CN110249465A - The manufacturing method of the membrane-electrode assembly of PEFC type fuel cell - Google Patents
The manufacturing method of the membrane-electrode assembly of PEFC type fuel cell Download PDFInfo
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- CN110249465A CN110249465A CN201880009967.2A CN201880009967A CN110249465A CN 110249465 A CN110249465 A CN 110249465A CN 201880009967 A CN201880009967 A CN 201880009967A CN 110249465 A CN110249465 A CN 110249465A
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- Prior art keywords
- dielectric film
- electrode
- coating
- membrane
- fuel cell
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/32—Processes for applying liquids or other fluent materials using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- 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
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- 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]
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- 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
-
- 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
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- 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
Abstract
Include the electrode ink of electrolyte solution, the carbon for being supported with catalyst, water or water and alcohol system to dielectric film that is thin and also deforming in air coating, to be made without the membrane-electrode assembly of deformation and the fuel cell with periphery.Masked radical material is laminated on the moving direction for the dielectric film being laminated with tergite or gas permeability substrate, on heating adsorption roller, it is normally located otherwise masking substrate with the moving direction of dielectric film at the end of the coating of electrode starts and is coated with, coating electrode is black and forms the periphery of electrode and uncoated portion.
Description
Technical field
The present invention relates to PEFC (Polymer Electrolyte membrane Fuel Cell: polymer dielectric film
Fuel cell) type fuel cell membrane-electrode assembly manufacturing method and the fuel cell that is produced by this method.
More specifically, it is related to being directly coated at the CCM of dielectric film to by electrode ink (electrode ink)
The electrode forming method of (Catalyst coated membrane: catalyst coated membranes) formula dielectric film.Coating of the invention does not have
Be particularly limited to, including roller coating, slit die (slot nozzle) coating, silk-screen printing (screen printing), curtain coating, point
It is granted with (dispense), ink-jet, the atomization (including fibrosis) including injection (spray), electrostatic atomization (including fibrosis)
It the construction method that particle or fiber are coated on to coated article such as grants, also includes that micro- curtain (micro-curtain) is granted.
Micro- curtain refer to solid injection mouth of wide-angle pattern (English: airless spray nozzle) etc. with 0.3MPa
Whens the comparison low-pressure fuel injection liquid etc. of left and right, using the part as the liquid film before mist and make coated article and the opposite shifting of jet blower
The method moved and be coated will not generate spray (English: over spray) particle in coating surface.Excessively passing through coated article
Distance turns to mist far from time-varying.
In addition, atomization (fibrosis) grants and refers to following method:, will be containing solid other than the granulating realized by injection
Liquid of body particle etc. is atomized while being dispersed using ultrasonic wave, or rotation, revolution using electrostatic spinning etc.
The centrifugal force of body carries out granulating or fibrosis to be coated.It also include that will be meltblown mode etc. to produce applied to liquid
The method of grain, fiber, refers to since the directionality for the particle being atomized in the ultrasonic atomization, centrifugal atomizing is unstable,
Therefore they are adhered to or are coated on by the power of compressed air (air assist: air assists) construction method of object.
In the present invention, they are referred to as and are illustrated below as injection.
Background technique
In the past, by electrolyte solution, the catalyst of micro mist being made of the platinum supported in carbon particle or carbon fiber etc. with it is molten
Agent is mixed to be incorporated as electrode ink and is coated on GDL (Gas diffusion layer: gas diffusion layers) and is crimped on dielectric film,
Or demoulding (Japanese: from the shape) film such as be coated on PTFE and be needed on dielectric film.About the compression bonding method, transfer modes, by
Yu Bujie has liquid, therefore generates resistance between dielectric film and electrode and reduce the performance of fuel cell.In order to solve
The problem proposes the method that the electrode catalyst ink of CCM mode is directly coated at dielectric film.
Patent document 1 is the CCM method invented by the present inventor, is following method: by roll-to-roll (Roll to
Roll dielectric film) rolls out and the absorption drum (roller) being adsorbed in after heating or absorption make electrode ink pass through spray in the state of
It penetrates etc. and to carry out stacking coating and keep the electrode ink dry.Due to adding in the heating by absorption drum etc. to which dielectric film is adsorbed
It is laminated in the state of heat by spraying etc. with film, therefore coated on dielectric film and has carried out levelling in injection particle
(levelling) moment, solvent instantaneously volatilize.Therefore, it not will cause the other adaptation of damage to electrolyte to improve, therefore electricity
The interface resistance (Japanese: resisting at interface) of pole and dielectric film can reduce to the limit, therefore be capable of forming as ideal CCM.
In addition, due to the gas permeability that keeps width wider than dielectric film paper or film between absorption it is bulging attract electrolyte between electrolyte
Film, therefore electrolyte film surface integrally equably can be attracted and be applied in a manner of not remaining the absorption trace of the porous bodies such as absorption drum
Cloth, therefore be ideal, but spray particle in the case where being sprayed and disperse, therefore it is required for sheltering part (mask).
Patent document 2 is also the method invented by the present inventor, proposes following method: in roll-to-roll (Roll to
Roll the two sides for the dielectric film) used has been bonded the film as masking part of electrode shape and has formed the recess portion of electrode shape, and one
While rolled out and with heating after adsorption roller or absorption band adsorbed on one side stacking coating electrode ink and batched.At this
In mode, it can be aligned with the two poles of the earth due to initially sheltering part, so productivity is high, it is ideal.But due to being to dig out electrode
Partial construction, therefore produce the waste of the material for the unused portion dug out.In addition, if such as dielectric film width is
250mm and electrode size are, for example, the square of 210mm × 210mm etc. and uncoated portion (periphery) width at 20mm or more, does not then have
It is problematic, if but wanting to be formed such as identical electrodes area is 60mm × 735mm and the length on the length direction of dielectric film
The operation (handling) of rectangle and narrow 3 electrodes at 10mm or so of periphery, then the masking substrate itself dug out is unstable
Determine and can not accurately be sheltered (masking).
Industry is thirsted for a kind of capable of accurately being sheltered, requiring especially to be taken into coideal in the discharge of water and oxygen
Three phase structures, particularly cathode be capable of forming micropore, mesoporous construction, by using injection, particularly impulse jet into
CCM mode in capable wet film and the device and method that can automatically manufacture high performance membrane-electrode assembly.Coating method is simultaneously
It is not limited to spray, slot nozzle etc. can also be used in the present invention.It, sometimes can also be with using slot nozzle
It without using one or both of the masking substrate intersected with length direction, but is required to improve the dimensional accuracy of electrode.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2004-351413
Patent document 2: Japanese Unexamined Patent Publication 2005-63780
Summary of the invention
Problems to be solved by the invention
If due to dielectric film be it is thin at 25 microns or less and then 15 microns or less and stretch, exist and extend, and even if
It is the substrate of extremely brittle weak (delicate) that the moisture in air also can be deformed simply, therefore the electrode of directly coating electrode ink
Formed extremely difficult, sought following method: Xiang Jiare is adsorbed in the dielectric film gunite, especially of heating adsorption roller etc.
It is that electrode ink is laminated while dielectric film interface makes solvent instantaneously volatilize with film shock pulse mode.Also, electricity
The uncoated portion (periphery) of the desired size for being assembled with separator, gasket etc. is needed around pole.
A technical solution to solve project
The present invention is completed to solve project above-mentioned, the object of the present invention is to provide a kind of high-quality and
The manufacturing method of PEFC type fuel cell membrane-electrode assembly (MEA) with durability and use fuel obtained from the MEA
Battery.
More specifically, to roll-to-roll (Roll to Roll) dielectric film directly with film coated electrode ink, according to
It is laminated, manufactures the high performance membrane-electrode assembly with the periphery of electrode ink uncoated portion, and then manufacture high property
The fuel cell of energy.
The present invention provides a kind of manufacturing method of the membrane-electrode assembly of fuel cell, will be laminated in tergite (back
Sheet) or the dielectric film of the strip of supporting base material (Japanese: サ ポ ー ト substrate) is continually or intermittently rolled up with rolling out device
Make the dielectric film mobile out, to dielectric film coating electrode ink, forms electrode in dielectric film and carried out with devices for taking-up
Batch, the manufacturing method is characterised by comprising: from it is described roll out process until being coated with starting position between in order to make
Make the edge or periphery of the electrode of dielectric film, and the first elongated masking substrate is laminated in the work of the dielectric film in two sides
Sequence；On one side the process for carrying out using apparatus for coating coating electrode ink while heating absorption to dielectric film；The work for keeping electrode ink dry
Sequence；And the process that the first masking substrate is removed between until being coated with end position to devices for taking-up.
The present invention provides a kind of manufacturing method of the membrane-electrode assembly of fuel cell, which is characterized in that is formed in the electricity
There are multiple in the width direction of dielectric film for the electrode of solution plasma membrane.
A kind of manufacturing method of the membrane-electrode of fuel cell is provided in the present invention, which is characterized in that the second masking substrate
It is orthogonally coated between end position and electrode pattern coating starting position between electrode pattern with the moving direction of dielectric film.
A kind of manufacturing method of the membrane-electrode assembly of fuel cell is provided in the present invention, which is characterized in that at least
Adhesive is granted in the side for being laminated in dielectric film of one masking substrate.
A kind of manufacturing method of the membrane-electrode assembly of fuel cell is provided in the present invention, which is characterized in that dielectric film
On at least first masking substrate be laminated and be taken up with dielectric film via adhesive in advance.
A kind of manufacturing method of the membrane-electrode assembly of fuel cell is provided in the present invention, which is characterized in that the first masking
The adhesive of substrate includes micro- adhesive, the position of the solvent contact of Yu Buyu electrode ink is granted, by cellular or in more
A to grant every spaced striated, the area of granting of described adhesive is 1/2 or less shelter substrate surface product.
A kind of manufacturing method of the membrane-electrode assembly of fuel cell is provided in the present invention, which is characterized in that with electrolyte
The second masking substrate that the moving direction of film orthogonally configures can with roll out device and devices for taking-up moves together, in electrolyte
At the end of the electrode ink coating of the moving direction of film and when coating starts, automatically moves to coating end position and coating starts
Position and sheltered.
Final purpose of the invention is that manufacture is used using with roll-to-roll (Roll to Roll) mobile fuel cell
The side of dielectric film form anode and form the membrane-electrode assembly (MEA) of the electrode of cathode in the opposite side of anode and
At fuel cell.Therefore, in the present invention, it is directly coated with first electrode ink to the dielectric film for the state for being laminated with tergite,
Keep the first electrode ink dry and form first electrode, to gas permeabilities pieces such as electrode forming surface stacking supporting base materials.In addition, with
Be formed with mode that the gas permeability piece that the dielectric film of electrode has been laminated does not shift the two sides of gas permeability piece and with it is described
The saturating of the bonding agent, adhesive that can be removed has been granted in position (edges such as periphery) stacking that electrode on dielectric film is not interfered
Gas substrate and form composite sheet.While forming composite sheet or later, tergite can be removed.As its an example, Neng Gouti
For the manufacturing method of the membrane-electrode assembly of following fuel cell, comprising: described in Xiang Jiare adsorption roller or heating absorption band absorption
The process of the gas permeability substrate side of composite sheet；The process for removing the tergite；Suction is heated via the gas permeability substrate on one side
Draw the process that the dielectric film is coated with second electrode ink on the dielectric film of the opposing face of the first electrode on one side；And
The process for keeping the second electrode ink dry and forming second electrode.Moreover, in the present invention, it also can be to the MEA produced
It is laminated GDL (gas diffusion layers), and then setting gasket, separator come production unit battery (cell), combine element cell
Hundreds of groups and being capable of making fuel cell.
It in the present invention, can be to dielectric film automatically stacking masking in the longitudinal direction when forming the electrode
Substrate and the uncoated portion (edge) that electrode is formed on the flow direction of electrolyte.It being capable of connecing with dielectric film to masking substrate
The edge of touching grants adhesive.After capable of especially removing the residue of adhesive be difficult to remain such micro- adhesive etc. this
A little adhesives every spaced thin striated are applied in cellular or in order to reduce bond area.In addition, with length
It spends the first of direction and shelters the orthogonal mode of substrate on the first masking substrate, adhesive will have been granted to necessary position
Second masking substrate particularly bond and is layered on the first masking substrate, as sheltered with electrode shape the dielectric film of part into
It goes and is coated with and production or in addition production on same production line, coating electrode is black from the upper side and makes electrode ink drying, by
This is capable of forming the electrode with periphery.Sheltering operation can be as described above in roll-to-roll (the Roll to of electrode ink coating
Roll it) is carried out on production line, other process can also be first passed through in advance and carried out.
In the present invention, due to being able to use heating adsorption roller, in the electrode for attracting and being applied to dielectric film
After ink has wet dielectric film, can instantaneously for example within 3 seconds solvent flashing amount 99% or more, therefore can be improved film with
The adaptation of electrode reduces interface resistance, therefore is ideal.In addition, masking substrate can be in solvent almost vaporized portion
Position later batch etc. and remove.
In addition, if using the impulse jet for belonging to gunite and further being attached to injection particle in the present invention
The construction method of speed and applied as the shock pulse of the registered trademark of Ma Taike Si Mate (MTEK-SMART) Co., Ltd.
Work method, then catalyst is further increased relative to the adaptation of dielectric film.
It, can will be every square centimeter by gunite, particularly shock pulse construction method moreover, in the _ present invention
1 layer of electrode amount is adjusted to 0.001~0.15 milligram, therefore is capable of forming the film stacking of such as 2~30 layers of electrode ink.Though
So can by reduce every 1 layer of coating weight based on the combination of the gunite of shock pulse and heating absorption drum etc., but in order to
Be further reduced every 1 layer of coating weight, for example, can make include the carbon of supported platinum catalyst, electrolyte solution and by water and
The nonvolatile component amount of the electrode ink for the solvent that alcohol is constituted is with weight ratio meter for 10% or less.Moreover, because to heating absorption drum
On heat transfer to dielectric film and 0.5 square metre of surface area of heating absorption drum apply 1.5 to 4kW hours heat
Amount, therefore the cooling under heat of gasification caused by the evaporation of the solvent of the dielectric film as being heated to 50 to 80 DEG C is also few, therefore
Even nonvolatile component can be set as to 5% or less, be further set as 1% or less.
It is more to be laminated in a manner of more film that solid component concentration, which is set as advantage as described above, then is more capable of forming
Uniform catalyst layer.In addition, the load to dielectric film is few and makes fuel cell due to that can be laminated with film
Performance improves.
Moreover, in the present invention, it can be via supporting base material such as gas permeability substrate, micro- porous substrate such as dust-free paper
Dielectric film is heated with such as 50 to 120 DEG C, and with the vacuum degree of for example commercially available cheap 60~100KPa degree
Vacuum pump attract in the face of the electrode for being especially formed with a side on heating adsorption roller, therefore can manufacture not only to one
The dielectric film that side is formed with electrode does not cause to damage and does not have defective membrane-electrode assembly.In addition, to the gas permeability base
The purpose that the method for adhesive is granted in the two sides of material is to prevent the offset before being adsorbed by heating adsorption roller, but be able to use gravure
(gravure) roller etc. spreads adhesive sparsely and is formed as cellular, and dielectric film is uniform by gas permeability substrate
Ground absorption.In addition, adhesive is able to use the micro- adhesive being easily peeled off in rear process.
Vacuum pump can be applied for example from 2002 or so in the CCM of fuel cell industry from commercially available less expensive
In KRF, KHA, KHH system of Orion (Japanese: オ リ オ Application) company of the vacuum degree with 60~100KPa degree that uses
It is selected in column etc..
In the present invention, even to for 25 microns or less and then 15 microns or less and being easily deformed and reluctant
Dielectric film also can by the method for the directly coating electrode ink such as injection method or slot nozzle mode based on above-mentioned reason
It is enough with film is coated and manufactures the membrane-electrode assembly of stay in grade.
The effect of invention
As described above, according to the present invention, can be obtained the direct coating electrode ink of the electrolyte to fragility ideal
The interface of membrane-electrode, and then the membrane-electrode assembly of the periphery with electrode uncoated of high-quality can be manufactured, and then can
Manufacture has used fuel cell obtained from the MEA.
Detailed description of the invention
Fig. 1 be embodiments of the present invention be related on the dielectric film moving direction adsorbed with heating adsorption roller from
The schematic sectional view of the construction of masking substrate has been laminated in its top.
Fig. 2 be embodiments of the present invention be related on the dielectric film moving direction adsorbed with heating adsorption roller from
The skeleton diagram in the width direction of masking substrate has been laminated in its top.
Fig. 3 is related with electrode and uncoated portion on the moving direction for the electrolytic film that embodiments of the present invention are related to
Figure.
It is orthogonal with the dielectric film moving direction adsorbed with absorption heating roller that Fig. 4 is that embodiments of the present invention are related to
Direction masking substrate configuration schematic sectional view.
Fig. 5 is to be relevant with embodiments of the present invention orthogonally setting on absorption heating roller with dielectric film moving direction
The schematic sectional view for the covering appts set.
Fig. 6 is the cross-sectional view of the application examples of Fig. 5.
Fig. 7 is the figure that electrode and periphery are formd on dielectric film that embodiments of the present invention are related to.
Fig. 8 is the moving direction masking that tergite, dielectric film, dielectric film has been laminated that embodiments of the present invention are related to
The schematic sectional view of substrate.
Fig. 9 be embodiments of the present invention be related to supporting base material (gas permeability piece etc.), in the electricity for being formed with electrode on one side
The skeleton diagram of solution plasma membrane and the masking substrate being laminated on the moving direction of dielectric film.
Figure 10 be embodiments of the present invention be related in dielectric film in a manner of remaining uncoated portion (periphery) part
Form the schematic sectional view of the electrode at the two poles of the earth.
Figure 11 is 3 configuration diagrams that embodiments of the present invention are related to.
Figure 12 is the figure of the spray pattern immediately below 3 that embodiments of the present invention are related to.
Figure 13 is the figure of 3 that embodiments of the present invention are related to control injection coated patterns.
Figure 14 be embodiments of the present invention be related to (Japanese: past) is gone to based on 3 control injection coated patterns
Mobile impulse jet coated pattern.
Figure 15 is the return (Japanese: multiple) based on 3 control injection coated patterns that embodiments of the present invention are related to
Mobile impulse jet coated pattern.
Figure 16 is the arteries and veins of the reciprocating movement in the control injection coated pattern based on 3 that embodiments of the present invention are related to
Punching injection coated pattern.
Figure 17 is the company of the reciprocating movement in the control injection coated pattern based on 3 that embodiments of the present invention are related to
Continuous injection coated pattern.
Specific embodiment
Hereinafter, referring to attached drawing, the preferred embodiment of the present invention will be described.In addition, the following embodiments and the accompanying drawings is not
Crossing is the example for easy understanding invented, it is not excluded that without departing from the scope of the invention by ability
Additional, displacement, deformation that field technique personnel can implement etc..
Attached drawing diagrammatically shows the preferred embodiments of the present invention.
In Fig. 1, dielectric film 2 is rolled out from device 8 is rolled out, with heating 1 adsorbing electrolyte film 2 of adsorption roller and makes to be electrolysed
Plasma membrane 2 is mobile.The movement of heating adsorption roller can continuously move, and can also intermittently move.It will in the front of apparatus for coating 5
Masking substrate 3 guides with roller 7 and is laminated in dielectric film, moves together with the dielectric film on heating adsorption roller, is arranged with painting
It sets 5 and electrode ink is coated on dielectric film.If making apparatus for coating slot nozzle, electrode ink can be applied with liquid film
Cloth, therefore be coated with capable of being almost not attached to masked radical material, to starting in coating, terminate also to be capable of forming as straight line
Electrode pattern is also effective, but in order to be laminated with film, the preferably injector head (spray of ultrasonic wave, 2 fluids
head).It is sprayed and is coated with desired injection stream 6.Can make spray pattern width is, for example, 5mm to 30mm's
Circular pattern, circular pattern, oval logo (also including the case where substantially orthogonal) orthogonal with dielectric film with multiple such as 10
A laterally column or two column are arranged in 25 patterns and simultaneously layer is pulsedly coated in such a way that pattern in the sky will not interfere
It is folded.In addition, when can jetted at the same time pattern configured in a manner of not interfering and carry out 2.5 to 15mm short distance it is past
It is multiple to move (short traverse) and be overlapped spray pattern.
It can make one or more ground of injector head, orthogonally be moved back and forth simultaneously continuously or pulsedly with dielectric film
Carry out injection coating.It especially configures, is moving back and forth in such a way that a small number of respective injection streams of injector head does not interfere
(traverse) during carrying out injection coating, the movement (rotation) for heating adsorption roller stops.It is movably sprayed going to
After penetrating, the spray pattern that with the electrode spray pattern on the dielectric film that going to is sprayed and with returning is sprayed
Make to heat adsorption roller mobile (rotation) in a manner of the overlapping of desired length on the moving direction of dielectric film and stop, one
Injection coating is carried out on one side while return moving, repeatedly the process.It is reciprocatingly coated being intended to utilize with a small number of heads
Method continuously move dielectric film come in the case where being coated, if using being coated in a side is mobile and on the contrary
The mobile method without coating carrys out repeatedly the process, then is able to carry out even spread.It is in such as 3 total effective patterns
It in the case where 45mm, is sprayed in going to, without injection in return, is with reciprocal required time advance 45mm
It can.In addition, from the viewpoint of coating efficiency, the speed gone to when injection can be 100mm/ seconds hereinafter, return speed
It is preferred in terms of productivity when degree is 200mm/ second or more of 2 times.
The place that is laminated of masking substrate can be from roll out device 8 and roll out portion to any application place
Place.In addition, apparatus for coating, means are also possible to slot nozzle etc. as described above, it is not limited to spray.
After coating, the removing that carries out masking substrate batch at desired position etc..Masking
The removing of substrate can be from coating end position to any part devices for taking-up 9.Alternatively, it is also possible to masking substrate
3 grant bonding agent or adhesive in the face to connect with dielectric film.If being resistant to heating and/or solvent environment and shelling
From when on dielectric film the composition of remaining residue is not more preferable.Furthermore it is possible to be shelter the adhesive of substrate in order to be easy from
Dielectric film remove and be formed as cellular or every spaced thin striated and for masking substrate area 2/3 hereinafter,
Preferably 1/3 or less.Moreover, adhesive is deviated due to that can prevent, can also be separated in the direction of movement interval 10 to
It is in 100mm to grant dottedly and make 1/100 or less bond area.
Fig. 2 is the detailed content of the composition of Fig. 1, can to the dielectric film 2 that has adsorbed of heating adsorption roller 1 by masked radical
Material 3 is pressed against and is laminated to dielectric film 2 with guide reel 7.Masking substrate also can use adhesive tape (tape) and grant bonding in advance
Agent.In the masking substrate 3 of 3 column, the width of the masking substrate 3 ' of center be 2 times of the masking substrate width at both ends and being capable of shape
At the uncoated portion of the moving direction of electrode, the electricity to form the one side of uncoated portion periphery of same size of 2 column can be manufactured
The MEA of pole or the two poles of the earth.
It is desirable that the electrode of 3 column is formed, masking component 3 needs 4 column.In addition, in order to be set as desired by MEA
Uncoated portion, with two sides masking substrate width compare by center masking substrate width it is wide for example, 2 times.
Apparatus for coating 5 can orthogonally be moved back and forth together using reciprocating moving device with the direction of travel of dielectric film
When continuously or pulsedly carry out injection coating.During being reciprocatingly coated, heating adsorption roller can stop revolving
Turn.It can be coated with the spray pattern 6 based on 1 apparatus for coating 5 or the composite pattern based on multiple apparatus for coating.Even
Continuously in the case where mobile dielectric film, if only in a side of the reciprocating movement based on reciprocating moving device is mobile, that is,
Injection coating only is carried out in returning to road in going to road or only, then coating can be made to be evenly distributed.In this case, make to apply
Cloth it is mobile for example go to slowing, being, for example, 100mm/ seconds or less and can be improved coating efficiency for road, if make without
The speed on the return road of coating is 200mm/ seconds or more of 2 times or more, then can be improved productivity.In the outside of dielectric film 2
To substrate (not shown), pulsedly coating electrode is black, moves outside to application chamber (booth) and makes the shield of coating weight measuring cell
(shutter) coating weight can be measured to close.In the case where coating weight is not the coating weight of target, although energy
Enough number of pulses, efflux time, reciprocating movement speed, hydraulic etc. are micro-adjusted, if but being come with 0.01 to 0.1mm/ second scale
Adjust the efflux time of pulse, then can further progress micro-adjustment and can be measured every time, therefore be easy.
Fig. 3 is electrode 10 that is black to dielectric film coating electrode and having removed masking component and electrode ink uncoated portion 11
(dielectric film).
Fig. 4 attached the second masking substrate 12 orthogonally configured with the dielectric film moved in Fig. 1.Second masking substrate
12 is mobile to the lower section of apparatus for coating 6 in the timing to dielectric film setting uncoated portion.It can be only fitted to electrolyte movement side
To the first masking substrate on and jetelectrode ink manufacture the pattern of quadrangle, in addition, the second masked radical can be used only
Electrode ink simultaneously sharply (sharp) is coated by material with slot nozzle on the direction of travel of dielectric film, can only by
Under low pressure more than the coating initial flow of electrode ink and tup drafting department that pattern is extended as hammer (hammer) pass through to
Second masking base part is coated with to eliminate the influence to dielectric film, or can be terminated by coating similarly second
Terminate to form electrode to equably coating electrode ink on masking substrate.
In Fig. 5, keep the second masking substrate 12 mobile in desired timing.The second masking is coated on apparatus for coating 5
Electrode ink on substrate is rolled out according to desired application frequency or time by the device 15 that rolls out of the second masking substrate 12, can
The second masking substrate that electrode ink is attached with a certain thickness is automatically batched by devices for taking-up 16.
Fig. 6 is the application type of Fig. 5, the 2nd masking substrate roll out device 15 and devices for taking-up 16 can be via by being located at
The free roll 30 and guide reel 31 of the connections such as side and bracket (not shown) batch.
In Fig. 7, including the electrode being compounded to form by the first masking substrate and the second masking substrate on dielectric film 2
10 and uncoated portion 11, uncoated portion periphery 11 is formed by severing.
Fig. 8 is the composition that masking film is laminated on the dielectric film 2 for being laminated in tergite 17, by this composition, by heating
Adsorption roller adsorbs and is coated with first electrode ink.
In Fig. 9, masked radical material 3 is laminated to the dielectric film for being formed with first electrode and is laminated with branch in first electrode side
Support group material 18.Adhesive 19 is granted in the two sides of supporting base material 18, adhesive 19 is contacted with dielectric film.About branch support group
Material is being coated with since the gas permeabilities such as porous membrane, dust-free paper substrate is capable of uncoated portion, the electrode of adsorbing electrolyte film
When second electrode ink, the deformation of dielectric film can be prevented, is therefore preferred.Breathable films or dust-free paper be preferably particle not
The ventilative size or construction of the carbon of platinum for being supported with electrode etc. can be transferred to.By using Breathable films or commercially available dustless
Paper, the absorption aperture of heating absorption drum can be 0.1mm to 0.6mm, and spacing also with saw tooth pattern and for 0.7mm to 2mm, uses
The vacuum pump that vacuum degree is 60 to 100KPa, thus, it is possible to obtain sufficient adsorption effect, by the way that electrode ink is coated on heating
The dielectric film of 50 to 80 DEG C of degree into 50 to 120 DEG C of degree, to dielectric film will not be made to deform.
Figure 10 is to form first electrode 10, second electrode 10 ' and uncoated on the two sides of dielectric film 2 through the invention
Portion and the figure that the severing of uncoated portion is manufactured to MEA20.
Figure 11 is matching for 3 head 5-a, 5-b, the 5-c for orthogonally moving and being sprayed with the direction of travel of dielectric film
It sets.Coating head is also possible to 1, is also possible to 5, can also be 5 or more.By to become spray pattern certain
Increase head number when size, can be improved speed of production.Match in such a way that injection stream respective when for multiple does not interfere
It sets, this is important the aspect being uniformly coated with.
Figure 12 is the injection coated pattern 41,42,43 of the underface of 3 heads.Each pattern is not in a manner of interfering
Configuration.
In Figure 13, when the moving direction of 3 heads and dielectric film is orthogonally reciprocatingly sprayed, with coating
The mode that pattern forms a line on the moving direction of dielectric film controls coating timing.From the viewpoint of overlapping coating,
It is preferred that configuring each head in such a way that coated pattern 41,42,43 is slightly overlapped.
In Figure 14, in going in mobile for injector head, pulsedly sprayed from each head, the arteries and veins of the moving direction of head
Pattern 41,42,43 is rushed to carry out being fully overlapped coating.During going to mobile, dielectric film and heating (not shown) absorption
Roller stops.
In Figure 15, when carrying out returning to mobile, in order to be fully overlapped pattern 41,42,43, make dielectric film and heating
It is mobile that adsorption roller is deviated (offset) together.Each pattern width is in the mobile 10mm of for example, 20mm hour offset, for example
For the mobile 15mm of 30mm hour offset.
If dielectric film and heating adsorption roller is made to have moved together the control figure from 3 heads when each pattern is, for example, 20mm
Total 60mm of case subtract 50mm obtained from half of pattern 10mm carry out it is next go to mobile injection and start, then can
Enough form uniform electrode.
In Figure 16, masking substrate 3 is laminated in the two sides of dielectric film 2.Electrode ink is pulsedly sprayed.In order to make week
The coating weight of electrode ink near edge also becomes uniformly, and the structure of masking substrate can be attached to using more than half of spray pattern
At.Also the coating weight of adjacent peripheral edges can be kept few in a manner of in masking substrate hardly attached pattern.
In Figure 17, it is set as capableing of the composition of the continuously impulse jet of injection scheme 16.The advantages of about continuous injection, by
In such as 1.5~10 times of reciprocating movement speed of the 50~100mm/ second that can make impulse jet, therefore electrode can be increased
The treating capacity of formation.Faster but if speed is fast, injection stream is more blown by mobile wind and coating efficiency reduces sharply.
Industrial availability
In accordance with the invention it is possible to the PEFC fuel cell membrane-electrode assembly (MEA) with periphery be manufactured, due to passing through
To the direct coating electrode ink of electrolytic film and keep the electrode ink dry and form the CCM mode of electrode to carry out, therefore can be with height
Quality is manufactured.
Description of symbols
1 heating adsorption roller
2 dielectric films
3 first masking substrates
4 electroded dielectric films
5 apparatus for coating
6 injection streams
7 guide reels
8 dielectric films roll out device
9 dielectric film devices for taking-ups
10 first electrodes
10 ' second electrodes
11 electrode ink uncoated portions (peripheral part)
12 second (orthogonal) masking substrates
15 second masking substrates roll out device
16 second masking component devices for taking-ups
17 tergites
18 supporting base materials (gas permeability substrate)
19 adhesives
20 membrane-electrode assemblies (MEA)
30 free rolls
31 guide reels
41,42,43 spray pattern
Claims (7)
1. a kind of manufacturing method of the membrane-electrode assembly of fuel cell, will be laminated in the electrolysis of the strip of tergite or supporting base material
Plasma membrane is continually or intermittently rolled out and is kept the dielectric film mobile with rolling out device, to dielectric film coating electrode ink, in electricity
Solution plasma membrane forms electrode and is batched with devices for taking-up,
The manufacturing method is characterised by comprising:
From it is described roll out process until being coated with starting position between in order to make dielectric film electrode edge or periphery, and
In the process that the first elongated masking substrate is laminated in the dielectric film by two sides；Heating absorption is carried out to dielectric film on one side
The process of apparatus for coating coating electrode ink is used on one side；The process for keeping electrode ink dry；And from coating end position to batching
The process of the first masking substrate is removed between until device.
2. the manufacturing method of the membrane-electrode assembly of fuel cell according to claim 1, which is characterized in that
Being formed in the electrode of the dielectric film, there are multiple in the width direction of dielectric film.
3. the manufacturing method of the membrane-electrode of fuel cell according to claim 1 or 2, which is characterized in that
The moving direction of second masking substrate and dielectric film is orthogonally coated with end position and electrode pattern between electrode pattern
It is coated between starting position.
4. the manufacturing method of the membrane-electrode assembly of fuel cell according to claim 1 or 2, which is characterized in that
At least adhesive has been granted in the side for being laminated in dielectric film of the first masking substrate.
5. the manufacturing method of the membrane-electrode assembly of fuel cell according to any one of claim 1 to 4, feature exist
In,
At least first masking substrate on dielectric film is laminated and is taken up with dielectric film via adhesive in advance.
6. the manufacturing method of the membrane-electrode assembly of fuel cell according to claim 4 or 5, which is characterized in that
The adhesive of the first masking substrate includes micro- adhesive, is granted the position of the solvent contact of Yu Buyu electrode ink,
It is granted in cellular or in multiple every spaced striated, the area of granting of described adhesive is to shelter substrate surface product
1/2 or less.
7. the manufacturing method of the membrane-electrode assembly of fuel cell according to any one of claim 1 to 6, feature exist
In,
The the second masking substrate orthogonally configured with the moving direction of the dielectric film can shelter rolling out for substrate with second
Device and devices for taking-up move together, at the end of the coating of the electrode ink of the moving direction of dielectric film and when coating starts, from
It is moved to coating end position and coating starting position dynamicly and is sheltered.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017018734A JP2018125247A (en) | 2017-02-03 | 2017-02-03 | Method of manufacturing membrane/electrode assembly of pefc type fuel cell |
| JP2017-018734 | 2017-02-03 | ||
| PCT/JP2018/002915 WO2018143179A1 (en) | 2017-02-03 | 2018-01-30 | Method for manufacturing membrane/electrode assembly of pefc-type fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110249465A true CN110249465A (en) | 2019-09-17 |
| CN110249465B CN110249465B (en) | 2022-10-25 |
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ID=63039586
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880009967.2A Active CN110249465B (en) | 2017-02-03 | 2018-01-30 | Method for manufacturing membrane-electrode assembly of fuel cell of PEFC type |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2018125247A (en) |
| CN (1) | CN110249465B (en) |
| WO (1) | WO2018143179A1 (en) |
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|---|---|---|---|---|
| JP6930709B2 (en) * | 2017-08-17 | 2021-09-01 | エムテックスマート株式会社 | Method for manufacturing catalyst-forming electrolyte membrane for PEFC type fuel cell |
| JP7180863B2 (en) * | 2018-08-21 | 2022-11-30 | エムテックスマート株式会社 | Method for manufacturing all-solid-state battery |
| JP7395127B2 (en) | 2019-08-23 | 2023-12-11 | エムテックスマート株式会社 | Battery manufacturing method and battery |
| JP2021079598A (en) * | 2019-11-18 | 2021-05-27 | パナック株式会社 | Manufacturing method of mask for pattern coating and manufacturing method of pattern coating sheet |
| JP2021087905A (en) * | 2019-12-02 | 2021-06-10 | エムテックスマート株式会社 | Coating of granular material or film-forming method |
| JP7136464B2 (en) * | 2019-12-24 | 2022-09-13 | 京楽産業．株式会社 | game machine |
| JP2021100463A (en) * | 2019-12-24 | 2021-07-08 | 京楽産業．株式会社 | Game machine |
| JP2022172677A (en) * | 2021-05-06 | 2022-11-17 | エムテックスマート株式会社 | Method for manufacturing laminate of membrane electrode assembly and gas-permeable substrate, laminate of membrane electrode assembly and gas-permeable substrate, and method for manufacturing fuel cell |
| JP2022178501A (en) * | 2021-05-20 | 2022-12-02 | エムテックスマート株式会社 | Method for manufacturing membrane/electrode assembly, method for manufacturing laminate of membrane/electrode assembly and air-permeable substrate, laminate of membrane/electrode assembly and air-permeable substrate, method for manufacturing fuel cell, and fuel cell |
| JP2023074174A (en) * | 2021-11-17 | 2023-05-29 | エムテックスマート株式会社 | Manufacturing method of fuel battery, manufacturing method of membrane electrode assembly, membrane electrode assembly, composite of membrane electrode assembly and air-permeability base material, and fuel battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001070863A (en) * | 1999-07-02 | 2001-03-21 | Toyota Motor Corp | Liquid applying device, rotary member used for the same and its production |
| JP2007095464A (en) * | 2005-09-28 | 2007-04-12 | Honda Motor Co Ltd | Method of manufacturing electrolyte structure |
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|---|---|---|---|---|
| DE10224452C1 (en) * | 2002-05-29 | 2003-11-20 | Fraunhofer Ges Forschung | Polymer membrane with segmented catalyst coating, used in planar micro-fuel cell array for mobile electrical or electronic equipment, is made by applying uniform catalyst coating and partial removal to leave segments |
| US7326736B2 (en) * | 2002-11-04 | 2008-02-05 | Giner Electrochemical Systems, Llc | Composite proton exchange membrane and method of manufacturing the same |
| JP4737924B2 (en) * | 2003-08-11 | 2011-08-03 | ノードソン コーポレーション | ELECTROLYTE MEMBRANE FOR FUEL CELL, ELECTROLYTE MEMBRANE COMPOSITION, METHOD FOR PRODUCING ROLL STOCK OF ELECTROLYTE MEMBRANE COMPOSITION, METHOD FOR PRODUCING ELECTROLYTE MEMBRANE / electrode assembly FOR FUEL CELL, AND METHOD FOR PRODUCING FUEL CELL |
| JP5101185B2 (en) * | 2005-09-15 | 2012-12-19 | パナソニック株式会社 | Membrane-membrane reinforcing member assembly, membrane-catalyst layer assembly, membrane-electrode assembly, and polymer electrolyte fuel cell |
| JP5343529B2 (en) * | 2008-11-26 | 2013-11-13 | 日産自動車株式会社 | Method for producing fuel cell electrode laminate |
| JP2011028915A (en) * | 2009-07-22 | 2011-02-10 | Toyota Motor Corp | Method of manufacturing fuel cell |
| JP2013161557A (en) * | 2012-02-02 | 2013-08-19 | Panasonic Corp | Manufacturing method of film-catalyst layer junction and manufacturing apparatus of film-catalyst layer junction |
-
2017
- 2017-02-03 JP JP2017018734A patent/JP2018125247A/en active Pending
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2018
- 2018-01-30 CN CN201880009967.2A patent/CN110249465B/en active Active
- 2018-01-30 WO PCT/JP2018/002915 patent/WO2018143179A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001070863A (en) * | 1999-07-02 | 2001-03-21 | Toyota Motor Corp | Liquid applying device, rotary member used for the same and its production |
| JP2007095464A (en) * | 2005-09-28 | 2007-04-12 | Honda Motor Co Ltd | Method of manufacturing electrolyte structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110249465B (en) | 2022-10-25 |
| JP2018125247A (en) | 2018-08-09 |
| WO2018143179A1 (en) | 2018-08-09 |
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