JP2014186947A - Electrolyte membrane with support base material, manufacturing method thereof, and method of manufacturing catalyst layer-electrolyte membrane laminate using the electrolyte membrane with support base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrolyte membrane with a support base material improved in mass-productivity without impairing quality of the electrolyte membrane.SOLUTION: An electrolyte membrane 7 with a support base material comprises: an electrolyte membrane 2; a first support base material 4 formed on at least one surface of the electrolyte membrane 2; and a second support base material 5 stuck on a surface of the first support base material 4 opposite to the surface stuck with the electrolyte membrane 2. In the first support base material 4, a cut C is formed to divide the first support base material into a first portion including at least a part of an outer edge and a second portion excluding the first portion.

Description

The present invention relates to an electrolyte membrane with a supporting substrate used for forming a catalyst layer-electrolyte membrane laminate constituting a polymer electrolyte fuel cell.

  A fuel cell is a cell in which electrodes are arranged on both sides of an electrolyte and generates electricity by an electrochemical reaction between hydrogen and oxygen, and only water is generated during power generation. Thus, unlike the conventional internal combustion engine, it is expected to spread as a next-generation clean energy system because it does not generate environmental load gas such as carbon dioxide. Among them, in particular, polymer electrolyte fuel cells have a low operating temperature and low electrolyte resistance. In addition, a highly active catalyst is used, so high output can be obtained even in a small size, and early commercialization is expected. Yes.

  The power generation site of the polymer electrolyte fuel cell is composed of a solid polymer electrolyte membrane that conducts protons and a catalyst layer that becomes an electrode, and the electrolyte membrane is formed by coating or hot pressing the catalyst layer on both sides of the electrolyte membrane. -An electrode laminated body can be obtained. However, the above-mentioned solid polymer electrolyte membrane has the property that the size changes greatly due to swelling or shrinkage due to heat or humidity. Therefore, when the catalyst layer is formed by coating, the dimensional accuracy of the electrolyte membrane and the catalyst layer is remarkably lowered by swelling with water or an organic solvent contained in the catalyst layer forming paste or shrinking when dried. To do. Further, when the catalyst layer is formed by hot pressing, there is a problem that the dimensional accuracy of the electrolyte membrane and the catalyst layer is remarkably lowered because the catalyst layer swells and shrinks due to temperature changes during hot pressing and cooling. When the dimensional accuracy of the electrolyte membrane and the catalyst layer is lowered, there is a problem that the size and position of the catalyst layer formed on both surfaces of the electrolyte membrane are shifted. Further, after the catalyst layer is formed on the electrolyte membrane, when the electrolyte membrane is reinforced by laminating a frame-like support base material on the outer peripheral portion thereof, the electrolyte membrane to be reinforced by the opening provided in advance in the support base material And there is a problem that the size of the catalyst layer does not match. In addition, when cells including such an electrolyte membrane-electrode laminate are stacked in layers, a portion where a significant pressure is applied in the stack is generated, resulting in a problem in durability.

  On the other hand, as disclosed in Patent Document 1 below, a method is known in which a frame-shaped support base material is provided around a catalyst layer of an electrolyte membrane and then a catalyst layer is formed in the frame. According to this method, it has been found that the swelling and shrinkage of the electrolyte membrane during the formation of the catalyst layer as described above can be suppressed, and the dimensional accuracy of the catalyst layer can be improved.

  However, the manufacturing method of the electrolyte membrane with a supporting substrate (corresponding to the solid polymer electrolyte membrane / insulating membrane adhesive sheet 13) described in Patent Document 1 is a support in which a central portion is cut out in advance to form a frame shape. This is a method of adhering a solid polymer electrolyte membrane to a base material (insulating film), and its mass productivity was poor because it was difficult to maintain the shape of the supporting base material (insulating film) until bonding.

  On the other hand, Patent Document 2 discloses a method for manufacturing an electrolyte membrane with a supporting substrate as shown in FIGS. Specifically, as shown in FIG. 28 (a), the support base (insulating film) 104 is first bonded to the solid polymer electrolyte membrane 102, and then the catalyst layer is formed as shown in FIG. 28 (b). After the cut (cut line) C is formed in the support substrate (insulating film) 104 in the region, the inner peripheral portion of the cut C is removed as shown in FIG. However, in Patent Document 2, after a support substrate 104 having a rectangular shape in a plan view is bonded to one surface and the other surface of the electrolyte membrane 102, the surface of the support substrate 104 is joined to the bonding surface with the electrolyte membrane 102 by a Thomson blade or the like. Since the reaching cut C is formed (FIG. 28B), there is a possibility that the electrolyte membrane 102 may be damaged if the blade bites too much. Moreover, when the said cut | interruption C is shallow, there existed a problem that the inner peripheral part enclosed by the cut | interruption C of the support base material 104 could not be removed.

  On the other hand, in Patent Document 3, when the inner peripheral portion of the support base material is cut, the support base material is first cut in half in the thickness direction from one surface (half cut), and then bonded to the electrolyte membrane to support it. A technique for cutting the remaining half in the thickness direction from the same position as the half-cut position on the opposite surface of the substrate is disclosed. This technique will be described with reference to FIG. First, as shown in FIG. 29A, the first half cut (half punching) is performed on the outer periphery of the predetermined cut region using the die cutting blade 210 with respect to the reinforcing film material 204. Subsequently, as shown in FIG. 29 (b), the half-cut surface of the reinforcing film material 204 is joined to the electrolyte membrane 202. Subsequently, as shown in FIG. 29 (c), the reinforcing film material 204 is on the side opposite to the first half-cut surface and at the same position as the first half-cut position. A second half cut is performed using the die cutting blade 211. Thereby, the cut | interruption which reaches the junction part with the electrolyte membrane 202 from the surface is formed in the film material 204 for reinforcement. Finally, as shown in FIG. 29 (d), the frame-shaped support base material 204 a is bonded to the outer peripheral edge portion of the electrolyte membrane 202 by removing the portion surrounded by the above-described cut line of the reinforcing film material 204. It becomes a structure. As described above, in Patent Document 3, a cut can be formed in the reinforcing film material 204 without damaging the electrolyte membrane 202.

However, in Patent Document 3 described above, as shown in FIG. 29 (c), when performing the second half-cut, the die cutting blade is set so as to correspond to the first half-cut position of the support base material 204. The position of 211 must be adjusted accurately. Therefore, a highly accurate position correction apparatus is required.

JP 2001-15127 A JP 2007-299551 A JP 2010-27227 A

  Thus, in the invention of Patent Document 1, there is no mass productivity of the electrolyte membrane with a supporting substrate, and in the invention of Patent Document 2, the electrolyte membrane is damaged when the supporting substrate is formed. There has been a problem that the quality of the electrolyte membrane used for the membrane laminate may be deteriorated. On the other hand, in the invention of Patent Document 3, it is possible to form a supporting base material without damaging the electrolyte membrane, but there is a problem that mass productivity is lowered because strict accuracy is required for the die cutting process.

Therefore, it is an electrolyte membrane with a supporting substrate that can suppress swelling and shrinkage of the electrolyte membrane during the formation of the catalyst layer and improve the dimensional accuracy of the electrolyte membrane and the catalyst layer, and is mass-productive without impairing the quality of the electrolyte membrane There has been a demand for a novel electrolyte membrane with a supporting base material that is excellent in the above.

  The present invention has been made to solve the above problems, and can support the swelling and shrinkage of the electrolyte membrane during the formation of the catalyst layer, and can improve the dimensional accuracy of the electrolyte membrane and the catalyst layer. An electrolyte membrane with a supporting substrate excellent in mass productivity without impairing the quality of the electrolyte membrane, and a method for producing the same, and a novel catalyst layer-electrolyte membrane laminate using the electrolyte membrane with a supporting substrate An object is to provide a manufacturing method.

  An electrolyte membrane with a supporting substrate according to the present invention is made to solve the above-described problems, and includes an electrolyte membrane, a first supporting substrate formed on at least one surface of the electrolyte membrane, and a first And a second support substrate bonded to a surface opposite to the surface bonded to the electrolyte membrane of the support substrate, and the first support substrate includes at least a part of the outer peripheral edge portion. A cut is formed that separates the first portion and the second portion excluding the first portion.

  According to such a configuration, since the swelling and shrinkage of the electrolyte membrane during formation of the catalyst layer can be suppressed by the first support substrate, the dimensional accuracy of the electrolyte membrane and the catalyst layer can be improved. In addition, since the cut can be formed in a state where the first support base and the second support base are bonded together, the number of times of making the cut is small, and alignment is performed using a high-performance apparatus. Since there is no need, it is excellent in mass productivity. In addition, since the cut can be formed before the first support substrate is bonded to the electrolyte membrane, there is no fear that the electrolyte membrane is damaged when the cut is formed. In addition, the electrolyte membrane with a supporting substrate according to the present invention is suitable for storage and transportation of the electrolyte membrane, and the supporting substrate can suppress dimensional changes of the electrolyte membrane with respect to changes in the external environment (temperature, humidity, etc.). .

  In the electrolyte membrane with a supporting substrate, at least a part of the cut may reach a part in the thickness direction of the second supporting substrate. That is, since the second supporting substrate is peeled off when the catalyst layer-electrolyte membrane laminate is produced, the break may reach a part of the second supporting substrate. With such a configuration, the first part and the second part of the first base material can be reliably separated and excised.

  In the electrolyte membrane with a supporting substrate, it is preferable that at least a part of the first portion has a higher adhesive strength with the electrolyte membrane than a portion adjacent to the cut of the second portion. With such a configuration, when the second portion is peeled off at the boundary of the first support base material, at least a portion of the first portion has a high adhesive strength with the electrolyte membrane. Can be easily peeled off.

  Moreover, the manufacturing method of the electrolyte membrane with a support base material which concerns on this invention was made | formed in order to solve the said subject, and the 1st process of bonding a 1st support base material and a 2nd support base material together. And the first support substrate bonded to the second support substrate, the first portion including at least a part of the outer peripheral edge portion, and the second portion excluding the first portion And a third step of forming an electrolyte membrane on the surface of the first support substrate opposite to the surface to which the second support substrate is bonded. According to such a method, since the cut can be formed in a state where the first support substrate and the second support substrate are bonded together, the number of cuts is small, and a high-performance apparatus is used. Therefore, it is not necessary to perform alignment or the like, so that the electrolyte membrane with a supporting substrate can be easily manufactured. In addition, since the cut can be formed before the first support substrate is bonded to the electrolyte membrane, there is no fear that the electrolyte membrane is damaged when the cut is formed.

  Moreover, the manufacturing method of the catalyst layer-electrolyte membrane laminated body which concerns on this invention, the process of preparing the electrolyte membrane with a support base material which concerns on this invention, the process of peeling the said 2nd support base material, and said 1st Separating the second portion of the support substrate, and forming a catalyst layer on the portion of the electrolyte membrane from which the second portion of the first support substrate is peeled off. And Thus, if the electrolyte membrane with a supporting substrate of the present invention is used, swelling and shrinkage of the electrolyte membrane during formation of the catalyst layer can be suppressed, so that the dimensional accuracy of the electrolyte membrane and the catalyst layer can be improved. Furthermore, since the electrolyte membrane is not damaged, a high-quality catalyst layer-electrolyte membrane laminate can be easily produced.

  An electrolyte membrane with a supporting substrate that can suppress swelling and shrinkage of the electrolyte membrane during the formation of the catalyst layer and can improve the dimensional accuracy of the electrolyte membrane and the catalyst layer, and is excellent in mass productivity without impairing the quality of the electrolyte membrane Further, it is possible to provide an electrolyte membrane with a supporting substrate and a method for producing the same, and a method for producing a novel catalyst layer-electrolyte membrane laminate using the electrolyte membrane with a supporting substrate.

It is sectional drawing which shows the structure of the electrolyte membrane with a support base material concerning Embodiment 1 of this invention. It is a top view of the 1st support base material which comprises the electrolyte membrane with a support base material shown in FIG. (A) And (b) is a top view which shows the modification of a 1st support base material. It is sectional drawing which shows the manufacturing method of the electrolyte membrane with a support base material shown in FIG. (A) And (b) is sectional drawing and a top view which show the manufacturing method of the electrolyte membrane with a support base material shown in FIG. 1, respectively. (A) is sectional drawing which shows the modification of the laminated body of a 1st support base material and a 2nd support base material, (b) is a 1st support base material and a 2nd support base material. It is a top view which shows the other modification of a laminated body. It is sectional drawing which shows the manufacturing method of the electrolyte membrane with a support base material shown in FIG. It is sectional drawing which shows the structure of the electrolyte membrane with a support base material hot-pressed. (A) And (c) is sectional drawing which shows the modification of the electrolyte membrane with a support base material, (b) is sectional drawing which shows the manufacturing method of the electrolyte membrane with a support base material of (a). (A) is sectional drawing which shows the modification of the electrolyte membrane with a support base material, (b) is a top view which shows the 1st support base material of the upper side of the said electrolyte membrane with a support base material, c) is a plan view showing a first support substrate on the lower side of the electrolyte membrane with a support substrate. (A) is sectional drawing which shows the other modification of the electrolyte membrane with a support base material, (b) and (c) are sectional drawings which show the manufacturing method of the said electrolyte membrane with a support base material, d) is a cross-sectional view showing a configuration in which the second support substrate is removed from the electrolyte membrane with a support substrate. (A) is sectional drawing which shows the structure of the catalyst layer transfer film in which the catalyst layer was formed, (b) is a top view which shows the structure of the said catalyst layer transfer film. (A)-(d) is sectional drawing which shows the manufacturing method of the catalyst layer-electrolyte membrane laminated body which concerns on Embodiment 2 of this invention using the electrolyte membrane with a support base material concerning Embodiment 1 of this invention. is there. (A)-(c) is sectional drawing which shows the manufacturing method of the catalyst layer-electrolyte membrane laminated body which concerns on Embodiment 2 of this invention. It is sectional drawing which shows the catalyst layer-electrolyte membrane laminated body which concerns on the modification of Embodiment 2 of this invention. It is sectional drawing which shows the structure of the catalyst layer-electrolyte membrane laminated body which concerns on the further another modification of Embodiment 2 of this invention. (A)-(c) is sectional drawing which shows an example of the manufacturing method of the catalyst layer-electrolyte membrane laminated body shown in FIG. (A)-(d) is sectional drawing which shows an example of the manufacturing method of the catalyst layer-electrolyte membrane laminated body shown in FIG. (A) And (b) is sectional drawing which shows an example of the manufacturing method of the catalyst layer-electrolyte membrane laminated body shown in FIG. (A)-(d) is sectional drawing which shows the other example of the manufacturing method of the catalyst layer-electrolyte membrane laminated body shown in FIG. It is sectional drawing which shows the structure of the catalyst layer-electrolyte membrane laminated body which concerns on the other modification of Embodiment 2 of this invention. It is sectional drawing which shows the manufacturing method of the catalyst layer-electrolyte membrane laminated body shown in FIG. (A)-(d) is sectional drawing which shows the manufacturing method of the catalyst layer-electrolyte membrane laminated body shown in FIG. (A) And (b) is sectional drawing which shows the manufacturing method of the catalyst layer-electrolyte membrane laminated body shown in FIG. (A) is a top view which shows the catalyst layer-electrolyte membrane laminated body which concerns on the further another modification of Embodiment 2 of this invention, (b) is FIG. 25 () of the said catalyst layer-electrolyte membrane laminated body. It is the top view seen from the opposite direction of a). (A) And (b) is a top view which shows the catalyst layer-electrolyte membrane laminated body which concerns on the further another modification of Embodiment 2 of this invention. (A) And (b) is sectional drawing which shows the structure of the catalyst layer-electrolyte membrane laminated body which concerns on the further another modification of Embodiment 2 of this invention. (A)-(c) is sectional drawing which shows the manufacturing method of the conventional catalyst layer-electrolyte membrane laminated body. (A)-(d) is sectional drawing which shows a part of manufacturing method of the other conventional catalyst layer-electrolyte membrane laminated body.

  Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. The present invention is not limited to the following embodiments.

  [Embodiment 1]

  The present invention relates to an “electrolyte membrane with a supporting substrate” that can be used for producing a “catalyst layer-electrolyte membrane laminate”.

(Configuration of electrolyte membrane with supporting substrate)
FIG. 1 is a cross-sectional view illustrating a configuration of an electrolyte membrane 7 with a supporting base material according to the present embodiment. FIG. 2 is a plan view of the first support substrate 4 constituting the electrolyte membrane 7 with the support substrate.
1 includes an electrolyte membrane 2, a first support substrate 4 bonded to one surface of the electrolyte membrane 2, and the electrolyte membrane 2 of the first support substrate 4. And a second support substrate 5 bonded to a surface opposite to the bonded surface.

  In addition, the first support base 4 has a cut C that separates a first portion including at least a part of the outer peripheral edge in the thickness direction and a second portion excluding the first portion. Is formed. That is, as shown in FIG. 2, the first support base 4 has a first portion P1 as an outer peripheral portion of the cut and a second portion P2 as an inner peripheral portion due to the cut C formed in a frame shape. It is divided into.

When providing the area | region which forms a catalyst layer, the cut | interruption C should just be formed so that the 2nd part P2 of the 1st support base material 4 can peel from the electrolyte membrane 2 by using the cut | interruption C as a notch. Therefore, although it is preferable that the cut C penetrates the first support base material 4 in the thickness direction, it may not completely penetrate, and at least a part of the cut C is the second support group. The thickness direction of the material 5 may be reached. Further, the size of the cut C may be appropriately set according to the size of the catalyst layer formed in the subsequent step.

In addition, although the rectangular frame shape was illustrated in FIG. 2, the one part may be rounded like FIG. 3 (a), and it is 1st instead of a frame shape like FIG.3 (b). The cut line C may be formed only along the two opposing sides of the supporting substrate 4. In this case, the cut C includes an outer portion P1 ′ (first portion) including portions along the left and right sides of the outer peripheral edge of the first support base 4 and an inner portion excluding the outer portion P1 ′. P2 ′ (second part) is separated. According to the shape as shown in FIG. 3B, since there are only two sides necessary for the first support substrate, it is excellent in mass productivity, and in particular, a long component such as a roll-to-roll. It is suitable for the method of continuously manufacturing long products by processing

  Thus, in this embodiment, as shown in FIG. 2 and FIG. 3A, the cut C includes an outer peripheral portion P1 and an outer peripheral portion P1 including all of the outer peripheral edge portion of the first support base 4. It is not necessary to form the outer peripheral portion P2 so as to be separated from the outer peripheral portion P2 except for the outer portion P1 where the cut C includes a part of the outer peripheral edge portion of the first support base 4 as shown in FIG. You may form so that 'and inner part P2' except this outer part may be divided. That is, the “first portion” may include the entire outer peripheral edge portion as in the outer peripheral portion P1 shown in FIG. 2, or the outer peripheral edge portion as in the outer portion P1 ′ shown in FIG. You may include only a part of.

(Materials of components)
Next, the detail of each component of the electrolyte membrane 7 with a support base material which concerns on this embodiment is demonstrated.

  The electrolyte membrane 2 is formed, for example, by applying a solution containing a hydrogen ion conductive polymer electrolyte on a substrate and drying it. Examples of the hydrogen ion conductive polymer electrolyte include a perfluorosulfonic acid-based fluorine ion exchange resin, more specifically, a perfluorocarbonsulfonic acid-based resin in which the C—H bond of a hydrocarbon ion-exchange membrane is substituted with fluorine. Examples include polymers (PFS polymers). By introducing a fluorine atom having high electronegativity, it is chemically very stable, the dissociation degree of the sulfonic acid group is high, and high ion conductivity can be realized. Specific examples of such a hydrogen ion conductive polymer electrolyte membrane include “Nafion” (registered trademark) manufactured by DuPont, “Flemion” (registered trademark) manufactured by Asahi Glass Co., Ltd., “ Examples include "Aciplex" (registered trademark), "Gore Select" (registered trademark) manufactured by Gore. The concentration of the hydrogen ion conductive polymer electrolyte contained in the hydrogen ion conductive polymer electrolyte-containing solution is usually about 5 to 60% by weight, preferably about 20 to 40% by weight. In addition to the hydrogen ion conductive polymer electrolyte membrane, an anion conductive solid polymer electrolyte membrane and a liquid substance-impregnated membrane are also included. Examples of the anion conductive electrolyte membrane include a hydrocarbon-based resin membrane or a fluorine-based resin membrane, and specific examples of the hydrocarbon-based resin membrane include Aciplex (registered trademark) A201, 2111, 221 manufactured by Asahi Kasei Corporation. And Neocepta (registered trademark) AM-1, AHA manufactured by Tokuyama Corporation, and the like, and examples of the fluorine-based resin film include Tosflex (registered trademark) IE-SF34 manufactured by Tosoh Corporation. Examples of the liquid substance-impregnated film include polybenzimidazole (PBI). The thickness of the electrolyte membrane 2 is preferably 5 to 50 μm. What is necessary is just to set the magnitude | size and shape of the electrolyte membrane 2 suitably according to the magnitude | size of the battery which incorporates them.

  The materials of the first support substrate 4 and the second support substrate 5 are polyester, polyamide, polyimide, polymethylpentene, polyphenylene oxide, polysulfone, polyether ether ketone, polyphenylene sulfide, a plastic such as fluororesin, or Metals such as aluminum, copper, and zinc can be used. Specific examples of the polyester include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polybutylene naphthalate. The base material is a laminate in which the plastic and metal are laminated, or a laminate in which the plastic is subjected to a surface treatment such as plasma or corona, and the plastic is laminated with an oxide such as alumina, silica, and titania. It can also be used as a layer. Among these, polyesters, particularly polyethylene naphthalate, have good gas barrier properties against water vapor, water, heat resistance, and thermal dimensional stability, so the effect of suppressing swelling and shrinkage of the electrolyte membrane during the formation of the catalyst layer and storage It is preferable because of its high stability. Moreover, it is preferable from a viewpoint of reduction of manufacturing cost.

  The material of the first support base material is, in particular, when the catalyst layer-electrolyte membrane laminate is incorporated in the polymer electrolyte fuel cell with the first portion of the first support base material remaining as will be described later. Polyethylene naphthalate is preferably selected from the viewpoints of gas barrier properties, heat resistance, and thermal dimensional stability. The material of the second support substrate 5 may be different from that of the first support substrate, but is preferably the same from the viewpoints of gas barrier properties, heat resistance, and thermal dimensional stability. In addition, the size and shape of the first support base 4 and the second support base 5 may be set as appropriate depending on the size of the battery in which they are incorporated, but the first support base 4 and the second support base 5 The magnitude | size of planar view of the support base material 5 may differ. Moreover, as for the thickness of the 1st support base material 4 and the 2nd support base material 5, 20-100 micrometers is preferable.

(Method for producing electrolyte membrane with supporting substrate)
Then, the manufacturing method of the electrolyte membrane 7 with a support base material is demonstrated. First, as shown in FIG. 4, the 1st support base material 4 and the 2nd support base material 5 are prepared, and they are bonded together. As a bonding method, there are a method by heat welding, a method using an adhesive, and the like. As a material for the pressure-sensitive adhesive, for example, an epoxy-based, acrylic-based, rubber-based, or silicone-based pressure-sensitive adhesive can be used. Specifically, acrylic ester copolymers, methacrylic ester copolymers, natural rubber (NR), synthetic natural rubber (IR), styrene-butadiene rubber (SBR), polyisobutylene (PIB), butyl rubber (IIR) And silicone rubber. Further, the interface between the first support substrate 4 and the second support substrate 5 may not have a uniform adhesive force. For example, if the second portion is firmly adhered to the second support substrate, the second portion is removed from the electrolyte membrane together when the second support substrate is peeled from the first support substrate. Can be peeled off. As the material for the adhesive, hot melt adhesives such as polyolefin, polypropylene and thermoplastic elastomer, acrylic adhesives, olefin adhesives such as polyester and polyolefin, ultraviolet curable resins, electron beam curable resins and the like can be used.

  Subsequently, as shown in FIGS. 5A and 5B, a cut C is formed in the thickness direction of the first support base 4. The cut C can be formed using, for example, a die cutting machine. The die cutting machine can exemplify a cutting device provided with a Thomson blade having a rectangular shape in plan view that can be reciprocated up and down, and the height of the Thomson blade is the same as or higher than that of the first support substrate 4. The cut C is formed by pressing against the first support substrate 4 after adjusting the thickness.

  Further, as shown in FIG. 6A, the cut C may reach a part in the thickness direction of the second support substrate 5. That is, there may be some errors in the depth of the cut C. Further, as shown in FIG. 6B, the cut C may be formed discontinuously (for example, in a broken line shape) in the surface direction.

  Next, the electrolyte membrane 2 is formed on the surface of the first support substrate 4 opposite to the surface bonded to the second support substrate 5. As shown in FIG. 7, the electrolyte membrane is formed by attaching a pre-formed electrolyte membrane 2 to the first support substrate 4 or hydrogen ion conductivity on the first support substrate 4. There is a method in which a solution containing a polymer electrolyte is applied and dried. As for the temperature at the time of bonding the electrolyte membrane 2 on the 1st support base material 4, 50-200 degreeC is preferable. In addition, when the electrolyte membrane is formed by coating, a known printing method such as a doctor blade or spray can be used. Moreover, drying temperature is 50-150 degreeC normally, and 60 to 130 degreeC is preferable.

In addition, from the viewpoint of adhesiveness, the first support substrate 4 may be subjected to an easy adhesion treatment. Examples of the easy adhesion treatment include a surface treatment such as plasma and corona, and a method of applying the above-described pressure-sensitive adhesive or adhesive. Further, as a method for improving the adhesiveness after forming the electrolyte membrane, there is a method of thermocompression bonding the first support base 4 and the electrolyte membrane. Although the temperature at the time of thermocompression bonding is not particularly limited, it is about 100 to 250 ° C., and is preferably higher than that at the time of bonding the support substrate and the electrolyte membrane. Moreover, it is preferable that the pressure at the time of thermocompression bonding is about 0.1 to 10 kN / cm.

In particular, when the adhesive strength of the first portion of the first support substrate 4 is increased by the method described above, the peelability of the second portion of the first support substrate 4 is improved. In addition, the dimensional stability of the electrolyte membrane when forming the catalyst layer can be further improved. Moreover, when it is incorporated into a polymer electrolyte fuel cell with the first portion of the first support substrate 4 left, an edge seal that suppresses swelling expansion and contraction of the electrolyte membrane 2 during operation is increased as the adhesiveness is higher. As well as it works. The size of the electrolyte membrane 2 in plan view may be the same as that of the first support substrate 4, but is preferably smaller than the first support substrate 4 from the viewpoint of cost.

  FIG. 8 is a cross-sectional view showing the hot-pressed electrolyte membrane 7 with a supporting substrate. In the electrolyte membrane 7 with the supporting base material, the adhesive strength in the region R1 where a part of the outer peripheral portion P1 and the electrolyte membrane 2 are joined out of the joint surfaces of the first supporting base material 4 with the electrolyte membrane 2 by hot pressing. However, it is larger than the other part of the joint surface. That is, at least a part of the outer peripheral portion P1 has a higher adhesive strength with the electrolyte membrane 2 than the portion R2 adjacent to the cut C1 of the inner peripheral portion P2. Thereby, in the step of producing the catalyst layer-electrolyte membrane laminate, when the inner peripheral portion P2 of the cut C of the first support substrate 4 is peeled off, the portion R2 adjacent to the cut C of the inner peripheral portion P2 is Since the adhesive strength with the electrolyte membrane 2 is small, the portion where the cut C is formed becomes the starting point of peeling. On the other hand, since a part of the outer peripheral part P1 has high adhesive strength with the electrolyte membrane 2, the outer peripheral part P1 is not peeled off. Therefore, the inner peripheral portion P2 can be easily peeled off.

  According to the manufacturing method of the present invention, the cut C of the first support base 4 is formed before the first support base 4 is bonded to the electrolyte membrane 2, so that the electrolyte membrane 2 is damaged. There is no inconvenience. In addition, since advanced alignment and adjustment of the slit are not required to form the cut C, no special technique or high-performance apparatus is required. Therefore, the electrolyte membrane 7 with a supporting substrate can be produced without damaging the electrolyte membrane 2 and without using a high-performance apparatus.

(Modification 1 of electrolyte membrane with supporting substrate)
Then, the modification of the electrolyte membrane with a support base material concerning this embodiment is demonstrated. Fig.9 (a) is sectional drawing which shows the structure of the electrolyte membrane 7a with a support base material which concerns on the modification 1 of this embodiment. The electrolyte membrane 7a with a supporting substrate is composed of the electrolyte membrane 2, the first supporting substrate 4 bonded to both surfaces of the electrolyte membrane 2, and the surface of the first supporting substrate 4 bonded to the electrolyte membrane 2. And a second support base material 5 bonded to the opposite surface of the first support base material 4. Each first support base material 4 includes a first portion including at least a part of an outer peripheral edge portion and the first portion. This is a configuration in which a break C is formed that separates the second portion excluding. As shown in FIG. 9B, such an electrolyte membrane 7a with a supporting substrate is obtained by forming a laminate of the first supporting substrate 4 and the second supporting substrate 5 shown in FIG. It can produce by pasting together. Further, the position of the cut C formed in the first support base 4 may be different on both sides. Specifically, as shown in FIG. 9C, the cut line C of the first support base 4 formed in a frame shape may be different in size in the vertical direction.

  Also in this modification, the cut line C may be formed along two opposing sides of the first support base. For example, it can also be configured like an electrolyte membrane 7b with a supporting substrate shown in FIGS. 10 (a) to 10 (c). Fig.10 (a) is sectional drawing which shows the electrolyte membrane 7b with a support base material. FIG. 10B is a plan view of the first support substrate 4a on the upper side of the electrolyte membrane 7b with the support substrate, and the first support substrate 4a has cut lines C along two left and right sides. Is formed. FIG. 10C is a plan view of the first support substrate 4b on the lower side of the electrolyte membrane 7b with a support substrate, and the first support substrate 4b has a cut C along two upper and lower sides. Is formed. In addition, you may form the cut | interruption C along two right and left sides like FIG.10 (b) in both 1st support base material 4a * 4b. In addition, in the electrolyte membrane 7b with a supporting base material, the first supporting base materials 4a and 4b are both formed with cuts that are not frame-shaped, but one of the first supporting base materials 4a and 4b has a frame-like shape. A cut line may be formed, and a cut line that is not a frame shape as shown in FIG. 10B or 10C may be formed on the other side.

(Variation 2 of electrolyte membrane with supporting substrate)
Then, the modification 2 of the electrolyte membrane with a support base material which concerns on this embodiment is demonstrated. Fig.11 (a) is sectional drawing which shows the structure of the electrolyte membrane 7c with a support base material which concerns on the modification 2 of this embodiment. 9A is different from the electrolyte membrane 7a with the supporting substrate in that the size of the first supporting substrate 4 and the second supporting substrate 5 formed on both surfaces of the electrolyte membrane 2 is larger than that of the electrolyte membrane 2. It is a point that the outer peripheral edge protrudes outside the outer peripheral edge of the electrolyte membrane 2. Moreover, the outer peripheral edge part of the 1st support base material 4 of both surfaces has adhere | attached via the adhesive agent A. FIG. In FIG. 11A, the distance x from the cut C of the first support substrate to the outer peripheral edge of the electrolyte membrane 2 may be about 10 to 100 mm, for example, and the distance x from the outer peripheral edge of the electrolyte membrane 2 The distance y to the outer peripheral edge of one supporting substrate 4 may be about 3 to 50 mm, for example.

Such an electrolyte membrane 7c with a supporting substrate can be prepared as follows. First, two laminates of the first support substrate 4 and the second support substrate 5 as shown in FIG. 11B are prepared. In the laminate of FIG. 11B, the first support base material 4 and the second support base material 5 are prepared and bonded together by the method described above, and then the thickness direction of the first support base material 4 is obtained. A cut line C is formed on the outer periphery, and the adhesive A is applied to the outer peripheral edge portion and dried. As the adhesive A, known materials can be used, but hot melt adhesives such as polyolefin, polypropylene and thermoplastic elastomer, acrylic adhesives, olefin adhesives such as polyester and polyolefin, ultraviolet curable resins, and electron beam curing. Resins are preferred. The adhesive A provided on the first support substrate 4 may be a pressure-sensitive adhesive. In the case of a pressure-sensitive adhesive, an epoxy-based, acrylic-based, rubber-based, or silicone-based pressure-sensitive adhesive is preferable. The area for forming the adhesive A is not limited as long as it is a region outside the cut C formed in the first support base material, but is preferably 1 to 3 mm outside the cut C. Further, the adhesive A does not necessarily have to be formed on the portion where the electrolyte membrane 2 is formed. The thinner the adhesive layer formed by the adhesive A, the more preferable, for example, 20 μm or less.

Next, as shown in FIG. 11 (c), the electrolyte membrane 2 having an area smaller than that of the first support substrate 4 is sandwiched between the laminates of FIG. 11 (b), and the laminate is placed on both surfaces of the electrolyte membrane 2. Paste. Then, if the part outside the cut line C formed on the first support base material 4 is pressed and adhered, an electrolyte membrane 7c with a support base material as shown in FIG. 11A can be created. The pressure at this time is preferably about 1 MPa, and may be heated as necessary.

Although not shown, in the present modification, when the cut C is formed along the two opposite sides of the first support base material 4, the adhesive A is applied to the two sides outside the cut C. That's fine. In addition, the size of the second support substrate 5 may be a size including the cut of the first support substrate 4, and may be smaller than the first support substrate 4.

As described above, if at least the first support base 4 is larger than the electrolyte membrane 2 and the first support bases 4 that protrude from both sides of the electrolyte 2 are bonded to each other, a catalyst layer is formed. The dimensional stability of the electrolyte membrane 2 can be further improved. In particular, as shown in FIG. 11 (d), only the second support substrate 5 is removed from the electrolyte membrane 7 c with the support substrate, leaving the first portion of the first support substrate 4. Incorporation into the polymer electrolyte fuel cell has the effect of sealing the leakage of fuel gas from the electrode to the outside of the cell or the other electrode, in addition to suppressing swelling and expansion of the electrolyte membrane 2 during operation.

[Embodiment 2]
(Method for producing catalyst layer-electrolyte membrane laminate)
Then, the manufacturing method of the catalyst layer-electrolyte membrane laminated body (laminated body in which the catalyst layer was formed in both surfaces of the electrolyte membrane) using the electrolyte membrane 7 with a support base material concerning Embodiment 1 is demonstrated.
The manufacturing method of the catalyst layer-electrolyte membrane laminated body of this invention should just have at least the following four processes.
(1) A step of preparing an electrolyte membrane with a supporting substrate of the present invention.
Specifically, the first support base material bonded to at least one surface of the electrolyte membrane, and the second support surface bonded to the surface of the first support base material opposite to the surface bonded to the electrolyte membrane. The first support substrate is provided with a cut that separates the first portion including at least a part of the outer peripheral edge portion and the second portion excluding the first portion. A step of preparing an electrolyte membrane with a supporting substrate.
(2) The process of peeling the 2nd support base material in the electrolyte membrane with a support base material.
(3) The process of peeling the 2nd part of the said 1st support base material in the said electrolyte membrane with a support base material.
(4) The process of forming a catalyst layer in the part which peeled the 2nd part of the said 1st support base material on the said electrolyte membrane.

Hereinafter, as an example, a method for producing the catalyst layer-electrolyte membrane laminate shown in FIG. 14C using a catalyst layer transfer film will be described.
First, as shown in FIGS. 12A and 12B, a catalyst layer transfer film in which the catalyst layer 3 is applied to the catalyst layer transfer film substrate 6 is prepared. The catalyst layer transfer film substrate 6 is a Teflon (registered trademark) substrate having a thickness of 10 to 100 μm, for example.

These catalyst layers 3 can be known platinum-containing catalyst layers. Specifically, it contains carbon particles carrying catalyst particles and a hydrogen ion conductive polymer electrolyte. As the hydrogen ion conductive polymer electrolyte, the same material as that used for the electrolyte membrane 2 described above can be used.

  Examples of the catalyst particles include platinum and platinum compounds. Examples of the platinum compound include an alloy of platinum and at least one metal selected from the group consisting of ruthenium, palladium, nickel, molybdenum, iridium, iron and the like. Usually, the catalyst particles contained in the cathode catalyst layer and the anode catalyst layer are platinum.

  The carbon particles are not limited as long as they have electrical conductivity, and known or commercially available carbon particles can be widely used. For example, carbon black, graphite, activated carbon, or the like can be used alone or in combination. Examples of carbon black include channel black, furnace black, ketjen black, acetylene black, and lamp black. The arithmetic average particle diameter of the carbon particles is usually about 5 nm to 200 nm, preferably about 20 nm to 80 nm. The average particle size of the carbon particles can be measured by, for example, a particle size distribution measuring device LA-920: manufactured by Horiba, Ltd.

  Next, as shown to Fig.13 (a), the electrolyte membrane 7 with a support base material is prepared. Subsequently, as shown in FIG. 13B, the second support base 5 is peeled from the first support base 4. Subsequently, as shown in FIG. 13 (c), the catalyst layer transfer film shown in FIG. 13 is arranged so as to face the surface of the electrolyte membrane 2 opposite to the surface on which the first support substrate 4 is formed. The catalyst layer 3 is disposed on the surface of the electrolyte membrane 2 opposite to the surface on which the first support substrate 4 is formed. At this time, the position of the catalyst layer 3 is not particularly limited, but from the viewpoint of transferability, the catalyst layer 3 may be formed inside the cut C so as not to overlap the cut C of the first support substrate 4. preferable. Then, the catalyst layer 3 is transferred to the electrolyte membrane 2 by peeling the catalyst layer transfer film substrate 6 from the catalyst layer 3 by hot pressing. The hot press conditions are preferably, for example, 50 to 200 ° C., 0.5 to 10 MPa, and 5 to 600 seconds. As a result, a catalyst layer 3u is formed on one surface of the electrolyte membrane 2 as shown in FIG.

Further, the inner peripheral portion P2 of the cut C of the first support base 4 is peeled off to expose a part of the electrolyte membrane 2. As a result, as shown in FIG. 14A, only the frame-shaped outer peripheral portion P1 of the first support substrate 4 remains in the electrolyte membrane 2 to form a frame-shaped support substrate 4d. The method for peeling the support substrate is not particularly limited, and for example, peeling with a cello tape (registered trademark) or an adhesive roll (for example, an adhesive roll having an adhesive layer formed on the surface) is applicable.

  Next, as shown in FIG. 14 (b), the catalyst layer transfer film is arranged so that the catalyst layer 3 and the electrolyte membrane 2 face each other, so that the electrolyte membrane 2 is accommodated in the inner peripheral portion of the support base 4d exposed. The catalyst layer 3 is disposed on the surface. Thereafter, the catalyst layer 3u is heat-pressed under the same conditions as in the transfer of the catalyst layer 3u, and the catalyst layer transfer film substrate 6 is peeled from the catalyst layer 3 to transfer the catalyst layer 3 to the electrolyte membrane 2. Thereby, the catalyst layer 3d is formed on the other surface of the electrolyte membrane 2, and the catalyst layer-electrolyte membrane laminate 1 as shown in FIG. 14C is produced. In FIG. 14, the sizes of the catalyst layer 3u and the catalyst layer 3d in plan view are different, but they may be different as shown in FIG. 14 or the same.

  Moreover, according to the manufacturing method of the present invention, unlike the flow of FIGS. 13 and 14, it can be formed from the catalyst layer on the surface of the electrolyte membrane 2 on which the first support substrate 4 is formed first. That is, after preparing the supporting membrane-attached electrolyte membrane 7, the second supporting substrate and the second portion of the first substrate are peeled off from the electrolyte membrane, and the catalyst layer transfer film is replaced with the first membrane of the electrolyte membrane 2. It is also possible to transfer the catalyst layer onto the electrolyte membrane by disposing it on the surface on which the support substrate 4 is formed. At this time, the peeling of the second supporting substrate 5 and the peeling of the inner peripheral portion P2 of the cut C of the first supporting substrate 4 may be performed simultaneously. In addition, after peeling the 2nd support substrate 5 and the 2nd part of the 1st support substrate 4 from the electrolyte membrane 2, a catalyst layer transfer film is arrange | positioned on both surfaces of the electrolyte membrane 2, and catalyst layer 3u and The catalyst layer 3d may be transferred simultaneously.

  Further, the support base material (the first portion of the first support base material) remaining in the catalyst layer-electrolyte membrane laminate may be removed from the catalyst layer-electrolyte membrane laminate, or it may be assembled in a battery as it is. May be. The method of removing the first portion of the first support substrate may be a method of peeling the first portion of the first support substrate from the catalyst layer-electrolyte membrane laminate, or the first support group. A method of cutting the first portion of the material and the outer peripheral edge of the electrolyte membrane together may be used. FIG. 15 shows an example of the support layer 4d cut from the catalyst layer-electrolyte membrane laminate 1 shown in FIG. 14 (c) together with the outer peripheral edge of the electrolyte membrane.

(Modification 1 of catalyst layer-electrolyte membrane laminate)
Then, the modification of the catalyst layer-electrolyte membrane laminated body which concerns on this embodiment is demonstrated.

  FIG. 16 is a cross-sectional view showing a configuration of a catalyst layer-electrolyte membrane laminate 1a according to a modification of the present embodiment. The catalyst layer-electrolyte membrane laminate 1a is different from FIG. 14C in that the support base 4u and the support base 4d are formed on both sides of the catalyst layer-electrolyte laminate 1. The manufacturing method will be described in detail below.

  First, as shown in FIG. 17A, an electrolyte membrane 7a with a supporting substrate in which a laminate of a supporting substrate 4 and a second supporting substrate 5 is bonded to both surfaces of the electrolyte membrane 2 is prepared. Subsequently, as shown in FIG. 17B, the second support substrate 5 on the upper side is peeled off, and further, as shown in FIG. 17C, a break C in the first support substrate 4 on the upper side. The inner peripheral portion P2 is peeled off, and a part of the electrolyte membrane 2 is exposed. As a result, only the frame-shaped outer peripheral portion P1 of the upper first support substrate 4 remains in the electrolyte membrane 2 to form the frame-shaped support substrate 4u. Moreover, you may perform peeling of the 2nd support base material 5, and peeling of the inner peripheral part of the cut | interruption C of the 1st support base material 4 simultaneously.

  Subsequently, as shown in FIGS. 18A and 18B, the catalyst layer is formed on the portion where the second portion P <b> 2 of the first support substrate 4 on the electrolyte membrane 2 is peeled off using the catalyst layer transfer film. 3u is formed. Subsequently, as shown in FIG. 18 (c), the lower second support substrate 5 is peeled, and as shown in FIG. 18 (d), the lower first support substrate 4 is removed. The inner peripheral portion P2 of the cut C is peeled off, and a part of the electrolyte membrane 2 is exposed.

  Subsequently, as shown in FIGS. 19A and 19B, the catalyst layer is formed on the portion where the second portion P <b> 2 of the first support substrate 4 on the electrolyte membrane 2 is peeled off using the catalyst layer transfer film. 3d is formed. Thereby, the catalyst layer-electrolyte membrane laminated body 1a is produced. Thus, in the catalyst layer-electrolyte membrane laminate 1a according to the modification of the present embodiment, since the electrolyte membrane 2 is supported by the support base materials 4u and 4d, the catalyst layers 3u and 3d are transferred to the electrolyte membrane 2. The dimensional change of the electrolyte membrane 2 at the time of performing can be suppressed.

  In addition, the order which forms a catalyst layer is not restricted to the above-mentioned flow. For example, as shown in FIGS. 20A to 20D, the second supporting base on both surfaces of the electrolyte membrane 2 is first peeled, and then the second supporting base 4 on the electrolyte membrane 2 is second. The portion P2 may be peeled off to form the catalyst layer 3u and the catalyst layer 3d. According to such an order, since there is no supporting substrate on the electrolyte membrane on the side opposite to the transfer side, the portion where the catalyst layer of the electrolyte membrane is formed when transferring the catalyst layer (particularly the end of the catalyst layer). And the pressure can be applied to the entire electrolyte membrane relatively uniformly. As a result, thinning of the electrolyte membrane generated around the catalyst layer can be prevented.

(Modification 2 of catalyst layer-electrolyte membrane laminate)
FIG. 21 is a cross-sectional view showing a configuration of a catalyst layer-electrolyte membrane laminate 1b according to another modification of the present embodiment. Compared with the catalyst layer-electrolyte membrane laminate 1b shown in FIG. 14 (c), the catalyst layer-electrolyte membrane laminate 1b has pin holes P formed on the outer peripheral edge of the electrolyte membrane 2 and the support base 4d. Is different. By forming the pin holes in this way, the positioning of the catalyst layers formed on both surfaces becomes easy.

  22-24 is explanatory drawing which shows an example of the manufacturing method of the catalyst layer-electrolyte membrane laminated body 1b. First, as shown in FIG. 22, the catalyst layer transfer film substrate 6 is overlapped and aligned with the electrolyte membrane 7 with a support substrate according to the first embodiment, and the outer peripheral edge of the catalyst layer transfer film substrate 6, the electrolyte membrane Two pin holes P penetrating in the thickness direction are formed in the outer peripheral edge portion 2, the outer peripheral portion P 1 of the first support base material 4, and the outer peripheral portion P 3 of the second support base material 5 with a die cutter. Note that the pin hole P does not necessarily reach the second support base 5. Further, the number of pin holes P is not particularly limited as long as the catalyst layer can be positioned.

  Subsequently, as shown in FIG. 23A, the second support substrate 5 is peeled off. Subsequently, as shown in FIG. 23 (b), the laminated body of the electrolyte membrane 2 and the first support substrate 4 is fixed to the pin hole P through the pin 8, and the pin hole as shown in FIG. 23 (c). The catalyst layer transfer film substrate 6 provided with the above is laminated from above the electrolyte membrane 7 with a supporting substrate so that the electrolyte membrane 2 and the catalyst layer 3 face each other. In this state, heat pressing is performed to transfer the catalyst layer 3 to the electrolyte membrane 2 to form a catalyst layer 3u as shown in FIG.

  Subsequently, by peeling off the inner peripheral portion P2 of the first support base material 4, a part of the electrolyte membrane 2 is exposed as shown in FIG. Furthermore, as shown in FIG. 24B, the catalyst layer-electrolyte film laminate 1b is produced by forming the catalyst layer 3d in the portion where the electrolyte membrane 2 is exposed. Thus, in the manufacturing process of the catalyst layer-electrolyte membrane laminate 1b, by providing the pin holes P in the electrolyte membrane 7 with the supporting base material, the positional accuracy when the catalyst layers are formed on both surfaces of the electrolyte membrane 2 is further increased. Can be increased.

  In this modification, pin holes are formed in a state where the catalyst layer transfer film substrate 6 and the electrolyte membrane 7 with a supporting substrate are overlapped, but the catalyst layer transfer film substrate 6 and the electrolyte membrane 7 with a supporting substrate are formed. Can be formed so that the relative positions of the pin holes are the same, the pin holes can be individually formed on the catalyst layer transfer film substrate 6 and the electrolyte membrane 7 with a supporting substrate. Good.

  In addition, the technique which improves the position accuracy of a catalyst layer is not limited to this. For example, an alignment mark may be provided on the electrolyte membrane and the alignment of the catalyst layer and the electrolyte membrane may be performed using the alignment mark.

(Modification 3 of catalyst layer-electrolyte membrane laminate)
25 (a) and 25 (b) show a catalyst layer-electrolyte membrane laminate 1c produced using the electrolyte membrane 7b with a supporting base shown in FIG. 10 (a), and still another modification of this embodiment. The catalyst layer-electrolyte membrane laminated body 1c which concerns on an example is shown. That is, FIG. 25A corresponds to the surface of FIG. 10B, and the support base 4 u extending in the vertical direction is formed on two sides sandwiching the catalyst layer 3 u on one surface of the electrolyte membrane 2. FIG. 25C corresponds to the surface of FIG. 10C, and a support base 4d extending in the lateral direction is formed on two sides with the catalyst layer 3d interposed therebetween. Thus, since the electrolyte membrane 2 is supported by the support bases 4u and 4d, when the catalyst layers 3u and 3d are transferred to the electrolyte membrane 2, the dimensional change of the electrolyte membrane 2 can be suppressed.

When the electrolyte membrane 2 is long, a rectangular catalyst layer 3 may be formed in a plurality of patterns on the electrolyte membrane 2 as in the catalyst layer-electrolyte membrane laminate 1d shown in FIG. Alternatively, the long catalyst layer 3 may be continuously formed as in the catalyst layer-electrolyte membrane laminate 1e shown in FIG. In this case, since a long catalyst layer-electrolyte membrane laminate is produced, it can be cut at an appropriate location and incorporated into the battery.

  As described above, in this embodiment, the catalyst layer may be transferred to the electrolyte layer using the catalyst layer transfer film (transfer method), or the catalyst layer may be directly applied to the electrolyte layer. Further, as in the catalyst layer-electrolyte membrane laminate 1 f shown in FIG. 27A, a form in which no gap is generated between the catalyst layers 3 u and 3 d and the support base materials 4 u and 4 d may be used.

  Further, like the catalyst layer-electrolyte membrane laminate 1g shown in FIG. 27 (b), the catalyst layers 3u and 3d may be formed so as to protrude from the inner peripheral portions of the support bases 4u and 4d.

(Manufacture of polymer electrolyte fuel cells)
A polymer electrolyte fuel cell is produced by laminating a gas diffusion layer on the catalyst layer-electrolyte membrane laminate produced by the above method and sandwiching it with a separator with a gasket interposed as necessary. be able to. In the case where the first portion of the first support substrate is incorporated into the battery while leaving the first portion, and the first portion of the first support substrate has the function of a gasket, the catalyst is not interposed without interposing the gasket. The layer-electrolyte membrane laminate can be sandwiched between separators. Moreover, when the 1st part of the 1st support base material does not have the function of a gasket, or when the 1st part of the 1st support base material is removed from the said catalyst layer-electrolyte membrane laminated body It is desirable that the catalyst layer-electrolyte membrane laminate is sandwiched by the separator in a state where a gasket is interposed between the support substrate of the catalyst layer-electrolyte membrane laminate and the separator.

(Additional notes)
The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope described in the claims. For example, technical means disclosed in different embodiments are appropriately combined. The form obtained in this manner is also included in the technical scope of the present invention.

  Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto.

<Production of electrolyte membrane with supporting substrate>
First, two rectangular planar polyethylene naphthalates (length 7.5 cm × width 7.5 cm, thickness 30 μm) were prepared as a first support base and a second support base, and these support bases Were laminated together to produce a laminate of the first support substrate and the second support substrate. Further, a rectangular cut having a length of 5.2 cm and a width of 5.2 cm was formed only on the first supporting substrate using a die cutter.

  Moreover, “Nafion N211” (registered trademark) manufactured by DuPont was used as the electrolyte membrane. The size of the electrolyte membrane is 7.5 cm long × 7.5 cm wide, and the thickness is 25 μm. The electrolyte membrane is attached to the surface of the first support substrate opposite to the surface on which the second support substrate is bonded, and hot-pressed at 120 ° C. to produce an electrolyte membrane with a support substrate. did.

<Production of catalyst layer-electrolyte membrane laminate>
Then, the catalyst layer-electrolyte film | membrane laminated body was produced from the above-mentioned electrolyte membrane with a support base material in the following ways.

  First, the 2nd support base material of the electrolyte membrane with a support base material was peeled using the cello tape (trademark). Furthermore, the inner peripheral part (second part) of the cut of the first supporting substrate was peeled off using cello tape (registered trademark).

  Subsequently, the electrolyte membrane with a supporting substrate was hot-pressed under the conditions of 160 ° C., 4 MPa, and 120 seconds. As a result, pressure was applied only to the outer peripheral portion of the electrolyte membrane with a supporting substrate, and the adhesive strength between the outer peripheral portion of the electrolyte membrane and the electrolyte membrane could be increased.

Then, the catalyst layer was formed in the electrolyte membrane part which peeled the 2nd part from the 1st support base material side on an electrolyte membrane by the transfer method. In this example, a catalyst layer was formed using a catalyst layer transfer film prepared as follows. Specifically, 4 g of platinum catalyst-supporting carbon particles (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., “TEC10E50E”), 40 g of an ion conductive polymer electrolyte membrane solution (Nafion 5 wt% solution: “DE-520” manufactured by DuPont), distillation A paste composition for forming a catalyst layer was prepared by blending 12 g of water, 20 g of n-butanol and 20 g of t-butanol, and stirring and mixing with a disperser. Next, the catalyst layer forming paste composition was coated on a Teflon (registered trademark) substrate using an applicator and dried at 95 ° C. for 30 minutes to prepare a catalyst layer transfer film. In addition, the coating amount of the catalyst layer was such that the amount of platinum supported was about 0.5 mg / cm ² . Further, the catalyst layer transfer film was cut into a size of 5 cm × 5 cm and arranged so that the inner peripheral portion of the first support substrate on the electrolyte membrane was accommodated in the peeled portion. Then, the anode catalyst layer was formed in the electrolyte membrane by heat-pressing on 135 degreeC, 4 Mpa, and 120 second conditions, and peeling the Teflon (trademark) base material of a catalyst layer transfer film. Similarly, a catalyst layer transfer film was prepared, and a cathode catalyst layer was formed on the electrolyte membrane opposite to the anode catalyst layer by a transfer method.

  In this example, the dimensional stability of the electrolyte membrane when forming the catalyst layer could be further improved by increasing the adhesive strength between the outer periphery of the electrolyte membrane and the electrolyte membrane by hot pressing.

DESCRIPTION OF SYMBOLS 1, 1a-1g Catalyst layer-electrolyte membrane laminated body 2 Electrolyte membrane 3 Catalyst layer 3u Catalyst layer 3d Catalyst layer 4 1st support base material 4u Support base material 4d Support base material 5 2nd support base material 6 Catalyst layer transfer Film substrate 7, 7a-7c Electrolyte membrane with support substrate 8 Pin A Adhesive C Cut P Pin hole

Claims (5)

An electrolyte membrane;
A first support substrate formed on at least one surface of the electrolyte membrane;
A second support substrate bonded to a surface opposite to the surface bonded to the electrolyte membrane of the first support substrate;
The first support base is formed with a cut that separates a first portion including at least a part of the outer peripheral edge portion and a second portion excluding the first portion. Electrolyte membrane with substrate.   The electrolyte membrane with a supporting base material according to claim 1, wherein at least a part of the cut reaches a part in a thickness direction of the second supporting base material.   3. The support base according to claim 1, wherein at least a part of the first portion has a higher adhesive strength to the electrolyte membrane than a portion adjacent to the cut of the second portion. Electrolyte membrane with material. A first step of bonding the first support substrate and the second support substrate;
The first support base material bonded to the second support base material is formed with a cut that separates the first portion including at least part of the outer peripheral edge portion and the second portion excluding the first portion. A second step of
A third step of forming an electrolyte membrane on the surface of the first support substrate opposite to the surface on which the second support substrate is bonded;
The manufacturing method of the electrolyte membrane with a support base material characterized by having. A first support substrate bonded to at least one surface of the electrolyte membrane; and a second support substrate bonded to a surface of the first support substrate opposite to the surface bonded to the electrolyte membrane. And the first supporting base material is provided with a support base-provided electrolyte in which a first portion including at least a part of the outer peripheral edge portion and a second portion excluding the first portion are separated. Preparing a membrane;
Peeling the second support substrate;
Peeling the second portion of the first support substrate;
Forming a catalyst layer on a portion where the second portion of the first support substrate on the electrolyte membrane is peeled off;
A method for producing a catalyst layer-electrolyte membrane laminate, comprising: