WO2005053071A1 - Ensemble electrode a membrane et pile a combustible equipee de celui-ci - Google Patents

Ensemble electrode a membrane et pile a combustible equipee de celui-ci Download PDF

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Publication number
WO2005053071A1
WO2005053071A1 PCT/JP2004/016969 JP2004016969W WO2005053071A1 WO 2005053071 A1 WO2005053071 A1 WO 2005053071A1 JP 2004016969 W JP2004016969 W JP 2004016969W WO 2005053071 A1 WO2005053071 A1 WO 2005053071A1
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WO
WIPO (PCT)
Prior art keywords
membrane
electrolyte membrane
active region
catalyst layer
catalyst
Prior art date
Application number
PCT/JP2004/016969
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English (en)
Japanese (ja)
Inventor
Yukihiro Okada
Nobuhiko Hojo
Kohji Yuasa
Original Assignee
Matsushita Electric Industrial Co., 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 Matsushita Electric Industrial Co., Ltd. filed Critical Matsushita Electric Industrial Co., Ltd.
Publication of WO2005053071A1 publication Critical patent/WO2005053071A1/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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a membrane electrode assembly and a fuel cell using the same.
  • Fuel cells have attracted attention in fields such as those for automobiles, homes, and portable devices because of their low power generation efficiency and low environmental load.
  • As fuel for automobile or home fuel cells hydrogen obtained by reforming hydrogen, city gas, gasoline, etc. is used.
  • fuel cells using organic fuels such as aqueous methanol solution are attracting attention.
  • These fuel cells include a membrane-electrode assembly (hereinafter, referred to as an electrolyte membrane) including a proton-conductive electrolyte membrane (hereinafter, referred to as an electrolyte membrane) and a pair of catalyst layers disposed on both sides of the electrolyte membrane and having a smaller area than the electrolyte membrane. , MEA).
  • an electrolyte membrane a polymer membrane of high hydrogen ion (proton) conductivity, perfluorosulfonic acid type or hydrocarbon type is known.
  • a sandwich structure is formed between the two diffusion layers on the anode side and the force source side with the MEA interposed therebetween. Further, the sandwich structure is sandwiched between an anode-side separator for supplying a fuel such as an aqueous solution of hydrogen / methanol and a power-side separator for supplying an oxidizing agent such as air.
  • the diffusion layer is an electrode layer having both air permeability and conductivity, for example, a carbon nonwoven fabric.
  • An electrolyte membrane having a cation exchange group expands and contracts according to its water content.
  • the electrolyte membrane expands.
  • the expansion of the electrolyte membrane is larger when an organic fuel such as an aqueous methanol solution is used than when hydrogen is used as a fuel.
  • the electrolyte membrane shrinks when the fuel cell is operated or when exposed to a dry atmosphere. If the expansion and contraction of the electrolyte membrane are repeated according to the water content, the electrolyte membrane may be broken.
  • a fuel cell using an electrolyte membrane having a reduced water content other than at the junction with the catalyst layer is disclosed in, for example, JP-A-2000-223136. It has been disclosed.
  • the electrolyte membrane is provided with a portion having less cation exchange groups.
  • FIG. 6 is a schematic sectional view showing a conventional MEA.
  • the electrolyte membrane 33 is sandwiched between a catalyst layer 34A on the force side and a catalyst layer 34B on the anode side.
  • the activity is relatively lower than that in the other active region 32 because the cation exchange group is small in order to lower the water content.
  • the central portion 43 of the active region 32 is affected not only by the catalyst layer opposed thereto but also by the surrounding catalyst layer. That is, portion 43 is affected by portion 41 of the catalyst layer. The amount of the portion 41 is almost constant when the portion 43 is near the center of the electrolyte membrane 33.
  • the portion 44 of the electrolyte at the periphery of the active region 32 (boundary to the inactive region 31) and facing the periphery of the catalyst layer is different from the portion 43. That is, although there is an opposed catalyst layer, it is affected only from a portion 42 where a part of the catalyst layer surrounding the portion is not present. Therefore, the amount of the catalyst layer in which the portion 44 is affected is smaller than that of the portion 43.
  • the amount and the state of the catalyst layer affected by the portion 43 and the portion 44 are different. Therefore, when a load is applied, the current density distribution in the active region 32 becomes non-uniform, and the characteristics such as the moisturizing performance are affected.
  • a design is made so that a space exists between the electrode layer and the surrounding frame, and an oxidant such as air or a fuel such as hydrogen or methanol is filled in the space.
  • an oxidant such as air or a fuel such as hydrogen or methanol is filled in the space.
  • Portion 43 is affected by the flow through the opposing catalyst layer, while portion 44 is affected by the flow without the partial catalyst layer. This difference causes a variation in the moisturizing performance of the entire electrolyte membrane, and affects the non-uniformity of the current density distribution and the service life.
  • the fuel cell has a problem called a so-called cross leak, in which a fuel such as hydrogen or methanol moves to the force source side through the electrolyte membrane.
  • a fuel such as hydrogen or methanol moves to the force source side through the electrolyte membrane.
  • the amount of cross leak varies between a portion where a catalyst layer is present and a portion where no catalyst layer is present.
  • the amount of cross leak is larger in the part where the catalyst layer is formed on the electrolyte membrane than in the part where only the electrolyte membrane is formed. Minutes are smaller. This is largely due to the relatively dense structure of the catalyst layer, which is slower than the diffusion force of fuel passing therethrough without the catalyst layer.
  • the amount of cross leak is closely related to the amount of cation exchange groups contained in the electrolyte membrane, and the smaller the number of cation exchange groups, the smaller.
  • the amount of the cation exchange group is changed at the boundary between the portion facing the catalyst layer 34A and the portion not facing the catalyst layer 34A.
  • the cross leak at this boundary increases. This is because, as shown by the bold arrow in the figure, when viewed obliquely from the space where the fuel exists at the boundary, the catalyst layer 34B is almost completely contained in the active region 32 with many cation exchange groups in the portion where the catalyst layer 34B is formed. This is because the fuel comes into contact without going through the layer 34B. If the cross leak changes at the boundary, the cross leak amount becomes uneven in the plane of the MEA.
  • the membrane electrode assembly of the present invention has a proton conductive electrolyte membrane and a pair of catalyst layers provided on both surfaces thereof.
  • the proton conductive electrolyte membrane has an active region having a cation exchange group, and an inactive region around the active region, in which the number of cation exchange groups per unit volume is smaller than that of the active region.
  • the inert region is inserted between the pair of catalyst layers. That is, each of the pair of catalyst layers has a larger area than the active region. With this configuration, nonuniformity of the reaction in the catalyst layer is suppressed.
  • the fuel cell of the present invention has the above-mentioned membrane electrode assembly. With this configuration, nonuniformity of the reaction in the catalyst layer is suppressed, and a long-life fuel cell is obtained.
  • FIG. 1A is a schematic cross-sectional view of a membrane electrode assembly (MEA) according to an embodiment of the present invention.
  • FIG. IB is a schematic front view of the MEA shown in FIG. 1A.
  • FIG. 2 is a schematic sectional view of a fuel cell according to an embodiment of the present invention.
  • FIG. 3 is a schematic cross-sectional view of a fuel cell described in an embodiment of the present invention for comparison.
  • FIG. 4 is a diagram showing the relationship between the length of overlap between the inactive region and the catalyst layer and the life when hydrogen is used as the fuel.
  • FIG. 5 is a diagram showing the relationship between the length of overlap between the inactive region and the catalyst layer and the life when methanol is used as a fuel.
  • FIG. 6 is a schematic cross-sectional view of a conventional MEA.
  • FIGS. 1A and IB are a schematic cross-sectional view and a schematic front view of a membrane electrode assembly (MEA) according to an embodiment of the present invention
  • FIG. 2 is a schematic cross-sectional view of a fuel cell having the MEA shown in FIG. 1A. It is.
  • the proton conductive electrolyte membrane (hereinafter, “membrane”) 13 includes an active region 12 having many cation exchange groups and having proton conductivity, and an inactive region having less cation exchange groups than the active region 12. Region 11.
  • the active region 12 is at the center of the film 13 and the inactive region 11 surrounds the active region 12.
  • the inactive region 11 has a smaller number of cation exchange groups per unit volume than the active region 12. It is preferable that the inactive region 11 has no cation exchange group in order to increase the effect.
  • a method for forming the inactive region 11 in the film 13 will be described later.
  • a catalyst layer 14A on the force side is provided on the first surface of the membrane 13, and a catalyst layer 14B on the anode side (fuel electrode side) is provided on the second surface opposite to the first surface. Te ru.
  • the catalyst layers 14A and 14B have a smaller area than the membrane 13.
  • the membrane 13 and the catalyst layers 14A and 14B are in contact with each other so that their centers are almost coincident.
  • the membrane electrode assembly (MEA) 21 has a membrane 13 and catalyst layers 14A and 14B.
  • the catalyst layers 14A and 14B include conductive particles such as carbon carrying a catalyst and a resin binder, and have gas permeability.
  • a diffusion layer 15A on the force side and a diffusion layer 15B on the anode side for dispersing a liquid or gas are in close contact with the catalyst layers 14A and 14B, respectively.
  • an adhesive or a paste may be arranged between the inactive area 11 and the frame 17! /.
  • a separator 18A on the force side and a separator 18B on the anode side are provided so as to sandwich the diffusion layers 15A, 15B and the frame 17.
  • Each of the separators 18A and 18B has a curved S-shaped tortuous channel 24 such as serpentine for supplying an oxidizing agent (air) or fuel.
  • the generated power is output to the catalyst layers 14A and 14B directly or from the diffusion layers 15A and 15B or through the separators 18A and 18B.
  • the catalyst layer 14 A has a contact surface 25 in contact with the inactive region 11 at the periphery.
  • the contact surface 25 surrounds the periphery of the catalyst layer 14A and has a substantially constant width. That is, the catalyst layer 14A covers at least the active layer 12, and has a larger area than the active layer 12.
  • the catalyst layer 14B also has the same contact surface, but the configuration and effects are the same as those of the catalyst layer 14A, and therefore the description is omitted.
  • the catalyst layer 14A Since the catalyst layer 14A has the contact surface 25, the catalyst layer 14A is larger than the active region 12 by the contact surface 25. Therefore, the amount of the catalyst layer affected by the electrolyte present in the active region 12 depends on whether the electrolyte exists in the center of the active region 12 or in the periphery (near the boundary with the inactive region 11). Will be almost the same. As a result, variations in the current density due to differences in the amount of surrounding catalyst, and the effects of flow and cross leaks caused by fuel and oxidant existing between the catalyst layer and the frame are greatly reduced, resulting in uneven reaction. Properties are greatly reduced. Therefore, in the MEA according to the present embodiment, it is possible to suppress a decrease in the life of the electrolyte membrane due to the non-uniformity of the reaction.
  • perfluorosulfonic acid-tetrafluoroethylene having a length of 12 cm, a width of 12 cm, a thickness of 183 ⁇ m, a tensile coefficient of 249 MPa at 50% RH and 23 ° C. and an electric conductivity of 0.083 SZcm, is used.
  • a copolymer film is used.
  • the membrane 13 has a sulfone group as a cation exchange group
  • the film 13 is irradiated with an electron beam to decompose a 3.1 cm-wide sulfone group around the membrane 13. Remove. Thus, the inactive region 11 is formed in the film 13. In addition, the film 13 was formed with a width of 3.1 cm on the periphery. The area other than the inactive area 11, that is, the masked area of 5.8 cm in length and 5.8 cm in width is the active area 12.
  • a method described in JP-A-2000-251905 may be applied. That is, a heavy metal is substituted in a place where a sulfone group is desired to be left, and after irradiation with an electron beam or the like, the heavy metal is replaced with a proton to decompose a sulfone group at a target site.
  • cross-linking may be performed to form a membrane matrix, and then only a necessary portion may be sulfonated by a chemical reaction.
  • a polymer membrane or inorganic thin film having microporosity is physically filled or chemically filled with a proton conductive electrolyte only in a target portion of a base material corresponding to the active region 12. They may be combined.
  • the proton conductivity of both active regions 12 was measured as an index for comparing the number of cation exchange groups per unit volume of the inactive region 11 with the number of cation exchange groups per unit volume. Is shown.
  • the active region 12 and the inactive region 11 are cut out, immersed in water, sandwiched between gold plates, and then measured for proton conductivity by an AC impedance method.
  • the active region 12, a 0. LSZcm, the inactive region 11, is less than 10- 4 S / cm.
  • the amount of cation exchange groups in the active region 12 was 1.77 meqZcm 3 .
  • MeqZcm 3 is an indicator of the ion exchange capacity per volume lcm 3 of the membrane in the dry state, The higher the number, the meaning taste that cation exchange groups is large.
  • the catalyst layer 14A on the force side is formed of catalyst-carrying particles in which 50% by weight of platinum particles having an average particle diameter of about 3nm are supported on conductive carbon particles having an average primary particle diameter of 30nm.
  • the catalyst layer 14B on the anode side is composed of catalyst-supporting particles in which 50% by weight of platinum ruthenium alloy particles having an average particle size of about 3 nm are supported on the same conductive carbon particles.
  • Each of the catalyst-carrying particles, a proton conductor similar to MEA, and water are mixed to prepare a catalyst paste.
  • Each of the pastes thus prepared is applied to one surface of the previously prepared film 13 by a spray method to form catalyst layers 14A and 14B.
  • Ocm are formed in the center of the film 13 using a mask having a hole having a length of 6. Ocm and a width of 6. Ocm.
  • the MEA 21 in which the overlap length of the inactive region 11 and the catalyst layers 14A and 14B is 1. Omm is formed.
  • the amount of the catalyst is about lmg / cm 2 in terms of platinum on both the anode side and the power source side.
  • a frame 17 having a length of 12 cm, a width of 12 cm, and a thickness of 300 / z m having a hole of 6.03 cm ⁇ 6.03 cm is installed on both sides of the MEA 21.
  • Diffusion layers 15A and 15B made of carbon paper having a size of OOcm x 6000cm and a thickness of 360m are placed in the holes.
  • a fuel cell (Sample A) as shown in Fig. 2 was obtained by sandwiching it between separators 18A and 18B, which are 4 mm thick and have a thickness of lmm and a width of lmm, in which grooves for liquid and gas flow are formed. Is received.
  • Separators 18A and 18B and a metal plate are provided with a fuel inlet 26 and a discharge outlet 27 on the anode side, and a suction port 28 and a discharge port 29 for an oxidant such as air on the power source side, respectively. Fuel and air and the like are supplied to the fuel cell using the respective pumps.
  • the size of the lead plate used in the preparation of Sample B is 5.94cm x 5.94cm. In this case, the overlap length of the inactive region 11 and the catalyst layers 14A and 14B is 0.3 mm.
  • the size of the lead plate used when preparing sample C is 5.90 cm X 5.90 cm. In this case, the overlap length of the inactive region 11 and the catalyst layers 14A and 14B is 0.5 mm.
  • the size of the lead plate used in the preparation of Sample D is 5. OOcm x 5. OOcm. In this case, the overlap length of the inert region 11 and the catalyst layers 14A and 14B is 5 mm.
  • Sample E The size of the lead plate used in the preparation of the sample is 4. OOcm X 4. OOcm. In this case, the overlap length of the inert region 11 and the catalyst layers 14A and 14B is 10 mm.
  • FIG. 3 shows a cross-sectional view of the fuel cell of Sample F.
  • a 2 mol ZL aqueous methanol solution is supplied as a fuel from the anode side at 2 mL Zmin, and air as an oxidant is supplied at 1 L Zmin from the power source side.
  • the temperature of the fuel cell is 60 ° C.
  • FIG. 5 shows the result of plotting this index with respect to the length of overlap between the inactive region 11 from which the sulfone group has been removed and the catalyst layers 14A and 14B.
  • Samples A to E the vicinity of the boundary between fuel and air existing between MEA 21 and surrounding frame 17 and the inactive region 11 of active region 12 is the same as Sample F shown in FIG. Compared to the structure of the above, they are isolated by the catalyst layers 14A and 14B. Therefore, the vicinity of the boundary between the active region 12 and the inactive region 11 is not affected by the flow of fuel or air. Therefore, variation in the moisturizing performance of the entire membrane 13 is suppressed, unevenness of the current density distribution is suppressed, and the life of the fuel cell is improved.
  • the difference in the influence of the fuel and air flows also affects the difference in the amount of cross leak. Since the amount of cross-leakage of hydrogen is relatively small, there is no difference in the initial voltage between sample F and samples A-E in power generation using hydrogen as fuel. When methanol is used as the fuel, which is susceptible to cross-leakage, the initial voltage of samples A to E is higher than that of sample F, and cross-leakage is suppressed.
  • the life of sample C in which the overlap region between the inactive region 11 and the catalyst layers 14A, 14B is 0.5 mm, is significantly improved as compared with the sample F and the sample B. are doing. That is, the length of the overlap between the inactive region 11 and the catalyst layers 14A and 14B (the length of the contact surface 25) is preferably 0.5 mm or more. 1 mm or more is more desirable.
  • the length of the contact surface 25 is desirably 5 mm or less.
  • the catalyst layers 14 A and 14 B have a smaller area than the membrane 13, but also for the same reason as described above, and for the reason that the fuel cell is sealed with the frame 17.
  • the frame 17 may not be used but may be configured by impregnating the diffusion layer with an adhesive, for example.
  • the length of the overlap between the catalyst layer 14A and the inactive region 11 and the length of the overlap between the catalyst layer 14B and the inactive region 11 may be different! / !. Further, the inactive region 11 may not be formed over the entire thickness direction of the film 13.
  • a hydrocarbon-based film or a material in which a porous substrate is filled with a proton-conductive substance can also provide the same effect.
  • the catalyst layers 14A and 14B may be made of the same proton conductor as the MEA but different in proton conductor.
  • methanol is used as the organic fuel.
  • other organic fuels having a high degree of swelling of the membrane 13 show the same tendency.
  • the present invention is effective when an organic fuel such as an alcohol, an ether, or a methoxy-containing compound is used.
  • the MEA according to the present invention is useful for a fuel cell having excellent life characteristics.

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

L'invention concerne un ensemble électrode à membrane comprenant une membrane électrolytique conductrice de protons et une paire de couches de catalyse disposées, respectivement, de chaque côté de la membrane. La membrane électrolytique conductrice de protons comprend une zone active contenant des groupes à échange cationique, et une zone inactive autour de la zone active. Le nombre de groupes à échange cationique par volume unitaire dans la zone inactive est inférieur à celui de la zone active. La zone inactive est interposée entre la paire de couches de catalyse.
PCT/JP2004/016969 2003-11-25 2004-11-16 Ensemble electrode a membrane et pile a combustible equipee de celui-ci WO2005053071A1 (fr)

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JP2003-393601 2003-11-25
JP2003393601 2003-11-25

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008029818A1 (fr) * 2006-09-06 2008-03-13 Toyota Jidosha Kabushiki Kaisha Membrane électrolytique, ensemble électrode à membrane et leurs procédés de réalisation
JP2008078123A (ja) * 2006-08-14 2008-04-03 Gm Global Technology Operations Inc 膜の局所的不活性化
JP2021061193A (ja) * 2019-10-08 2021-04-15 日本碍子株式会社 電気化学セル用電解質、及び電気化学セル

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JPS60200467A (ja) * 1984-03-23 1985-10-09 Hitachi Ltd 燃料電池の組立方法
JPH09199145A (ja) * 1996-01-22 1997-07-31 Toyota Motor Corp 燃料電池および燃料電池の製造方法
JP2000223136A (ja) * 1999-01-27 2000-08-11 Aisin Seiki Co Ltd 燃料電池用固体高分子電解質膜およびその製造方法および燃料電池
WO2000054351A1 (fr) * 1999-03-08 2000-09-14 Center For Advanced Science And Technology Incubation, Ltd. Membrane electrolytique pour pile a combustible et son procede de fabrication, et pile a combustible et son procede de fabrication
JP2002083612A (ja) * 2000-09-07 2002-03-22 Takehisa Yamaguchi 電解質膜及びその製造方法、並びに燃料電池及びその製造方法
JP2003234015A (ja) * 2002-02-12 2003-08-22 Isamu Uchida 固体高分子イオン伝導体およびその製造方法
JP2003263999A (ja) * 2002-03-07 2003-09-19 Toyota Central Res & Dev Lab Inc 膜電極接合体並びにこれを備える燃料電池及び電気分解セル
JP2004362905A (ja) * 2003-06-04 2004-12-24 Nippon Telegr & Teleph Corp <Ntt> 直接メタノール型燃料電池用電解質膜の製造方法

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JPS60200467A (ja) * 1984-03-23 1985-10-09 Hitachi Ltd 燃料電池の組立方法
JPH09199145A (ja) * 1996-01-22 1997-07-31 Toyota Motor Corp 燃料電池および燃料電池の製造方法
JP2000223136A (ja) * 1999-01-27 2000-08-11 Aisin Seiki Co Ltd 燃料電池用固体高分子電解質膜およびその製造方法および燃料電池
WO2000054351A1 (fr) * 1999-03-08 2000-09-14 Center For Advanced Science And Technology Incubation, Ltd. Membrane electrolytique pour pile a combustible et son procede de fabrication, et pile a combustible et son procede de fabrication
JP2002083612A (ja) * 2000-09-07 2002-03-22 Takehisa Yamaguchi 電解質膜及びその製造方法、並びに燃料電池及びその製造方法
JP2003234015A (ja) * 2002-02-12 2003-08-22 Isamu Uchida 固体高分子イオン伝導体およびその製造方法
JP2003263999A (ja) * 2002-03-07 2003-09-19 Toyota Central Res & Dev Lab Inc 膜電極接合体並びにこれを備える燃料電池及び電気分解セル
JP2004362905A (ja) * 2003-06-04 2004-12-24 Nippon Telegr & Teleph Corp <Ntt> 直接メタノール型燃料電池用電解質膜の製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008078123A (ja) * 2006-08-14 2008-04-03 Gm Global Technology Operations Inc 膜の局所的不活性化
US8617760B2 (en) 2006-08-14 2013-12-31 GM Global Technology Operations LLC Localized deactivation of a membrane
WO2008029818A1 (fr) * 2006-09-06 2008-03-13 Toyota Jidosha Kabushiki Kaisha Membrane électrolytique, ensemble électrode à membrane et leurs procédés de réalisation
JP2008066084A (ja) * 2006-09-06 2008-03-21 Toyota Motor Corp 電解質膜および膜電極接合体並びにそれらの製造方法
JP2021061193A (ja) * 2019-10-08 2021-04-15 日本碍子株式会社 電気化学セル用電解質、及び電気化学セル

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