US20120152451A1 - Method for producing fuel cell electrolyte membrane and method for producing membrane-electrolyte assembly - Google Patents
Method for producing fuel cell electrolyte membrane and method for producing membrane-electrolyte assembly Download PDFInfo
- Publication number
- US20120152451A1 US20120152451A1 US13/403,512 US201213403512A US2012152451A1 US 20120152451 A1 US20120152451 A1 US 20120152451A1 US 201213403512 A US201213403512 A US 201213403512A US 2012152451 A1 US2012152451 A1 US 2012152451A1
- Authority
- US
- United States
- Prior art keywords
- membrane
- electrolyte
- electrolyte membrane
- projections
- recesses
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
Images
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]
- H01M8/1006—Corrugated, curved or wave-shaped 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
-
- 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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1093—After-treatment of the membrane other than by polymerisation mechanical, e.g. pressing, puncturing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
- Y10T156/1002—Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
- Y10T156/1039—Surface deformation only of sandwich or lamina [e.g., embossed panels]
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
- Y10T156/1089—Methods of surface bonding and/or assembly therefor of discrete laminae to single face of additional lamina
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
- Y10T156/1089—Methods of surface bonding and/or assembly therefor of discrete laminae to single face of additional lamina
- Y10T156/109—Embedding of laminae within face of additional laminae
Definitions
- the present invention relates to a method for producing a fuel cell electrolyte membrane and a method for producing membrane-electrode assembly using the produced electrolyte membrane.
- a polymer electrolyte fuel cell has been known as one type of fuel cell. Since a polymer electrolyte fuel cell is characterized by low operating temperatures (up to approximately 80° C. to 100° C.), low cost, and its compact size when compared with different types of fuel cells, it is expected to serve as an automobile power source and the like.
- a membrane-electrode assembly (MEA) 50 which is used as a main component, is sandwiched by separators 51 each having a fuel (hydrogen) gas channel and an air gas channel such that a single fuel cell 55 , referred to as a single cell, is formed.
- a membrane-electrode assembly 50 has a structure in which an anode-side electrode catalyst layer 53 a is laminated on one side of an electrolyte membrane 52 serving as an ion exchange membrane and a cathode-side electrode catalyst layer 53 b is laminated on the other side thereof.
- a perfluorosulfonic acid polymer thin film (Nation membrane, DuPont, the U.S.) comprising an electrolyte resin (ion exchange resin) is mainly used as such an electrolyte membrane 52 .
- an electrolyte resin solution may be allowed to impregnate a porous reinforcing membrane (e.g., a thin film prepared by stretching PTFE, polyolefin resin, or the like) such that a reinforced electrolyte membrane is obtained (see Patent Document 1, etc.).
- an electrode catalyst material comprising an electrode catalyst such as platinum-supporting carbon and an electrolyte resin is mainly used.
- a membrane-electrode assembly 50 is obtained by applying such electrode catalyst material to an electrolyte membrane 52 by a screen printing method or the like, followed by drying (see Patent Document 2, etc.).
- a membrane-electrode assembly In view of improvement of power generation performance, it is desirable for a membrane-electrode assembly to have a large effective contact area between an electrolyte membrane and an electrode catalyst layer. In order to achieve such purpose, it has been suggested that a membrane-electrode assembly be obtained by forming recesses and projections on the electrode catalyst layer side in a preliminary step with the use of a press or the like and pressure-welding an electrolyte membrane thereto (see Patent Document 3, etc.).
- Any electrolyte membrane comprising a conventional electrolyte resin thin film or reinforced electrolyte membrane produced in a manner as described in Patent Document 1 has a flat surface.
- a membrane-electrode assembly is obtained using such a membrane by a conventional method as described in Patent Document 2
- the effective contact area between an electrolyte membrane and an electrode catalyst layer remains as the surface area of a flat face.
- an electrolyte membrane is likely to be damaged when an electrode catalyst layer on which recesses and projections have been formed is pressure-welded to an electrolyte membrane having a flat face.
- the presence of the interface between an electrolyte membrane and an electrode catalyst layer makes it impossible to prevent reduction in power generation efficiency of a membrane-electrode assembly caused by interface resistance.
- the present invention has been made in view of the above circumstances. It is an objective of the present invention to provide a method for producing a fuel cell electrolyte membrane with which it is possible to increase the effective contact area between an electrolyte membrane and an electrode catalyst layer, and to provide a method for producing a membrane-electrode assembly using such electrolyte membrane, whereby the interface resistance generated between an electrolyte membrane and an electrode catalyst layer is reduced such that power generation performance can be improved.
- the first invention relates to a method for producing a fuel cell electrolyte membrane, comprising at least a step of heating and pressing an electrolyte membrane comprising a fluorine-based electrolyte with the use of a plate having recesses and projections on the surface thereof so as to form recesses and projections on the electrolyte membrane surface.
- An electrolyte membrane produced by the above production method has recesses and projections on the surface thereof and thus the surface area is increased due to such recesses and projections.
- Such recesses and projections may be of any size and shape. The size and shape are appropriately determined based on the necessary size of the surface area. In usual cases, the recess depth (or projection height) is several micrometers to several tens of micrometers. Recesses and projections may be formed on a continuous curved surface or may be formed with many concave grooves and columnar concave portions.
- an electrolyte resin used as a base material for an electrolyte membrane a fluorine-based electrolyte made of a precursor polymer for an electrolyte polymer is used in view of its thermal stability.
- a step of imparting ion exchange properties to an electrolyte polymer via hydrolysis or the like is carried out following a step of forming recesses and projections on the electrolyte membrane surface.
- the second invention relates to a method for producing a fuel cell electrolyte membrane, comprising at least the following steps: an application step of applying fluorine-based electrolyte particles to the surface of a porous reinforcing membrane; an impregnation step of heating the porous reinforcing membrane, to which electrolyte particles have been applied, with the use of a heated plate, melting the electrolyte particles, and allowing the electrolyte particles to impregnate the porous reinforcing membrane so as to obtain an electrolyte membrane; and a step of pressing the electrolyte membrane with a plate having recesses and projections on the surface thereof so as to form recesses and projections on the electrolyte membrane surface.
- porous reinforcing membrane As a porous reinforcing membrane used herein, a porous reinforcing membrane prepared by stretching PTFE (polytetrafluoroethylene), a polyolefin resin, or the like which has been used for a conventional reinforced electrolyte membrane in a single axial or biaxial direction can be appropriately used. Fluorine-based electrolyte particles to be applied to the surface of a porous reinforcing membrane are obtained by forming a fluorine-based electrolyte into resin particles, the particle size of which is preferably 100 ⁇ m or less and more preferably approximately 0.1 ⁇ m to 50 ⁇ m.
- a porous reinforcing membrane to which fluorine-based electrolyte particles have been applied is heated with a heated plate such that electrolyte particles become molten and impregnate the porous reinforcing membrane.
- the molten electrolyte impregnates the porous reinforcing membrane without the need to be actively externally pressed. Thus, no damage is caused to the porous reinforcing membrane due to pressing.
- such reinforced electrolyte membrane impregnated with the electrolyte resin is pressed with a plate having recesses and projections on the surface thereof such that recesses and projections are formed on the electrolyte membrane surface.
- a heating plate used to melt electrolyte particles may differ from a pressing plate used to form recesses and projections on the electrolyte membrane surface.
- a reinforced electrolyte membrane impregnated with an electrolyte resin is transferred between the two plates. It is also possible to carry out the above two steps in a consecutive manner with the use of a plate comprising a heating means and having recesses and projections on the surface thereof. In such case, electrolyte particles become molten and are allowed to impregnate a porous reinforcing membrane while a plate is maintained in a heated state.
- a reinforced electrolyte membrane having recesses and projections on the surface thereof and comprising a porous reinforcing membrane can be obtained.
- fluorine-based electrolyte particles made from a precursor polymer for an electrolyte polymer have thermal stability, they are used as electrolyte resin particles for a base material. If necessary, a step of imparting ion exchange properties to an electrolyte polymer via hydrolysis or the like is further carried out following a step of forming recesses and projections on the reinforced electrolyte membrane surface.
- At least the impregnation step is preferably carried out in a reduced pressure environment.
- deaeration inside the porous reinforcing membrane and substitution of deaerated spaces with the molten electrolyte are promoted. Accordingly, the time period for electrolyte impregnation of the porous reinforcing membrane can be shortened. In addition, a sufficient state of impregnation can be realized.
- a step of pressing an electrolyte membrane with a plate having recesses and projections on the surface thereof so as to form recesses and projections on the electrolyte membrane surface by may be carried out in a reduced pressure environment.
- the present application further discloses the following method as a method for producing a membrane-electrode assembly using a fuel cell electrolyte membrane produced by the above method: a method for producing a membrane electrode laminate, comprising applying electrode catalyst particles or a mixture of an electrode catalyst resin and fluorine-based electrolyte particles to the surface of an electrolyte membrane, on which recesses and projections have been formed prior to a treatment for imparting ion exchange properties to an electrolyte polymer, so as to obtain a laminate; heating the laminate such that the electrode catalyst layer binds to the electrolyte membrane so as to be combined therewith; and carrying out a treatment for imparting ion exchange properties to an electrolyte polymer.
- the electrode catalyst particles used are conventionally known electrode catalyst particles in which a catalyst component such as platinum is supported by a conductive carrier such as carbon. Such particles are obtained by forming a fluorine-based electrolyte resin into fluorine-based electrolyte particles.
- the particle size thereof is preferably 100 ⁇ m or less, more preferably approximately 0.1 ⁇ m to 50 ⁇ m, and further preferably 1 ⁇ m or less.
- the formed laminate is heated to a temperature at least sufficient to melt a fluorine-based electrolyte resin.
- the heating temperature is from approximately 200° C. to 270° C. Heating can be carried out by an arbitrary method. However, a method wherein the above laminate is positioned between a pair of heating plates and heating is carried out with the heat generated from heating plates is preferable.
- a fluorine-based electrolyte resin constituting an electrolyte membrane and an electrode catalyst resin When a fluorine-based electrolyte resin constituting an electrolyte membrane and an electrode catalyst resin are applied, the applied fluorine-based electrolyte particles become molten by heating. Then, the molten fluorine-based electrolyte resin acts as a binder and thus binds to applied electrode catalyst particles so as to be combined therewith.
- a membrane-electrode assembly is obtained under a condition in which an electrolyte membrane having recesses and projections formed on the surface thereof binds to an electrode catalyst layer comprising electrode catalyst particles so as to be combined therewith while there is no gap therebetween or there are few, if any, gaps therebetween.
- the obtained membrane-electrode assembly is subjected to a treatment for imparting ion exchange properties to an electrolyte polymer, such as hydrolysis.
- the resulting membrane electrode laminate has an increased effective contact area between an electrolyte layer and an electrode catalyst layer and further has a significantly reduced interface resistance.
- a membrane electrode laminate having high power generation efficiency and a long lifetime can be obtained.
- an electrolyte membrane has recesses and projections on the surface thereof such that the effective contact area between the electrolyte membrane surface and an electrode catalyst layer can be increased. Further, the interface resistance generated between the electrolyte membrane surface and the electrode catalyst layer can be reduced in a membrane-electrode assembly. Thus, a membrane-electrode assembly having high power generation performance can be obtained.
- FIG. 1 is an explanatory diagram of one embodiment of the method for producing a fuel cell electrolyte membrane of the present invention.
- FIG. 2 is an explanatory diagram of another embodiment of the method for producing a fuel cell electrolyte membrane of the present invention.
- FIG. 3 is an explanatory diagram of one embodiment of the production of the membrane-electrode assembly of the present invention with the use of a prepared fuel cell electrolyte membrane.
- FIG. 4 schematically shows one embodiment of a fuel cell.
- 1 fluorine-based electrolyte membrane as a starting material
- 2 a , 2 b recesses and projections formed on an electrolyte membrane
- 3 the electrolyte membrane of the present invention
- 3 A the reinforced electrolyte membrane of the present invention
- 4 porous reinforcing membrane
- 5 , 8 fluorine-based electrolyte resin particle
- 6 laminate
- 7 electrode catalyst particle
- 10 a , 10 b heating plate
- 11 recesses and projections of a heating plate
- 12 shielding wall
- 13 shield space
- 15 vacuum pump
- 21 electrode catalyst layer
- 20 membrane-electrode assembly.
- FIGS. 1 and 2 show explanatory diagrams of the method for producing a fuel cell electrolyte membrane of the present invention.
- FIG. 3 is an explanatory diagram of one embodiment of the production of the membrane-electrode assembly of the present invention with the use of a prepared fuel cell electrolyte membrane.
- a fluorine-based electrolyte membrane 1 (thickness: approximately 25 ⁇ m to 70 ⁇ m) is used as a starting material ( FIG. 1 a ).
- the electrolyte membrane 1 is positioned between upper and lower heating plates 10 a and 10 b each having recesses and projections 11 on the surface thereof ( FIG. 1 b ).
- the electrolyte membrane 1 is heated and pressed by lowering the heating plate 10 a ( FIG. 1 c ).
- the temperatures of heating plates 10 a and 10 b are preferably approximately 170° C. to 300° C.
- the depth of a recess (or the height of a projection) formed on each surface of heating plates 10 a and 10 b is preferably approximately several micrometers to several tens of micrometers.
- recesses and projections may be formed on a continuous curved surface or may be formed with many concave grooves. As shown in FIG. 1 , many columnar portions may be formed.
- the surface areas of the plates can be increased to become approximately four times as large as the areas when the plates have flat faces.
- an electrolyte membrane 3 can be obtained, such membrane having recesses and projections 2 a and 2 b on the surface thereof, which are obtained by transferring recesses and projections 11 formed on each surface of the heating plates 10 a and 10 b .
- recesses and projections 2 a and 2 b are formed on the surface of an electrolyte membrane 3 , the effective surface area thereof can be increased to become greater than that of the original electrolyte membrane 1 .
- recesses and projections 2 a and 2 b formed on the surface thereof are formed by heating and pressing the fluorine-based electrolyte membrane 1 . Thus, such recesses and projections are fixed in such state.
- FIG. 2 corresponds to the case of production of a reinforced electrolyte membrane 3 A.
- a conventionally known porous PTFE membrane is used as a porous reinforcing membrane 4 .
- fluorine-based electrolyte resin particles 5 each having a particle size of approximately 0.1 ⁇ m to 50 ⁇ m are applied to the surface of the porous reinforcing membrane 4 such that a laminate 6 (thickness: D 1 ) is prepared.
- the laminate 6 is positioned between upper and lower heating plates 10 a and 10 b each having recesses and projections 11 on the surfaces thereof ( FIG. 2 b ).
- the position of the upper heating plate 10 a can be controlled at the micrometer-level by a controlling mechanism comprising a servomotor (not shown).
- a controlling mechanism comprising a servomotor (not shown).
- the space between the lower heating plate 10 b and the upper heating plate 10 a is covered with a shielding wall 12 such that a shield space 13 is formed therein.
- an opening 14 formed on a portion of the shielding wall 12 is connected to a vacuum pump 15 such that the shield space 13 can be depressurized.
- the upper and lower heating plates 10 a and 10 b are heated to a temperature of approximately 170° C. to 300° C. Further, the vacuum pump 15 is operated such that the shield space 13 inside the shielding wall 12 is maintained in a depressurized state. As a result of such depressurization, deaeration inside pores of the porous reinforcing membrane 4 is promoted. Thus, impregnation of the pores with a molten electrolyte resin (described below) progresses in a short period of time.
- a molten electrolyte resin described below
- the upper heating plate 10 a is lowered by operating the controlling mechanism until the distance between the upper and lower heating plates 10 a and 10 b becomes equivalent to the thickness of the laminate 6 (D 1 ). As a result, the upper and lower surfaces of the laminate 6 come into contact with the surfaces of the heating plates 10 a and 10 b , respectively. Heating is carried out while such contact state is maintained. Thereafter, the heating plate 10 a is lowered by several micrometers and stopped at such position ( FIG. 2 c ). Accordingly, the effects derived from variations on the resin surface are suppressed and heat variations inside the resin surface are equalized such that resin fluidity can be improved substantially without changes in the thickness of the laminate 6 .
- molten fluorine-based electrolyte resin particles 5 uniformly impregnate the porous reinforcing membrane 4 .
- the shield space 13 inside the shielding wall 12 is in a reduced pressure environment and thus the rate of molten resin impregnation is accelerated. Even if such space is not in a reduced pressure environment, a vacuum pump 15 may be stopped as long as molten resin impregnation smoothly progresses.
- the upper heating plate 10 a is lowered until the above distance becomes equivalent to D 2 , corresponding to the thickness of an electrolyte membrane 3 A (to be obtained) ( FIG. 2 d ).
- recesses and projections are formed on the electrolyte membrane surface by transferring recesses and projections 11 formed on each surface of the heating plates 10 a and 10 b .
- heating of the upper and lower heating plates 10 a and 10 b is terminated, followed by cooling. Then, the heating plates 10 a and 10 b are opened. Accordingly, as schematically shown in FIG.
- a reinforced electrolyte membrane 3 A can be obtained, such membrane having recesses and projections 2 a and 2 b on the surface thereof, which are obtained by transferring recesses and projections 11 formed on each surface of the heating plates 10 a and 10 b.
- a membrane-electrode assembly can be produced by a conventionally known method.
- a fluorine-based electrolyte resin having good thermal stability is used as an electrolyte resin.
- an electrolyte membrane 3 ( 3 A) is subjected to a treatment for imparting ion exchange properties to an electrolyte polymer by a conventionally known method. Ion exchange properties are imparted by hydrolysis or the like. Then, for instance, as shown in FIG.
- an electrode catalyst ink comprising an electrode catalyst such as platinum-supporting carbon, an electrolyte resin, and a solvent is applied to the electrolyte membrane 3 ( 3 A) by a screen printing method or the like, followed by drying.
- an anode-side electrode catalyst layer 21 a and a cathode-side electrode catalyst layer 21 b are formed.
- a membrane-electrode assembly 20 can be obtained.
- the real surface area of the electrolyte membrane 3 ( 3 A) is increased since recesses and projections 2 a and 2 b have been formed on the surface.
- Electrode catalyst particles 7 shown in FIG. 3 a 1
- a mixture of electrode catalyst particles 7 and fluorine-based electrolyte particles 8 are applied to the surface of an electrolyte membrane 3 such that a laminate 9 or 9 A having the thickness of D 3 is obtained.
- a laminate 9 ( 9 A) is positioned between heating plates 30 a and 30 b heated to 170° C. to 300° C. and maintained in a heated state, provided that the distance between the heating plates 30 a and 30 b is designated as “h” (D 3 —several micrometers).
- h the distance between the heating plates 30 a and 30 b
- a fluorine-based electrolyte resin is allowed to become molten substantially without changes in the laminate thickness.
- a fluorine-based electrolyte resin to become molten is contained in a portion on the surface of a fluorine-based electrolyte resin constituting a membrane-electrode assembly 3 .
- a fluorine-based electrolyte resin to become molten is contained in both a portion on the surface of a fluorine-based electrolyte resin constituting a membrane-electrode assembly 3 and applied fluorine-based electrolyte particles 8 .
- the molten fluorine-based electrolyte resin acts as a binder and thus binds to applied electrode catalyst particles 7 so as to be combined therewith. Accordingly, an electrolyte membrane 3 ( 3 A) having recesses and projections formed on the surface thereof binds to an electrode catalyst layer comprising electrode catalyst particles 7 so as to be combined therewith substantially without the presence of an interface therebetween. After cooling, heating plates 30 a and 30 b are opened. As a result, a membrane-electrode assembly 20 A can be obtained, such assembly being formed by laminating an anode-side electrode catalyst layer 21 a and a cathode-side electrode catalyst layer 21 b on both sides of an electrolyte membrane 3 (schematically shown in FIG. 3 ) so as to combine them together. Then, the membrane-electrode assembly is subjected to a treatment such as hydrolysis such that ion exchange properties are imparted to an electrolyte polymer.
- a treatment such as hydrolysis such that ion exchange properties
Abstract
An electrolyte membrane having recesses and projections on the surface thereof is obtained. In addition, a membrane-electrode assembly including the electrolyte membrane, in which the effective contact area between the electrolyte membrane surface and an electrode catalyst layer is increased, is obtained. An electrolyte membrane which includes a fluorine-based electrolyte is heated and pressed with the use of plates each having recesses and projections on the surface thereof such that recesses and projections are formed on the surface of the electrolyte membrane. Thereafter, the electrolyte membrane is subjected to a treatment for imparting ion exchange properties to an electrolyte polymer, such as hydrolysis, such that an electrolyte membrane having recesses and projections on the surface thereof is obtained. Electrode catalyst layers are separately laminated on the both surfaces of the electrolyte membrane such that a membrane-electrode assembly is obtained.
Description
- The present invention relates to a method for producing a fuel cell electrolyte membrane and a method for producing membrane-electrode assembly using the produced electrolyte membrane.
- A polymer electrolyte fuel cell has been known as one type of fuel cell. Since a polymer electrolyte fuel cell is characterized by low operating temperatures (up to approximately 80° C. to 100° C.), low cost, and its compact size when compared with different types of fuel cells, it is expected to serve as an automobile power source and the like.
- As shown in
FIG. 4 , in a polymer electrolyte fuel cell, a membrane-electrode assembly (MEA) 50, which is used as a main component, is sandwiched byseparators 51 each having a fuel (hydrogen) gas channel and an air gas channel such that asingle fuel cell 55, referred to as a single cell, is formed. A membrane-electrode assembly 50 has a structure in which an anode-sideelectrode catalyst layer 53 a is laminated on one side of anelectrolyte membrane 52 serving as an ion exchange membrane and a cathode-sideelectrode catalyst layer 53 b is laminated on the other side thereof. - A perfluorosulfonic acid polymer thin film (Nation membrane, DuPont, the U.S.) comprising an electrolyte resin (ion exchange resin) is mainly used as such an
electrolyte membrane 52. In addition, since sufficient strength cannot be achieved with the use of a thin film consisting of an electrolyte resin, an electrolyte resin solution may be allowed to impregnate a porous reinforcing membrane (e.g., a thin film prepared by stretching PTFE, polyolefin resin, or the like) such that a reinforced electrolyte membrane is obtained (seePatent Document 1, etc.). - For
electrode catalyst layers electrode assembly 50 is obtained by applying such electrode catalyst material to anelectrolyte membrane 52 by a screen printing method or the like, followed by drying (see Patent Document 2, etc.). - In view of improvement of power generation performance, it is desirable for a membrane-electrode assembly to have a large effective contact area between an electrolyte membrane and an electrode catalyst layer. In order to achieve such purpose, it has been suggested that a membrane-electrode assembly be obtained by forming recesses and projections on the electrode catalyst layer side in a preliminary step with the use of a press or the like and pressure-welding an electrolyte membrane thereto (see
Patent Document 3, etc.). - Patent Document 1: JP Patent Publication (Kokai) No. 9-194609 A (1997)
- Patent Document 2: JP Patent Publication (Kokai) No. 9-180728 A (1997)
- Patent Document 3: JP Patent Publication (Kokai) No. 2005-293923 A
- Any electrolyte membrane comprising a conventional electrolyte resin thin film or reinforced electrolyte membrane produced in a manner as described in
Patent Document 1 has a flat surface. When a membrane-electrode assembly is obtained using such a membrane by a conventional method as described in Patent Document 2, the effective contact area between an electrolyte membrane and an electrode catalyst layer remains as the surface area of a flat face. With the use of the method described inPatent Document 3, it is possible to increase the effective contact area between an electrolyte membrane and an electrode catalyst layer as a result of formation of recesses and projections on the electrode catalyst layer side. However, an electrolyte membrane is likely to be damaged when an electrode catalyst layer on which recesses and projections have been formed is pressure-welded to an electrolyte membrane having a flat face. In addition, the presence of the interface between an electrolyte membrane and an electrode catalyst layer makes it impossible to prevent reduction in power generation efficiency of a membrane-electrode assembly caused by interface resistance. - The present invention has been made in view of the above circumstances. It is an objective of the present invention to provide a method for producing a fuel cell electrolyte membrane with which it is possible to increase the effective contact area between an electrolyte membrane and an electrode catalyst layer, and to provide a method for producing a membrane-electrode assembly using such electrolyte membrane, whereby the interface resistance generated between an electrolyte membrane and an electrode catalyst layer is reduced such that power generation performance can be improved.
- The first invention according to the present application relates to a method for producing a fuel cell electrolyte membrane, comprising at least a step of heating and pressing an electrolyte membrane comprising a fluorine-based electrolyte with the use of a plate having recesses and projections on the surface thereof so as to form recesses and projections on the electrolyte membrane surface.
- An electrolyte membrane produced by the above production method has recesses and projections on the surface thereof and thus the surface area is increased due to such recesses and projections. Such recesses and projections may be of any size and shape. The size and shape are appropriately determined based on the necessary size of the surface area. In usual cases, the recess depth (or projection height) is several micrometers to several tens of micrometers. Recesses and projections may be formed on a continuous curved surface or may be formed with many concave grooves and columnar concave portions. As an electrolyte resin used as a base material for an electrolyte membrane, a fluorine-based electrolyte made of a precursor polymer for an electrolyte polymer is used in view of its thermal stability. In addition, if necessary, a step of imparting ion exchange properties to an electrolyte polymer via hydrolysis or the like is carried out following a step of forming recesses and projections on the electrolyte membrane surface.
- The second invention according to the present application relates to a method for producing a fuel cell electrolyte membrane, comprising at least the following steps: an application step of applying fluorine-based electrolyte particles to the surface of a porous reinforcing membrane; an impregnation step of heating the porous reinforcing membrane, to which electrolyte particles have been applied, with the use of a heated plate, melting the electrolyte particles, and allowing the electrolyte particles to impregnate the porous reinforcing membrane so as to obtain an electrolyte membrane; and a step of pressing the electrolyte membrane with a plate having recesses and projections on the surface thereof so as to form recesses and projections on the electrolyte membrane surface.
- As a porous reinforcing membrane used herein, a porous reinforcing membrane prepared by stretching PTFE (polytetrafluoroethylene), a polyolefin resin, or the like which has been used for a conventional reinforced electrolyte membrane in a single axial or biaxial direction can be appropriately used. Fluorine-based electrolyte particles to be applied to the surface of a porous reinforcing membrane are obtained by forming a fluorine-based electrolyte into resin particles, the particle size of which is preferably 100 μm or less and more preferably approximately 0.1 μm to 50 μm.
- A porous reinforcing membrane to which fluorine-based electrolyte particles have been applied is heated with a heated plate such that electrolyte particles become molten and impregnate the porous reinforcing membrane. The molten electrolyte impregnates the porous reinforcing membrane without the need to be actively externally pressed. Thus, no damage is caused to the porous reinforcing membrane due to pressing. Next, such reinforced electrolyte membrane impregnated with the electrolyte resin is pressed with a plate having recesses and projections on the surface thereof such that recesses and projections are formed on the electrolyte membrane surface.
- A heating plate used to melt electrolyte particles may differ from a pressing plate used to form recesses and projections on the electrolyte membrane surface. In such case, a reinforced electrolyte membrane impregnated with an electrolyte resin is transferred between the two plates. It is also possible to carry out the above two steps in a consecutive manner with the use of a plate comprising a heating means and having recesses and projections on the surface thereof. In such case, electrolyte particles become molten and are allowed to impregnate a porous reinforcing membrane while a plate is maintained in a heated state. Then, the plate is transferred after resin impregnation such that the reinforced electrolyte membrane is pressed, followed by the termination of heating and the initiation of recooling. Accordingly, a reinforced electrolyte membrane having recesses and projections on the surface thereof and comprising a porous reinforcing membrane can be obtained.
- Also in the case of the above production method, since fluorine-based electrolyte particles made from a precursor polymer for an electrolyte polymer have thermal stability, they are used as electrolyte resin particles for a base material. If necessary, a step of imparting ion exchange properties to an electrolyte polymer via hydrolysis or the like is further carried out following a step of forming recesses and projections on the reinforced electrolyte membrane surface.
- According to the above second invention, at least the impregnation step is preferably carried out in a reduced pressure environment. Thus, deaeration inside the porous reinforcing membrane and substitution of deaerated spaces with the molten electrolyte are promoted. Accordingly, the time period for electrolyte impregnation of the porous reinforcing membrane can be shortened. In addition, a sufficient state of impregnation can be realized. A step of pressing an electrolyte membrane with a plate having recesses and projections on the surface thereof so as to form recesses and projections on the electrolyte membrane surface by may be carried out in a reduced pressure environment.
- In addition, the present application further discloses the following method as a method for producing a membrane-electrode assembly using a fuel cell electrolyte membrane produced by the above method: a method for producing a membrane electrode laminate, comprising applying electrode catalyst particles or a mixture of an electrode catalyst resin and fluorine-based electrolyte particles to the surface of an electrolyte membrane, on which recesses and projections have been formed prior to a treatment for imparting ion exchange properties to an electrolyte polymer, so as to obtain a laminate; heating the laminate such that the electrode catalyst layer binds to the electrolyte membrane so as to be combined therewith; and carrying out a treatment for imparting ion exchange properties to an electrolyte polymer.
- In the above invention, the electrode catalyst particles used are conventionally known electrode catalyst particles in which a catalyst component such as platinum is supported by a conductive carrier such as carbon. Such particles are obtained by forming a fluorine-based electrolyte resin into fluorine-based electrolyte particles. The particle size thereof is preferably 100 μm or less, more preferably approximately 0.1 μm to 50 μm, and further preferably 1 μm or less.
- According to the above method for producing a membrane-electrode assembly, the formed laminate is heated to a temperature at least sufficient to melt a fluorine-based electrolyte resin. The heating temperature is from approximately 200° C. to 270° C. Heating can be carried out by an arbitrary method. However, a method wherein the above laminate is positioned between a pair of heating plates and heating is carried out with the heat generated from heating plates is preferable.
- When a fluorine-based electrolyte resin constituting an electrolyte membrane and an electrode catalyst resin are applied, the applied fluorine-based electrolyte particles become molten by heating. Then, the molten fluorine-based electrolyte resin acts as a binder and thus binds to applied electrode catalyst particles so as to be combined therewith. Thus, a membrane-electrode assembly is obtained under a condition in which an electrolyte membrane having recesses and projections formed on the surface thereof binds to an electrode catalyst layer comprising electrode catalyst particles so as to be combined therewith while there is no gap therebetween or there are few, if any, gaps therebetween. Then, the obtained membrane-electrode assembly is subjected to a treatment for imparting ion exchange properties to an electrolyte polymer, such as hydrolysis. The resulting membrane electrode laminate has an increased effective contact area between an electrolyte layer and an electrode catalyst layer and further has a significantly reduced interface resistance. Thus, a membrane electrode laminate having high power generation efficiency and a long lifetime can be obtained.
- In addition, it is obviously possible to obtain a membrane-electrode assembly by applying a conventionally known electrode catalyst ink to the electrolyte membrane produced by the present invention, followed by drying. In such case, it is preferable to subject an electrolyte membrane to a treatment for imparting ion exchange properties to an electrolyte polymer, such as hydrolysis, before applying an electrode catalyst ink.
- According to the present invention, an electrolyte membrane has recesses and projections on the surface thereof such that the effective contact area between the electrolyte membrane surface and an electrode catalyst layer can be increased. Further, the interface resistance generated between the electrolyte membrane surface and the electrode catalyst layer can be reduced in a membrane-electrode assembly. Thus, a membrane-electrode assembly having high power generation performance can be obtained.
-
FIG. 1 is an explanatory diagram of one embodiment of the method for producing a fuel cell electrolyte membrane of the present invention. -
FIG. 2 is an explanatory diagram of another embodiment of the method for producing a fuel cell electrolyte membrane of the present invention. -
FIG. 3 is an explanatory diagram of one embodiment of the production of the membrane-electrode assembly of the present invention with the use of a prepared fuel cell electrolyte membrane. -
FIG. 4 schematically shows one embodiment of a fuel cell. - 1: fluorine-based electrolyte membrane as a starting material; 2 a, 2 b: recesses and projections formed on an electrolyte membrane; 3: the electrolyte membrane of the present invention; 3A: the reinforced electrolyte membrane of the present invention; 4: porous reinforcing membrane; 5, 8: fluorine-based electrolyte resin particle; 6: laminate; 7: electrode catalyst particle; 10 a, 10 b: heating plate; 11: recesses and projections of a heating plate; 12: shielding wall; 13: shield space; 15: vacuum pump; 21: electrode catalyst layer; and 20: membrane-electrode assembly.
- Hereinafter, the present invention is described based on the embodiments thereof with reference to the drawings.
FIGS. 1 and 2 show explanatory diagrams of the method for producing a fuel cell electrolyte membrane of the present invention.FIG. 3 is an explanatory diagram of one embodiment of the production of the membrane-electrode assembly of the present invention with the use of a prepared fuel cell electrolyte membrane. - In the embodiment shown in
FIG. 1 , a fluorine-based electrolyte membrane 1 (thickness: approximately 25 μm to 70 μm) is used as a starting material (FIG. 1 a). Theelectrolyte membrane 1 is positioned between upper andlower heating plates projections 11 on the surface thereof (FIG. 1 b). Theelectrolyte membrane 1 is heated and pressed by lowering theheating plate 10 a (FIG. 1 c). The temperatures ofheating plates - The depth of a recess (or the height of a projection) formed on each surface of
heating plates FIG. 1 , many columnar portions may be formed. When such recesses and projections are formed onheating plates - After the maintenance of heating and pressing conditions for a certain period of time, cooling is carried out and then
plates FIG. 1 d, anelectrolyte membrane 3 can be obtained, such membrane having recesses andprojections projections 11 formed on each surface of theheating plates projections electrolyte membrane 3, the effective surface area thereof can be increased to become greater than that of theoriginal electrolyte membrane 1. In addition, recesses andprojections electrolyte membrane 1. Thus, such recesses and projections are fixed in such state. - The embodiment shown in
FIG. 2 corresponds to the case of production of a reinforcedelectrolyte membrane 3A. Herein, a conventionally known porous PTFE membrane is used as a porous reinforcingmembrane 4. At first, as shown inFIG. 2 a, fluorine-basedelectrolyte resin particles 5 each having a particle size of approximately 0.1 μm to 50 μm are applied to the surface of the porous reinforcingmembrane 4 such that a laminate 6 (thickness: D1) is prepared. Thelaminate 6 is positioned between upper andlower heating plates projections 11 on the surfaces thereof (FIG. 2 b). - In the above example, the position of the
upper heating plate 10 a can be controlled at the micrometer-level by a controlling mechanism comprising a servomotor (not shown). In addition, the space between thelower heating plate 10 b and theupper heating plate 10 a is covered with a shieldingwall 12 such that ashield space 13 is formed therein. Further, anopening 14 formed on a portion of the shieldingwall 12 is connected to avacuum pump 15 such that theshield space 13 can be depressurized. - The upper and
lower heating plates vacuum pump 15 is operated such that theshield space 13 inside the shieldingwall 12 is maintained in a depressurized state. As a result of such depressurization, deaeration inside pores of the porous reinforcingmembrane 4 is promoted. Thus, impregnation of the pores with a molten electrolyte resin (described below) progresses in a short period of time. - The
upper heating plate 10 a is lowered by operating the controlling mechanism until the distance between the upper andlower heating plates laminate 6 come into contact with the surfaces of theheating plates heating plate 10 a is lowered by several micrometers and stopped at such position (FIG. 2 c). Accordingly, the effects derived from variations on the resin surface are suppressed and heat variations inside the resin surface are equalized such that resin fluidity can be improved substantially without changes in the thickness of thelaminate 6. Thus, molten fluorine-basedelectrolyte resin particles 5 uniformly impregnate the porous reinforcingmembrane 4. Theshield space 13 inside the shieldingwall 12 is in a reduced pressure environment and thus the rate of molten resin impregnation is accelerated. Even if such space is not in a reduced pressure environment, avacuum pump 15 may be stopped as long as molten resin impregnation smoothly progresses. - After resin impregnation, the
upper heating plate 10 a is lowered until the above distance becomes equivalent to D2, corresponding to the thickness of anelectrolyte membrane 3A (to be obtained) (FIG. 2 d). Thus, recesses and projections are formed on the electrolyte membrane surface by transferring recesses andprojections 11 formed on each surface of theheating plates lower heating plates heating plates FIG. 2 e, a reinforcedelectrolyte membrane 3A can be obtained, such membrane having recesses andprojections projections 11 formed on each surface of theheating plates - With the use of the
aforementioned electrolyte membrane 3 and the reinforcedelectrolyte membrane 3A, a membrane-electrode assembly can be produced by a conventionally known method. In such case, according to the present invention, a fluorine-based electrolyte resin having good thermal stability is used as an electrolyte resin. Thus, an electrolyte membrane 3 (3A) is subjected to a treatment for imparting ion exchange properties to an electrolyte polymer by a conventionally known method. Ion exchange properties are imparted by hydrolysis or the like. Then, for instance, as shown inFIG. 1 e as an example, an electrode catalyst ink comprising an electrode catalyst such as platinum-supporting carbon, an electrolyte resin, and a solvent is applied to the electrolyte membrane 3 (3A) by a screen printing method or the like, followed by drying. Thus, an anode-sideelectrode catalyst layer 21 a and a cathode-side electrode catalyst layer 21 b are formed. Accordingly, a membrane-electrode assembly 20 can be obtained. Regarding such membrane-electrode assembly 20, the real surface area of the electrolyte membrane 3 (3A) is increased since recesses andprojections - Another method for producing a membrane-electrode assembly using the
above electrolyte membrane 3 and the reinforcedelectrolyte membrane 3A is described with reference toFIG. 3 . In addition, theelectrolyte membrane 3 is used for explanation below. However, the same applies to the reinforcedelectrolyte membrane 3A. At first, electrode catalyst particles 7 (shown inFIG. 3 a 1) or a mixture ofelectrode catalyst particles 7 and fluorine-based electrolyte particles 8 (shown inFIG. 3 a 2) are applied to the surface of anelectrolyte membrane 3 such that alaminate - As shown in
FIG. 3 b, a laminate 9 (9A) is positioned betweenheating plates heating plates laminate 9, a fluorine-based electrolyte resin to become molten is contained in a portion on the surface of a fluorine-based electrolyte resin constituting a membrane-electrode assembly 3. In the case of alaminate 9A, a fluorine-based electrolyte resin to become molten is contained in both a portion on the surface of a fluorine-based electrolyte resin constituting a membrane-electrode assembly 3 and applied fluorine-basedelectrolyte particles 8. - The molten fluorine-based electrolyte resin acts as a binder and thus binds to applied
electrode catalyst particles 7 so as to be combined therewith. Accordingly, an electrolyte membrane 3 (3A) having recesses and projections formed on the surface thereof binds to an electrode catalyst layer comprisingelectrode catalyst particles 7 so as to be combined therewith substantially without the presence of an interface therebetween. After cooling,heating plates electrode assembly 20A can be obtained, such assembly being formed by laminating an anode-sideelectrode catalyst layer 21 a and a cathode-side electrode catalyst layer 21 b on both sides of an electrolyte membrane 3 (schematically shown inFIG. 3 ) so as to combine them together. Then, the membrane-electrode assembly is subjected to a treatment such as hydrolysis such that ion exchange properties are imparted to an electrolyte polymer.
Claims (3)
1-5. (canceled)
6. A method for producing a fuel cell electrolyte membrane, comprising:
applying fluorine-based electrolyte particles to a surface of a porous reinforcing membrane;
impregnating the porous reinforcing membrane, the impregnating comprising heating the porous reinforcing membrane, to which electrolyte particles have been applied, with the use of a heated plate, melting the electrolyte particles, and allowing the electrolyte particles to impregnate the porous reinforcing membrane so as to obtain an electrolyte membrane;
pressing the electrolyte membrane with a plate having recesses and projections on the surface thereof so as to form recesses and projections on a surface of the electrolyte membrane; and
separating the plate and the electrolyte membrane from one another after the pressing.
7. A method for producing a membrane-electrode assembly using a fuel cell electrolyte membrane produced by a method, comprising:
applying fluorine-based electrolyte particles to a surface of a porous reinforcing membrane;
impregnating the porous reinforcing membrane, the impregnating comprising heating the porous reinforcing membrane, to which electrolyte particles have been applied, with the use of a heated plate, melting the electrolyte particles, and allowing the electrolyte particles to impregnate the porous reinforcing membrane so as to obtain an electrolyte membrane;
pressing the electrolyte membrane with a plate having recesses and projections on the surface thereof so as to form recesses and projections on a surface of the electrolyte membrane;
separating the plate and the electrolyte membrane from one another after the pressing;
applying electrode catalyst particles or a mixture of an electrode catalyst resin and fluorine-based electrolyte particles to the surface of the electrolyte membrane, on which recesses and projections have been formed, so as to obtain a laminate;
heating the laminate such that the electrode catalyst layer binds to the electrolyte membrane so as to be combined therewith; and
carrying out a treatment for imparting ion exchange properties to an electrolyte polymer constituting the electrolyte membrane.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/403,512 US20120152451A1 (en) | 2006-06-26 | 2012-02-23 | Method for producing fuel cell electrolyte membrane and method for producing membrane-electrolyte assembly |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006-175324 | 2006-06-26 | ||
JP2006175324A JP4882541B2 (en) | 2006-06-26 | 2006-06-26 | Manufacturing method of electrolyte membrane for fuel cell and membrane electrode assembly |
PCT/JP2007/062643 WO2008001701A1 (en) | 2006-06-26 | 2007-06-18 | Method for producing electrolyte membrane for fuel cell and method for producing membrane-electrode assembly |
US30481908A | 2008-12-15 | 2008-12-15 | |
US13/403,512 US20120152451A1 (en) | 2006-06-26 | 2012-02-23 | Method for producing fuel cell electrolyte membrane and method for producing membrane-electrolyte assembly |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2007/062643 Division WO2008001701A1 (en) | 2006-06-26 | 2007-06-18 | Method for producing electrolyte membrane for fuel cell and method for producing membrane-electrode assembly |
US30481908A Division | 2006-06-26 | 2008-12-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
US20120152451A1 true US20120152451A1 (en) | 2012-06-21 |
Family
ID=38845466
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/304,819 Active 2028-05-22 US8197632B2 (en) | 2006-06-26 | 2007-06-18 | Method for producing fuel cell electrolyte membrane and method for producing membrane-electrode assembly |
US13/403,512 Abandoned US20120152451A1 (en) | 2006-06-26 | 2012-02-23 | Method for producing fuel cell electrolyte membrane and method for producing membrane-electrolyte assembly |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/304,819 Active 2028-05-22 US8197632B2 (en) | 2006-06-26 | 2007-06-18 | Method for producing fuel cell electrolyte membrane and method for producing membrane-electrode assembly |
Country Status (6)
Country | Link |
---|---|
US (2) | US8197632B2 (en) |
JP (1) | JP4882541B2 (en) |
CN (1) | CN101473476B (en) |
CA (1) | CA2654919C (en) |
DE (1) | DE112007001512B4 (en) |
WO (1) | WO2008001701A1 (en) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2161771A4 (en) * | 2007-06-15 | 2010-07-28 | Sumitomo Chemical Co | Membrane-electrode assembly, method for production thereof, and solid polymer fuel cell |
US7883654B2 (en) * | 2007-06-27 | 2011-02-08 | Atomic Energy Council-Institute Of Nuclear Energy Research | Method for fabricating membrane electrode assembly |
JP5194869B2 (en) * | 2008-02-18 | 2013-05-08 | トヨタ自動車株式会社 | Manufacturing method of membrane / electrode assembly for fuel cell |
KR20090123819A (en) * | 2008-05-28 | 2009-12-02 | 주식회사 엘지화학 | Ion conductive electrolyte membrane and method for preparation of same, membrane-electrode assembly and proton exchange membrane fuel cell |
CN102473934B (en) * | 2009-08-26 | 2014-09-03 | 松下电器产业株式会社 | Method for operating polymer fuel cell |
JP4988963B2 (en) * | 2010-02-04 | 2012-08-01 | パナソニック株式会社 | Method for producing polymer electrolyte membrane for fuel cell |
JP5742457B2 (en) * | 2011-05-17 | 2015-07-01 | トヨタ自動車株式会社 | Manufacturing method of electrolyte membrane for fuel cell |
CN103165906A (en) * | 2013-03-25 | 2013-06-19 | 南通百应能源有限公司 | Microcosmic three-dimensional fuel cell membrane electrode |
CN103413960B (en) * | 2013-08-26 | 2015-07-29 | 中国东方电气集团有限公司 | Flow battery and liquid stream battery stack |
CN103413954B (en) * | 2013-08-26 | 2016-03-02 | 中国东方电气集团有限公司 | The preparation method of membrane electrode assembly, flow battery and electrode |
KR101660566B1 (en) * | 2013-11-29 | 2016-09-27 | 주식회사 엘지화학 | Method of manufacturing flow battery |
CN107078328B (en) | 2014-11-18 | 2021-05-04 | 株式会社Lg化学 | Method for manufacturing solid oxide fuel cell |
CN105047944B (en) * | 2015-05-29 | 2018-03-27 | 武汉喜玛拉雅光电科技股份有限公司 | A kind of new fuel cell based on graphene thermal electricity management level |
CN105047963B (en) * | 2015-05-29 | 2017-12-08 | 武汉喜玛拉雅光电科技股份有限公司 | A kind of fuel cell preparation method based on graphene thermal electricity management level |
JP6971534B2 (en) | 2015-08-20 | 2021-11-24 | 株式会社東芝 | Membrane electrode complex and electrochemical cell |
KR101926784B1 (en) * | 2016-03-31 | 2018-12-07 | 코오롱인더스트리 주식회사 | Ion exchanging membrane, method for manufacturing the same and energy storage system comprising the same |
JP6427215B2 (en) * | 2017-03-07 | 2018-11-21 | 本田技研工業株式会社 | Method and apparatus for pressing a film molded article for polymer electrolyte fuel cell |
KR102440588B1 (en) * | 2017-05-10 | 2022-09-05 | 현대자동차 주식회사 | Device and method for manufacturing membrane-electrode assembly of fuel cell |
KR102644540B1 (en) * | 2018-07-04 | 2024-03-06 | 현대자동차주식회사 | A method of manufacturing a thin membrane electrode assembly with minimized interfacial resistance |
CN109295479A (en) * | 2018-10-12 | 2019-02-01 | 浙江田成环境科技有限公司 | The rotating flow electrowinning plant of heavy metal in a kind of recycling slag |
WO2023101305A1 (en) * | 2021-12-03 | 2023-06-08 | 코오롱인더스트리 주식회사 | Membrane-electrode assembly and fuel cell including same |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5415888A (en) * | 1993-04-26 | 1995-05-16 | E. I. Du Pont De Nemours And Company | Method of imprinting catalytically active particles on membrane |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2219447A (en) * | 1931-07-15 | 1940-10-29 | Union Carbide & Carbon Corp | Process for making composite materials |
JPS60109176A (en) * | 1983-11-16 | 1985-06-14 | Fuji Electric Corp Res & Dev Ltd | Gas diffusion electrode of fuel cell |
JPS6441174A (en) | 1987-08-06 | 1989-02-13 | Toshiba Corp | Manufacture of fuel cell electrolytic matrix |
JP2831061B2 (en) | 1989-11-28 | 1998-12-02 | 三菱重工業株式会社 | Gas diffusion electrode and solid polymer electrolyte fuel cell body using the same |
JPH0758617B2 (en) | 1990-11-01 | 1995-06-21 | 三菱重工業株式会社 | Assembly of solid polymer electrolyte membrane and electrode |
JP3242737B2 (en) | 1993-03-10 | 2001-12-25 | 三菱電機株式会社 | Fuel cell, electrochemical dehumidifying device, and method of manufacturing electrochemical device |
DE19509748C2 (en) * | 1995-03-17 | 1997-01-23 | Deutsche Forsch Luft Raumfahrt | Process for producing a composite of electrode material, catalyst material and a solid electrolyte membrane |
JP3256649B2 (en) | 1995-08-29 | 2002-02-12 | 三菱電機株式会社 | Method for manufacturing polymer electrolyte fuel cell and polymer electrolyte fuel cell |
JPH09180728A (en) | 1995-12-27 | 1997-07-11 | Tokyo Gas Co Ltd | Electrode for solid polymer fuel cell, manufacture thereof, and apparatus therefor |
JPH09194609A (en) | 1996-01-25 | 1997-07-29 | Sumitomo Electric Ind Ltd | Ion-exchange membrane and its preparation |
US6306536B1 (en) * | 1998-03-27 | 2001-10-23 | Ballard Power Systems Inc. | Method of reducing fuel cell performance degradation of an electrode comprising porous components |
KR100409042B1 (en) * | 2001-02-24 | 2003-12-11 | (주)퓨얼셀 파워 | Membrane Electrode Assembly and method for producing the same |
EP1328035A1 (en) * | 2002-01-09 | 2003-07-16 | HTceramix S.A. - High Technology Electroceramics | PEN of solid oxide fuel cell |
US6869712B2 (en) * | 2002-03-07 | 2005-03-22 | Hewlett-Packard Development Company, L.P. | Ion exchange system structure with a microtextured surface, method of manufacture, and method of use thereof |
JP4355822B2 (en) * | 2002-10-21 | 2009-11-04 | 国立大学法人福井大学 | Process for producing fuel cell electrode and electrolyte composite |
JP4017510B2 (en) | 2002-12-02 | 2007-12-05 | 三洋電機株式会社 | Method for producing polymer electrolyte fuel cell |
US7445742B2 (en) * | 2003-08-15 | 2008-11-04 | Hewlett-Packard Development Company, L.P. | Imprinting nanoscale patterns for catalysis and fuel cells |
JP4576813B2 (en) * | 2003-09-05 | 2010-11-10 | 株式会社豊田中央研究所 | Polymer electrolyte membrane and membrane electrode assembly |
JP2005214172A (en) | 2004-02-02 | 2005-08-11 | Nissan Diesel Motor Co Ltd | Engine exhaust emission control device |
JP4438475B2 (en) | 2004-03-31 | 2010-03-24 | セイコーエプソン株式会社 | Manufacturing method of membrane electrode assembly |
JP4581477B2 (en) * | 2004-05-12 | 2010-11-17 | トヨタ自動車株式会社 | Method for producing solid polymer electrolyte, solid polymer electrolyte membrane, and fuel cell |
US7592375B2 (en) * | 2005-05-13 | 2009-09-22 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Ion conductive polymers and imide monomers |
KR100728781B1 (en) * | 2005-07-27 | 2007-06-19 | 삼성에스디아이 주식회사 | Membrane-electrode assembly for fuel cell and fuel cell system comprising same |
-
2006
- 2006-06-26 JP JP2006175324A patent/JP4882541B2/en not_active Expired - Fee Related
-
2007
- 2007-06-18 CN CN2007800229714A patent/CN101473476B/en active Active
- 2007-06-18 WO PCT/JP2007/062643 patent/WO2008001701A1/en active Search and Examination
- 2007-06-18 CA CA2654919A patent/CA2654919C/en active Active
- 2007-06-18 US US12/304,819 patent/US8197632B2/en active Active
- 2007-06-18 DE DE112007001512.8T patent/DE112007001512B4/en not_active Expired - Fee Related
-
2012
- 2012-02-23 US US13/403,512 patent/US20120152451A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5415888A (en) * | 1993-04-26 | 1995-05-16 | E. I. Du Pont De Nemours And Company | Method of imprinting catalytically active particles on membrane |
Also Published As
Publication number | Publication date |
---|---|
CN101473476B (en) | 2012-12-12 |
CA2654919A1 (en) | 2008-01-03 |
CA2654919C (en) | 2011-11-15 |
JP4882541B2 (en) | 2012-02-22 |
DE112007001512T5 (en) | 2009-05-14 |
US20090173442A1 (en) | 2009-07-09 |
US8197632B2 (en) | 2012-06-12 |
JP2008004486A (en) | 2008-01-10 |
CN101473476A (en) | 2009-07-01 |
DE112007001512B4 (en) | 2017-09-14 |
WO2008001701A1 (en) | 2008-01-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8197632B2 (en) | Method for producing fuel cell electrolyte membrane and method for producing membrane-electrode assembly | |
KR101000427B1 (en) | Method for manufacturing membrane electrode assembly and reinforced electrolyte membrane in polymer electrolyte fuel cell, and membrane electrode assembly and reinforced electrolyte membrane obtained by manufacturing method | |
KR101122473B1 (en) | Unitized Membrane Electrode Assembly and Process for Its Preparation | |
KR20040081140A (en) | Unitized Membrane Electrode Assembly and Process for Its Preparation | |
WO2016051633A1 (en) | Gas diffusion layer for fuel cell, fuel cell, and formation method for gas diffusion layer for fuel cell | |
KR20140031148A (en) | Method for fabricating a fuel cell including a membrane-electrode assembly | |
KR101710253B1 (en) | Fuel cell gas diffusion layer and method for forming same | |
KR101173059B1 (en) | Separation plate for Polymer Electrolyte Membrane Fuel Cell and method for manufacturing the same | |
JP2010123491A (en) | Apparatus for manufacturing membrane electrode assembly | |
KR101755506B1 (en) | Component for fuel cell and manufacturing for the same | |
US20090311566A1 (en) | Separating plate for fuel cell stack and method of manufacturing the same | |
KR101743924B1 (en) | Carbon fiber felt integrated bipolar plate for batteries and method for manufacturing same | |
JP5233286B2 (en) | Manufacturing method of membrane electrode assembly | |
WO2008029818A1 (en) | Electrolyte membrane, membrane electrode assembly, and methods for manufacturing the same | |
JP2008146928A (en) | Gas diffusing electrode for fuel cell and its manufacturing method | |
JP5341321B2 (en) | Electrolyte membrane / electrode structure for polymer electrolyte fuel cells | |
JP2008226601A (en) | Membrane-membrane reinforcing member assembly, membrane-catalyst layer assembly, membrane-electrode assembly, polymer electrolyte fuel cell, and manufacturing method of membrane-membrane reinforcing member assembly | |
JP2019139993A (en) | Fuel cell module and manufacturing method thereof | |
JP7226350B2 (en) | FUEL BATTERY CELL AND METHOD FOR MANUFACTURING FUEL BATTERY CELL | |
US20180131014A1 (en) | Composite Material Separation Plate for Fuel Cell and Method for Manufacturing Same | |
JP4821096B2 (en) | Manufacturing method of fuel cell | |
JP2006128014A (en) | Manufacturing method for fiber-reinforced solid polymer electrolyte | |
KR20090087627A (en) | Bipolar-plate for fuel cell and manufacturing method thereof | |
JP2006066160A (en) | Fuel cell film/electrode junction and manufacturing method thereof | |
JP2008277183A (en) | Manufacturing method of separator for fuel cell |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |