CN111758178B - Method for manufacturing membrane electrode assembly of fuel cell - Google Patents
Method for manufacturing membrane electrode assembly of fuel cell Download PDFInfo
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- CN111758178B CN111758178B CN201980015184.XA CN201980015184A CN111758178B CN 111758178 B CN111758178 B CN 111758178B CN 201980015184 A CN201980015184 A CN 201980015184A CN 111758178 B CN111758178 B CN 111758178B
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- electrolyte membrane
- electrode
- roller
- heated
- fuel cell
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- 239000012528 membrane Substances 0.000 title claims abstract description 129
- 239000000446 fuel Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 100
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 5
- 238000001179 sorption measurement Methods 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 13
- 230000001681 protective effect Effects 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 10
- 230000035699 permeability Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 239000010409 thin film Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000005456 alcohol based solvent Substances 0.000 abstract description 3
- 239000008151 electrolyte solution Substances 0.000 abstract description 3
- 239000011258 core-shell material Substances 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 20
- 239000000463 material Substances 0.000 description 15
- 239000010408 film Substances 0.000 description 14
- 238000005507 spraying Methods 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000004804 winding Methods 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 238000010030 laminating Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920000554 ionomer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 201000000760 cerebral cavernous malformation Diseases 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
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- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- -1 shape Substances 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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]
-
- 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
- B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
-
- 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
-
- 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
-
- 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
-
- 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
An electrode ink containing an electrolyte solution, a catalyst-supporting carbon, and water or an alcohol-based solvent or both water and alcohol-based solvent, or a core-shell electrode ink is coated on a thin and sensitive electrolyte membrane for a fuel cell with a thin film to produce a deformation-free membrane electrode assembly. A small diameter roller is provided upstream of the heated suction roller, and electrode ink is applied using a slot nozzle on or off the small diameter roller to form at least one side electrode, and solvent is instantaneously evaporated by the heated suction roller to form the electrode.
Description
Technical Field
The present invention relates generally to a method of applying a liquid film to a long object, using a head called slot die (slot die), slot nozzle (slot nozzle), or the like. Examples include a method of forming an electrode of a fuel cell, particularly a PEFC (Polymer Electrolyte Membrane Fuel Cell) type fuel cell, and an MEA (membrane electrode assembly) and a fuel cell manufactured by the method.
The material, shape, and coating material of the coating material are not particularly limited, but are particularly effective in terms of productivity when an electrode is formed by coating an electrode ink on an electrolyte membrane through a direct slot nozzle in order to apply the coating material to CCM (Catalyst Coated Membrane, catalyst coating film) of an MEA, a method of forming an electrolyte membrane electrode, and the like.
Background
Conventionally, an electrode catalyst ink is formed by mixing an electrolyte solution, which is one of the ionomers, with fine particles of platinum or the like supported on carbon particles or carbon fibers, and then applying the ink to GDLs (Gas Diffusion Layer, gas diffusion layers) to press-contact the electrolyte membrane, or to a PTFE plasma membrane to transfer the ink to the electrolyte membrane. Since no liquid is present in the pressure bonding method and the transfer method, an electric resistance is generated between the electrolyte membrane and the electrode, and the fuel cell performance is lowered. In order to solve this problem, a method of directly applying an electrode catalyst ink of CCM system to an electrolyte membrane has been proposed.
Patent document 1 proposes a method of unwinding an electrolyte membrane for Roll-To-Roll (Roll To Roll), and laminating and applying electrode ink by spraying or the like in a state of being adsorbed on a heated adsorption drum or adsorption belt, and drying the electrode ink. Since the electrolyte membrane is laminated as a thin film by spraying or the like in a state where the electrolyte membrane is adsorbed and heated by heating of an adsorption drum or the like, the solvent is instantaneously volatilized at the moment when the sprayed particles are coated on the electrolyte membrane and leveled. Therefore, since the adhesion is improved without damaging the electrolyte, the interfacial resistance between the electrode and the electrolyte membrane can be reduced to the limit, and thus an ideal CCM can be formed. In addition, since an air-permeable paper having a width wider than that of the electrolyte membrane is present between the adsorption drum and the electrolyte to attract the electrolyte membrane, it has been proposed to attract the entire electrolyte membrane surface uniformly so as not to leave adsorption marks of the porous body such as the adsorption drum.
Patent document 2 also discloses a method of laminating a film as a mask for electrode shape on both surfaces of an electrolyte film for Roll-To-Roll (Roll) To form electrode-shaped recesses, and laminating and winding electrode ink while unwinding the film and adsorbing the film with a heated adsorption Roll or adsorption belt. In this method, it is recommended that the electrode ink be applied while the electrolyte membrane is attracted by a heated adsorption drum or the like for the gas-permeable substrate.
The CCM method is ideal, but since the electrolyte membrane is sensitive to moisture and the like and there is a Nafion membrane or the like that deforms at a moment when the electrode catalyst ink is applied, as described above, an attempt is made to adsorb the electrolyte membrane on a heated adsorption belt, a heated adsorption roller or the like, move it without deformation, and apply it by a spray nozzle, a slot nozzle or the like. In order to obtain a desired electrode pattern, the spraying must use a mask, which has difficulty in increasing the production speed.
The slot nozzle is effective for increasing the production speed, but has the following problems when disposed on the "on roller" of the heated suction roller. Since the electrode ink is composed of platinum supported on carbon, an ionomer, water, an alcohol solvent, and the like, when the heated roller is set to about 100 ℃ or higher, condensation occurs on the tip of the slot nozzle which is not heated across the electrolyte membrane due to a temperature difference, due to water and/or solvent vapor of the electrode ink applied, and the like, thereby adversely affecting the application surface.
In order to prevent this, there is a method of heating a device including a nozzle, but if the temperature of the slot nozzle is high, the nozzle tip is liable to dry, skinning occurs in the nozzle opening portion, and the ejection of the electrode ink tends to become unstable.
In addition, even in the suction roll whose roundness is polished to several micrometers or less at room temperature by a polishing device, the roll is subjected to large deflection deformation due to the complicated structure at the time of heating, and the roundness is extremely poor.
In recent years, an amount of an electrode catalyst is required to be 0.15mg or less per square centimeter at the anode, 0.3mg or less at the cathode, and a small amount, and a specific gravity of a platinum catalyst is 20 or more, so that a film thickness becomes thin.
The ratio of platinum to platinum-supporting carbon is also platinum: carbon is 5:5, further 7:3, the dry film thickness including the ionomer is substantially 1 μm or less and extremely thin, and when the solid content is 10%, the wet film thickness is also 10 μm or less, and the film thickness is extremely thin.
When the heated suction roll is deformed, if the method called slit nozzle, slot nozzle or slot die is adopted, which is in contact with the liquid film through a gap, there is a problem that the distance between the nozzle tip and the electrolyte membrane changes, and an excessively far portion is generated. When such a phenomenon occurs, the coating amount of the electrode ink is extremely small, and therefore, it is extremely difficult to obtain uniform coating because the electrode ink is coated as a thin film and a porous coating surface becomes a scale-like shape at a position where the nozzle tip is distant from the electrolyte membrane.
In order to solve this problem, japanese patent application laid-open No. 2010-149957, which is invented by the present inventors, proposes a method of polishing the surface of the suction roll in a state of being heated to an application temperature, so that the roundness can be made to be 5 μm or less. However, this method requires polishing every time the roller temperature is changed, and is extremely poor in workability.
In addition, japanese patent application laid-open No. 2015-15258, which assumes that the adsorption roller is polished at normal temperature or after cooling, proposes a method in which the roller that adsorbs the electrolyte membrane is cooled, the electrode ink is applied to the electrolyte membrane by a slit nozzle, and the electrode ink adsorbed to the electrolyte membrane on the cooling roller by rotating the roller is heated by hot air or infrared rays in a subsequent process.
However, in this method, it is expected that the time from cooling to heating and drying after coating, for example, nafion membrane or the like is damaged by solvent impact on the interface of the electrolyte membrane.
Prior art literature
Patent document 1: japanese patent laid-open No. 2004-351413
Patent document 2: japanese patent laid-open No. 2005-63780
Disclosure of Invention
The present invention has been made to solve the above-described problems, and its means is to dry the electrode ink applied to the electrolyte membrane quickly and without deformation, without pursuing the roundness of the heat suction roller. Therefore, since emphasis is not placed on roundness, manufacturing costs can be reduced to a limit. On the other hand, it is common knowledge in the industry that the straightness of the tip of the slot nozzle is reduced to 5 μm or less at room temperature and further to 2 μm or less by polishing with a polishing device, and therefore it is important to use the slot nozzle at room temperature to reduce the influence of heat of the heat suction roller or the heat roller.
In addition, by polishing with a polishing apparatus, roundness of a small diameter roller, for example, a diameter of 200 mm or less at room temperature can be suppressed to several micrometers or less. On the other hand, even when heated, a small diameter roller having a simple internal structure can achieve a roundness of several micrometers or less, and therefore is used as a pressure bonding roller for an electrode of a secondary battery.
Therefore, by effectively using these small diameter rolls in combination with a large diameter heat suction roll having a diameter of 200 mm or more or a heat roll having a diameter of 250 mm or more, and providing the groove nozzle at a position on or apart from the roll, it is possible to maintain the distance between the electrolyte membrane and the tip of the groove nozzle with high accuracy and to pattern-coat the electrode ink.
Since the electrolyte membrane is generally manufactured by a casting method, there is a back plate supporting a substrate, and thus coating for forming one electrode may be performed by spraying or slot-die coating without deforming the electrolyte membrane. However, since the electrolyte membrane is thinned and stretched to 25 micrometers or less and even 15 micrometers or less, and there is an extremely sensitive base material that is simply deformed by moisture in the air as described above, it is extremely difficult to form the electrode on the opposite surface and it is extremely difficult to wind the electrolyte membrane on which the electrode is formed on both sides of the electrolyte membrane.
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for producing a membrane electrode for a PEFC fuel cell, which has high quality and durability, and to provide CCMs or MEAs in large quantities at high speed.
More specifically, electrode ink is directly applied to an electrolyte membrane of a Roll-to-Roll (Roll to Roll) to produce a high-performance membrane electrode assembly and, in turn, a high-performance fuel cell.
The present invention provides a method for producing a membrane electrode assembly of a fuel cell, which is a method for forming an electrode by continuously or intermittently moving a long electrolyte membrane for a fuel cell and applying electrode ink to at least one side of the electrolyte membrane by a slot nozzle, the method comprising:
a step of providing a heated adsorption roller for thermally adsorbing the electrolyte membrane coated with the electrode ink;
a step of providing at least one roller having a smaller diameter than the heated suction roller upstream of the heated suction roller and in proximity to the heated suction roller; and
and coating electrode ink with a slot nozzle between the position on the small diameter roller and the position where the electrolyte membrane contacts the heated adsorption roller.
The invention provides a method for manufacturing a membrane electrode assembly of a fuel cell, characterized in that the heating adsorption roller is a heating roller, and the heating adsorption roller is moved under the condition that 20-80N tension is applied to the electrolyte membrane.
The invention provides a method for manufacturing a membrane electrode assembly of a fuel cell, which is characterized in that the heating adsorption roller is a heating adsorption belt.
The invention provides a method for manufacturing a membrane electrode assembly of a fuel cell, which is characterized in that tension of 20-80N is applied to electrolyte membranes in front of and behind a small-diameter roller, and electrode ink is coated on the positions of the electrolyte membranes in front of and behind the small-diameter roller, which are separated from the roller.
The invention provides a method for manufacturing a membrane electrode assembly of a fuel cell, which is characterized in that the slot nozzle is a gas-assisted slot nozzle or a spray slit nozzle, and the distance between an electrolyte membrane and a nozzle head is set to be 0-10 mm.
The invention provides a method for manufacturing a membrane electrode assembly of a fuel cell, characterized in that the roundness of the heating adsorption roller or the heating roller is less than +/-50 mu m, and electrode ink is coated on the position of an electrolyte membrane, which is just before the electrolyte membrane is contacted with the heating adsorption roller or the heating roller, and the position of the electrolyte membrane is separated from the roller.
The invention provides a method for manufacturing a membrane electrode assembly of a fuel cell, which comprises the following steps: applying an anode ink to the electrolyte membrane by a slot nozzle, drying the anode ink, bringing the reversed electrode surface into contact with a gas-permeable substrate when applying a cathode ink in the form of particles or fibers, sucking the electrolyte membrane through the gas-permeable substrate on a heated suction roll, and peeling a back plate laminated on the electrolyte membrane; and forming an electrode containing a catalyst for the cathode on the opposite side of the anode.
The invention provides a method for manufacturing a membrane electrode assembly of a fuel cell, which is characterized in that electrode ink is coated on an electrolyte membrane laminated with a back plate and dried to form an electrode, a protective base material with first air permeability is laminated on the electrode, the electrolyte membrane and the electrode are adsorbed through a heating adsorption drum by the protective base material with the first air permeability, the back plate is peeled off, electrode ink with opposite poles is coated to form the electrode, the air permeability protective base material is recovered, a new second air permeability base material is laminated, and the electrode of the two is wound under the condition that the second air permeability base material is used for protecting the electrode.
The electrode ink catalyst in the present invention may use a core-shell type catalyst.
According to the method for manufacturing a membrane electrode assembly of a fuel cell of the present invention, even an extremely thin electrolyte membrane that is sensitive and, for example, 15 μm or less, electrode ink can be directly applied on each face of the electrolyte membrane. In addition, in order to reduce the load on the electrolyte membrane, it is preferable that the electrode ink applied to the electrolyte membrane by heat suction is capable of volatilizing 99% or more of the solvent amount immediately after wetting the electrolyte membrane, for example, within 3 seconds, so that the adhesion between the membrane and the electrode can be improved and the interface resistance can be reduced to the maximum extent.
In the present invention, the cathode is not limited to the slot-die nozzle system, and if a spraying method or a pulse spraying method belonging to the spraying and a method of further adding a velocity to sprayed particles, that is, an impact pulse method registered by the trademark of MTEK-SMART corporation is used alone or in combination with the slot-die nozzle, the adhesion of the catalyst to the electrolyte membrane can be further improved, and an electrode having preferable micropores, mesopores, and macropores can be formed. Furthermore, gas-assisted slot nozzles, spray slot nozzles, melt-blown spray nozzles may be used for spraying or pulse spraying.
In the present invention, the present invention is not limited to a single nozzle head, and a plurality of heads may be arranged in series in the movement direction of the electrolyte membrane to laminate the electrolyte membrane with a thin film. In particular, by using a gas-assisted slit nozzle, a spray slit nozzle, or a melt-blown nozzle head, the electrode amount of 1 layer per square centimeter can be adjusted to 0.01 to 0.3mg, so that, for example, a film of 2 to 30 layers of electrode ink can be laminated. The amount of coating per layer can be reduced by combining with a heated adsorption drum or the like, but in order to further reduce the amount of coating per layer, for example, the solid content of the electrode ink composed of carbon supported by a platinum catalyst, an electrolyte solution, an alcohol-based solvent, or water and alcohol may be set to 10% or less, for example, 3% or less by weight.
The advantage of setting the solid content concentration to the above-described one is that the further the film is laminated, the smaller the load of solvent impact of the electrolyte membrane becomes, the more uniform the coating amount per unit area becomes, so that the performance of the fuel cell is improved.
Further, in the present invention, the gas-permeable substrate, such as dust-free paper or gas-permeable plastic film, having the electrolyte membrane interposed therebetween can be heated, such as a heated adsorption drum, at 50 to 120 ℃, and the adsorption drum can be sucked by a commercially available vacuum pump having a vacuum degree of about-60 kPa, so that it is possible to manufacture a membrane-electrode assembly without damaging the electrolyte membrane and without defects. It is economical to use a breathable substrate wrapped around a heated adsorbent drum. Further, the adhesive is spread in a porous form using gravure rolls or the like on both sides in particular other than the electrode forming portion of the electrolyte membrane, and the mask base material cut into the electrode size is attached and moved, so that an accurate electrode pattern can be formed without being limited to the use of a slot nozzle or a spray method. The mask base material is particularly useful for a spray method or the like for granulating electrode ink.
The surface of the heated suction roll can be manufactured by forming a plurality of holes of 0.1 to 1mm diameter in a cylinder of stainless steel or the like at intervals of 1 to 3mm, for example, alternately. The plurality of openings may be typically made by laser or electron beam, etc. In order to make the adsorption distribution more uniform even in the case of large holes and coarse holes, dust-free paper, a porous film of micrometer order, or the like may be wound around the surface of the drum and fixed to the heated adsorption drum. For example, it is possible to produce a heating adsorption drum at low cost by performing multi-layer winding or preparing a plurality of breathable base materials and sequentially stacking fine materials in order from coarse, which is economical. In addition, when a breathable substrate of micrometer or nanometer scale is used, the breathable substrate has the same effect as a heating adsorption drum of micrometer or nanometer scale, so that the breathable substrate is superior in cost performance from the aspect of performance. Alternatively, they are not limited to the singular plural, and may be used in a wound state together with the electrolyte membrane.
The present invention is to manufacture a membrane electrode assembly having stable quality by directly laminating electrode ink in a thin film state by a slot nozzle, a spray coating method, or the like, as required, on an electrolyte membrane which is not an extremely thin film and is easily deformed and is difficult to handle at the time of application of a liquid coating and drying method of japanese patent application laid-open No. 2004-351413.
As described above, according to the present invention, even if electrode ink is directly applied to a sensitive electrolyte, a desired interface of a membrane electrode can be obtained, and a high-quality membrane electrode assembly and a fuel cell can be manufactured.
Drawings
Fig. 1 is a schematic cross-sectional view showing the arrangement of a heating (adsorbing) roll, a small diameter roll, an electrolyte membrane, and a slot nozzle according to an embodiment of the present invention.
Fig. 2 is a schematic cross-sectional view of a combination of a heating (adsorption) roller, a small diameter roller, an electrolyte membrane, and a slot nozzle according to an embodiment of the present invention.
Fig. 3 is a schematic cross-sectional view of the arrangement of the heating (adsorption) roller, electrolyte membrane, small diameter roller, slot nozzle, etc. and the moving direction of the breathable substrate, etc. according to the embodiment of the present invention.
Fig. 4 is a schematic cross-sectional view of an inverted electrolyte membrane and other components for forming a second electrode according to an embodiment of the present invention.
Fig. 5 is a schematic cross-sectional view of the movement direction of an electrolyte membrane or the like in an application of the second electrode formation according to the embodiment of the present invention.
Fig. 6 is a schematic cross-sectional view of a membrane electrode assembly according to an embodiment of the present invention.
Detailed Description
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. The following embodiments are merely examples for easy understanding of the present invention, and do not exclude any addition, substitution, modification, and the like that can be performed by those skilled in the art without departing from the technical spirit of the present invention.
The drawings schematically illustrate preferred embodiments of the present invention.
In fig. 1, a small diameter roller 4 having a smaller diameter than the heat-absorbing drum 1 is provided upstream of the heat-absorbing drum 1, an electrolyte membrane 2 unwound by an unwinding device 5 is coated with electrode ink, not shown, by a slot nozzle 3 at a position apart from the roller between the small diameter roller 4 and the heat-absorbing drum 1 via a pull roller 10, and a film-forming electrode assembly is wound by a downstream winding device 6. One or more layers of a micrometer-sized breathable substrate, not shown, can be stacked on the heated suction roll. Opposite-pole electrodes may be formed on the electrolyte membrane. The electrolyte membrane may be coated with the slot nozzle 3 either on the small diameter roll 4 (on roll) or at a position before and after the small diameter roll and before the heat suction roll (off roll). In this case, the heat absorption is preferably started almost simultaneously with the coating when the heat absorption is performed at a position immediately before reaching the position of the heat absorption roller away from the roller. In particular, when the operation is performed at a position away from the roll, it is desirable to apply a tension of 20 to 80N to the electrolyte membrane. Since the on-off valve mechanism in the slot nozzle can be cleaned by suction, a rectangular or square electrode pattern can be formed. In addition, in the case where a plurality of patterns are intended to be provided orthogonal to the moving direction, it is convenient to assemble the gasket formed in a desired size.
Fig. 2 is a view in which a plurality of small diameter rollers (14, 14') are provided in the structure of fig. 1. The slot jet 13 may be disposed on the rolls of the small diameter rolls 14, 14' or at positions apart from the rolls before and after the rolls. In addition, the small diameter roller may also be heated.
Fig. 3 shows an electrode pattern 205 formed by applying electrode ink to an electrolyte membrane 32 with a slot nozzle 33 on a roll on a small diameter roll 34. The dried electrode 205 is unwound from the protective substrate 38 by the protective substrate unwinding device 39 on the heated suction roll 31, and laminated on the electrolyte membrane 32 and the electrode 205, and wound as a composite by the winding device 36. The protective substrate may be a gas-permeable substrate, and is not limited to a material, a type, or a shape as long as the protective substrate is a pre-formed first electrode, and may be selected from substrates that are not transferred electrodes or are difficult to transfer electrodes, which are least expensive in terms of cost.
In fig. 4, backing plate 165 is peeled off upstream of electrolyte membrane 42 on which the first electrode is formed, and wound by backing plate winding device 102. Electrode ink is applied in order to detect the position where the first electrode is formed on the opposite surface by the detection sensor and to form the second electrode by the slot nozzle 43. The air-permeable substrate 138 that protects the first electrode and moves on the heated suction roller is wound by the air-permeable substrate winding device 101. The electrolyte membrane formed with the first and second electrodes is wound by the winding device 46 together with the new protective base 148. The protective substrate may be a gas permeable substrate, and a low cost substrate having no effect on the electrode surface should be selected.
Fig. 5 is a view of forming a second electrode with spray instead of a slot nozzle. The structure is substantially the same as that of fig. 4 except for the spraying. A mask having substantially the same shape as the first electrode should be provided in addition to the spraying according to a gas-assisted coating method in which the electrode ink is applied together with an air curtain of the electrode ink flowing out from the spray slit nozzle or the slot nozzle as mist. The formation of the first electrode is performed to increase the speed of the slot nozzle, and the second electrode can form micropores on the electrode of the corresponding cathode by spraying, thus being effective in terms of performance.
Fig. 6 is a cross-sectional view of a first electrode 305 and a second electrode 305' formed on both sides of an electrolyte membrane 302, and a protective substrate 348 laminated on the second electrode.
Industrial applicability
According to the present invention, a membrane electrode assembly for a PEFC fuel cell can be manufactured at high speed and with high quality.
Description of the reference numerals
1. 11, 31, 41, 51 heating (heat adsorption) drum
2. 12, 32, 42, 302 electrolyte membranes
3. 13, 33, 43 slot nozzle
4. 14, 14', 34', 44 minor diameter rolls
5. 25, 35, 45, 55 electrolyte membrane unwinding device
6. 26, 36, 46, 56 electrolyte membrane winding device
7、17 CCM
10. 20, 30, 40, 50 traction roller
38. 138, 148, 248, 348 electrode protective substrate (breathable substrate)
39. Unwinding device for 49 and 59 electrode protection substrate
101. 201 electrode protection substrate coiling device
102. 202 backboard winding device
203. Spray coating head
205. Electrode
305. First electrode
305' second electrode
Claims (8)
1. A method for manufacturing a membrane electrode assembly of a fuel cell, which is a method for forming an electrode by continuously or intermittently moving a long electrolyte membrane for a fuel cell and applying electrode ink to at least one side of the electrolyte membrane using a slot nozzle, comprising:
a step of providing a heated adsorption roller for thermally adsorbing the electrolyte membrane coated with the electrode ink;
a step of providing at least one roller having a smaller diameter than the heated suction roller upstream of the heated suction roller and in proximity to the heated suction roller; and
and coating electrode ink with a slot nozzle between the position of the small diameter roller and the position of the electrolyte membrane contacting the heated adsorption roller.
2. The method for manufacturing a membrane electrode assembly of a fuel cell according to claim 1, wherein the heat suction roller is a heat roller that is moved in a state in which a tension of 20 to 80N is applied to the electrolyte membrane.
3. The method for manufacturing a membrane electrode assembly of a fuel cell according to claim 1, wherein the heated adsorption roller is a heated adsorption belt.
4. The method for producing a membrane electrode assembly of a fuel cell according to any one of claims 1 to 3, wherein a tension of 20 to 80N is applied to the electrolyte membrane before and after the small diameter roller, and electrode ink is applied to the electrolyte membrane before and after the small diameter roller at a position where the electrolyte membrane is separated from the roller.
5. The method of manufacturing a membrane electrode assembly of a fuel cell according to claim 1, wherein the slot nozzle is a gas-assisted slot nozzle or a spray slot nozzle, and the distance between the electrolyte membrane and the nozzle head is set to 0 to 10mm.
6. The method for producing a membrane electrode assembly of a fuel cell according to claim 1 or 2, wherein the roundness of the heated suction roll or the heated roll is ±50 μm or less, and the electrode ink is applied to a position of the electrolyte membrane immediately before the electrolyte membrane comes into contact with the heated suction roll or the heated roll, at which the electrolyte membrane leaves the roll.
7. The method for manufacturing a membrane electrode assembly of a fuel cell according to claim 1 or 5, wherein electrodes of a desired pattern are formed on both sides of the electrolyte membrane, and at least one protective substrate having gas permeability is interposed so that the electrodes do not contact each other when wound in such a manner that the electrodes are not attracted on a heated suction roll.
8. A method of manufacturing a membrane electrode assembly of a fuel cell, comprising:
a step of applying and drying an anode ink by a slot nozzle until an electrolyte membrane with a back plate, to which tension is applied, is brought into contact with a heated suction roller, then bringing the reversed electrode surface into contact with a gas-permeable substrate when applying a cathode ink in the form of particles or fibers, sucking the electrolyte membrane on the heated suction roller through the gas-permeable substrate, and peeling the back plate laminated on the electrolyte membrane; and
and forming an electrode containing a catalyst for the cathode on the opposite side of the anode.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110285447.8A CN113054227B (en) | 2018-02-26 | 2019-02-19 | Method for manufacturing fuel cell and fuel cell |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2018032316A JP6984848B2 (en) | 2018-02-26 | 2018-02-26 | Manufacturing method of membrane electrode assembly for fuel cells |
| JP2018-032316 | 2018-02-26 | ||
| PCT/JP2019/006126 WO2019163783A1 (en) | 2018-02-26 | 2019-02-19 | Method for manufacturing membrane electrode assembly for fuel cell |
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| CN202110285447.8A Division CN113054227B (en) | 2018-02-26 | 2019-02-19 | Method for manufacturing fuel cell and fuel cell |
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| CN111758178A CN111758178A (en) | 2020-10-09 |
| CN111758178B true CN111758178B (en) | 2024-03-12 |
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| CN202110285447.8A Active CN113054227B (en) | 2018-02-26 | 2019-02-19 | Method for manufacturing fuel cell and fuel cell |
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| CN (2) | CN111758178B (en) |
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| JP6984848B2 (en) * | 2018-02-26 | 2021-12-22 | エムテックスマート株式会社 | Manufacturing method of membrane electrode assembly for fuel cells |
| 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 |
| JP7215697B2 (en) * | 2021-02-09 | 2023-01-31 | エムテックスマート株式会社 | Fuel cell manufacturing equipment |
| JP7075087B2 (en) * | 2021-02-09 | 2022-05-25 | エムテックスマート株式会社 | Fuel cell manufacturing method |
| CN114196966B (en) * | 2021-12-03 | 2023-03-28 | 中国科学院大连化学物理研究所 | Proton membrane and CCM (continuous current module) integrated preparation method and device for PEM (proton exchange membrane) water electrolysis |
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| JP6984848B2 (en) | 2021-12-22 |
| CN111758178A (en) | 2020-10-09 |
| JP2019149256A (en) | 2019-09-05 |
| CN113054227B (en) | 2023-11-10 |
| WO2019163783A1 (en) | 2019-08-29 |
| CN113054227A (en) | 2021-06-29 |
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