pressurize vertically or by rotating the pin.
  • the porous carbonaceous film layer is heat treated after forming pores in the polyimide film.
  • the porous carbonaceous film layer is formed by forming a late hole heat-treated in the polyimide film.
  • the polyimide film is a known polyimide film.
  • the polyimide film is obtained by heating a polyamic acid solution.
  • the polyimide film is obtained by casting a polyamic acid solution into a film form and thermally decyclizing desolvent, or mixing a cyclization catalyst and a dehydrating agent in a polyamic acid solution and chemically recapturing it. To produce a gel film, which is obtained by heating and desolvation.
  • the polyamic acid solution is obtained by polymerizing an aromatic diamine component, an aromatic acid dianhydride component, or a chemical having a dimer as a main component in an organic solvent.
  • the aromatic diamine component in one embodiment of the present invention, the aromatic diamine component,
  • Paraphenylenediamine and may further include 4, 4'-diaminodiphenyl ether.
  • the aromatic anhydride component is pyromellitic dianhydride and / or 3, 3 ', 4, 4'-biphenyltetracarboxylic dianhydride.
  • the polyamic acid solution further comprises an additional diamine component.
  • the additional diamine component is 3,
  • Phenylphosphine oxide bis- (4-aminophenyl) - ⁇ -phenylamine
  • 5-dimethylheptamethylenediamine 5—methylnonamethylenediamine, 1, 4-diaminocyclonucleic acid, 1, 12-diaminooctadecane, 2, 5-diamino-1, 3, 4-oxadiazole, 2 ,
  • the polyamic acid solution is an additional acid dihydrate.
  • the additional acid dihydrate is 2, 3 ', 3,
  • 4-dicarboxyphenyl) ethane dianhydride 1, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxy Phenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfon dianhydride, benzene-1,2,3,
  • 4-tetracarboxylic dianhydride 3, 4, 3 ', 4'-benzophenone tetracarboxylic dianhydride, or a combination thereof.
  • the polyamic acid solution is an organic solvent.
  • the organic solvent is dimethyl sulfoxide
  • Sulfoxide solvents such as diethyl sulfoxide, ⁇ , ⁇ -dimethylformamide, N,
  • Formamide solvents such as ⁇ -diethylformamide, ⁇ , ⁇ -dimethylacetamide, ⁇ , Acetamide solvents such as N-diethylacetamide, N-methyl- 2-pyridone,
  • Pyrrolidone solvents such as ⁇ -vinyl-2-pyrrolidone, phenol, 0-, m-, or phenol solvents such as P-cresol, xylenol, halogenated phenol and catechol are also nucleated methylphosphor.
  • Aprotic polar solvents such as amides, ⁇ -butylolactones, or mixtures thereof
  • the organic solvent further comprises an aromatic hydrocarbon of xylene and toluene.
  • the carbonaceous film layer is formed on both sides of the porous carbonaceous film layer.
  • the fluorine ionomer layer is provided.
  • the fluorine-based ionomer layer is
  • Polytetrafluoroethylene (polytetrafluoroethylene: PTFE),
  • PVdF Polyvinylidene fluoride
  • PVdF-HFP polyvinylidene fluoride-nucleofluoropropylene copolymer
  • SBR styrene-butadiene rubber
  • a fuel cell membrane-electrode assembly includes the fuel cell electrolyte separator; And an anode electrode and a cathode electrode disposed to face each other with the electrolyte separator interposed therebetween.
  • the electrolyte separation membrane is a carbon cloth (carbon
  • the anode electrode and the cathode electrode according to the present invention each comprise an electrolyte membrane and a catalyst layer.
  • the catalyst layer of the anode electrode is platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy and
  • It includes one or more catalysts selected from the group consisting of platinum-transition metal alloys.
  • the catalyst layer of the cathode electrode is platinum
  • the anode electrode or the catalyst of the cathode electrode is supported on a carbon-based carrier.
  • a fuel cell according to the present invention includes the membrane-electrode assembly and the membrane-electrode assembly.
  • a stack including a separator interposed therebetween; a fuel supply unit supplying fuel to the stack; and an oxidant supply unit supplying an oxidant to the stack.
  • the separator according to the present invention prevents the membrane-electrode assembly from being electrically connected to each other, and delivers fuel and oxidant supplied from the outside to the membrane-electrode assembly and connects the anode and the cathode in series. Plays a role.
  • a fuel supply unit serves to supply fuel to the stack, and stores fuel in the fuel tank and the fuel stored in the fuel tank.
  • the pump may be supplied.
  • the fuel is hydrogen or hydrocarbon fuel in gas or liquid state.
  • the hydrocarbon fuel is methanol, ethanol, propanol, butanol or natural gas.
  • An oxidant supply unit serves to supply an oxidant to the stack.
  • the oxidizing agent is oxygen or air.
  • the oxidant is injected into a pump.
  • the fuel cell is a polymer electrolyte fuel cell or a direct methanol fuel cell.
  • the polymer film was prepared by winding a polyimide film having a thickness of 50, manufactured by TAIMADE, with a thickness of 50, in a roll-shaped jig, and then introducing the polyimide film into a first heater having a first temperature section. It was then converted into carbonaceous carbonized film. in the first temperature range, and maintained at 500 ° C 1000 o after the temperature was raised up to ° C per minute, 10 C, for about 2 hours to a temperature of 1000 ° C.
  • the carbonaceous film converted from the first heater has a length of 5000 imn
  • the carbonaceous film is moved to 1.00 mm / sec in the transverse direction
  • the second heater which is argon gas, has a pressure atmosphere of 5 kgf / cm 2 .
  • the graphite film was prepared by incorporating it into graphite film.
  • the second temperature section In the second temperature section, the second temperature section of 1000 ° C to 1500 ° C and
  • the thickness of the manufactured graphite layer is 25 /, the average pore diameter is 10, average pore The area ratio was 50% and the porosity was 58%.
  • An electrolyte separation membrane was prepared by coating a fluorine-based ionomer layer on both sides of the prepared graphite layer by using the Nafion (spray name: Nafion) all spray coating method of perfluorosulfonic acid polymer.
  • the polymer electrolyte except for the electrode portion of 210, is formed by stacking carbon paper as a gas diffusion layer on both sides of the electrolyte separation membrane prepared according to Example 1-1 to maintain gas tightness based on the membrane-electrode assembly.
  • Unit cell by closely adhering to the part and adhering the cathode plate having the flow path for applying hydrogen and uniform pressure to the membrane-electrode assembly, and the anode plate for uniform pressure to the air injection and the membrane-electrode assembly. was prepared.
  • the thickness of the graphite layer obtained is 25, the average pore diameter is 10 / m, and the average pore size.
  • the area ratio was 50% and the porosity was 70%.
  • Nafion (trade name: Nafion) manufactured by DuPont, a perfluorosulfonic acid polymer, was coated by spray coating to prepare a fluorine-based ionomer layer.
  • GD-025, manufactured by GuardNeck is a RFP-3P20 laser irradiation device manufactured by UHT for a 25-inch graphite film with a frequency of 60 kHz, output power of 1.2 W, and 15 shots / hole. And a graphite layer obtained in the same manner as in Production Example 1 except that the jig was wound with a polyimide film subjected to a pretreatment step of irradiating a laser under a condition of an irradiation time of 7.3 seconds.
  • the manufactured graphite layer had a thickness of 25, an average pore diameter of 10, and an average pore size.
  • the area ratio was 50% and the porosity was 58%.
  • Nafion (trade name: Nafion), which is a perfluorosulfonic acid polymer, was coated using a spray coating method to prepare an electrolyte separator using a fluorine-based ionomer layer.
  • Example 3-2 Fabrication of Unit Battery A unit cell was manufactured in the same manner as in Example 1-2, except that the electrolyte membrane prepared according to Example 3-1 was used as the electrolyte membrane. [100] ⁇ Example 4-1> Produce
  • the product name GD-025 manufactured by GuardNeck is a RFP-3P20 laser product manufactured by UHT for a graphite film having a thickness of 25, and a frequency of 60 kHz, a processing stage output of 1.2 W
  • a graphite layer obtained in the same manner as in Production Example 1 was prepared except that the jig was wound with a polyimide film subjected to a pretreatment step of irradiating the laser under the condition of 15 shots / hole of irradiation times and 7.3 seconds of irradiation time.
  • the thickness of the manufactured graphite layer is 25 /, the average pore diameter is 10 m, the average pore
  • the area ratio was 5% and the porosity was 6%.
  • Nafion (trade name: Nafion), manufactured by DuPont, a perfluorosulfonic acid polymer, was coated on both surfaces of the prepared graphite layer using a spray coating method to prepare an electrolyte separation membrane by preparing a fluorine-based ionomer layer.
  • Production Example 1 a product name GD-025 manufactured by Guardnex Inc. was manufactured by UHT for a graphite film having a thickness of 25 zm.
  • a graphite layer obtained in the same manner as in Production Example 1 was produced except that the jig was wound with a polyimide film subjected to a pretreatment step of irradiating the laser under conditions of 15 shots / hole of irradiation times and 7.3 seconds of irradiation time.
  • the prepared graphite layer had a thickness of 25 ⁇ m and an average pore diameter of 10 /.
  • the area ratio was 70% and the porosity was 81%.
  • Nafion (trade name: Nafion), manufactured by DuPont, a perfluorosulfonic acid polymer, was coated on both surfaces of the prepared graphite layer using a spray coating method to prepare an electrolyte separation membrane using a fluorine-based ionomer layer.
  • the thickness of the manufactured graphite layer is 25, average pore diameter is 10 / m, average pore size
  • the area ratio was 85% and the porosity was 89%.
  • Nafion (trade name: Nafion) manufactured by DuPont, a perfluorosulfonic acid polymer, was coated on both sides of the prepared graphite layer using a spray coating method to prepare an electrolyte separator using a fluorine-based ionomer layer.
  • an electrolyte membrane As an electrolyte membrane, an electrolyte membrane prepared according to Example 6-1 was used.
  • the product name GD-025 manufactured by GuardNeck for a graphite film having a thickness of 25 was manufactured by UHT under the trade name RFP-3P20, which is a product of RFP-3P20.
  • a graphite layer obtained in the same manner as in Production Example 1 was prepared except that the jig was wound with a polyimide film subjected to a pretreatment step of irradiating the laser under the condition of 15 shots / hole of irradiation times and 7.3 seconds of irradiation time.
  • the thickness of the manufactured graphite layer has an average pore diameter of 10 / m and an average pore size.
  • the area ratio was 92% and the porosity was 96%.
  • Nafion (trade name: Nafion), a perfluorosulfonic acid polymer, was coated on both sides of the prepared graphite layer using a spray coating method to prepare an electrolyte separator using a fluorine-based ionomer layer.
  • the electrolyte membrane was prepared by using the electrolyte membrane prepared according to Example 7-1.
  • the thickness of the electrolyte separator was 25.
  • a unit cell was manufactured in the same manner as in Example 1-2, except that the electrolyte membrane of Comparative Example 1-1 was used as the electrolyte membrane.
  • ⁇ PES containing sulfone was dissolved in a polar solvent (DMAc, NMP) solvent to prepare a membrane using the casting method, and used as a fuel cell electrolyte membrane.
  • the thickness of the electrolyte separator was 25.
  • a unit cell was manufactured in the same manner as in Example 1-2, except that the electrolyte membrane of Comparative Example 2-1 was used as the electrolyte membrane.
  • Test Example 1 Performance Measurement of Unit Battery
  • the performance of the unit cell was measured under the following conditions.
  • Example 5-2 the unit cell according to Example 5-2, Comparative Example 1-2, and Comparative Example 2-2 was subjected to constant voltage.
  • Example 5-2 using the electrolyte membrane according to the present invention exhibited better generation performance than Comparative Example 1-2 and Comparative Example 2-2 using the electrolyte membrane.
  • the current-voltage curve is shown in FIG. 2 by measuring the current-voltage value of the unit cell according to Examples 3-2 to 7-2.
  • Example 5-2 having the average pore area ratio of the porous graphite layer of the electrolyte membrane has the highest generation performance, and then the average pore area ratio is 50% and 83%.
  • the power generation performance of 3-2 and Example 6-2 was next superior, and the power generation performance of Example 7-2 and Example 4-2 with an average pore area of 92% and 5% reached a certain level of power generation performance. You can see that it can't.
  • the membrane resistance of the unit cell according to Example 5-2, Comparative Example 1-2 and Comparative Example 2-2 was measured by using electrochemical impedance spectroscopy (EIS). 3 and 4.
  • Example 5-2 using the electrolyte membrane according to the present invention exhibits a lower resistance than Comparative Examples 1-2 and Comparative Example 2-2 using the hydrocarbon-based electrolyte membrane, the development of the electrolyte membrane and the fuel cell using the same according to the present invention. The efficiency was better.
  • Example 5-2 using an electrolyte membrane according to the present invention has a lower current density than Comparative Examples 1-2 and Comparative Examples 2-2 using a perfluorosulfonic acid electrolyte membrane or a hydrocarbon-based electrolyte membrane. It was confirmed that the electrolyte membrane according to the invention and the fuel cell using the same were superior.

Abstract

The present invention relates to a fuel cell electrolyte film comprising a porous carbonaceous film layer, a film-electrode assembly comprising same, and a fuel cell comprising the film-electrode assembly, the porous carbonaceous film layer having pores with average diameter of 0.1-100 µm, and being provided with fluorine ionomer layers on both sides.

Description

명세서  Specification
발명의명칭:다공탄소질필름층을포함하는연료전지용전해질막 기술분야 NAME OF THE INVENTION: TECHNICAL FIELD
[1] 본발명은다공탄소질필름층을포함하는연료전지용전해질막，이를  [1] The present invention relates to a fuel cell electrolyte membrane comprising a porous carbonaceous film layer.
포함하는막 -전극접합체및이를포함하는연료전지에관한것이다.  It includes a membrane-electrode assembly and a fuel cell comprising the same.
[2] 본출원은 2016년 9월 27일에한국특허청에제출된한국특허출원제  [2] The present application was filed with the Korean Patent Office on September 27, 2016.
10-2016-0124180호의출원일의이익을주장하며,그내용전부는본명세서에 포함된다.  Claims are made on the date of filing of 10-2016-0124180, the entire contents of which are included in this specification.
배경기술  Background
[3] 연료전지 (Fuel Cell)란연료의산화로인해생기는화학에너지를직접전기 에너지로변환하는전지로서，최근화석연료의고갈문제,이산화탄소발생에 의한온실효과와지구온난화등의문제점을극복하고자태양전지등과함께 많은연구가이루어지고있다.  [3] Fuel cell is a cell that converts chemical energy into direct electric energy due to oxidation of fuel, and overcomes problems such as depletion of fossil fuel, greenhouse effect due to carbon dioxide generation and global warming. A lot of research is being done with solar cells.
[4] 연료전지는일반적으로수소와산소의산화，환원반웅을이용하여  [4] fuel cells generally utilize oxidation and reduction reactions of hydrogen and oxygen
화학에너지를전기에너지로변환한다.애노드 (anode)에서수소가산화되어 수소이온과전자로분리되고，수소이온은전해질 (electrolyte)을통해캐소드 (cathode)로이동한다.이때,전자는회로를통해양극으로이동한다.양극에서 수소이온,전자및산소가반응하여물을생성하는환원반응이일어난다.  It converts chemical energy into electrical energy, and hydrogen is oxidized at the anode to separate hydrogen ions and electrons, and the hydrogen ions move through the electrolyte to the cathode, where the electrons pass through the circuit. The cathode reacts with hydrogen ions, electrons, and oxygen to produce a water-reducing reaction.
[5] 전해질막은캐소드와애노드사이에위치하여수소이온의전달체역할을함과 동시에산소기체와수소기체의접촉을방지하는역할을한다.따라서， 연료전지의전해질막은수소이온전도성이높아야하며,기계적및화학적 안정성이높아야한다.  [5] The electrolyte membrane is located between the cathode and the anode to serve as a carrier of hydrogen ions and to prevent contact between oxygen gas and hydrogen gas. Therefore, the electrolyte membrane of a fuel cell must have high hydrogen ion conductivity and mechanical properties. And high chemical stability.
[6] 종래에는전해질분리막으로술폰계고분자막，또는탄화수소계고분자막에 불소계이오노머를코팅한전해질분리막이사용되고있었다.  [6] In the past, an electrolyte separation membrane coated with a sulfone polymer membrane or a hydrocarbon-based polymer membrane with a fluorine ionomer was used as the electrolyte separation membrane.
[7] 그러나,이러한종래의전해질분리막은열전도성이우수하지못하여,발전 효율이저하되는문제점이있었으며，술폰계고분자막또는탄화수소계 고분자막의기계적안정성및화학적안정성아만족할만할수준에도달하지 못한문제점이있었다.  [7] However, these conventional electrolyte separation membranes have problems of poor thermal conductivity, resulting in poor power generation efficiency, and problems of mechanical stability and chemical stability of sulfone polymer membranes or hydrocarbon polymer membranes are not satisfactory. there was.
발명의상세한설명  Detailed description of the invention
기술적과제  Technical task
[8] 본발명은균일한기공분포및높은기공율 ·가지면서도,열전달효율이  [8] The present invention has a uniform pore distribution and high porosity and high heat transfer efficiency.
뛰어나우수한발전효율을나타내는연료전지용전해질막，이를포함하는 막 -전극접합체및이를포함하는연료전지를제공하고자한다.  The present invention provides a fuel cell electrolyte membrane, a membrane-electrode assembly including the same, and a fuel cell including the same, which exhibit excellent power generation efficiency.
과제해결수단  Task solution
[9] 본발명은균일한기공분포및높은기공율을가지면서도,열전달효율이  [9] The present invention has a uniform pore distribution and high porosity, but also high heat transfer efficiency.
뛰어나우수한발전효율을나타내는연료전지용전해질막;이를포함하는 막 -전극접합체및이를포함하는연료전지를제공하고자한다. 발명의효과 Electrolyte membranes for fuel cells exhibiting excellent power generation efficiency ; Which includes A membrane-electrode assembly and a fuel cell comprising the same are provided. Effects of the Invention
[10] 본발명에따른전해질막은높은기공율및균일한기공분포를가짐으로써 열전달효율이우수하여연료전지용전해질분리막의함수율을적정한 수준으로유지시키며,이를포함하는막 -전극접합체및연료전지는우수한 우수한발전효율을나타낸다.  [10] The electrolyte membrane according to the present invention has a high porosity and a uniform pore distribution, so that the heat transfer efficiency is excellent, thereby maintaining the water content of the electrolyte separator for fuel cells at a suitable level, and the membrane-electrode assembly and the fuel cell including the same have excellent excellent power generation. Indicates efficiency.
[11] 또한，본발명에따른전해질막은다공탄소질필름층으로인하여우수한 기계적안정성및화학적안정성을갖는다.  In addition, the electrolyte membrane according to the present invention has excellent mechanical and chemical stability due to the porous carbonaceous film layer.
도면의간단한설명  Brief description of the drawings
[12] 도 1은하기시험예 1에따라하기실시예 5-2，비교예 1-2및비교예 2-2에따른 단위전지의전류 -전압값을측정하여전류-전압곡선을도시한것이다.  1 shows a current-voltage curve by measuring current-voltage values of a unit cell according to Example 5-2, Comparative Example 1-2, and Comparative Example 2-2 according to Test Example 1 below. .
[13] 도 2는하기시험예 1에따라하기실시예 3-2내지 7-2에따른단위전지의 전류 -전압값을측정하여전류 -전압곡선을도시한것이다. FIG. 2 illustrates a current-voltage curve by measuring current-voltage values of unit cells according to Examples 3-2 to 7-2 according to Test Example 1 below.
[14] 도 3및도 4는하기시험예 2에따라，하기실시예 5-2，비교예 1-2및비교예3 and 4 are in accordance with the following Test Example 2, Example 5-2, Comparative Examples 1-2 and Comparative Examples
2-2에따른단위전지의막저항을측정한결과를도시한것이다. The result of measuring the film resistance of the unit cell according to 2-2 is shown.
[15] 도 5는하기시험예 3에따라,하기실시예 5-2,비교예 1-2및비교예 2-2에따른 화학적내구성의측정결과를도시한것이다. FIG. 5 shows measurement results of chemical durability according to Example 5-2, Comparative Example 1-2, and Comparative Example 2-2, according to Test Example 3 below.
발명의실시를위한형태  Mode for Carrying Out the Invention
[16] 이하,본발명에따른연료전지용전해질막을설명한다. Hereinafter, a fuel cell electrolyte membrane according to the present invention will be described.
[17] 본발명에따른연료전지용전해질막은다공탄소질필름층을포함한다. The fuel cell electrolyte membrane according to the present invention includes a porous carbonaceous film layer.
[18] 본발명에따른다공탄소질필름층의기공의평균직경은 0.1 내지 100 zm이다. According to the present invention, the average diameter of the pores of the carbonaceous film layer is 0.1 to 100 zm.
[19] 본발명의일실시상태에있어서,상기다공탄소질필름층의평균기공  [19] An average pore of the porous carbonaceous film layer in one embodiment of the present invention
면적율은 10%내지 90%이고，바람직하게는 50%내지 90%이며，더  Area ratio is 10% to 90%, preferably 50% to 90%, more
바람직하게는 70%내지 90%이다.상기다공탄소질필름층의평균기공 면적율이 10%미만이면，탄소질필름층사이로함침된이오노머함량이 과도하게감소하므로，연료전지운전시프로톤이온이이동하는 water channel 형성이어려워져연료전지의성능특성이급격히감소하며， 90%초과되면, 탄소질사이에힘침된이오노머함량이과도하게증가되므로,연료전지성능 운전중전해질막의부피팽창계수가과도하게증가되어，탄소질필름이 파괴되면서탄소질필름층과이오노머간의결합력이약해져연료전지의성능 특성이감소한다.  Preferably it is 70% to 90%. If the average pore area ratio of the porous carbonaceous film layer is less than 10%, the ionomer content impregnated between the carbonaceous film layers is excessively reduced, so that proton ions move during fuel cell operation. Due to the difficulty of water channel formation, the performance characteristics of the fuel cell are drastically reduced, and when exceeding 90%, the ionomer impregnated between carbonaceous materials is excessively increased, so that the expansion coefficient of the electrolyte membrane during fuel cell performance is excessively increased. As the carbonaceous film is destroyed, the bonding force between the carbonaceous film layer and the ionomer is weakened, which reduces the performance characteristics of the fuel cell.
[20] 본명세서에있어서，평균기공면적율은다공탄소질필름층의단위면적당 평균기공의면적의비율의백분율을의미한다.  [20] In the present specification, the average pore area ratio means a percentage of the ratio of the average pore area per unit area of the porous carbonaceous film layer.
[21] 본발명의일실시상태에있어서,상기다공탄소질필름층의기공율은 20% 내지 90%이다. In one embodiment of the present invention, the porosity of the porous carbonaceous film layer is 20% to 90%.
[22] 본발명의일실시상태에있어서，상기다공탄소질필름층의단위면적 100 mm2당기공수는 63000개내지 64000개이다. [22] In the exemplary embodiment of the present invention, the unit area of the porous carbonaceous film layer is 100. mm 2 The current maneuver is between 63000 and 64000.
[23] 본발명의일실시상태에있어서,상기다공탄소질필름층의두께는 1 / 내지 200 이다. [23] In one embodiment of the present invention, the thickness of the porous carbonaceous film layer is 1 / -200.
[24] 본발명의일실시상태에있어서，상기다공탄소질필름층은폴리이미드  [24] In one embodiment of the present invention, the porous carbonaceous film layer is made of polyimide
필름을열처리하여탄화한것이다.  The film is carbonized by heat treatment.
[25] 본발명의일실시상태에있어서，상기다공탄소질필름층은다공 [25] In one embodiment of the present invention, the porous carbonaceous film layer is porous
그래파이트층이다.  It is a graphite layer.
[26] 본발명의일실시상태에있어서，상기다공그래파이트층의탄소함량은상기 다공그래파이트층전체증량에대하여 , 20중량 <¾이상이다. In an exemplary embodiment of the present invention, the carbon content of the porous graphite layer is 20 weights < ¾ or more, based on the total increase of the porous graphite layer.
[27] 본발명의일실시상태에있어서 ,상기열처리는탄화단계및그래파이트 단계를포함하는방법이다. In one embodiment of the present invention, the heat treatment is a method comprising a carbonization step and a graphite step.
[28] 본발명의일실시상태에있어서，상기탄화단계는제 1온도구간을갖는제 1 히터내로폴리이미드필름을도입시킴으로써상기고분자필름을탄화시켜 탄소질필름으로변환시키는단계를포함한다. In one embodiment of the present invention, the carbonizing step includes carbonizing the polymer film and converting the polymer film into a carbonaceous film by introducing a polyimide film into a first heater having a first temperature section.
[29] 본발명의일실시상태에있어서，상기제 1온도구간은 500±50°C내지 [29] In the exemplary embodiment of the present invention, the first temperature range is 500 ± 50 ° C.
1000°C로순차상승하는구간이다.  It is a section that sequentially rises to 1000 ° C.
[30] 본발명의일실시상태에있어서，상기그래파이트단계는선형적으로온도가 상승하는구간인제 2온도구간을갖는제 2히터내로상기탄소질필름을 도입시켜그라파이트필름으로변환시키는단계를포함한다. In an exemplary embodiment of the present invention, the graphite step includes converting the carbonaceous film into a graphite film into a second heater having a second temperature section, which is a section where the temperature rises linearly. .
[31] 본발명의일실시상태에있어서，상기제 2히터는 4000 mm내지 6000 mm의 길이를갖는다. In one embodiment of the present invention, the second heater has a length of 4000 mm to 6000 mm.
[32] 본발명의일실시상태에있어서，상기제 2온도구간은 1000°C내지 2800oC로 순차상승하는구간이다. [32] is in the exemplary embodiment of the present invention, the second temperature interval range sequentially raised to 1000 ° C to 2800 o C.
[33] 본발명의일실시상태에있어서 ,상기제 2온도구간은 1000°C내지 1500°C의 제 2-1온도구간, 1500°C내지 2200°C의제 2-2온도구간，및 2200°C내지[33] In one embodiment of the present invention, the second temperature section is a temperature range of 1000 ° C. to 1500 ° C., 2-1 temperature range, 1500 ° C. to 2200 ° C., 2-2 temperature range, and 2200 ° C. C to
2800oC의제 2-3온도구간을포함한다. Includes 2-3 temperature ranges at 2800 o C.
[34] 본발명의일실시상태에있어서，상기그래파이트단계는상기제 2-1 [34] In an exemplary embodiment of the present invention, the graphite step is the second to 1-1.
온도구간내에서상기탄소질필름을횡방향으로 0.33 mm/초내지 1.33 mm/초로 이동하게하고，상기제 2히터의내부온도를분당 10C내지 5°C로상승시키면서Move the carbonaceous film from 0.33 mm / sec to 1.33 mm / sec in the lateral direction within the temperature range, while increasing the internal temperature of the second heater from 1 0 C to 5 ° C per minute.
1시간내지 4시간동안상기탄소질필름에대하여열처리를진행하는단계를 포함한다. Performing a heat treatment on the carbonaceous film for 1 to 4 hours.
[35] 본발명의일실시상태에있어서，상기다공탄소질필름층은핀을가압또는 레이저를조사하여기공을형성하는것이다.  In one embodiment of the present invention, the porous carbonaceous film layer forms pores by pressing a pin or irradiating a laser.
[36] 본발명의일실시상태에있어서 ,상기핀은평균직경이 1 μηι내지 100 [36] In one embodiment of the present invention, the pin has an average diameter of 1 μηι to 100
μπι이다.  μπι.
[37] 본발명의일실시상태에있어서，상기핀은하나이상의것이며，상기핀들의 간격은평균 10 μπι이상이다.  In one embodiment of the present invention, the pins are one or more, and the spacing of the pins is, on average, 10 μπι or more.
[38] 본발명의일실시상태에있어서，상기핀은하나이상의것이며，상기핀들은 사각형 ,원형，타원형,마름모형，또는이들의조합인패턴을형성하는것이다. [38] In one embodiment of the present invention, the pins are one or more, and the pins are To form a pattern that is a rectangle, a circle, an ellipse, a diamond, or a combination of these.
[39] 본발명의일실시상태에있어서,상기핀의가압방향은상기다공탄소질 필름층의일면의수직방향또는그배면의수직방향이다. In one embodiment of the present invention, the pressing direction of the pin is a vertical direction of one surface of the porous carbonaceous film layer or a vertical direction of the rear surface thereof.
[40] 본발명의일실시상태에있어서，상기핀의가압방법은수직으로가압또는 핀을회전하며가압하는것이다. In one embodiment of the present invention, the pressing method of the pin is to pressurize vertically or by rotating the pin.
[41] 본발명의일실시상태에있어서，상기다공탄소질필름층은상기폴리이미드 필름에기공을형성한후열처리한것이다. In an exemplary embodiment of the present invention, the porous carbonaceous film layer is heat treated after forming pores in the polyimide film.
[42] 본발명의일실시상태에있어서,상기다공탄소질필름층은상기폴리이미드 필름에열처리한후기공을형성한것이다. In an exemplary embodiment of the present invention, the porous carbonaceous film layer is formed by forming a late hole heat-treated in the polyimide film.
[43] 본발명의일실시상태에있어서,상기폴리이미드필름은공지의폴리이미드 필름이다. In one embodiment of the present invention, the polyimide film is a known polyimide film.
[44] 본발명의일실시상태에있어서，상기폴리이미드필름은폴리아믹산용액을 가열하여수득되는것이다.  In one embodiment of the present invention, the polyimide film is obtained by heating a polyamic acid solution.
[45] 본발명의일실시상태에있어서，상기폴리이미드필름은폴리아믹산용액을 필름형상으로캐스트하고열적으로탈환화탈용매시켜서수득하는것，또는 폴리아믹산용액에환화촉매및탈수제를흔합하고화학적으로탈환화시켜서 겔필름을제작하고，이것을가열탈용매하여수득하는것이다.  [45] In one embodiment of the present invention, the polyimide film is obtained by casting a polyamic acid solution into a film form and thermally decyclizing desolvent, or mixing a cyclization catalyst and a dehydrating agent in a polyamic acid solution and chemically recapturing it. To produce a gel film, which is obtained by heating and desolvation.
[46] 본발명의일실시상태쎄있어서，상기폴리아믹산용액은,원료의방향족 디아민성분과방향족산이무수물성분，또는이양자를주성분으로하는 화학물질을유기용매중에서중합시킴으로써수득하는것이다.  In one embodiment of the present invention, the polyamic acid solution is obtained by polymerizing an aromatic diamine component, an aromatic acid dianhydride component, or a chemical having a dimer as a main component in an organic solvent.
[47] 본발명의일실시상태에있어서，상기방향족디아민성분은,  [47] In one embodiment of the present invention, the aromatic diamine component,
파라페닐렌디아민을포함하는것이며， 4， 4'-디아미노디페닐에테르를더포함할 수있다.  Paraphenylenediamine, and may further include 4, 4'-diaminodiphenyl ether.
[48] 본발명의일실시상태에있어서，상기방향족무수물성분은，피로메리트산 이무수물및 /또는 3， 3', 4, 4'-비페닐테트라카르본산이무수물이다.  In one embodiment of the present invention, the aromatic anhydride component is pyromellitic dianhydride and / or 3, 3 ', 4, 4'-biphenyltetracarboxylic dianhydride.
[49] 본발명의일실시상태에있어서，상기폴리아믹산용액은추가디아민성분을 더포함한다.  In one embodiment of the present invention, the polyamic acid solution further comprises an additional diamine component.
[50] 본발명의일실시상태에있어서 ,상기추가디아민성분은, 3，  [50] In one embodiment of the present invention, the additional diamine component is 3,
3'-디아미노디페닐에테르，메타페닐렌디아민, 4, 4'-디아미노디페닐프로판， 3, 3'-diaminodiphenyl ether, methaphenylenediamine, 4, 4'-diaminodiphenylpropane, 3,
4'-디아미노디페닐프로판， 3, 3'-디아미노디페닐프로판, 4， 4'-diaminodiphenylpropane, 3, 3'-diaminodiphenylpropane, 4,
4'-디아미노디페닐메탄， 3, 4'-디아미노디페닐메탄, 3, 3'-디아미노디페닐메탄, 벤지딘， 4, 4'-디아미노디페닐설파이드, 3, 4'-디아미노디페닐설파이드, 3, 4'-diaminodiphenylmethane, 3, 4'-diaminodiphenylmethane, 3, 3'-diaminodiphenylmethane, benzidine, 4, 4'-diaminodiphenylsulfide, 3, 4'-dia Minodiphenylsulfide, 3,
3'-디아미노디페닐설파이드, 4, 4'-디아미노디페닐설폰， 3, 3'-diaminodiphenylsulfide, 4, 4'-diaminodiphenylsulfone, 3,
4'-디아미노디페닐설폰， 3, 3'-디아미노디페닐설폰, 2, 6-디아미노피리딘, 비스 -(4-아미노페닐)디에틸실란, 3, 3'-디클로로벤지딘，  4'-diaminodiphenylsulfone, 3, 3'-diaminodiphenylsulfone, 2, 6-diaminopyridine, bis- (4-aminophenyl) diethylsilane, 3, 3'-dichlorobenzidine,
비스 _(4-아미노페닐)에틸포스핀옥사이드，비스 -(4-아미노페닐)  Bis _ (4-aminophenyl) ethyl phosphine oxide, bis-(4-aminophenyl)
페닐포스핀옥사이드,비스 -(4-아미노페닐) -Ν-페닐아민,  Phenylphosphine oxide, bis- (4-aminophenyl) -Ν-phenylamine,
비스 -(4-아미노페닐) -Ν-메틸아민， 1， 5-디아미노나프탈렌, 3, 3'-디메틸 -4， 4'-디아미노비페닐， 3， 4'-디메틸 -3'， 4-디아미노비페닐 -3， 3'-디메특시벤지딘， 2，Bis- (4-aminophenyl) -Ν-methylamine, 1, 5-diaminonaphthalene, 3, 3'-dimethyl-4, 4'-diaminobiphenyl, 3, 4'-dimethyl-3 ', 4-diaminobiphenyl-3, 3'-dimethoxybenzidine, 2,
4-비스 (ρ-β-아미노 -t-부틸페닐)에테르，비스 (ρ-β-아미노 -t-부틸페닐)에테르, P-비스 (2-메틸 -4-아미노펜틸)벤젠, P-비스 -(1, 1-디메틸 -5—아미노펜틸)벤젠, m-자일릴렌디아민, P-자일릴렌디아민， 1, 3-디아미노아다만탄， 3, 3'-디아미노 -1，4-bis (ρ-β-amino-t-butylphenyl) ether, bis (ρ-β-amino -t-butylphenyl) ether, P-bis (2-methyl-4-aminopentyl) benzene, P-bis -(1,1-dimethyl-5-aminopentyl) benzene, m-xylylenediamine, P-xylylenediamine, 1, 3-diaminoadamantane, 3, 3'-diamino-1,
1'-디아미노아다만탄, 3, 3'-디아미노메틸 -1， 1'-디아다만탄， 1'-diaminoadamantane, 3, 3'-diaminomethyl-1, 1'-diaadamantane,
비스 (P-아미노시클로핵실)메탄，핵사메틸렌디아민，헵타메틸렌디아민， 옥타메틸렌디아민，노나메틸렌디아민,데카메틸렌디아민，  Bis (P-aminocyclonuclear) methane, nucleated methylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine,
3—메틸헵타메틸렌디아민, 4， 4'-디메틸헵타메틸렌디아민, 2, 11-디아미노도데칸, 3—methylheptamethylenediamine, 4, 4'-dimethylheptamethylenediamine, 2, 11-diaminododecane,
1, 2-비스 (3-아미노프로폭시)에탄， 2, 2—디메틸프로필렌디아민, 1, 2-bis (3-aminopropoxy) ethane, 2, 2-dimethylpropylenediamine,
3-메톡시핵사에틸렌디아민， 2， 5-디메틸핵사메틸렌디아민， 2,  3-methoxy nucleated ethylenediamine, 2, 5-dimethylnuclear methylenediamine, 2,
5-디메틸헵타메틸렌디아민, 5—메틸노나메틸렌디아민， 1, 4-디아미노시클로핵산， 1, 12-디아미노옥타데칸, 2, 5-디아미노 -1， 3, 4-옥사디아졸, 2,  5-dimethylheptamethylenediamine, 5—methylnonamethylenediamine, 1, 4-diaminocyclonucleic acid, 1, 12-diaminooctadecane, 2, 5-diamino-1, 3, 4-oxadiazole, 2 ,
2-비스 (4-아미노페닐)핵사플루오르프로판,  2-bis (4-aminophenyl) nucleofluoropropane,
N-(3-아미노페닐) -4-아미노벤즈아미드， 4-아미노페닐 -3-아미노벤조에이트，또는 이들의흔합물이다.  N- (3-aminophenyl) -4-aminobenzamide, 4-aminophenyl-3-aminobenzoate, or a combination thereof.
[51] 본발명의일실시상태에있어서，상기폴리아믹산용액은추가산이수물  [51] In one embodiment of the present invention, the polyamic acid solution is an additional acid dihydrate.
성분을더포함한다.  It further contains an ingredient.
[52] 본발명의일실시상태에있어서，상기추가산이수물은， 2, 3', 3，  [52] In one embodiment of the present invention, the additional acid dihydrate is 2, 3 ', 3,
4'-비페닐테트라카르본산이무수물， 3， 3'， 4, 4'-벤조페논테트라카르본산 이무수물, 2， 3, 6, 7—나프탈렌디카르본산이무수물, 2, 2-비스 (3,  4'-biphenyltetracarboxylic dianhydride, 3, 3 ', 4, 4'-benzophenonetetracarboxylic dianhydride, 2, 3, 6, 7-naphthalenedicarboxylic dianhydride, 2, 2-bis ( 3,
4-디카르복시페닐)에테르，피리딘 -2， 3， 5， 6—테트라카르본산이무수물， 1, 2, 4, 4-dicarboxyphenyl) ether, pyridine-2, 3, 5, 6—tetracarboxylic dianhydride, 1, 2, 4,
5-나프탈렌테트라카르본산이무수물， 1， 4， 5， 8-나프탈렌테트라카르본산 이무수물， 1, 4， 5, 8-데카히드로나프탈렌테트라카르본산이무수물, 4, 5-naphthalenetetracarboxylic dianhydride, 1, 4, 5, 8-naphthalenetetracarboxylic dianhydride, 1, 4, 5, 8-decahydronaphthalenetetracarboxylic dianhydride, 4,
8-디메틸 -1， 2， 5, 6-핵사히드로나프탈렌테트라카르본산이무수물, 2,  8-dimethyl-1, 2, 5, 6-nucleohydronaphthalenetetracarboxylic dianhydride, 2,
6-디클로로 -1， 4, 5, 8-나프탈렌테트라카르본산이무수물， 2, 7-디클로로 -1, 4, 5， 8-나프탈렌테트라카르본산이무수물, 2， 3, 6, 7-테트라클로로 -1, 4， 5,  6-dichloro-1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,7-dichloro-1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-tetrachloro -1, 4, 5,
8-나프탈렌테트라카르본산이무수물, 1, 8， 9, 10-페난트렌테트라카르본산 이무수물， 2, 2-비스 (2， 3—디카르복시페닐)프로판이무수물， 1， 1-비스 (3,  8-naphthalenetetracarboxylic dianhydride, 1, 8, 9, 10-phenanthrenetetracarboxylic dianhydride, 2, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1, 1-bis (3 ,
4-디카르복시페닐)에탄이무수물， 1, 1-비스 (2， 3-디카르복시페닐)에탄이무수물， 비스 (2, 3-디카르복시페닐)메탄이무수물，비스 (3， 4-디카르복시페닐)메탄 이무수물，비스 (3, 4-디카르복시페닐)설폰이무수물，벤젠 -1， 2, 3,  4-dicarboxyphenyl) ethane dianhydride, 1, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxy Phenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfon dianhydride, benzene-1,2,3,
4-테트라카르본산이무수물， 3, 4， 3', 4'-벤조페논테트라카르본산이무수물，또는 이들의흔합물이다.  4-tetracarboxylic dianhydride, 3, 4, 3 ', 4'-benzophenone tetracarboxylic dianhydride, or a combination thereof.
[53] 본발명의일실시상태에있어서，상기폴리아믹산용액은유기용매를더  [53] In one embodiment of the present invention, the polyamic acid solution is an organic solvent.
포함한다.  Include.
[54] 본발명의일실시상태에있어서，상기유기용매는디메틸설폭시드，  [54] In one embodiment of the present invention, the organic solvent is dimethyl sulfoxide,
디에틸설폭시드등의설폭시드계용매， Ν, Ν-디메틸포름아미드， N,  Sulfoxide solvents such as diethyl sulfoxide, Ν, Ν-dimethylformamide, N,
Ν-디에틸포름아미드등의포름아미드계용매 , Ν, Ν-디메틸아세트아미드 , Ν, N-디에틸아세트아미드등의아세트아미드계용매 , Ν-메틸— 2-피를리돈， Formamide solvents such as Ν-diethylformamide, Ν, Ν-dimethylacetamide, Ν, Acetamide solvents such as N-diethylacetamide, N-methyl- 2-pyridone,
Ν-비닐 -2-피롤리돈등의피롤리돈계용매,페놀， 0-, m-,또는 P-크레졸,크실레놀, 할로겐화페놀,카테콜등의페놀계용매는，또한핵사메틸포스포르아미드， γ-부틸올락톤등의비프로톤성극성용매,또는이들의혼합물이다ᅳ  Pyrrolidone solvents such as Ν-vinyl-2-pyrrolidone, phenol, 0-, m-, or phenol solvents such as P-cresol, xylenol, halogenated phenol and catechol are also nucleated methylphosphor. Aprotic polar solvents such as amides, γ-butylolactones, or mixtures thereof
[55] 본발명의일실시상태에있어서，상기유기용매는크실렌，롤루엔둥의방향족 탄화수소를더포함한다.  In one embodiment of the present invention, the organic solvent further comprises an aromatic hydrocarbon of xylene and toluene.
[56] 본발명에따른다공탄소질필름층은상기다공탄소질필름층의양면에 According to the present invention, the carbonaceous film layer is formed on both sides of the porous carbonaceous film layer.
불소계이오노머층이구비된것이다.  The fluorine ionomer layer is provided.
[57] 본발명의일실시상태에있어서 ,상기불소계이오노머층은 [57] In one embodiment of the present invention, the fluorine-based ionomer layer is
폴리테트라플루오로에틸렌, (polytetrafluoroethylene:PTFE),  Polytetrafluoroethylene, (polytetrafluoroethylene: PTFE),
폴리비닐리덴플루오라이드 (PVdF),폴리비닐알코올，셀를로오스아세테이트, 폴리비닐리덴플루오라이드 -핵사플루오로프로필렌의코폴리머 (PVdF-HFP)및 스티렌—부타디엔고무 (SBR)로이루어진군에서선택되는어느하나이상이다.  Polyvinylidene fluoride (PVdF), polyvinyl alcohol, cellulose acetate, polyvinylidene fluoride-nucleofluoropropylene copolymer (PVdF-HFP) and styrene-butadiene rubber (SBR) It is more than one.
[58] 이하,본발명에따른연료전지용막—전극접합체를설명한다. Hereinafter, a fuel cell membrane-electrode assembly according to the present invention will be described.
[59] 본발명에따른연료전지용막 -전극접합체는상기연료전지용전해질분리막; 및상기전해질분리막을사이에두고서로대향하여위치하는애노드전극및 캐소드전극;을포함한다. A fuel cell membrane-electrode assembly according to the present invention includes the fuel cell electrolyte separator; And an anode electrode and a cathode electrode disposed to face each other with the electrolyte separator interposed therebetween.
[60] 본발명의일실시상태에있어서,상기전해질분리막은카본천 (carbon [60] In one embodiment of the present invention, the electrolyte separation membrane is a carbon cloth (carbon
cloth)이나카본페이퍼 (carbon paper)이다.  cloth or carbon paper.
[61] 본발명에따른애노드전극및캐소드전극은각각전해질막및촉매층을 [61] The anode electrode and the cathode electrode according to the present invention each comprise an electrolyte membrane and a catalyst layer.
포함한다.  Include.
[62] 본발명의일실시상태에있어서,상기애노드전극의촉매층은백금，루테늄， 오스뮴,백금-루테늄합금,백금-오스뮴합금，백금-팔라듐합금및  In one embodiment of the present invention, the catalyst layer of the anode electrode is platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy and
백금-전이금속합금으로이루어진군에서선택되는어느하나이상의촉매를 포함한다.  It includes one or more catalysts selected from the group consisting of platinum-transition metal alloys.
[63] 본발명의일실시상태에있어서,상기캐소드전극의촉매층은백금을  In one embodiment of the present invention, the catalyst layer of the cathode electrode is platinum
포함한다.  Include.
[64] 본발명의일실시상태에있어서，상기애노드전극또는상기캐소드전극의 촉매는탄소계담체에담지된다.  In one embodiment of the present invention, the anode electrode or the catalyst of the cathode electrode is supported on a carbon-based carrier.
[65] 이하，본발명에따른연료전지를설명한다. Hereinafter, a fuel cell according to the present invention will be described.
[66] 본발명에따른연료전지는상기막 -전극접합체와，상기막 -전극접합체들  A fuel cell according to the present invention includes the membrane-electrode assembly and the membrane-electrode assembly.
사이에개재하는세퍼레이터를포함하는스택;연료를상기스택으로공급하는 연료공급부;및산화제를상기스택으로공급하는산화제공급부를포함한다.  A stack including a separator interposed therebetween; a fuel supply unit supplying fuel to the stack; and an oxidant supply unit supplying an oxidant to the stack.
[67] 본발명에따른세퍼레이터는막 -전극접합체들이전기적으로연결되는것을 막고외부에서공급된연료및산화제를막 -전극접합체로전달하는역할과 애노드전극과캐소드전극을직렬로연결시켜주는전도체의역할을한다.  [67] The separator according to the present invention prevents the membrane-electrode assembly from being electrically connected to each other, and delivers fuel and oxidant supplied from the outside to the membrane-electrode assembly and connects the anode and the cathode in series. Plays a role.
[68] 본발명에따른연료공급부는연료를상기스택으로공급하는역할을하며， 연료를저장하는연료탱크및상기연료탱크에저장된연료를스택으로 공급하는펌프를포함할수있다. A fuel supply unit according to the present invention serves to supply fuel to the stack, and stores fuel in the fuel tank and the fuel stored in the fuel tank. The pump may be supplied.
[69] 본발명의 일실시상태에 있어서，상기연료로는기체또는액체상태의수소 또는탄화수소연료이다. , In one embodiment of the present invention, the fuel is hydrogen or hydrocarbon fuel in gas or liquid state. ,
[70] 본발명의 일실시상태에 있어서，상기탄화수소연료는메탄올，에탄올， 프로판올,부탄올또는천연가스이다.  In one embodiment of the present invention, the hydrocarbon fuel is methanol, ethanol, propanol, butanol or natural gas.
[71] 본발명에따른산화제공급부는산화제를상기스택으로공급하는역할을 한다.  An oxidant supply unit according to the present invention serves to supply an oxidant to the stack.
[72] 본발명의 일실시상태에 있어서，상기산화제는산소또는공기이다.  In one embodiment of the present invention, the oxidizing agent is oxygen or air.
[73] 본발명의 일실시상태에 있어서，상기산화제는펌프로주입된다.  In one embodiment of the present invention, the oxidant is injected into a pump.
[74] 본발명의 일실시상태에 있어서，상기 연료전지는고분자전해질형 연료전지 또는직접메탄올형 연료전지이다.  In one embodiment of the present invention, the fuel cell is a polymer electrolyte fuel cell or a direct methanol fuel cell.
[75] 이하，실시예를들어본발명을보다자세하게설명한다.그러나이러한 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples.
실시예들은본발명을구체적으로설명하려는것일뿐,이러한실시예에의하여 본발명의권리범위가제한되는것은아니다.  The examples are only intended to illustrate the invention, and the scope of the invention is not limited by these embodiments.
[76] <제조예 1>그래파이트필름의제조 [76] <Preparation Example 1> Preparation of Graphite Film
[77] TAIMADE사에서제조된상품명 TL-050인두께가 50 의폴리이미드필름을 롤형태로지그에권취시킨후，제 1온도구간을갖는제 1히터내로폴리이미드 필름을도입시킴으로써상기고분자필름을탄화시켜탄소질필름으로 변환시켰다.상기제 1온도구간에서는, 500°C에서 1000oC까지분당 10°C로 승온시킨후， 1000°C의온도를 2시간정도동안유지하였다. [77] The polymer film was prepared by winding a polyimide film having a thickness of 50, manufactured by TAIMADE, with a thickness of 50, in a roll-shaped jig, and then introducing the polyimide film into a first heater having a first temperature section. It was then converted into carbonaceous carbonized film. in the first temperature range, and maintained at 500 ° C 1000 o after the temperature was raised up to ° C per minute, 10 C, for about 2 hours to a temperature of 1000 ° C.
[78] 이후,제 1히터에서 변환된탄소질필름은 5000 imn의길이를갖게되며 ,상기 탄소질필름을횡방향으로 1.00 mm/초로이동하고,아르곤가스를 5kgf/cm2의 압력분위기인제 2히터내로도입시킴으로써그라파이트필름으로변환시켜 그래파이트필름을제조하였다. Afterwards, the carbonaceous film converted from the first heater has a length of 5000 imn, the carbonaceous film is moved to 1.00 mm / sec in the transverse direction, and the second heater, which is argon gas, has a pressure atmosphere of 5 kgf / cm 2 . The graphite film was prepared by incorporating it into graphite film.
[79] 상기제 2온도구간에서는, 1000°C내지 1500°C의제 2-1온도구간과，  In the second temperature section, the second temperature section of 1000 ° C to 1500 ° C and
1500oC~2200°C의제 2-2온도구간，그리고， 2200°C내지 2800oC의 제 2-3은도 구간을순차적으로적용하였으며， The second 2-2 temperature range from 1500 o C to 2200 ° C, and the second 2-3 from 2200 ° C to 2800 o C are applied sequentially.
[80] 상기제 2-1온도구간인 1000°C내지 1500oC에서는분당 3 0C로승온을 3 시간동안진행시켰고，상기제 2-2온도구간인 1500°C내지 2200°C에서는분당 50C로 2시간동안진행시켰으며 , [80] The pharmaceutical composition of claim 2-1, the temperature range of 1000 ° C to 1500 o C in the sikyeotgo to proceed for 3 min the temperature was raised to 0 C three times, and the second-second temperature range of 1500 ° C to 2200 ° C 5 min 2 hours at 0 C,
[81] 제 2-3온도구간인 2200°C내지 2800°C에서는분당 10°C로승온시킨후  [81] At a temperature range of 2200 ° C to 2800 ° C, the second 2-3 temperature range, the temperature is raised to 10 ° C per minute
2800°C의온도를유지시키는구간을 2시간동안진행시켰다.  A section maintaining a temperature of 2800 ° C. was run for 2 hours.
[82] <실시예 1-1>전해질막의제조  Example 1-1 Preparation of Electrolyte Membrane
[83] 상기제조에 1에서제조된그래파이트필름에 , UHT사에서제조된상품명 RFP-3P20인레이저조사기기로주파수 60kHz,가공단출력 1.2 W,조사횟수 15shot/hole및조사시간 7.3초의조건으로레이져를조사하여그래파이트층을 제조하였다.  [83] A graphite film manufactured in 1 above, which was manufactured by UHT, under the brand name RFP-3P20 laser irradiation apparatus, which had a frequency of 60 kHz, a cutting edge output 1.2 W, irradiation time of 15 shots / hole, and irradiation time of 7.3 seconds. Was investigated to prepare a graphite layer.
[84] 제조된그래파이트층의두께는 25 / ，평균기공직경은 10 ，평균기공 면적율은 50%，기공율은 58%었다. [84] The thickness of the manufactured graphite layer is 25 /, the average pore diameter is 10, average pore The area ratio was 50% and the porosity was 58%.
[85] 제조된그래파이트층의양면에각각퍼플루오르술폰산폴리머인듀풍사의 나피온 (상품명： Nafion)올스프레이코팅법을사용해코팅하여，불소계 이오노머층을구비하여전해질분리막을제조하였다. [0085] An electrolyte separation membrane was prepared by coating a fluorine-based ionomer layer on both sides of the prepared graphite layer by using the Nafion (spray name: Nafion) all spray coating method of perfluorosulfonic acid polymer.
[86] <실시예 1-2>단위전지의제조 Example 1-2 Preparation of Unit Battery
[87] 상기실시예 1- 1에따라제조한전해질분리막의양면에기체확산층으로서 탄소페이퍼를겹친후막 -전극접합체를중심으로가스의기밀성을유지하기 위한 210； 의가스켓을전극부분을제외한고분자전해질부분에밀착시키고, 막 -전극접합체에수소의투입및균일한압력을주기위한유로를가진음극용 판과，공기의투입및막 -전극접합체에균일한압력을주기위한양극용판을 밀착시켜단위전지를제조하였다.  [0087] The polymer electrolyte, except for the electrode portion of 210, is formed by stacking carbon paper as a gas diffusion layer on both sides of the electrolyte separation membrane prepared according to Example 1-1 to maintain gas tightness based on the membrane-electrode assembly. Unit cell by closely adhering to the part and adhering the cathode plate having the flow path for applying hydrogen and uniform pressure to the membrane-electrode assembly, and the anode plate for uniform pressure to the air injection and the membrane-electrode assembly. Was prepared.
[88] <실시예 2-1>전해질막의제조  Example 2-1 Preparation of Electrolyte Membrane
[89] 상기제조에 1에서，폴리이미드필름에대하여 UHT사에서제조된상품명 RFP-3P20인레이저조사기기로주파수 60kHz,가공단출력 1.2 W,조사횟수 15shot/hole및조사시간 7.3초의조건으로레이져를조사하는전처리단계를 실시한폴리이미드필름을지그에권취한것을제외하고는상기제조예 1과 동일한과정으로수득한그래파이트층을제조하였다.  [89] The laser-producing apparatus under the trade name RFP-3P20 manufactured by UHT for polyimide film as described in item 1 above, with a frequency of 60 kHz, a processing stage output of 1.2 W, irradiation time of 15 shots / hole, and irradiation time of 7.3 seconds. A graphite layer obtained in the same manner as in Production Example 1 was prepared except that the polyimide film subjected to the pretreatment step of irradiating was wound on a jig.
[90] 제^된그래파이트층의두께는 25 ，평균기공직경은 10 /m，평균기공  [90] The thickness of the graphite layer obtained is 25, the average pore diameter is 10 / m, and the average pore size.
면적율은 50%，기공율은 70%이었다.  The area ratio was 50% and the porosity was 70%.
[91] 제조된그래파이트층의양면에각각퍼플루오르술폰산폴리머인듀퐁사의 나피온 (상품명： Nafion)을스프레이코팅법을사용해코팅하여，불소계 이오노머층을구비하였다.  On both sides of the prepared graphite layer, Nafion (trade name: Nafion) manufactured by DuPont, a perfluorosulfonic acid polymer, was coated by spray coating to prepare a fluorine-based ionomer layer.
[92] <실시예 2-2>단위전지의제조  Example 2-2 Fabrication of Unit Battery
[93] 전해질막으로상기실시예 2- 1에따라제조된전해질막을사용한것을  [93] An electrolyte membrane prepared according to Example 2-1 was used as an electrolyte membrane.
제외하고는상기실시예 1-2와동일한과정으로단위전지를제조하였다.  Except for manufacturing the unit cell in the same manner as in Example 1-2.
[94] <실시예 3-1>전해질막의제조 Example 3-1 Preparation of Electrolyte Membrane
[95] 가드넥사에서제조된상품명 GD-025인두께가 25卿의그래파이트필름에 대하여 UHT사에서제조된상품명 RFP-3P20인레이저조사기기로주파수 60kHz,가공단출력 1.2 W,조사횟수 15shot/hole및조사시간 7.3초의조건으로 레이져를조사하는전처리단계를실시한폴리이미드필름을지그에권취한 것을제외하고는상기제조예 1과동일한과정으로수득한그래파이트층을 제조하였다.  [95] GD-025, manufactured by GuardNeck, is a RFP-3P20 laser irradiation device manufactured by UHT for a 25-inch graphite film with a frequency of 60 kHz, output power of 1.2 W, and 15 shots / hole. And a graphite layer obtained in the same manner as in Production Example 1 except that the jig was wound with a polyimide film subjected to a pretreatment step of irradiating a laser under a condition of an irradiation time of 7.3 seconds.
[96] 제조된그래파이트층의두께는 25 ,평균기공직경은 10 ，평균기공  [96] The manufactured graphite layer had a thickness of 25, an average pore diameter of 10, and an average pore size.
면적율은 50%,기공율은 58%이었다.  The area ratio was 50% and the porosity was 58%.
[97] 제조된그래파이트층의양면에각각퍼플루오르술폰산폴리머인듀퐁사의 나피온 (상품명： Nafion)을스프레이코팅법을사용해코팅하여，불소계 이오노머층을구비하여전해질분리막을제조하였다. On both sides of the prepared graphite layer, Nafion (trade name: Nafion), which is a perfluorosulfonic acid polymer, was coated using a spray coating method to prepare an electrolyte separator using a fluorine-based ionomer layer.
[98] <실시예 3-2>단위전지의제조 [99] 전해질막으로상기실시예 3-1에따라제조된전해질막을사용한것을 제외하고는상기실시예 1-2와동일한과정으로단위전지를제조하였다ᅳ [100] <실시예 4-1>전해질막의제조 Example 3-2 Fabrication of Unit Battery A unit cell was manufactured in the same manner as in Example 1-2, except that the electrolyte membrane prepared according to Example 3-1 was used as the electrolyte membrane. [100] <Example 4-1> Produce
[101] 상기제조예 1에서,가드넥사에서제조된상품명 GD-025인두께가 25 의 그래파이트필름에 대하여 UHT사에서제조된상품명 RFP-3P20인레이저 조사기기로주파수 60kHz,가공단출력 1.2 W,조사횟수 15shot/hole및조사시간 7.3초의조건으로레이저를조사하는전처리단계를실시한폴리이미드필름을 지그에권취한것을제외하고는상기제조예 1과동일한과정으로수득한 그래파이트층을제조하였다.  In Production Example 1, the product name GD-025 manufactured by GuardNeck is a RFP-3P20 laser product manufactured by UHT for a graphite film having a thickness of 25, and a frequency of 60 kHz, a processing stage output of 1.2 W, A graphite layer obtained in the same manner as in Production Example 1 was prepared except that the jig was wound with a polyimide film subjected to a pretreatment step of irradiating the laser under the condition of 15 shots / hole of irradiation times and 7.3 seconds of irradiation time.
[102] 제조된그래파이트층의두께는 25 / ，평균기공직경은 10 m,평균기공  [102] The thickness of the manufactured graphite layer is 25 /, the average pore diameter is 10 m, the average pore
면적율은 5%,기공율은 6%이었다.  The area ratio was 5% and the porosity was 6%.
[103] 제조된그래파이트층의 양면에각각퍼플루오르술폰산폴리머인듀퐁사의 나피온 (상품명： Nafion)을스프레이코팅법을사용해코팅하여 ,불소계 이오노머층을구비하여 전해질분리막을제조하였다.  [0094] Nafion (trade name: Nafion), manufactured by DuPont, a perfluorosulfonic acid polymer, was coated on both surfaces of the prepared graphite layer using a spray coating method to prepare an electrolyte separation membrane by preparing a fluorine-based ionomer layer.
[104] <실시예 4-2>단위전지의제조  Example 4-2 Fabrication of Unit Battery
[105] 전해질막으로상기실시예 4-1에따라제조된전해질막을사용한것을  [105] An electrolyte membrane prepared according to Example 4-1 was used as an electrolyte membrane.
제외하고는상기실시예 1-2와동일한과정으로단위전지를제조하였다.  Except for manufacturing the unit cell in the same manner as in Example 1-2.
[106] <실시예 5-1>전해질막의제조 Example 5-1 Preparation of Electrolyte Membrane
[107] 상기제조예 1에서，가드넥사에서제조된상품명 GD-025인두께가 25 zm의 그래파이트필름에 대하여 UHT사에서 제조된상품명 RFP-3P20인레이저 조사기기로주파수 60kHz,가공단출력 1.2 W,조사횟수 15shot/hole및조사시간 7.3초의조건으로레이저를조사하는전처리단계를실시한폴리이미드필름을 지그에권취한것을제외하고는상기제조예 1과동일한과정으로수득한 그래파이트층을제조하였다.  In Production Example 1, a product name GD-025 manufactured by Guardnex Inc. was manufactured by UHT for a graphite film having a thickness of 25 zm. A graphite layer obtained in the same manner as in Production Example 1 was produced except that the jig was wound with a polyimide film subjected to a pretreatment step of irradiating the laser under conditions of 15 shots / hole of irradiation times and 7.3 seconds of irradiation time.
[108] 제조된그래파이트층의두께는 25 μm,평균기공직경은 10 / ,평균기공  [108] The prepared graphite layer had a thickness of 25 μm and an average pore diameter of 10 /.
면적율은 70%,기공율은 81%이었다.  The area ratio was 70% and the porosity was 81%.
[109] 제조된그래파이트층의 양면에각각퍼플루오르술폰산폴리머인듀퐁사의 나피온 (상품명： Nafion)을스프레이코팅법을사용해코팅하여 ,불소계 이오노머층을구비하여전해질분리막을제조하였다.  [0109] Nafion (trade name: Nafion), manufactured by DuPont, a perfluorosulfonic acid polymer, was coated on both surfaces of the prepared graphite layer using a spray coating method to prepare an electrolyte separation membrane using a fluorine-based ionomer layer.
[110] <실시예 5-2>단위전지의제조  Example 5-2 Fabrication of Unit Battery
[111] 전해질막으로상기실시예 5-1에따라제조된전해질막을사용한것을  [111] An electrolyte membrane prepared according to Example 5-1 was used as an electrolyte membrane.
제외하고는상기실시예 1-2와동일한과정으로단위전지를제조하였다.  Except for manufacturing the unit cell in the same manner as in Example 1-2.
[112] <실시예 6-1>전해질막의제조 Example 6-1 Preparation of Electrolyte Membrane
[113] 상기제조예 1에서，가드넥사에서제조된상품명 GD-025인두께가 25 의 그래파이트필름에 대하여 UHT사에서제조된상품명 RFP-3P20인레이저 조사기기로주파수 60kHz,가공단출력 1.2 W,조사흿수 15shot/hole및조사시간 7.3초의조건으로레이저를조사하는전처리단계를실시한폴리이미드필름을 지그에권취한것을제외하고는상기제조예 1과동일한과정으로수득한 그래파이트층을제조하였다. [113] In the above Production Example 1, a product name GD-025 manufactured by GuardNeck for a graphite film having a thickness of 25 was manufactured by UHT under the trade name RFP-3P20 manufactured by UHT. The same procedure as in Production Example 1 was obtained except that the jig was wound with a polyimide film subjected to a pretreatment step of irradiating the laser under the condition of 15 shots / hole of irradiation time and 7.3 seconds of irradiation time. A graphite layer was prepared.
[114] 제조된그래파이트층의두께는 25 ，평균기공직경은 10 /m,평균기공  [114] The thickness of the manufactured graphite layer is 25, average pore diameter is 10 / m, average pore size
면적율은 85%,기공율은 89%이었다.  The area ratio was 85% and the porosity was 89%.
[115] 제조된그래파이트층의양면에각각퍼플루오르술폰산폴리머인듀퐁사의 나피온 (상품명: Nafion)을스프레이코팅법을사용해코팅하여,불소계 이오노머층을구비하여전해질분리막을제조하였다. [0079] Nafion (trade name: Nafion) manufactured by DuPont, a perfluorosulfonic acid polymer, was coated on both sides of the prepared graphite layer using a spray coating method to prepare an electrolyte separator using a fluorine-based ionomer layer.
[116] <실시예 6-2>단위전지의제조 Example 6-2 Fabrication of Unit Battery
[117] 전해질막으로상기실시예 6-1에따라제조된전해질막을사용한것을  As an electrolyte membrane, an electrolyte membrane prepared according to Example 6-1 was used.
제외하고는상기실시예 1-2와동일한과정으로단위전지를제조하였다.  Except for manufacturing the unit cell in the same manner as in Example 1-2.
[118] <실시예 7-1>전해질막의제조 Example 7-1 Preparation of Electrolyte Membrane
[119] 상기제조예 1에서，가드넥사에서제조된상품명 GD-025인두께가 25 의 그래파이트필름에대하여 UHT사에서제조된상품명 RFP-3P20인레이저 조사기기로주파수 60kHz,가공단출력 1.2 W,조사횟수 15shot/hole및조사시간 7.3초의조건으로레이저를조사하는전처리단계를실시한폴리이미드필름을 지그에권취한것을제외하고는상기제조예 1과동일한과정으로수득한 그래파이트층을제조하였다.  [119] In the production example 1, the product name GD-025 manufactured by GuardNeck for a graphite film having a thickness of 25 was manufactured by UHT under the trade name RFP-3P20, which is a product of RFP-3P20. A graphite layer obtained in the same manner as in Production Example 1 was prepared except that the jig was wound with a polyimide film subjected to a pretreatment step of irradiating the laser under the condition of 15 shots / hole of irradiation times and 7.3 seconds of irradiation time.
[120] 제조된그래파이트층의두께는 평균기공직경은 10 / m,평균기공  [120] The thickness of the manufactured graphite layer has an average pore diameter of 10 / m and an average pore size.
면적율은 92%,기공율은 96%이었다.  The area ratio was 92% and the porosity was 96%.
[121] 제조된그래파이트층의양면에각각퍼플루오르술폰산폴리머인듀퐁사의 나피온 (상품명： Nafion)을스프레이코팅법을사용해코팅하여 ,불소계 이오노머층을구비하여전해질분리막을제조하였다.  [0101] Nafion (trade name: Nafion), a perfluorosulfonic acid polymer, was coated on both sides of the prepared graphite layer using a spray coating method to prepare an electrolyte separator using a fluorine-based ionomer layer.
[122] <실시예 7-2>단위전지의제조  Example 7-2 Fabrication of Unit Battery
[123] 전해질막으로상기실시예 7-1에따라제조된전해질막올사용한것을  [123] The electrolyte membrane was prepared by using the electrolyte membrane prepared according to Example 7-1.
제외하고는상기실시예 1-2와동일한과정으로단위전지를제조하였다.  Except for manufacturing the unit cell in the same manner as in Example 1-2.
[124] <비교예 1-1>퍼플루오르술폰산계전해질막의 입수  Comparative Example 1-1 Obtaining a Perfluorosulfonic Acid-Based Electrolyte Membrane
[125] Dupont사에서제조된상품명 N211을연료전지용전해질분리막으로  [125] The brand name N211 manufactured by Dupont was used as a fuel cell electrolyte separator.
입수하였다ᅳ상기전해질분리막의두께는 25 이다.  The thickness of the electrolyte separator was 25.
[126] <비교예 1-2>단위전지의제조  [126] <Comparative Example 1-2> Manufacturing of Unit Battery
[127] 전해질막으로상기비교예 1-1의전해질막을사용한것을제외하고는상기 실시예 1-2와동일한과정으로단위전지를제조하였다.  A unit cell was manufactured in the same manner as in Example 1-2, except that the electrolyte membrane of Comparative Example 1-1 was used as the electrolyte membrane.
[128] <비교예 2-1>탄화수소계전해질막의 입수 [128] <Comparative Example 2-1> Obtaining Hydrocarbon Electrolyte Membranes
[129] 중량대비 40 wt. ^ sulfone을함유한 PES를극성용매 (DMAc, NMP)용매에 녹여캐스팅법을이용하여막을제작하고이를연료전지용전해질막으로 사용하였다.전해질분리막의두께는 25 이다.  [129] 40 wt.% By weight. ^ PES containing sulfone was dissolved in a polar solvent (DMAc, NMP) solvent to prepare a membrane using the casting method, and used as a fuel cell electrolyte membrane. The thickness of the electrolyte separator was 25.
[130] <비교예 2-2>단위전지의제조  [130] <Comparative Example 2-2> Manufacturing of unit cell
[131] 전해질막으로상기비교예 2-1의전해질막을사용한것을제외하고는상기 실시예 1-2와동일한과정으로단위전지를제조하였다.  A unit cell was manufactured in the same manner as in Example 1-2, except that the electrolyte membrane of Comparative Example 2-1 was used as the electrolyte membrane.
[132] <시험예 1>단위전지의성능측정 [133] 본발명에따른연료전지의성능을다른전해질막을사용한연료전지와 비교하기위하여，하기조건하에서단위전지의성능을측정하였다. Test Example 1 Performance Measurement of Unit Battery In order to compare the performance of the fuel cell according to the present invention with the fuel cell using another electrolyte membrane, the performance of the unit cell was measured under the following conditions.
[134] 상대습도: 80% [134] Relative Humidity: 80%
[135] 전지온도: 65°C [135] Battery Temperature: 65 ° C.
[136] 기체공급:애노드 -수소 /캐소드 -공기  [136] Gas Supply: Anode-Hydrogen / Cathode-Air
[137] 측정장치： CNL사의연료전지성능 TEST STATION  [137] Measuring equipment: CNL's fuel cell performance test station
[138] 전해질막표면적: 25 cm2 [138] electrolyte membrane surface area: 25 cm 2
[139] 우선，상기실시예 5-2,비교예 1-2및비교예 2-2에따른단위전지를정전압 First, the unit cell according to Example 5-2, Comparative Example 1-2, and Comparative Example 2-2 was subjected to constant voltage.
0.6V조건에서출력전류를측정한결과는하기표 1과같다. The result of measuring the output current under the 0.6V condition is shown in Table 1 below.
[140] [표 1] [140] [Table 1]
Figure imgf000012_0001
Figure imgf000012_0001
[141] 또한，상기실시예 5-2，비교예 1-2및비교예 2-2에따른단위전지의전류 -전압 값을측정하여도 1에전류 -전압곡선을도시하였다.  In addition, the current-voltage curve is shown in FIG. 1 when the current-voltage value of the unit cell according to Example 5-2, Comparative Example 1-2, and Comparative Example 2-2 is measured.
[142] 도 1에나타낸바와같이,퍼플루오르술폰산계전해질막또는탄화수소계  As shown in Fig. 1, perfluorosulfonic acid-based electrolyte membrane or hydrocarbon-based
전해질막을사용한비교예 1-2및비교예 2-2보다,본발명에따른전해질막을 사용한실시예 5-2가더우수한발전성능을나타냄을확인할수있다.  It can be seen that Example 5-2 using the electrolyte membrane according to the present invention exhibited better generation performance than Comparative Example 1-2 and Comparative Example 2-2 using the electrolyte membrane.
[143] 또한,상기실시예 3-2내지 7-2에따른단위전지의전류 -전압값을측정하여도 2에전류 -전압곡선을도시하였다.  In addition, the current-voltage curve is shown in FIG. 2 by measuring the current-voltage value of the unit cell according to Examples 3-2 to 7-2.
[144] 도 2에나타낸바와같이，전해질막의다공그래파이트층의평균기공면적율이 70%인실시예 5-2가발전성능이가장우수하고，그다음으로평균기공면적율이 50%, 83%인실시예 3-2및실시예 6-2의발전성능이그다음으로우수하며， 평균기공면적율이 92%, 5%인실시예 7-2및실시예 4-2의발전성능은일정 수준의발전성능에도달하지못함을확인할수있다.  As shown in FIG. 2, Example 5-2 having the average pore area ratio of the porous graphite layer of the electrolyte membrane has the highest generation performance, and then the average pore area ratio is 50% and 83%. The power generation performance of 3-2 and Example 6-2 was next superior, and the power generation performance of Example 7-2 and Example 4-2 with an average pore area of 92% and 5% reached a certain level of power generation performance. You can see that it can't.
[145] <시험예 2>막저항의측정  Test Example 2 Measurement of Film Resistance
[146] 전기화학적임피던스분광법 (EIS, electrochemical impedance spectroscopy)을 이용하여,상기실시예 5-2，비교예 1-2및비교예 2-2에따른단위전지의 막저항을측정하였으며，그결과를도 3및도 4에도시하였다.  The membrane resistance of the unit cell according to Example 5-2, Comparative Example 1-2 and Comparative Example 2-2 was measured by using electrochemical impedance spectroscopy (EIS). 3 and 4.
[147] 도 3및도 4에나타난바와같이，퍼플루오르술폰산계전해질막또는  3 and 4, a perfluorosulfonic acid electrolyte membrane or
탄화수소계전해질막을사용한비교예 1-2및비교예 2-2보다,본발명에따른 전해질막을사용한실시예 5-2가낮은저항올나타내므로，본발명에따른 전해질막및이를사용한연료전지의발전효율이더우수함을확인할수 있었다.  Since Example 5-2 using the electrolyte membrane according to the present invention exhibits a lower resistance than Comparative Examples 1-2 and Comparative Example 2-2 using the hydrocarbon-based electrolyte membrane, the development of the electrolyte membrane and the fuel cell using the same according to the present invention. The efficiency was better.
[148] <시험예 3>화학적내구성의측정  Test Example 3 Measurement of Chemical Durability
[149] 일정속도전위훑음법 (LSV, linear sweep voltammetry)을이용하여전해질막의 수소기체투과도및산화안정성을측정하였으며，그결과를도 5에도시하였다. 도 4에나타난바와같이,퍼플루오르술폰산계전해질막또는탄화수소계 전해질막을사용한비교예 1-2및비교예 2-2보다，본발명에따른전해질막을 사용한실시예 5-2가전류밀도가낮아본발명에따른전해질막및이를사용한 연료전지의내구성이더우수함을확.인할수있었다. The hydrogen gas permeability and oxidation stability of the electrolyte membrane were measured using linear sweep voltammetry (LSV), and the results are shown in FIG. As shown in Fig. 4, Example 5-2 using an electrolyte membrane according to the present invention has a lower current density than Comparative Examples 1-2 and Comparative Examples 2-2 using a perfluorosulfonic acid electrolyte membrane or a hydrocarbon-based electrolyte membrane. It was confirmed that the electrolyte membrane according to the invention and the fuel cell using the same were superior.

Claims

청구범위 Claim
[청구항 1] 다공탄소질필름층을포함하는연료전지용전해질막으로서,  [Claim 1] An electrolyte membrane for a fuel cell comprising a porous carbonaceous film layer,
상기다공탄소질필름층의기공의평균직경은 0.1 내지 100 이고, 상기다공탄소질필름층의양면에불소계이오노머층이구비된것인 연료전지용전해질막.  The average diameter of the pores of the porous carbonaceous film layer is 0.1 to 100, the electrolyte membrane for a fuel cell is a fluorine-based ionomer layer is provided on both sides of the porous carbonaceous film layer.
[청구항 2] 계 1항에있어서，  [Claim 2] In Section 1,
상기다공탄소질필름층의평균기공면적율은 10%내지 90%인， 연료전지용전해질막.  The average pore area ratio of the porous carbonaceous film layer is 10% to 90%, fuel cell electrolyte membrane.
[청구항 3] 제 1항에있어서, [Claim 3] In paragraph 1,
상기다공탄소질필름층의기공율은 20%내지 90%인，연료전지용 전해질막.  The porosity of the porous carbonaceous film layer is 20% to 90%, the electrolyte membrane for a fuel cell.
[청구항 4] 제 1항에있어서， [Claim 4] In paragraph 1,
상기다공탄소질필름층의두께는 1 내지 200 인,연료전지용 전해질막.  The porous carbonaceous film layer has a thickness of 1 to 200, an electrolyte membrane for a fuel cell.
[청구항 5] 제 1항에있어서， [Claim 5] In paragraph 1,
상기다공탄소질필름층은다공그래파이트층인，연료전지용전해질막. [청구항 6] 거 15항에있어서，  The porous carbonaceous film layer is a porous graphite layer, fuel cell electrolyte membrane. [Claim 6] In Para. 15,
상기다공그래파이트층은폴리이미드필름을열처리하여탄화한것인, 연료전지용전해질막.  The porous graphite layer is obtained by heat treatment of a polyimide film and carbonized.
[청구항 7] 게 6항에있어서， [Claim 7] In crab 6,
상기폴리이미드필름은다공폴리이미드필름인것인，연료전지용 전해질막.  The polyimide film is a porous polyimide film, an electrolyte membrane for a fuel cell.
[청구항 8] 제 6항에있어서， [Claim 8] In paragraph 6,
상기다공그래파이트층은상기폴리이미드필름에기공을형성한후 열처리한것인，연료전지용전해질막.  The porous graphite layer is a heat treatment after forming pores in the polyimide film, fuel cell electrolyte membrane.
[청구항 9] 게 6항에있어서， [Claim 9] In Crab 6,
상기다공탄소질필름층은상기폴리이미드필름에열처리한후기공을 형성한것인，연료전지용전해질막.  The porous carbonaceous film layer is to form a late hole heat-treated in the polyimide film, fuel cell electrolyte membrane.
[청구항 10] 제 1항에있어서, [Claim 10] In paragraph 1,
상기불소계이오노머층은폴리테트라플루오로에틸렌， The fluorine-based ionomer layer is polytetrafluoroethylene,
(polytetrafluoroethylene:PTFE),폴리비닐리덴플루오라이드 (PVdF), 폴리비닐알코올，셀를로오스아세테이트， (polytetrafluoroethylene: PTFE), polyvinylidene fluoride (PVdF), polyvinyl alcohol, cellulose acetate,
폴리비닐리덴플루오라이드 -핵사플루오로프로필렌의  Polyvinylidene fluoride-of nucleated fluoropropylene
코폴리머 (PVdF-HFP)및스티렌-부타디엔고무 (SBR)로이루어진군에서 선택되는어느하나이상으로이루어진군에서선택되는어느하나 이상인것 ,연료전지용전해질막. - [청구항 11] 제 1항에있어서， 상기다공탄소질필름층은핀을가압또는레이저를조사하여기공을 형성하는것인,연료전지용전해질막. At least one selected from the group consisting of copolymers (PVdF-HFP) and styrene-butadiene rubber (SBR), electrolyte membrane for fuel cells. -[Claim 11] in paragraph 1, The porous carbonaceous film layer is to form pores by pressing a pin or irradiating a laser, fuel cell electrolyte membrane.
[청구항 1 전해질막;및 Claim 1 Electrolyte Membrane; and
상기전해질막막을사이에두고서로대향하여위치하는애노드전극및 캐소드전극;을포함하고，  An anode electrode and a cathode electrode disposed opposite to each other with the electrolyte membrane film interposed therebetween;
상기애노드전극및캐소드전극은기체확산층및촉매층을포함하며, 상기전해질막은제 1항내지제 11항중어느한항에따른연료전지용 전해질막인것인，연료전지용막 -전극접합체 .  The anode electrode and the cathode electrode comprises a gas diffusion layer and a catalyst layer, the electrolyte membrane is a fuel cell electrolyte membrane according to any one of claims 1 to 11, fuel cell membrane-electrode assembly.
[청구항 13] 하나또는둘이상의제 12항에따른막 -전극접합체와상기막 -전극  13.Membrane-electrode assembly and the membrane-electrode according to claim 12
접합체들사이에개재하는세퍼레이터를포함하는스택 ; 연료를상기스택으로공급하는연료공급부;및  A stack comprising a separator interposed between the joints; A fuel supply unit supplying fuel to the stack; and
산화제를상기스택으로공급하는산화제공급부를포함하는연료전지.  A fuel cell comprising an oxidant supply unit for supplying an oxidant to the stack.
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