JP2006012525A - Method and apparatus for manufacturing membrane/electrode assembly - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and an apparatus for manufacturing a membrane/electrode joining body involving low consumption of a coating liquid and providing high production efficiency. <P>SOLUTION: The manufacturing method is provided for a membrane/electrode joining body in which a pair of catalyst layers (electrodes) 12A, 12b opposed to each other are stacked on both front and back surfaces of an electrolyte membrane 10. The method comprises: a first step 100 of applying a coating liquid for formation of the first catalyst layer with a coating head 114 onto one of the surfaces of the electrolyte membrane 10 passed around and conveyed by each of a plurality of rolls; and a second step 200 of applying a coating liquid for formation of the second catalyst layer with a coating head 214 onto the other surface of the electrolyte membrane 10. The electrolyte membrane 10 is formed of a mask-joined membrane U having removable masks 14, 16 joined to both front and back surfaces thereof, with openings 15, 16 formed in the masks 14, 16 at a predetermined pitch. The openings are opposed to each other with the electrolyte membrane 10 located in between, and correspond to the first and second catalyst layers 12a, 12b. By removing the used masks 14, 16 after each step, the first and second catalyst layers 12a, 12b are formed at a predetermined pitch on both surfaces of the electrolyte membrane 10. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method and apparatus for producing a membrane / electrode assembly used in a polymer electrolyte fuel cell.

  Hydrogen / oxygen fuel cells are attracting attention as a power generation system whose reaction product is in principle only water and has little impact on the global environment. The practical application is greatly expected.

  As shown in FIG. 10, the polymer electrolyte fuel cell has a fuel gas on the anode side A of the membrane / electrode assembly in which the catalyst layers 2a and 2b constituting the gas diffusible electrode are joined to both the front and back surfaces of the electrolyte membrane 1. However, in order to manufacture this membrane / electrode assembly, an oxidizing gas containing oxygen is supplied to the cathode side B, respectively, and reacts and outputs. In order to manufacture this membrane-electrode assembly, a coating solution containing a catalyst is applied to the electrolyte membrane and dried. The method is known.

And the following patent document 1 discloses a method shown in FIG. 11 as a method for producing a membrane / electrode assembly, and a belt-like base material having a predetermined width provided with guide rolls 3a and 3b and support rolls 4a to 4d. In the conveyance line of the film 5, first, the first coating head 6a is used to apply the coating liquid for forming the first catalyst layer 2a to the base film 5, and then the second coating head 6b is used to form the electrolyte membrane 1. After the coating liquid for forming is applied onto the first catalyst layer 2a, and the coating liquid for forming the second catalyst layer 2b is further applied onto the electrolyte membrane 1 by the third coating head 6c. By stripping the base film 5, it is possible to manufacture a band-like membrane / electrode assembly in which the catalyst layers (electrodes) 2 a and 2 b are bonded and integrated on both the front and back surfaces. Then, the strip-shaped membrane / electrode assembly is cut into pieces of a predetermined size, and the peripheral portion of the catalyst layer of the piece is peeled off to dispose the gasket on the peripheral portion of the piece. Spaces 1a and 1b (see FIG. 10) are formed.
Republished patent (WO 02/005371)

  However, the above-described method can produce a strip-shaped membrane / electrode assembly in which catalyst layers are continuously formed on both the front and back surfaces of the electrolyte membrane, but the catalyst layer to be peeled and removed thereafter is also applied. Therefore, the consumption of the expensive coating liquid for forming the catalyst layer is large, which is a cause of increasing the production cost of the membrane / electrode assembly. That is, the catalyst layer (in the forming coating solution) contains expensive platinum, and it is desirable to use the coating solution for forming the catalyst layer as much as possible.

  Therefore, a manufacturing method that does not waste the coating solution has been proposed. As shown in FIGS. 12 and 13, the electrolyte membrane 1 formed in advance in a predetermined size (for example, 300 × 300 mm) is placed on a rectangular frame-shaped adsorption plate 8 in which a mesh layer 8 a is provided in the opening. And adsorb and hold at a negative pressure. Then, a coating mask 7 composed of a rectangular frame-shaped adhesive sheet having a predetermined opening 7a is applied to a predetermined position including the peripheral edge of the electrolyte membrane 1, and the first coating head 6d disposed above is used. Then, the coating liquid for forming the first catalyst layer 2a is applied to the opening 7a of the coating mask 7. Reference numeral 9 denotes a hot plate 9 through which hot water circulates so that the suction plate 8 can be placed thereon. After the first catalyst layer (coating film) 2a is dried, the mask 7 is peeled off, the electrolyte membrane 1 is inverted so that the coating film 2a is at the bottom, and another coating mask 7 is attached to the peripheral portion of the electrolyte membrane 1 again. And a second coating head 6d (not shown) using a second coating head 6d (not shown) in the same procedure as that for forming the first catalyst layer 2a. The coating solution for forming the second catalyst layer 2b is applied. Then, if the mask 7 is peeled off when the second catalyst layer (coating film) 2b is dried, the membrane / electrode joint in which the catalyst layers (electrodes) 2a and 2b are joined and integrated on both the front and back surfaces of the electrolyte membrane 1 The body is manufactured.

  However, in this second manufacturing method, the coating liquid is wasted by forming the opening 7a of the mask 7 in advance so as to match the size of the catalyst layers (electrodes) 2a and 2b. However, there is another problem that the production efficiency is very poor and the cost reduction of the membrane / electrode assembly cannot be realized because the mask 7 is attached and peeled off manually.

  In particular, it is difficult to attach the mask 7 used in the first and second coating operations to the electrolyte membrane 1 so as to face each other accurately, so that the front and back surfaces of the electrolyte membrane are opposed to each other. The size and position of the catalyst layers (electrodes) 2a and 2b may be slightly different, and the yield is very poor. The point of poor yield is also the same in the method of Patent Document 1 described above, because it is difficult to accurately peel the peripheral edge of the catalyst layer on the front and back surfaces of the membrane / electrode assembly piece by the same width.

  The present invention has been made in view of the above-described problems of the prior art, and its object is to produce a membrane / electrode assembly manufacturing method and apparatus that do not waste an expensive coating solution and improve production efficiency. Is to provide.

In order to achieve the above object, in the method for manufacturing a membrane-electrode assembly according to claim 1, an electrolyte membrane and a first electrode arranged opposite to each other through the electrolyte membrane and facing each other And a method for producing a membrane-electrode assembly composed of a first catalyst layer and a second catalyst layer which are second electrodes,
A first coating step in which a first coating liquid for forming a catalyst layer is applied by a first coating head to one surface of an electrolyte membrane that is wound around and conveyed by a plurality of rolls;
A second coating step of coating the other surface of the electrolyte membrane that has undergone the first coating step with a second coating liquid for forming a second catalyst layer by a second coating head;
Masks capable of peeling the electrolyte membrane on both the front and back surfaces are joined and integrated, and openings corresponding to the first and second catalyst layers are opposed to each other across the center electrolyte membrane. Configured as a mask bonding film formed with
The mask bonding film is intermittently conveyed in conjunction with the processing speed of the coating process,
Before the second coating step after the first coating step, the used mask used in the first coating step is peeled off and used in the second coating step after the second coating step. The used mask was peeled off.

In order to achieve the above object, in the apparatus for manufacturing a membrane / electrode assembly according to claim 5, the electrolyte membrane and the first electrode arranged to face each other through the electrolyte membrane and to be adjacent to each other And an apparatus for producing a membrane-electrode assembly composed of a first catalyst layer and a second catalyst layer which are second electrodes,
A first coating step in which a first coating liquid for forming a catalyst layer is applied by a first coating head to one surface of an electrolyte membrane that is wound around and conveyed by a plurality of rolls;
A second coating step of coating the other surface of the electrolyte membrane that has undergone the first coating step with a second coating liquid for forming a second catalyst layer by a second coating head;
Masks capable of peeling the electrolyte membrane on both the front and back surfaces are joined and integrated, and openings corresponding to the first and second catalyst layers are opposed to each other across the center electrolyte membrane. Configured as a mask bonding film formed with
The mask bonding film is intermittently conveyed in conjunction with the processing speed of the coating process,
In the first and second coating steps, the mask bonding film is vacuum-sucked and held by suction holding surfaces on the outer periphery of the respective rotary drums, and the coating liquid is applied to the mask by the first and second coating heads. While applying to each predetermined opening,
Each used mask was wound up by a mask winding drum from the mask bonding film after the coating process sent from the first and second rotating drums.

  (Operation of Claims 1 and 5) In the first coating step, the first catalyst layer is formed in the opening of the first mask in the mask bonding film (which is adsorbed and held by the first rotating drum in claim 5). After the coating liquid for forming is applied, the used mask (first mask) is peeled off (taken up by the first mask take-up drum in claim 5) and peeled off. A coating film having a size corresponding to the opening of one mask is left on the electrolyte membrane, and the first catalyst layer is formed at a predetermined pitch on one surface (first coating treatment surface) of the electrolyte membrane; Become. Further, in the second coating step, the second catalyst layer forming coating solution is applied to the opening of the second mask in the mask bonding film (which is adsorbed and held by the second rotating drum in claim 5). After application, when the used mask (second mask) is peeled off (wound onto the second mask take-up drum in claim 5), it corresponds to the peeled second mask opening. In which the coating film of the size to be left is left on the electrolyte membrane, and the second catalyst layer is formed on the other surface of the electrolyte membrane (second coating treatment surface) at a predetermined pitch (both front and back surfaces of the electrolyte membrane) The catalyst layer is formed at a predetermined pitch.

  In particular, since the opening of the first mask and the opening of the second mask that face each other across the electrolyte membrane of the mask bonding film coincide with each other with high accuracy in advance, each mask is peeled off after the coating process. Thus, the first and second catalyst layers formed so as to face each other with the electrolyte membrane interposed therebetween are in a form in which the sizes and positions coincide with each other with high accuracy.

  Further, in claim 1, since the mask bonding film is intermittently conveyed in conjunction with the processing speeds of the first and second coating processes, the first coating process and the second coating process are performed in one line. In claim 5, the first bonding step and the second coating step are carried out by holding the mask bonding film on each rotary drum in vacuum suction and holding in the first and second coating steps. Since the mask bonding film is intermittently conveyed so as to be continuous, the catalyst layer forming process on both the front and back surfaces of the electrolyte film can be automated.

  Further, in the method according to claim 2 (the apparatus according to claim 6), the method for producing the membrane-electrode assembly according to claim 1 (in the membrane-electrode assembly production apparatus according to claim 5, It is desirable that the mask is made of paper having excellent liquid absorbency.

  (Operation of Claims 2 and 6) In the first and second coating steps, the coating liquid that protrudes from the opening of the mask is sucked into a paper mask having excellent liquid absorbing properties, and is then absorbed into the opening of the mask. A coating film is formed accurately.

  Further, in the method according to claim 3, in the method of manufacturing a membrane-electrode assembly according to claim 1 or 2, in the first coating step and the second coating step, the mask bonding film is It is desirable to apply in a form laminated on a base paper having a wider liquid absorbency than the mask bonding film.

  Moreover, in the apparatus which concerns on Claim 7, in the manufacturing apparatus of the membrane electrode assembly which concerns on Claim 5 or 6, the mask joining of each rotary drum in the said 1st coating process and a 2nd coating process A base paper unwinding drum and a base paper wind-up drum are provided on the film feeding side and the sending side, respectively, and a liquid absorption property wider than the mask bonding film unwound from the base paper coil supported by the base paper unwinding drum. It is preferable that the base paper excellent in the above is wound on the base paper take-up drum after being wound around the rotary drum in a form laminated with the mask bonding film.

  (Effects of Claims 3 and 7) In the first and second coating steps, the coating liquid that protrudes beyond the mask width is sucked into a wide base paper having excellent liquid absorbency. The manufactured membrane / electrode assembly is not likely to be contaminated by the coating solution.

  In particular, according to the seventh aspect of the present invention, since the base paper is interposed between the base paper unwinding drum and the base paper take-up drum provided with the rotating drum interposed therebetween, the base paper does not interfere with the coating line. .

  According to the method of claim 4, in the method of manufacturing a membrane / electrode assembly according to claim 1, the first and second coating steps are performed in a vacuum atmosphere. Is desirable.

  Moreover, according to the apparatus which concerns on Claim 8, in the manufacturing apparatus of the membrane electrode assembly in any one of Claims 5-7, the rotating drum and coating head in the said 1st, 2nd coating process It is desirable to arrange each in a vacuum chamber and to provide heating means in each rotary drum.

  (Effects of Claims 4 and 8) In the coating process, the coating film is generally dried by heating, but since it is heated in a vacuum atmosphere, the drying time of the coating film is longer than in the case of heating in the air. Shorten.

In the method for manufacturing a membrane-electrode intermediate assembly according to claim 9, the electrolyte membrane is a first electrode and a second electrode that are opposed to each other with the electrolyte membrane interposed therebetween. A membrane in which one of the first and second catalyst layers is joined and integrated with the electrolyte membrane in the course of manufacturing a membrane-electrode assembly composed of a first catalyst layer and a second catalyst layer -In the method of manufacturing the electrode intermediate assembly,
A coating step of coating a coating liquid for forming a catalyst layer by a coating head on one surface of an electrolyte membrane that is wound around and conveyed by a plurality of rolls;
Masks capable of peeling the electrolyte membrane on both the front and back surfaces are joined and integrated, and openings corresponding to the first and second catalyst layers are opposed to each other across the center electrolyte membrane. The mask bonding film is configured to be intermittently transported in association with the processing speed of the coating process, and the used mask is peeled off after the coating process.

The apparatus for manufacturing a membrane / electrode intermediate assembly according to claim 10 includes an electrolyte membrane, and a first electrode and a second electrode that are disposed opposite to each other with the electrolyte membrane interposed therebetween. A membrane in which one of the first and second catalyst layers is joined and integrated with the electrolyte membrane in the course of manufacturing a membrane-electrode assembly composed of a first catalyst layer and a second catalyst layer In an apparatus for manufacturing an electrode intermediate assembly,
Provided with a coating step of coating a coating liquid for forming a catalyst layer with a coating head on one surface of an electrolyte membrane that is wound around and conveyed by a plurality of rolls,
Masks capable of peeling the electrolyte membrane on both the front and back surfaces are joined and integrated, and openings corresponding to the first and second catalyst layers are opposed to each other across the center electrolyte membrane. The mask bonding film is intermittently transported in conjunction with the processing speed of the coating process, and in the coating process, the mask bonding film is adsorbed and held on the outer periphery of the rotary drum. The mask is configured to be held by vacuum suction so that the coating liquid is applied to a predetermined opening of the mask by the coating head, and the used mask from the mask bonding film after the coating process sent from the rotating drum. Was configured to be wound with a mask winding drum.

  (Effects of Claims 9 and 10) In the coating process, after the coating liquid for forming the catalyst layer is applied to the opening of the mask in the mask bonding film (which is adsorbed and held by the rotating drum in claim 10), When the used mask is peeled off (wound on the mask take-up drum in claim 10), a coating film having a size corresponding to the opening of the peeled mask is left on the electrolyte film, and the electrolyte film The catalyst layer is formed on one side (coating surface) at a predetermined pitch (membrane / electrode intermediate assembly).

  Then, by applying the method of claim 9 (device of claim 10) again to the membrane-electrode intermediate assembly produced by the method of claim 9 (device of claim 10), The catalyst layer is also formed on the surface at a predetermined pitch. In other words, after the coating liquid for forming the catalyst layer is applied to the opening of the mask of the membrane / electrode intermediate assembly, the used mask is peeled off (taken up by the mask take-up drum). The coating film having a size corresponding to the opening of the mask is left on the electrolyte membrane, and catalyst layers are formed on the other surface of the electrolyte membrane at a predetermined pitch (the catalyst layers are provided on both sides of the electrolyte membrane). Form formed with a pitch).

  According to the method for manufacturing a membrane / electrode assembly according to claim 1 (the apparatus for manufacturing a membrane / electrode assembly according to claim 5), the coating liquid for forming the catalyst layer corresponds to the opening area of the mask corresponding to the electrode. Since only the amount is used, the coating liquid is not wasted, and the process of forming the catalyst layer on both the front and back surfaces of the electrolyte membrane can be automated, so the first and second electrodes (catalysts) are sandwiched between the electrolyte membranes. The manufacturing cost of the membrane / electrode assembly in which the layer) is accurately opposed to each other can be significantly reduced.

  According to the method according to claim 2 (the apparatus according to claim 6), the coating film is accurately formed in the opening of the mask and the mask is easily peeled off after the coating process. A membrane / electrode assembly having a catalyst layer (electrode) of the same size can be produced.

  According to the method according to claim 3 (the apparatus according to claim 7), there is no fear that the coating equipment and the membrane / electrode assembly to be manufactured are contaminated with the coating liquid. Yield is improved.

  According to the method according to claim 4 (apparatus according to claim 8), the time required for the manufacturing process of the membrane-electrode assembly is shortened, because the drying time of the coating film in the coating process is shortened. The production efficiency of the membrane / electrode assembly is further improved.

  According to the method according to claim 9 (the device according to claim 10), in the membrane / electrode which is an intermediate product of the membrane-electrode assembly manufactured by the method according to claim 1 (the device according to claim 5) An inter-joint can be easily manufactured.

  Further, by re-applying the method according to claim 9 (apparatus according to claim 10) to the manufactured membrane-electrode intermediate assembly, the electrolyte membrane is sandwiched without wasting the coating liquid. A membrane / electrode assembly in which the first and second electrodes (catalyst layers) are accurately opposed to each other can be produced.

  Next, embodiments of the present invention will be described based on examples.

  1 to 7 show an embodiment of a method and apparatus for manufacturing a membrane / electrode assembly according to the first aspect of the present invention. FIG. 1 shows an embodiment of a manufacturing method (apparatus) for a membrane / electrode assembly. FIG. 2 is a perspective view of a mask bonding film used in the method (apparatus) of the embodiment, FIG. 3 is a sectional view of the mask bonding film, and FIG. 4 is the same embodiment. FIG. 5 is an overall configuration diagram of the apparatus of the same embodiment, FIG. 6 is a process explanatory diagram for explaining the first coating process, and FIG. It is process explanatory drawing explaining a 2nd coating process.

  In FIG. 1, P denotes a solid polymer fuel cell in which catalyst layers 12 a and 12 b constituting gas diffusible electrodes are joined and integrated on both front and back surfaces of a rectangular electrolyte membrane 10 having a predetermined vertical and horizontal dimensions. In this membrane / electrode assembly, a fuel gas is supplied to the anode side A of the electrode assembly P and an oxidizing gas containing oxygen is supplied to the cathode side B to react and output. Reference numerals 10 a and 10 b are non-electrode-forming regions for gasket arrangement formed along the side edges of the electrolyte membrane 10.

  Hereinafter, a method and an apparatus for manufacturing the membrane / electrode assembly P will be described with reference to FIGS.

  2 and 3, a symbol U1 denotes a joined body in which masks 14 and 16 made of paper having excellent liquid absorbability that can be peeled on both the front and back surfaces of a belt-shaped electrolyte membrane 10 having a predetermined width are joined and integrated (hereinafter, referred to as “joint”). Each of the strip-shaped masks 14 and 16 is opposed to each other with the central electrolyte membrane 10 interposed therebetween, and corresponds to the catalyst layers 12a and 12b (see FIG. 1) as the first and second electrodes. Openings 15 and 17 are formed at a predetermined pitch. In addition, as a joining structure in which the electrolyte membrane 10 and the masks 14 and 16 can be peeled, these 10, 14, and 16 are joined through an adhesive, and when the masks 14 and 16 are peeled off, the adhesive is removed from the mask 14 and 16. 16 is preferably peeled off from the electrolyte membrane 10 together with the adhesive 16 so that no adhesive remains on the electrolyte membrane 10.

  Then, the mask bonding film U1 is wound around a plurality of rolls and conveyed, so that the first coating step 100 includes platinum for forming the first catalyst layer 12a on one surface of the electrolyte film 10. The coating liquid is applied, and further, a coating liquid containing platinum for forming the second catalyst layer 12b is applied to the other surface of the electrolyte membrane 10 by the second coating process 200, as shown in FIG. As described above, the strip-shaped membrane / electrode assembly U2 in which the catalyst layers 12a and 12b having a size corresponding to the openings 15 and 17 of the masks 14 and 16 are formed on the front and back surfaces of the strip-shaped electrolyte membrane 10 at a predetermined pitch is manufactured. It has become so.

  In FIG. 5, reference numeral 110 denotes a first vacuum chamber provided with a rotary drum 112 and a coating head 114 therein, and reference numeral 111 denotes a vacuum pump for making the inside of the vacuum chamber 110 a predetermined vacuum atmosphere. Reference numeral 102 denotes a mask bonding film unwinding drum that supports the mask bonding film coil C1 wound around the mask bonding film U1, and reference numeral M102 denotes a motor for driving the mask bonding film unwinding drum 102. Reference numeral 104 denotes a base paper unwinding drum that supports the base paper coil C2 wound with the base paper 20, and reference numeral M104 denotes a motor for driving the base paper unwinding drum 104. The base paper 20 is wider than the mask bonding film U1. Thus, it is made of paper having excellent liquid absorbency. Then, the mask bonding film U1 (see FIG. 6A) and the base paper 20 unwound from the mask bonding film coil C1 and the base paper coil C2 are laminated through the guide roll 106a (FIG. 6B). And is sent to the rotating drum 112 in the vacuum chamber 110.

  A suction holding surface 112a having a mesh structure is provided on the outer periphery of the rotating drum 112, and the base paper 20 and the mask bonding film U1 wound around the rotating drum 112 by the negative pressure generated inside the drum 112 are formed on the suction holding surface 112a. The coating liquid is applied by the coating head 114 while being sucked and held together. Reference numeral 113 denotes a vacuum pump that generates a negative pressure inside the suction holding surface 112 a of the rotary drum 112.

  The coating head 114 is moved in the width direction of the strip-shaped mask bonding film U1 (perpendicular to the paper surface of FIG. 5) by driving of the drive motor M114, and the predetermined mask 14 in the strip-shaped mask bonding film U1 is stationary. The coating liquid can be applied over the entire width of the opening 15 region, and the movement of the coating head 114 (running in the width direction) and the intermittent rotation of the rotating drum 112 at a predetermined minute angle are repeated, A coating solution for forming the first catalyst layer 12 a is applied to the entire area of the opening 15. When the application of the mask 14 to the opening 15 of the mask 14 by the coating head 114 is completed, the motor M112 is driven to rotate the rotary drum 112 by a predetermined angle (to a predetermined position where the subsequent opening 15 faces the coating head 114). Similarly, the coating liquid for forming the first catalyst layer 12 a is applied to the subsequent opening 15.

  Further, since the coating range by the coating head 114 is set somewhat larger than the area of the opening 15 of the mask 14 so that no coating remains in the opening 15 of the mask 14, the coating liquid is used in the mask 14. However, since the protruding coating liquid is sucked by the paper mask 14 having excellent liquid absorption, it is difficult to peel off the mask 14 after the coating process. There is no possibility that a catalyst layer (electrode) having a size that does not match the opening 15 is formed.

  Further, since the base paper 20 to be laminated with the mask bonding film U1 in the coating process is made of paper having a wider width and superior liquid absorbability than the mask bonding film U1, even the width of the mask 14 (mask bonding film U1). Even if a coating process exceeding 1 is performed, the protruding coating liquid is sucked by the wide base paper 20 having excellent liquid absorbency, so that the coating equipment such as the rotating drum 112 and the guide roll 106b is manufactured. The membrane / electrode assembly U1 ′ (see FIG. 6E) is not soiled by the first coating liquid.

  Further, in the rotary drum 112, a heating means (not shown) (for example, a water circulation path of about 80 ° C.) for drying the coated film is provided. Furthermore, a predetermined degree of vacuum is ensured in the vacuum chamber 110 by the vacuum pump 111, and the time required for drying the coating film is remarkably shortened compared to a structure in which only the heating means is provided. FIG. 6C shows a cross-section of the mask bonding film / underlying paper laminate delivered from the vacuum chamber 110, and a coating film constituting the first catalyst layer 12 a is formed in the opening 15 of the mask 14. ing.

  Reference numeral 105 is provided in the vicinity of the mask bonding film delivery side of the vacuum chamber 110 and is a base paper winding drum for winding the base paper 20 from the coated mask bonding film / base paper laminate, and reference numeral 103 is a coating Mask take-up drums M103 and M105, which wind up and peel off the used mask 14 used in the coating process from the processed mask bonding film U1, are drive motors for the take-up drums 103 and 105, and are used as the unwind drum 102. 104 and the winding drums 103 and 105 intermittently rotate in conjunction with the rotation of the rotating drum 112.

  That is, when the base paper 20 is wound up by the base paper take-up drum 105 from the mask bonding film / base paper laminate (see FIG. 6C) after the coating process sent from the vacuum chamber 110, FIG. As shown in FIG. 6 (e), the coated mask bonding film U1 is formed, and when the used mask (first mask) 14 is wound up by the mask winding drum 103 through the guide roll 106c. As shown in the figure, a coating film having a size corresponding to the opening 15 of the first mask 14 is left behind in the electrolyte membrane 10, and the first catalyst layer 12 a is formed at a predetermined pitch on one surface of the electrolyte membrane 10. As a result, the first coating process 100 is completed. The mask bonding film U1 'after the first coating process is sent to the second coating process 200 for forming the second catalyst layer 12b on the other surface through the guide rolls 106d and 106e.

  In FIG. 5, reference numeral 210 denotes a second vacuum chamber having a rotary drum 212 and a coating head 214 therein, and reference numeral 211 denotes a vacuum pump for making the inside of the vacuum chamber 210 a predetermined vacuum atmosphere. Reference numeral 204 denotes a base paper unwinding drum that supports the base paper coil C3 wound around the base paper 20, and reference numeral M204 denotes a motor for driving the base paper unwinding drum 204. The base paper 20 is made of paper that is wider than the mask bonding film U <b> 1 ′ and has excellent liquid absorption. Then, a mask bonding film U1 ′ (see FIG. 6 (e)) in which the first catalyst layer 12a is formed at a predetermined pitch on one side of the electrolyte membrane 10 by the first coating process 100. By passing through the guide roll 106f together with the base paper 20 unwound from the base paper coil C3, both U1 'and 20 are stacked as shown in FIG. 7 (f), and the rotating drum 212 in the vacuum chamber 210 is formed. Sent to.

  A suction holding surface 212a having a mesh structure is provided on the outer periphery of the rotating drum 212, and the base paper 20 and the mask bonding film U1 'wound around the rotating drum 212 by the negative pressure generated inside the drum 212 are sucked and holding the surface 212a. The coating liquid is applied by the coating head 214. Reference numeral 213 denotes a vacuum pump that generates a negative pressure inside the suction holding surface 212 a of the rotary drum 212.

  The coating head 214 is moved in the width direction (vertical direction in FIG. 5) of the strip-shaped mask bonding film U1 ′ by driving of the drive motor M214, and the mask 16 in the stationary strip-shaped mask bonding film U1 ′ is stationary. The coating liquid can be applied over the entire width of the predetermined opening 17 region, and the movement of the coating head 214 (running in the width direction) and the intermittent rotation of the rotary drum 212 at a predetermined minute angle are repeated. Thus, the coating solution for forming the second catalyst layer 12b is applied to the entire area of the opening 17. When the application of the mask 16 to the opening 17 by the coating head 214 is completed, the motor M212 is driven to rotate the rotary drum 212 by a predetermined angle (to a predetermined position where the subsequent opening 17 faces the coating head 214). Similarly, the coating liquid for forming the second catalyst layer 12b is applied to the subsequent opening 17.

  In addition, the coating range by the coating head 214 is set somewhat larger than the area of the opening 17 of the mask 16 so that there is no unpainted area in the opening 17 of the mask 16. However, it is difficult for the mask 16 to be peeled off after the coating process because the protruding coating liquid is sucked by the paper mask 16 having excellent liquid absorbency. There is no possibility that a catalyst layer (electrode) having a size that does not match the opening 17 is formed.

  Furthermore, since the base paper 20 to be laminated with the mask bonding film U1 ′ in the coating process is made of paper that is wider than the mask bonding film U1 ′ and has excellent liquid absorbency, even the mask 16 (mask bonding film U1 ′). ), The protruding coating liquid is absorbed by the wide base paper 20 having excellent liquid absorbency, so that the coating equipment such as the rotary drum 212 and the guide roll 106g The manufactured membrane / electrode assembly U2 is not soiled by the second coating liquid.

  The rotating drum 212 contains a heating means (not shown) (for example, a water circulation path of about 80 ° C.) for drying the coated film. Furthermore, a predetermined vacuum degree is secured in the vacuum chamber 210 by the vacuum pump 211, and the time required for drying the coating film is remarkably shortened as compared with the structure in which only the heating means is provided. FIG. 7G shows a cross section of the mask bonding film / underlying paper laminate sent from the vacuum chamber 210, and a coating film constituting the second catalyst layer 12 b is formed in the opening 17 of the mask 16. ing.

  Reference numeral 205 denotes a base paper winding which is provided in the vicinity of the mask bonding film delivery side of the vacuum chamber 210 and winds the base paper 20 from the coated mask bonding film / base paper laminate (see FIG. 7G). It is a drum. Reference numeral 203 denotes a mask take-up drum that takes up the used mask 16 used in the coating process from the mask bonding film U1 ′ (see FIG. 7 (h)) that has been coated and peels it off at the position of the guide roll 106h. . Reference numeral 208 denotes a separate film unwinding drum, and reference numeral 209 denotes a membrane / electrode assembly winding drum, which is a strip-shaped membrane / electrode assembly U2 (removed from the mask bonding film U1 ′). 7 (i)) is wound around the membrane / electrode assembly take-up drum 209 together with the separate film 22 unwound from the separate film unwind drum 208 (separate film coil C4). In addition, as shown in FIG.7 (j), the separate film 22 is for preventing the contact between the coating films (catalyst layers) when the membrane-electrode assembly U2 is wound in a coil shape. Reference numerals M203, M205, and M209 are drive motors for the take-up drums 203, 205, and 209, and reference numerals M204 and M208 are drive motors for the unwind drums 204 and 208, respectively. , 209 intermittently rotate in conjunction with the rotation of the rotary drum 212.

  That is, when the base paper 20 is wound up from the mask bonding film / base paper laminate (see FIG. 7G) after the second coating process sent from the vacuum chamber 210, as shown in FIG. 7H. When the used mask (second mask) 16 is wound up by the mask winding drum 203, the size corresponding to the opening 17 of the second mask 16 is obtained as shown in FIG. The coating film is left behind on the electrolyte membrane 10, and a strip-shaped membrane / electrode assembly in which the second catalyst layer 12 b is formed at a predetermined pitch on the other surface of the electrolyte membrane 10 (opposite both surfaces of the electrolyte membrane 10). Membrane / electrode assembly) U2 (see FIG. 4) in which the first and second catalyst layers 12a and 12b are formed at a predetermined pitch. Then, the strip-shaped membrane / electrode assembly U2 is wound around the winding drum 209 together with the separate film 22 as a membrane / electrode assembly coil C5. FIG. 7J shows a stacked state of the separate film 22 and the membrane / electrode assembly U2 in the membrane / electrode assembly coil C5.

  Then, the membrane / electrode assembly coil C5 removed from the take-up drum 209 is set in a cutting device (not shown), and the strip-like membrane / electrode assembly U2 is cut at a predetermined position (see the phantom line in FIG. 4). Thus, the membrane / electrode assembly P having a predetermined dimension shown in FIG. 1 is obtained.

  Further, the masks 14 and 16 joined and integrated with the electrolyte membrane 10 are made of paper that does not generate environmental harmful substances when burned like a synthetic resin film after the coating process. The used masks 14, 16 wound with the coating liquid wound around the drums 103, 203 are burned to separate and recover expensive platinum, and the recovered platinum is reused as an additive to the coating liquid for forming the catalyst layer. It can also be used.

  8 and 9 show an embodiment of a method and apparatus for manufacturing a membrane / electrode intermediate assembly, FIG. 8 is an overall configuration diagram of the apparatus of the same embodiment, and FIG. 9 is a view of a membrane / electrode manufactured by the apparatus of the same embodiment. It is a perspective view of an electrode intermediate joined body.

  In the embodiment of the first invention described above, the first catalyst is applied to one surface of the electrolyte membrane 10 by the first coating process 100 by the mask bonding film U1 being wound around a plurality of rolls and conveyed. The coating solution for forming the layer 12a is applied, and the coating solution for forming the second catalyst layer 12b is applied to the other surface of the electrolyte membrane 10 by the second coating step 200, and the electrode film A strip-shaped membrane / electrode assembly U2 (see FIG. 4) is produced in which catalyst layers 12a and 12b having a size corresponding to the openings 15 and 17 of the masks 14 and 16 are formed on both the front and back surfaces of the mask 10 and 16. However, in this embodiment, the mask bonding film U1 is wound around a plurality of rolls and conveyed, so that the first catalyst is applied to one surface of the electrolyte film 10 by the first coating process 100. The coating liquid for forming the layer 12a is applied, as shown in FIG. An indirect in-band film / electrode having a structure in which a catalyst layer 12a having a size corresponding to the opening 15 of the peeled mask 14 is formed on the surface of the electrode film 10 to which the disk 16 is bonded to the back surface thereof. A combined mask bonding film U1 ′ is manufactured.

  This membrane / electrode intermediate assembly (mask bonding film) U1 ′ is nothing but the intermediate product (see FIG. 6 (e)) of the above-described method (apparatus) of the first invention. Each element constituting the first coating process 100 is the same as each element constituting the first coating process 100 in the first embodiment described above, and is duplicated by attaching the same reference numeral. Description is omitted.

  In FIG. 8, reference numeral 107 denotes a membrane / electrode intermediate assembly winding drum, reference numeral M107 denotes a driving motor for the winding drum 107, reference numeral 108 denotes a separate film winding drum, and reference numeral M108 denotes driving of the winding drum 108. The belt-shaped membrane / electrode assembly (mask bonding film) U1 ′ manufactured by the first coating process 100 using a motor passes through the guide roll 106d, and then separate film unwinding drum 108 (separate film coil C6). Together with the separate film 24 unwound from the film, the film-electrode intermediate assembly take-up drum 107 is wound as a film-electrode intermediate assembly (mask bonding film) coil C7.

  Then, the coating head 114 is set to be supplied with the coating liquid for forming the second catalyst layer, and the film / electrode intermediate assembly (mask bonding film) coil C7 removed from the winding drum 107 is masked. Separating film set on the bonding film unwinding drum 102 and fed into the vacuum chamber 110 using the separate film 24 as the base paper 20, or unwound from the film / electrode intermediate bonded body (mask bonding film) coil C7. 24 is wound up by a separate film winding drum (not shown), and the unwound membrane / electrode intermediate assembly U1 ′ is sent into the vacuum chamber 110 together with the base paper 20 unwound from the base paper coil C2, By performing the coating process 100, the other electrode film 10 of the membrane / electrode intermediate assembly (mask bonding film) U1 ′ Forming a second catalyst layer 12b which faces the catalyst layer 12a (the surface on the side where the catalyst layer 12a is not formed) at a predetermined pitch.

  That is, after the coating solution for forming the second catalyst layer is applied to the opening 17 of the other mask 16 of the membrane / electrode intermediate assembly (mask bonding film) U1 ′, the used mask 16 is taken up by the mask. The second coating film having a size corresponding to the opening 17 of the mask 16 wound and peeled off by the drum 103 is left on the electrolyte film 10, and as shown in FIG. The catalyst layer 12b is formed on the other surface at a predetermined pitch (the catalyst layers 12a and 12b are formed on the front and back surfaces of the electrolyte membrane 10 at a predetermined pitch).

It is a longitudinal cross-sectional view of the membrane electrode assembly manufactured by one Example of the manufacturing method (apparatus) of the membrane electrode assembly which concerns on 1st this invention. It is a perspective view of the mask bonding film | membrane used for the Example method (apparatus). It is sectional drawing of the same mask bonding film. It is a perspective view of the strip | belt-shaped membrane electrode assembly manufactured by the Example method (apparatus). It is a whole block diagram of the Example apparatus film | membrane. It is process explanatory drawing explaining a 1st coating process. It is process explanatory drawing explaining a 2nd coating process. It is a whole block diagram of one Example of the manufacturing method (apparatus) of the membrane electrode assembly which concerns on 2nd this invention. FIG. 3 is a perspective view of a membrane / electrode intermediate assembly manufactured by the same apparatus. It is sectional drawing of the membrane electrode assembly manufactured with the manufacturing method which concerns on a 1st prior art. It is a figure which shows the manufacturing method of the membrane electrode assembly which concerns on a 1st prior art. It is a disassembled perspective view of the manufacturing apparatus of the membrane electrode assembly which concerns on 2nd prior art. It is a longitudinal cross-sectional view of the same manufacturing apparatus.

Explanation of symbols

U1 Band-shaped mask bonding membrane (joint of mask and electrolyte membrane)
U1 ′ Mask bonding film after the first coating process (band-shaped film / electrode intermediate bonded body)
U2 belt-like membrane / electrode assembly P membrane / electrode assembly 10 electrolyte membrane 12a first catalyst layer 12b constituting the first electrode 12b second catalyst layer constituting the second electrode 14 first mask 15 first 1 mask opening 16 second mask 17 second mask opening 20 ground paper 100 first coating process 102 mask bonding film unwinding drum 103, 203 mask winding drum 104, 204 ground paper unwinding drum 105, 205 Substrate unwinding drum 110, 210 Vacuum chamber 111, 113, 211, 213 Vacuum pump 112, 212 Rotating drum 112a, 212a Vacuum suction holding surface on outer periphery of rotating drum 114 First coating head 214 Second coating head 200 Second coating process 208 Separate film unwinding drum 209 Membrane / electrode assembly winding drum Arm 214 coating head C1 mask bonding film coil C2, C3 base paper coil C4, C6 separate film coil C5 membrane electrode assembly coil C7 membrane-electrode in the intermediate conjugate coil

Claims (10)

A membrane composed of an electrolyte membrane, and a first catalyst layer and a second catalyst layer, which are first and second electrodes, facing each other through the electrolyte membrane and arranged adjacent to each other -In the manufacturing method of the electrode assembly,
A first coating step in which a first coating liquid for forming a catalyst layer is applied by a first coating head to one surface of an electrolyte membrane that is wound around and conveyed by a plurality of rolls;
A second coating step of coating the other surface of the electrolyte membrane that has undergone the first coating step with a second coating liquid for forming a second catalyst layer by a second coating head;
Removable masks are joined and integrated on both the front and back surfaces of the electrolyte membrane, and openings corresponding to the first and second catalyst layers are opposed to each other across the center electrolyte membrane. It is configured as a mask bonding film formed with
The mask bonding film is intermittently conveyed in conjunction with the processing speed of the coating process,
Before the second coating step after the first coating step, the used mask used in the first coating step is peeled off and used in the second coating step after the second coating step. A method for producing a membrane / electrode assembly, wherein the used mask is peeled off. 2. The method for producing a membrane-electrode assembly according to claim 1, wherein the mask is made of paper having excellent liquid absorbency.   In the first coating step and the second coating step, the mask bonding film is applied in a form of being laminated on a base paper having a wider liquid absorption than the mask bonding film. The method for producing a membrane-electrode assembly according to claim 1 or 2.   The method for producing a membrane / electrode assembly according to any one of claims 1 to 3, wherein the first and second coating steps are performed in a vacuum atmosphere. A membrane composed of an electrolyte membrane, and a first catalyst layer and a second catalyst layer, which are first and second electrodes, facing each other through the electrolyte membrane and arranged adjacent to each other -In an apparatus for manufacturing an electrode assembly,
A first coating step in which a first coating liquid for forming a catalyst layer is applied by a first coating head to one surface of an electrolyte membrane that is wound around and conveyed by a plurality of rolls;
A second coating step of coating the other surface of the electrolyte membrane that has undergone the first coating step with a second coating liquid for forming a second catalyst layer by a second coating head;
Removable masks are joined and integrated on both the front and back surfaces of the electrolyte membrane, and openings corresponding to the first and second catalyst layers are opposed to each other across the center electrolyte membrane. It is configured as a mask bonding film formed with
The mask bonding film is intermittently conveyed in conjunction with the processing speed of the coating process,
In the first and second coating steps, the mask bonding film is vacuum-sucked and held on the suction-holding surfaces on the outer circumferences of the respective rotary drums, and the first and second coating heads apply the coating liquid to the mask. It is configured to be applied to each predetermined opening,
The membrane / electrode is configured such that each used mask is wound around the mask winding drum from the mask bonding film after coating applied from each of the first and second rotating drums. Bonded body manufacturing equipment. 6. The apparatus for producing a membrane / electrode assembly according to claim 5, wherein the mask is made of paper having excellent liquid absorbency.   In the first coating step and the second coating step, a base paper unwinding drum and a base paper winding drum are respectively provided on the mask bonding film feeding side and the feeding side of the respective rotating drums, and the base paper unwinding is provided. The base paper excellent in liquid absorbency wider than the mask bonding film unwound from the base paper coil supported by the drum is wound around the rotary drum in a form laminated with the mask bonding film, The apparatus for producing a membrane / electrode assembly according to claim 5 or 6, wherein the apparatus is configured to be wound around the base paper winding drum.   The rotating drum and the coating head in the first and second coating steps are respectively disposed in a vacuum chamber, and heating means is provided in each of the rotating drums. The manufacturing apparatus of the membrane electrode assembly in any one of 5-7. A membrane composed of an electrolyte membrane, and a first catalyst layer and a second catalyst layer, which are first and second electrodes, facing each other through the electrolyte membrane and arranged adjacent to each other -In the process of producing an electrode assembly, in the method of producing a membrane-electrode intermediate assembly in which either one of the first or second catalyst layers is joined and integrated with the electrolyte membrane,
A coating step of coating a coating liquid for forming a catalyst layer by a coating head on one surface of an electrolyte membrane that is wound around and conveyed by a plurality of rolls;
Removable masks are joined and integrated on both the front and back surfaces of the electrolyte membrane, and openings corresponding to the first and second catalyst layers are opposed to each other across the center electrolyte membrane. It is configured as a mask bonding film formed with
The mask bonding film is intermittently conveyed in conjunction with the processing speed of the coating process,
A method for producing a membrane / electrode intermediate assembly, wherein a used mask is peeled off after the coating step. A membrane composed of an electrolyte membrane, and a first catalyst layer and a second catalyst layer, which are first and second electrodes, facing each other through the electrolyte membrane and arranged adjacent to each other -In the process of producing an electrode assembly, in the apparatus for producing a membrane-electrode intermediate assembly in which either one of the first or second catalyst layers is joined and integrated with the electrolyte membrane,
Provided with a coating step of coating a coating liquid for forming a catalyst layer with a coating head on one surface of an electrolyte membrane that is wound around and conveyed by a plurality of rolls,
Removable masks are joined and integrated on both the front and back surfaces of the electrolyte membrane, and openings corresponding to the first and second catalyst layers are opposed to each other across the center electrolyte membrane. It is configured as a mask bonding film formed with
The mask bonding film is intermittently conveyed in conjunction with the processing speed of the coating process,
In the coating process, the mask bonding film is vacuum-sucked and held on the suction holding surface on the outer periphery of the rotary drum, and the coating liquid is applied to a predetermined opening of the mask by the coating head. ,
An apparatus for manufacturing a membrane / electrode intermediate assembly, wherein a used mask is wound up by a mask winding drum from a mask bonding film after coating applied from the rotating drum.

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