WO2002021619A1 - Pile a combustible electrolytique a polymere solide - Google Patents

Pile a combustible electrolytique a polymere solide Download PDF

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Publication number
WO2002021619A1
WO2002021619A1 PCT/JP2000/005971 JP0005971W WO0221619A1 WO 2002021619 A1 WO2002021619 A1 WO 2002021619A1 JP 0005971 W JP0005971 W JP 0005971W WO 0221619 A1 WO0221619 A1 WO 0221619A1
Authority
WO
WIPO (PCT)
Prior art keywords
dodecene
fuel cell
solid polymer
electrolyte membrane
polymer electrolyte
Prior art date
Application number
PCT/JP2000/005971
Other languages
English (en)
Japanese (ja)
Inventor
Kenji Yamaga
Toshiyuki Kobayashi
Yoshitaka Takezawa
Tomoichi Kamo
Original Assignee
Hitachi, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi, Ltd. filed Critical Hitachi, Ltd.
Priority to PCT/JP2000/005971 priority Critical patent/WO2002021619A1/fr
Priority to JP2002525931A priority patent/JPWO2002021619A1/ja
Publication of WO2002021619A1 publication Critical patent/WO2002021619A1/fr

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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
    • H01M8/1004—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
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • 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 reformed gas contains by-products mainly composed of CO in the range of several hundred ppm to several%, and this CO is used as a platinum catalyst, which is a reaction field of the electrochemical reaction of PEFC.
  • the performance of the battery decreases because the reaction is inhibited by selective adsorption on the surface (catalyst poisoning).
  • PEFC has a large reduction reaction polarization at the cathode.
  • reduction of reaction polarization is a research topic.
  • the present invention includes the following inventions.
  • amorphous polyolefin having a cyclic structure for example, the following formula:
  • bicyclohept-2-ene or a derivative thereof examples include, for example, bicyclohept-2-ene, 6-methylbicyclohept-12-ene, 5,6-dimethylbicyclohept-2-ene, 1 1-Methylbicyclohept-2-ene, 6-Ethylbicyclo Mouth Hept-2-ene, 6-n-Butylbicyclohept-1-ene, 6-Isobutylbicyclohept-2-ene, 7-Methylbicyclohept — 2-ene.
  • the structure of the solid polymer electrolyte fuel cell of the present invention is not particularly limited.
  • an electrode and an electrode for guiding gas are provided on both sides of an electrolyte membrane containing a matrix serving as a membrane base material and a proton donor.
  • An example is a structure in which a diffusion layer and a gas separator, which prevents gas mixing, ensures current collection in the electrode surface and conduction in the battery thickness direction, and forms an outer shell of the cell, are sequentially arranged.
  • the proton donor of the electrolyte membrane and the matrix form an atomic group in which at least an oxygen atom and one atom selected from Si, Ti and Zr, preferably Si are bonded. It is preferable to use an electrolyte membrane that is bonded through the intermediary. As a result, the ion-exchange group is firmly fixed to the matrix, so that the phenomenon that the ion-exchange group is released outside the membrane with time and the resistance of the membrane increases can be greatly suppressed, and a longer life can be realized. .
  • the proton donor that imparts ionic conductivity to the electrolyte membrane also requires heat resistance.
  • water since water has a boiling point of 10 O ⁇ C at normal pressure, the entire atmosphere must be pressurized to keep the membrane moist at higher temperatures. From such a point, it is preferable to use a metal oxide having proton conductivity as the proton donor, and it is preferable to use a polyacid as a material that exhibits good proton conductivity and does not deteriorate in ionic conductivity even at a high temperature. More preferred.
  • polyacid those containing at least one selected from the group consisting of W, Si, Sn, Zn, P and Mo as a central ion are preferable.
  • the resistance is low even under high temperature conditions, and the amount of water vapor for wetting the electrolyte membrane can be kept low. This is because the material itself holds water molecules in the form of water of hydration, or adsorbs it on the surface of the material, so that a proton conduction path can be secured even in an environment with low relative humidity. This allows the operating pressure of the battery to be set low, which is effective in simplifying the system configuration.
  • the metal oxide having proton conductivity used as the proton donor at least silicon oxide containing P can be used.
  • phosphate glass has high heat resistance (e.g., P 2 O 5 ⁇ y S I_ ⁇ 2, xP 2 0 5 - yZ r 0 2 - in z S I_ ⁇ 2 (here, x, y and z is represents any number.), high temperature stability as an electrolyte membrane by using a more specifically include compositions such as 5 P 2 0 5 ⁇ 5 Z r 0 2 ⁇ 90 S i 0 2.) Can be further improved.
  • the phosphoric acid-based glass preferably has a porous structure in order to increase the amount of adsorbed water and adsorbed hydroxyl groups serving as proton conduction paths and the amount of water contained therein.
  • FIG. 1 shows a typical structure of an electrolyte membrane constituting a solid polymer electrolyte fuel cell of the present invention. It has a structure in which a substituent R 2 is bonded to an amorphous polyolefin main chain. Where R 2 is
  • Electrolyte membrane matrix material as J SR Inc. Art TM (specific gravity 1.08, glass transition temperature 17 1, the thermal conductivity of 0. lekcal Zm 'hr' ⁇ ) 4 single glass powder 80 g of toluene 220 m 1 The mixture was added to a neck flask, and stirred under a nitrogen atmosphere to obtain an electrolyte membrane matrix solution a. 8 g of 3f succinatepropyltriethoxysilane was added to solution a, and the mixture was stirred under reflux at 75 ° C. under a nitrogen atmosphere for 24 hours to prepare solution b.
  • the resultant was developed into a film having a thickness of m and dried in air at 75 ° C for 10 hours to obtain an electrolyte membrane d. Even when the electrolyte membrane was left in a boiling aqueous solution, no change was observed in the proton concentration of the solution. This is because kytungstic acid, which is an ion exchange group, is chemically fixed to the matrix by coupling.
  • a catalyst paste e was prepared by mixing 2.5 g of a catalyst obtained by depositing fine platinum particles on carbon powder and 90 g of an electrolyte solution c ′.
  • the catalyst paste e was spread on the surface of the electrolyte membrane d by screen printing into a square thin film having a side of 10 cm to form a catalyst layer.
  • the spreading amount that is, the catalyst layer thickness was adjusted so that the amount of platinum used was 0.3 mg per 1 cm 2 of the coated catalyst area.
  • Apply catalyst layer on both sides of electrolyte membrane d Thereafter, a drying treatment was performed at 75 ° C. for 10 hours in a nitrogen atmosphere.
  • This treatment has the meaning of dispersing the solvent in the catalyst layer and promoting the gelling reaction of the electrolyte membrane base in the catalyst layer.
  • An electrode diffusion layer (Carbon-CL, manufactured by Japan Gortex Co., Ltd.), which also has a current collecting function, is placed on both sides of the catalyst surface of this integrated electrode f, and a single cell for testing is combined with a carbon separator that forms a gas flow path. And This cell is referred to as a first embodiment.
  • This single cell was placed in a thermostat, and hydrogen was supplied as anode gas and air was supplied as power source gas, and a power generation test was performed.
  • the anode gas and cathodic gas were humidified by passing through a temperature-adjustable bubbler, preventing an increase in ion conduction resistance due to drying of the electrolyte membrane.
  • Pressure regulating valves are provided at the gas line outlets of the anode and cathode, respectively, so that gas humidification can be performed even at a cell temperature of 100 ° C or more.
  • the cell temperature was set at 130 ° C
  • the humidification temperature of the anode gas and the force gas was also set at 130 ° C.
  • an electrolyte membrane matrix material 80 g of Arton 1 ⁇ (specific gravity: 1.08, glass transition temperature: 171 ° (thermal conductivity: 0.16 kca 1 Zm ⁇ hr ⁇ ° C) manufactured by JSR Corporation) 220 ml of toluene was added to a glass four-necked flask, and stirred under a nitrogen atmosphere to obtain an electrolyte membrane matrix solution a.8 g of 3-isocyanatepropyltriethoxysilane was added to the solution a, and the solution was added at 75 ° C. The mixture was refluxed and mixed under a nitrogen atmosphere for 24 hours to prepare a solution b.
  • Arton 1 ⁇ specific gravity: 1.08, glass transition temperature: 171 ° (thermal conductivity: 0.16 kca 1 Zm ⁇ hr ⁇ ° C) manufactured by JSR Corporation
  • solution b 50 g of solution b was added to 25 g of phosphoric acid-based glass i crushed by a pole mill for 5 hours, and 0.1 N hydrochloric acid was added to prepare an electrolyte solution j.
  • An electrolyte membrane k was obtained.
  • a catalyst layer was formed on the opposite surface in the same manner as above to obtain an integrated electrode m.
  • An electrode diffusion layer (CARBEL-CL, manufactured by Japan Gore-Tex Corporation) and a carbon separator were arranged on the integrated electrode m to form a single cell. This cell was used as a comparative example. Humidified hydrogen and humidified air were supplied to the comparative example cell, and a power generation test was performed at a cell temperature of 130 ° C.
  • FIG. 2 shows the change over time in the cell voltage when a current of 0.5 A was applied per 1 cm 2 of electrode area for Examples 1, 2 and Comparative Example.
  • Comparative Example 1 the battery voltage was reduced after several hundred hours under the operating condition of 130 ° C. This is probably because the water content of the electrolyte membrane decreased and the proton conductivity increased under high temperature conditions and low relative humidity.
  • the perfluorocarbon sulfonic acid-based electrolyte membrane has a structure in which a hydrophilic group forms a cluster structure to secure a proton channel. This is also due to the increase in
  • FIG. 3 shows the results of measuring the conductivity of Examples 1, 2 and Comparative Example when the relative humidity of the supply gas was changed at 130 ° C.
  • the conductivity was evaluated by an AC 1 kHz four-terminal method.
  • the conductivity of the electrolyte membrane of the comparative example decreases sharply at low relative humidity.
  • the present invention it is possible to operate a fuel cell at a high temperature, to improve the CO poisoning resistance of the electrode catalyst, to improve the performance by reducing the reaction resistance of the force sword reaction, and to reduce the exhaust heat of the cell as one of the heat sources of the fuel reforming section. It is possible to improve the system efficiency by collecting it in the section.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne une pile à combustible électrolytique à polymère solide comprenant des électrodes, une couche de diffusion d'électrode d'introduction de gaz, des séparateurs destinés à empêcher le mélange de gaz et assurer le captage de courant dans la surface d'électrode ainsi que la connexion électrique dans le sens de l'épaisseur de la pile, et à constituer l'enveloppe d'une pile unitaire sur les deux côtés d'un film électrolytique contenant, dans l'ordre, une matrice servant de matière de base de film et un donneur de protons, une polyoléfine non cristalline étant utilisée pour la matrice de film électrolytique.
PCT/JP2000/005971 2000-09-01 2000-09-01 Pile a combustible electrolytique a polymere solide WO2002021619A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/JP2000/005971 WO2002021619A1 (fr) 2000-09-01 2000-09-01 Pile a combustible electrolytique a polymere solide
JP2002525931A JPWO2002021619A1 (ja) 2000-09-01 2000-09-01 固体高分子電解質型燃料電池

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2000/005971 WO2002021619A1 (fr) 2000-09-01 2000-09-01 Pile a combustible electrolytique a polymere solide

Publications (1)

Publication Number Publication Date
WO2002021619A1 true WO2002021619A1 (fr) 2002-03-14

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JP (1) JPWO2002021619A1 (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003157863A (ja) * 2001-01-09 2003-05-30 National Institute Of Advanced Industrial & Technology プロトン伝導性膜、その製造方法及びそれを用いた燃料電池
JP2004296275A (ja) * 2003-03-27 2004-10-21 Kyocera Corp 発電装置

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60220503A (ja) * 1984-04-16 1985-11-05 松下電器産業株式会社 プロトン伝導体
JPH06340781A (ja) * 1993-04-05 1994-12-13 Sumitomo Bakelite Co Ltd ポリオレフィン系ポリマーアロイ
JPH07157601A (ja) * 1993-10-15 1995-06-20 Sumitomo Bakelite Co Ltd 導電性非晶性ポリオレフィン樹脂組成物
JPH07296634A (ja) * 1994-04-22 1995-11-10 Asahi Chem Ind Co Ltd 複合電解質膜
JPH11135137A (ja) * 1997-10-31 1999-05-21 Asahi Glass Co Ltd 固体高分子電解質型メタノール燃料電池
EP0926754A1 (fr) * 1997-12-10 1999-06-30 De Nora S.P.A. Cellule électrochimique à membrane polymère fonctionnant à une température supérieure à 100 C
JP2000200616A (ja) * 1998-05-13 2000-07-18 Daikin Ind Ltd 燃料電池に使用するのに適した固体高分子電解質用材料

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60220503A (ja) * 1984-04-16 1985-11-05 松下電器産業株式会社 プロトン伝導体
JPH06340781A (ja) * 1993-04-05 1994-12-13 Sumitomo Bakelite Co Ltd ポリオレフィン系ポリマーアロイ
JPH07157601A (ja) * 1993-10-15 1995-06-20 Sumitomo Bakelite Co Ltd 導電性非晶性ポリオレフィン樹脂組成物
JPH07296634A (ja) * 1994-04-22 1995-11-10 Asahi Chem Ind Co Ltd 複合電解質膜
JPH11135137A (ja) * 1997-10-31 1999-05-21 Asahi Glass Co Ltd 固体高分子電解質型メタノール燃料電池
EP0926754A1 (fr) * 1997-12-10 1999-06-30 De Nora S.P.A. Cellule électrochimique à membrane polymère fonctionnant à une température supérieure à 100 C
JP2000200616A (ja) * 1998-05-13 2000-07-18 Daikin Ind Ltd 燃料電池に使用するのに適した固体高分子電解質用材料

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003157863A (ja) * 2001-01-09 2003-05-30 National Institute Of Advanced Industrial & Technology プロトン伝導性膜、その製造方法及びそれを用いた燃料電池
JP2004296275A (ja) * 2003-03-27 2004-10-21 Kyocera Corp 発電装置
JP4671585B2 (ja) * 2003-03-27 2011-04-20 京セラ株式会社 発電装置

Also Published As

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