JP2017117786A - Assembly manufacturing method and manufacturing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an assembly manufacturing method and a manufacturing device which enable successive manufacturing of an assembly including a frame material, and enable the suppression of a damage such as a wrinkle to an electrolyte film owing to the bonding of a frame material.SOLUTION: A manufacturing method for successively manufacturing an assembly including a polymer electrolyte film, and a frame material covering at least a part of a peripheral edge of the polymer electrolyte film comprises a press-conveying step for conveying at least (A) the polymer electrolyte film and the frame material, (B) the polymer electrolyte film with the frame material bonded thereto, and a gas diffusion layer, or (C) the gas diffusion layer with the frame material bonded thereto, and the polymer electrolyte film (in (A)-(C), the polymer electrolyte film may have a catalyst layer formed thereon) in a state of being laminated while pressurizing them by a fixed pressure in a face-contact manner.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a joined body including a polymer electrolyte membrane used as a member of a polymer electrolyte fuel cell, and more particularly to a method and a manufacturing apparatus for a joined body in which a frame material is joined.

  BACKGROUND ART A fuel cell is a kind of power generation device that extracts electrical energy by electrochemically oxidizing a fuel such as hydrogen or methanol, and has recently attracted attention as a clean energy supply source. In particular, the polymer electrolyte fuel cell has a standard operating temperature as low as around 100 ° C. and a high energy density, so that it is a relatively small-scale distributed power generation facility, a mobile power generator such as an automobile or a ship. As a wide range of applications are expected. It is also attracting attention as a power source for small mobile devices and portable devices, and is expected to be installed in mobile phones and personal computers in place of secondary batteries such as nickel metal hydride batteries and lithium ion batteries.

  In a fuel cell, an anode electrode and a cathode electrode, in which a reaction responsible for power generation occurs, and a polymer electrolyte membrane serving as a proton conductor between the anode and the cathode constitute a membrane-electrode assembly (MEA). A cell in which the MEA is sandwiched between separators is configured as a unit. MEA is roughly manufactured by two manufacturing methods. In the first method, first, an electrolyte membrane with a catalyst layer (Catalyst Coated Membrane; CCM) in which a catalyst layer is formed on the surface of the polymer electrolyte membrane is created, and a gas diffusion layer (GDL) is joined to both sides thereof. It is a method to do. The second method is a method in which a gas diffusion electrode (GDE) having a catalyst layer formed on the surface of a gas diffusion layer is first created and bonded to both surfaces of the polymer electrolyte membrane.

  In recent years, the use of polymer electrolyte membranes as materials for hydrogen infrastructure equipment has been expanded, and the quality of CCM and MEA used for solid polymer electrolyte membrane water electrolysis devices and electrochemical hydrogen pumps is also It has become important from the viewpoint of performance reliability. As a CCM manufacturing apparatus or manufacturing method, for example, Patent Document 1 proposes a method of transferring a catalyst layer of a catalyst-carrying film onto an electrolyte membrane with a hot roller.

  By the way, in addition to the above-mentioned members, CCM and MEA aim to improve the handling of the electrolyte membrane and to prevent the electrolyte membrane from being damaged due to the direct contact between the electrolyte membrane and the gas diffusion layer. In some cases, a member that covers the periphery of the electrolyte membrane is provided. Hereinafter, such a member is referred to as a “frame material” in the present specification. For example, Patent Document 2 describes a joined body including a “capsule-encapsulating film” as a frame material, and a method of joining only by hot pressing only a portion where the encapsulated film and the electrolyte membrane are in contact with each other. The joined body is manufactured.

JP 2001-196070 A Special table 2007-50388

  However, the method using hot pressing as in Patent Document 2 cannot continuously produce a joined body. Moreover, when it is going to manufacture the conjugate | zygote containing a frame material using a hot roller (heating pressure roller) like patent document 1, the contact with a catalyst layer carrying | support film and electrolyte membrane, and a hot roller is a line contact. Therefore, pressure control becomes difficult, and damage such as wrinkles may occur in the electrolyte membrane.

  An object of the present invention is to provide a method and an apparatus for manufacturing a joined body capable of continuously producing a joined body including a frame material and suppressing damage such as wrinkles of an electrolyte membrane due to joining of the frame material. Is to provide.

The present invention for solving the above-mentioned problems is a production method for continuously producing a joined body comprising a polymer electrolyte membrane and a frame material covering at least a part of the peripheral edge of the polymer electrolyte membrane. , At least (A) a polymer electrolyte membrane, a frame material,
(B) a polymer electrolyte membrane joined with a frame material, a gas diffusion layer, or (C) a gas diffusion layer joined with a frame material, and a polymer electrolyte membrane (in (A) to (C) above, This is a method for producing a bonded body having a pressure conveying step of conveying a molecular electrolyte membrane while a catalyst layer may be formed on the molecular electrolyte membrane while pressing the surface of the molecular electrolyte membrane at a constant pressure.

  According to the present invention, the CCM with a frame material and the MEA can be continuously manufactured while suppressing the occurrence of damage such as deformation and wrinkling of the electrolyte membrane.

It is a schematic diagram which shows the manufacturing apparatus which concerns on the 1st Embodiment of this invention. It is a schematic diagram which shows the cross section before joining (A) and after joining (B) of the joined body manufactured by this invention. It is a schematic diagram which shows the manufacturing apparatus which concerns on the 2nd Embodiment of this invention. It is a schematic diagram which shows the manufacturing apparatus which concerns on the 3rd Embodiment of this invention.

  Hereinafter, the present invention will be described in detail.

  The polymer electrolyte membrane (hereinafter sometimes simply referred to as “electrolyte membrane”) used in the method for producing a joined body of the present invention has proton conductivity and is used as an electrolyte membrane for a polymer electrolyte fuel cell. It does not specifically limit as long as it operate | moves, A well-known or commercially available thing can be used. As such a polymer electrolyte membrane, an electrolyte membrane made of perfluorosulfonic acid, specifically, “Nafion” (registered trademark) manufactured by DuPont, “Flemion” (registered trademark) manufactured by Asahi Glass, and manufactured by Asahi Kasei "Aciplex" (registered trademark), "GORE-SELECT" (registered trademark) manufactured by Gore, and the like. A polymer electrolyte membrane made of a hydrocarbon polymer in which proton conductivity is imparted to a hydrocarbon skeleton can also be used. Such hydrocarbon polymers include polysulfone, polyethersulfone, polyphenylene oxide, polyarylene ether polymer, polyphenylene sulfide, polyphenylene sulfide sulfone, polyparaphenylene, polyarylene polymer, polyarylene ketone, polyether ketone, poly Aromatic hydrocarbons having an aromatic ring in the main chain, such as arylene phosphine hydroxide, polyether phosphine oxide, polybenzoxazole, polybenzthiazole, polybenzimidazole, aromatic polyamide, polyimide, polyetherimide, polyimidesulfone, etc. A preferred example is a polymer.

  Polyethersulfone is a general term for polymers having a sulfone bond in the molecular chain. Polyetherketone is a general term for polymers having an ether bond and a ketone bond in the molecular chain.

  Among these polymers, polysulfone, polyethersulfone, polyphenylene oxide, polyarylene ether polymer, polyphenylene sulfide, polyphenylene sulfide sulfone, polyarylene ketone, polyether ketone, polyarylene phosphine oxide, polyether phosphine oxide, etc. A polymer is preferably used in terms of mechanical strength, physical durability, processability, and hydrolysis resistance.

  In particular, in the case of an electrolyte membrane made of an aromatic hydrocarbon polymer, the elastic modulus of the membrane is high, and if there is uneven pressure in the surface, the electrolyte membrane is likely to wrinkle. Applicable.

  The “junction” in the present invention refers to a membrane / electrode assembly (MEA) itself and a conjugate comprising a polymer electrolyte membrane produced as an intermediate product for producing MEA. The “frame material” is a member that covers at least a part of the peripheral edge of the polymer electrolyte membrane. Such a frame material is usually incorporated into a joined body for the purpose of improving the handleability of the electrolyte membrane and preventing the electrolyte membrane from being damaged by direct contact between the electrolyte membrane and the gas diffusion layer. . The frame material is typically a frame-shaped member that covers the four sides of the polymer electrolyte membrane, but it can also be used to cover only two sides of the polymer electrolyte membrane using a long member. . To join the frame material to a long polymer electrolyte membrane used in a continuous manufacturing process, the length of the unnecessary inner part cut out in advance so as to cover only the peripheral part according to the size of the polymer electrolyte membrane. It is preferable to use a frame-like frame material. A joined body with a frame material can be manufactured by joining the above-mentioned frame material to the polymer electrolyte membrane and then cutting it.

  The thickness of the frame material is preferably 2 μm or more and 200 μm or less. If it is 2 micrometers or more, the handleability of the electrolyte membrane by a frame material will improve, and the yield improvement effect in post processes, such as a cell group and stacking, will be large. If the thickness is 200 μm or less, when the frame material and the electrolyte membrane, or the frame material and the gas diffusion layer are in contact with each other, stress is hardly concentrated on the edge of the frame material, and the electrolyte membrane or the gas diffusion layer is damaged. Hard to occur. The thickness of the frame material is more preferably 5 μm or more and 150 μm or less, and further preferably 10 μm or more and 100 μm or less. Further, the frame material may cover at least a part of the peripheral portion of the polymer electrolyte membrane, and the area covering the polymer electrolyte membrane is not particularly limited, but the covered area is 1% or more and 30% or less. It is preferable that If it is less than 1%, the coverage is too small, and the effect of improving the handleability of the electrolyte membrane by the frame material is small. If it is more than 30%, there are many portions that cannot contribute to power generation performance in the electrolyte membrane.

  The material of the frame material is not particularly limited, and examples thereof include silicone materials, general-purpose plastics, and engineering plastics. Examples of general-purpose plastics and engineering plastics include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate, polycarbonate (PC), polyphenylene ether, polyether Examples include sulfone, polyarylate, polyetherimide, polyamideimide, polyetheretherketone, polyphenylene sulfide (PPS), and aromatic polyimide aromatic hydrocarbon polymer. The frame material is not limited to a single material, but may be a combination of a plurality of materials.

  The frame material in the present invention may have a hole through which gas or liquid passes or a hole through which fastening bolts pass depending on the cell or stack design. In particular, when a gas sealing material such as a gasket is in contact, it is particularly preferable that the surface has few wrinkles and is high quality.

  Further, the frame material may have an adhesive layer in order to improve the adhesion with the polymer electrolyte membrane or the gas diffusion layer. The adhesive layer may be formed on only one side of the frame material or on both sides. By having the adhesive layer, it is possible to prevent the frame material from being displaced even if the electrolyte membrane swells or contracts during the operation of the fuel cell. The material and physical properties of the adhesive layer are not particularly limited as long as they do not affect the power generation performance and the durability of the polymer electrolyte membrane, but they can be bonded by heat from the simplicity of the manufacturing process. It is preferable to use an adhesive.

  Typically, the present invention manufactures a joined body in which a polymer electrolyte membrane or CCM and a frame material are joined by joining a polymer electrolyte membrane or an electrolyte membrane with a catalyst layer (CCM) and a frame material. (A). However, when the MEA is manufactured by bonding the polymer electrolyte membrane or CCM with the frame material already bonded to the gas diffusion layer (B), the gas diffusion layer with the frame material already bonded, and the polymer electrolyte It is also preferably used when manufacturing MEA by bonding a membrane or CCM. In the aspect in which the CCM and the frame material are joined, a catalyst layer may be interposed between the polymer electrolyte membrane and the frame material. It is expressed as “coating” the molecular electrolyte membrane. Similarly, the expression that the polymer electrolyte membrane and the frame material are “laminated” includes a state in which the polymer electrolyte membrane and the frame material are overlapped via the catalyst layer. That is, in this specification, “lamination” does not mean only a state in which (A), (B), or (C) are in direct contact with each other, and other layers such as a catalyst layer are interposed therebetween. It shall include the state that is overlapped in the state.

  As the gas diffusion layer (GDL), for example, carbon paper, carbon cloth, carbon felt, or a porous metal such as stainless steel or titanium is used when carbons cannot be used depending on the potential of the intended use. Moreover, you may use what performed the water-repellent process to these. Moreover, you may use the gas diffusion electrode (GDE) which formed the catalyst layer in the surface of GDL.

  It is only necessary that the members to be joined include at least those listed as (A), (B) or (C), and the case where other additional members are included is not excluded. For example, in the embodiment (A), not only when the polymer electrolyte membrane and the frame material are joined, but also when the catalyst layer is transferred to the polymer electrolyte membrane simultaneously with the joining of the polymer electrolyte membrane and the frame material. The production method of the present invention can also be used when GDL or GDE is bonded simultaneously with the bonding of the polymer electrolyte membrane and the frame material. Similarly, in the embodiments (B) and (C), the catalyst layer may be transferred to the polymer electrolyte membrane simultaneously with the joining.

  The production method of the present invention is characterized in that it includes a pressurizing and transporting step in which at least the above (A), (B), or (C) is stacked and transported while pressing the surface with a constant pressure. Here, “surface pressing” means that the pressing member and the object to be pressed such as the frame material are not in a single linear contact as in the case of pressing with a set of rollers, It means contacting with a width in the transport direction. The contact width between the object to be pressed and the pressing member is not particularly limited, and can be appropriately set according to the size of the electrolyte membrane to be manufactured. Generally, the width is 30 cm or more in the transport direction. It is preferable to contact with. Further, “constant pressure” means that a substantially uniform pressure is applied to the contact surface with no pressure variation in a direction orthogonal to the conveyance direction. The variation in pressure on the pressing surface is not particularly limited as long as the pressure is substantially uniform, but is preferably 0.15 MPa or less.

  The pressure conveying step is preferably performed by a double belt press mechanism that sandwiches the stacked state (A), (B), or (C) from both sides with a conveying belt. Furthermore, it is preferable that the double belt press mechanism has a built-in pressurizing unit that applies a uniform surface pressure to the transport belt. Such a pressurizing means is not particularly limited as long as it can apply a uniform surface pressure, but it is in a hydraulic system, that is, in contact with an object to be pressurized of a conveyor belt constituting a double belt press mechanism. It is particularly preferable that the surface to be applied is configured to apply a uniform force from the inside of the conveyor belt using a hydraulic device. Or you may comprise so that a frame material etc. may be surface-pressed by a fixed pressure by applying sufficiently strong tension | tensile_strength to a conveyance belt and driving a double belt press mechanism.

  Although any pressure can be applied as the pressure applied to the polymer electrolyte membrane and the frame material in the pressure conveying step, it is preferably 0.15 to 10 MPa. When the pressure is less than 0.15 MPa, the frame material may not be sufficiently applied to the polymer electrolyte membrane. When the pressure is higher than 10 MPa, excessive pressure is applied to the polymer electrolyte membrane, so that damage to the polymer electrolyte membrane increases and durability may decrease. The pressure in the pressure conveying step is more preferably 0.3 MPa or more and 5 MPa or less, and further preferably 0.5 MPa or more and 3 MPa or less.

  In addition, it is preferable to have a heating step which conveys (A), (B), or (C) of the laminated state, heating to 100 degreeC or more during a pressurization conveyance process. By heating, the bonding of (A), (B) or (C) can be further strengthened, and the durability of the polymer electrolyte membrane can be enhanced.

  The heating temperature of the polymer electrolyte membrane in the heating step can be appropriately set according to the material of the polymer electrolyte membrane or the frame material so that the polymer electrolyte membrane is reliably bonded to the frame material. Generally, the temperature is preferably 100 ° C. or higher and 200 ° C. or lower. When the temperature is lower than 100 ° C., the frame material may not be sufficiently bonded to the polymer electrolyte membrane. On the other hand, when it exceeds 200 ° C., the polymer electrolyte membrane may be damaged by heat. The heating temperature of the polymer electrolyte membrane is more preferably 100 ° C. or higher and 180 ° C. or lower. The heating temperature of the polymer electrolyte membrane means an actual measurement value measured by installing a temperature element on the polymer electrolyte membrane and the catalyst transfer sheet that pass through in the heating step.

  The passage time of the heating step is not particularly limited, but is preferably 1 second or longer and 10 minutes or shorter. If it is less than 1 second, the frame material may not be sufficiently bonded to the polymer electrolyte membrane. If it is longer than 10 minutes, the polymer electrolyte membrane may be damaged by heat. The passing time of the heating step is more preferably 1 second to 5 minutes, further preferably 1 second to 1 minute, and still more preferably 1 second to 20 seconds.

  Also, during the pressurizing and conveying step, the pre-heating step for conveying the laminated (A), (B) or (C) at a temperature of less than 100 ° C. for 1 second or more, and a temperature higher than the pre-heating step. It is more preferable to have a heating step for conveying while heating. By pre-pressurizing the electrolyte membrane in the pre-heating step and proceeding to the heating step, wrinkles of the electrolyte membrane can be prevented and damage to the electrolyte membrane in the heating step can be reduced.

  The temperature of the polymer electrolyte membrane and the frame material during the pre-heating step is less than 100 ° C. In the case of 100 ° C. or higher, the surface of the polymer electrolyte membrane or CCM is dried simultaneously with pressurization, and wrinkles are likely to occur. When the temperature is lower than 5 ° C, the flexibility of the surface of the polymer electrolyte membrane or the CCM is lost, and the frame may not be formed well. The temperature of the polymer electrolyte membrane and the frame material in the pre-heating step is more preferably 20 ° C. or higher and lower than 100 ° C. In the pre-heating step, the temperature change from the temperature of the polymer electrolyte membrane before the start of the pre-heating step is preferably within 30 ° C.

  The passage time of the pre-heating step is not particularly limited as long as it is 1 second or longer, but is preferably 1 second or longer and 30 minutes or shorter. When the time is less than 1 second, the polymer electrolyte membrane and the frame material cannot be sufficiently brought into contact with each other, and wrinkles are likely to occur in the polymer electrolyte membrane. In the case of 30 minutes or more, the process time is very long, and the productivity may decrease. The passing time of the pre-heating step is more preferably 1 second to 10 minutes, further preferably 1 second to 1 minute, and still more preferably 1 second to 20 seconds.

  Moreover, it is preferable to set the initial temperature increase rate in the pre-heating step to be 20 ° C./second or less. The initial temperature rise rate means the slope of the temperature rise curve of the polymer electrolyte membrane and the frame material immediately after the start of the pre-heating step, that is, immediately after entering the pressure transfer process in this embodiment. The initial temperature increase rate in the pre-heating step is more preferably 15 ° C./second or less, and further preferably 10 ° C./second or less. Further, when the pre-heating step is performed for 5 seconds or more, it is preferable to set the rate of temperature increase 5 seconds after the start of the pre-heating step to 20 ° C./second or less, more preferably 15 ° C./second or less. More preferably, it is not more than ° C / second. By setting in this way, when there is a difference between the amount of residual volatiles such as moisture in the polymer electrolyte membrane and the amount of residual volatiles in the frame material, the volatile components in the polymer electrolyte membrane are rapidly evaporated, and the polymer It is possible to reduce the exposed area of the electrolyte membrane from the frame material and the occurrence of peeling or tearing at the boundary between the frame material and the polymer electrolyte membrane, or the occurrence of wrinkles in the polymer electrolyte membrane. The initial temperature rise rate is measured by installing a temperature element on a polymer electrolyte membrane, a frame material, or a test sheet that simulates the pre-transfer step.

  And it is further more preferable to have the cooling step which conveys in this order, cooling (A), (B), or (C) of a heating state after a pre-heating step during a pressurization conveyance process. Here, “cooling” means an operation of lowering the temperature of the polymer electrolyte membrane after completion of the heating step. By having a cooling step, the joining state of the joined body after joining by heat can be stabilized at an early stage, and the productivity of the joined body is also improved.

  The cooling means in the cooling step is not particularly limited as long as it lowers the temperature of the polymer electrolyte membrane that has undergone the heating step. As such a cooling means, for example, a cooling device using a refrigerant such as water or alcohol, a gas such as cold air or compressed air, an electronic device such as a Peltier element, or a combination of these can be used. However, even if it is not accompanied by such an operation of actively lowering the temperature, if there is no heating means, the cooling of the polymer electrolyte membrane after the heating step is consequently reduced. It can be regarded as a means.

  The temperature of the polymer electrolyte membrane immediately after passing through the cooling step is preferably 5 ° C. or higher and lower than 100 ° C. If it is less than 100 degreeC, the curvature of a polymer electrolyte membrane can be suppressed effectively. When the temperature is lower than 5 ° C., interface peeling between the frame material and the polymer electrolyte membrane may occur. Furthermore, in the case of a polymer electrolyte membrane with a catalyst layer, interface peeling from the polymer electrolyte membrane may occur. The temperature of the polymer electrolyte membrane immediately after passing through the cooling step is more preferably 20 ° C. or higher and 80 ° C. or lower. In the cooling step, the temperature of the polymer electrolyte membrane after the heating step is preferably lowered by 40 ° C. to 120 ° C., more preferably 60 ° C. to 100 ° C.

  Further, the passage time of the cooling step is not particularly limited, but is preferably 1 second or more and 50 minutes or less. When the time is less than 1 second, the polymer electrolyte membrane is rapidly cooled, so that the bonding interface between the polymer electrolyte membrane and the frame material may be disturbed. Furthermore, in the case of a polymer electrolyte membrane with a catalyst layer, the bonding interface between the polymer electrolyte membrane and the catalyst layer may be disturbed. If it is longer than 50 minutes, it may take too much time to cool and may be damaged by heat. The passing time of the cooling step is more preferably 1 second to 10 minutes, and further preferably 1 second to 1 minute.

Although the above description is about the manufacturing method of the present invention, as will be readily understood by those skilled in the art, this specification also discloses the following manufacturing apparatus for carrying out the manufacturing method. It is.
(1) A manufacturing apparatus for continuously manufacturing a joined body including a polymer electrolyte membrane and a frame material that covers at least a part of a peripheral portion of the polymer electrolyte membrane,
(A) a polymer electrolyte membrane, a frame material,
(B) The polymer electrolyte membrane joined with the frame material and the gas diffusion layer, or (C) the gas diffusion layer joined with the frame material, and the polymer electrolyte membrane are laminated at a constant pressure. (2) Double belt that sandwiches (A), (B), or (C) in a stacked state from both sides with a conveyor belt. The joined body manufacturing apparatus (3) according to (1) configured by a press mechanism includes a heating unit for heating (A), (B), or (C) in a stacked state. The joined body manufacturing apparatus according to (1) or (2), wherein the pressure conveying unit is further cooled by (A), (B) or (C) heated by the heating means. The joined body manufacturing apparatus according to (3)

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to these embodiments.

[First Embodiment]
First, the manufacturing method of the joined body which concerns on 1st Embodiment using the manufacturing apparatus 100 shown in FIG. 1 is demonstrated. In the following description of the embodiments, for convenience, the upper side of each drawing is described as “up” and the lower side is “lower”, but the vertical direction of each drawing does not necessarily mean the direction perpendicular to the ground. In addition, the case where the CCM and the frame material are joined will be described unless otherwise specified. As will be readily understood by those skilled in the art, any of the above aspects (A), (B), and (C) Can be joined in the same manner. In the following description, in the case of the mode (B), “CCM” can be read as “polymer electrolyte membrane to which a frame material is bonded”, and “frame material” can be read as “gas diffusion layer”. . In the case of the mode (C), “CCM” can be read as “polymer electrolyte membrane”, and “frame material” can be read as “gas diffusion layer to which the frame material is bonded”.

  First, the CCM supply roller 102 unwinds and supplies the CCM 10. Frame material supply rollers 104A and 104B are installed above and below the unrolled CCM 10, respectively. The frame material 20A for forming the frame material formed on the upper surface of the CCM 10 is supplied from the frame material supply roller 104A, and the frame material sheet 20B formed on the lower surface of the CCM 10 is supplied by being unwound from the frame material supply roller 104B. . As described above, in the manufacturing apparatus 100 of the present embodiment, the frame material is bonded to both surfaces of the CCM 10, but the frame material may be bonded to only one surface of the CCM 10.

  The CCM 10 and the frame materials 20A and 20B supplied in this way pass between the guide rollers 106A and 106B. The guide rollers 106A and 106B convey the supplied CCM 10 and the frame materials 20A and 20B by sandwiching them and rotating them. In this process, the CCM 10 and the frame materials 20A and 20B are positioned in a state in which the frame material 20A is in contact with the upper surface of the CCM 10 and the frame material 20B is in contact with the lower surface of the CCM 10, that is, in the state shown in FIG. The

  The positioned CCM 10 and the frame members 20A and 20B enter the pressure conveyance unit P while being in contact with each other. In the present embodiment, the pressure conveyance unit P is arranged so that the upper belt mechanism provided with the conveyance belt 110A that wraps around the two drums 108A and runs and the upper belt mechanism is opposed to the upper belt mechanism. The lower belt mechanism provided with the conveyor belt 110B that is disposed and similarly wound around the two drums 108B, and the upper belt mechanism and the lower belt mechanism are respectively built in, and the conveyor belts 110A and 110B are respectively attached to the frame material 20A, This is a double belt press mechanism composed of pressurizing means 124A and 124B for applying pressure so as to press against 20B. The pressurizing means is configured to apply a uniform surface pressure to the conveyor belt by a hydraulic method. In the pressure conveying unit P, the CCM 10 and the frame members 20A and 20B are sandwiched between the upper belt mechanism and the lower belt mechanism, and are conveyed in a state of receiving a certain pressure from above and below.

  In the present embodiment, the heating means 116 extends over substantially the entire length of the upper belt mechanism and the lower belt mechanism in contact with the CCM 10 and the frame members 20A and 20B. Accordingly, the CCM 10 and the frame materials 20A and 20B are sandwiched between the upper belt mechanism and the lower belt mechanism, and are conveyed while being pressurized with a constant pressure, and at the same time are heated by the heat from the heating means 116. That is, in this embodiment, it has only the step (heating step) which conveys CCM and a frame material, heating in a pressurization conveyance process. In the heating step, the frame materials 20A and 20B are joined to the upper surface and the lower surface of the CCM 10, respectively. That is, after passing through the heating step, a joined body 12 as shown in FIG. 2B is obtained in which the frame material is joined to the CCM.

  As the heating means, various heating media such as various heaters, steam, and oil can be used, but are not particularly limited. Moreover, it is preferable to form the conveyance belt which comprises a double belt press mechanism with materials with high heat capacity and heat conductivity, such as steel and stainless steel.

  The joined body 12 that has passed through the pressure conveying section P passes between the guide rollers 118A and 118B, is wound up in a roll shape by the joined body winding roller 120, and the production is completed. Further, the base materials 22A and 22B carrying the frame material are wound up in a roll shape by the base material winding rollers 122A and 122B. When only the frame material is supplied without using such a base material, the base material take-up rollers 122A and 122B are not necessary.

[Second Embodiment]
Next, the manufacturing method of the joined body according to the second embodiment using the manufacturing apparatus 100 shown in FIG. 3 will be described focusing on the difference from the case where the manufacturing apparatus shown in FIG. 1 is used.

  In the manufacturing apparatus 100 shown in FIG. 3, the heating means 116 is provided only on the downstream side (right side) of the upper belt mechanism and the lower belt mechanism. Therefore, the CCM 10 and the frame members 20A and 20B that have entered the pressure conveyance unit P are first conveyed while being pressurized by the double belt press mechanism at a position away from the heating means 116. Then, the CCM 10 and the frame members 20A and 20B are gradually heated by the heat from the heating unit 116 as they are conveyed to near the position of the heating unit 116, and finally reach 100 ° C. or higher. That is, in the manufacturing method of the joined body according to the present embodiment, during the pressurizing and transporting process, the step of transporting the CCM and the frame material at less than 100 ° C. for 1 second or longer (step before heating) and heating to 100 ° C. or higher are performed. And a step (heating step) of transporting in this order. In the heating step, the frame materials 20A and 20B are transferred to the upper surface and the lower surface of the CCM 10, respectively. That is, the CCM 10 that has passed through the heating step becomes the joined body 12 in which the frame material is joined to the CCM, and the frame materials 20A and 20B lose the frame and only the base materials 22A and 22B remain.

[Third Embodiment]
Next, the manufacturing method of the joined body according to the third embodiment using the manufacturing apparatus 100 shown in FIG. 4 will be described focusing on the difference from the case where the manufacturing apparatus shown in FIG. 1 is used.

  In the manufacturing apparatus 100 shown in FIG. 4, heating means or the like is not provided in the upstream portions of the upper belt mechanism and the lower belt mechanism, and only pressure is applied. A heating means 116 is provided in each middle stream portion of the upper belt mechanism and the lower belt mechanism. Further, a cooling means 126 is provided in each downstream portion of the upper belt mechanism and the lower belt mechanism. Therefore, the CCM 10 and the frame members 20A and 20B that have entered the pressure conveyance unit P are first conveyed if they are pressurized with a constant pressure by a double belt press mechanism at a position away from the heating means 116. Then, the CCM 10 and the frame members 20A and 20B are gradually heated by the heat from the heating unit 116 as they are conveyed to near the position of the heating unit 116, and finally reach 100 ° C. or higher. By this heating, the frames 20A and 20B are joined to the upper surface and the lower surface of the CCM 10, respectively. The CCM 10 that has passed through the heating step becomes the joined body 12 in which the frame material is joined to the CCM, and the frame materials 20A and 20B lose the frame and only the base materials 22A and 22B remain. When the joined body 12 and the base materials 22A and 22B are further conveyed to the position of the cooling means 126, the joined body 12 and the base materials 22A and 22B are cooled by the cooling means 126. That is, in the method for producing a polymer electrolyte membrane according to the present embodiment, the step of conveying the polymer electrolyte membrane and the reinforcing layer sheet at less than 100 ° C. for 1 second or longer without heating during the pressure conveying step (before heating) Step), a step of transporting while heating to 100 ° C. or higher (heating step), and a step of transporting while cooling (cooling step).

  In the present embodiment, not only the CCM 10 but also the conveyor belts 110A and 110B are cooled when traveling around the cooling means 126, respectively. As a result, the transport belts 110A and 110B are in a state where the heat is sufficiently removed when the belts travel next upstream of the upper belt mechanism and the lower belt mechanism, and excess heat is applied to the polymer electrolyte membrane or the like in the pre-heating step. Can be prevented. As a result, damage to the polymer electrolyte membrane due to heat may be reduced, and durability may be improved.

  The joined body manufacturing apparatus 100 of the present embodiment is an example in which the upstream portion of the double belt press mechanism has no heating means and the like, the heating means is in the midstream portion, and the cooling means is in the downstream portion. Temperature control means capable of setting the temperature in the middle stream part and the downstream part, by operating the set temperature of each temperature control means, and by turning on / off the switch of each temperature control means, the pre-heating step, the heating step And / or may be configured to perform a cooling step. Such an apparatus can be applied to any of the manufacturing methods of the first, second, and third embodiments.

  The joined body produced by the production method of the present invention can be applied to various uses in addition to fuel cells. For example, extracorporeal circulation column, medical use such as artificial skin, filtration use, ion exchange resin use such as chlorine-resistant reverse osmosis membrane, various structural materials use, electrochemical use, humidification membrane, anti-fogging membrane, antistatic membrane, Applicable to solar cell membranes and gas barrier materials. It is also suitable as an artificial muscle and actuator material. Among these, it can be preferably used for various electrochemical applications. Examples of electrochemical applications include fuel cells, redox flow batteries, water electrolysis devices, chloroalkali electrolysis devices, hydrogen compression devices, hydrogen purification devices, oxygen removal devices, and gas sensors. An apparatus, a hydrogen compression apparatus, and a hydrogen purification apparatus are most preferable.

10: CCM
12: joined body 20A, 20B: frame material 22A, 22B: base material 100: joined body manufacturing apparatus 102: CCM supply roller 104A, 104B: frame material supply roller 106A, 106B, 118A, 118B: guide roller 108A, 108B, 112A, 112B: Drum 110A, 110B: Conveying belt 116: Heating means 120: Joined body winding roller 122A, 122B: Substrate winding roller 124A, 124B: Pressurizing means 126: Cooling means

Claims (14)

A production method for continuously producing a joined body comprising a polymer electrolyte membrane and a frame material covering at least a part of a peripheral portion of the polymer electrolyte membrane, wherein at least (A) the polymer electrolyte membrane and The frame material,
(B) The polymer electrolyte membrane to which the frame material is bonded, a gas diffusion layer, or (C) the gas diffusion layer to which the frame material is bonded, and the polymer electrolyte membrane (the above (A) to (C ), A catalyst layer may be formed on the polymer electrolyte membrane), and in a state in which the polymer electrolyte membrane is laminated, a method for producing a joined body having a pressure carrying step of carrying out surface pressure with a constant pressure. The method for manufacturing a joined body according to claim 1, wherein variation in pressure on the pressure surface in the pressure conveying step is 0.1 MPa or less. The manufacturing method of the joined body according to claim 1 or 2 which performs said pressurization conveyance process with a double belt press mechanism which sandwiches (A), (B), or (C) of a layered state with a conveyance belt from both sides. . The method for manufacturing a joined body according to claim 3, wherein the double belt press mechanism includes a pressurizing unit that applies a surface-uniform pressure to the transport belt. The method for manufacturing a joined body according to claim 4, wherein the pressurizing means is a hydraulic system. The method for producing a joined body according to any one of claims 1 to 5, further comprising a step of conveying the laminated state (A), (B), or (C) while heating during the pressure conveying step. . During the pressurizing and conveying step, the pre-heating step of conveying the stacked (A), (B) or (C) at a temperature of less than 100 ° C. for 1 second or more, and heating to a temperature higher than the pre-heating step The manufacturing method of the joined body of Claim 6 which has a heating step conveyed in this order. The method for manufacturing a joined body according to claim 7, wherein an initial temperature increase rate in the pre-heating step is 20 ° C./second or less. During the pressurizing and conveying step, the pre-heating step of conveying the stacked (A), (B) or (C) at a temperature of less than 100 ° C., and conveying while heating to a temperature higher than the pre-heating step. The manufacturing method of the joined body according to claim 8, comprising a heating step and a cooling step of conveying while cooling. The method for producing a joined body according to any one of claims 1 to 9, wherein the frame material is a frame-shaped member that covers a peripheral edge portion of the polymer electrolyte membrane in the joined body. A manufacturing apparatus for continuously manufacturing a joined body including a polymer electrolyte membrane and a frame material that covers at least a part of a peripheral edge of the polymer electrolyte membrane,
(A) the polymer electrolyte membrane, the frame material,
(B) The polymer electrolyte membrane to which the frame material is bonded, a gas diffusion layer, or (C) the gas diffusion layer to which the frame material is bonded, and the polymer electrolyte membrane (the above (A) to (C ), A catalyst layer may be formed on the polymer electrolyte membrane), and a joined body manufacturing apparatus having a pressurizing and transporting section that transports the surface while pressurizing at a constant pressure. The said pressurization conveyance part is a manufacturing apparatus of the conjugate | zygote of Claim 11 comprised by the double belt press mechanism which pinches | interposes (A), (B) or (C) of the laminated state from both surfaces with a conveyance belt. . The manufacturing apparatus of the joined body according to claim 11 or 12, wherein the pressure conveying unit includes a heating unit for heating the stacked (A), (B), or (C). The said pressurization conveyance part is a manufacturing apparatus of the conjugate | zygote of Claim 13 provided with the cooling means for cooling (A), (B) or (C) further heated by the said heating means.

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