JP5799730B2 - Manufacturing method of electrolyte membrane - Google Patents

Description

  The present invention relates to a method for manufacturing an electrolyte membrane.

  A polymer electrolyte fuel cell (hereinafter simply referred to as “fuel cell”) includes a membrane electrode assembly (MEA) in which electrodes are arranged on both surfaces of an electrolyte membrane. Electrolyte membranes used in fuel cells tend to be thinned in order to improve ionic conductivity, but thinned electrolyte membranes have low mechanical strength, so workability and handleability are reduced. . Therefore, when transporting such a thin electrolyte membrane, workability and handleability are improved by bringing a support material such as a highly rigid backup film into close contact with the entire surface of the electrolyte membrane.

  However, when such a support material and the electrolyte membrane are closely adhered to each other, when the electrolyte membrane is peeled from the support material, a tensile stress is applied to the electrolyte membrane, thereby causing the electrolyte membrane to contract in the film width direction (hereinafter, “ Also known as “neck-in”), wrinkles, and deflection. For example, Patent Document 1 discloses a technique for holding an outer peripheral portion of an electrolyte membrane with a reinforcing planar material. However, although this technique suppresses the generation of wrinkles due to swelling and shrinkage of the electrolyte membrane that occurs during power generation of the fuel cell, when the central portion of the reinforcing planar material is peeled off from the electrolyte membrane. The deformation of the electrolyte membrane that occurs in the above was not considered. Such a problem is not limited to solid polymer fuel cells, but is common to fuel cells using thin electrolyte membranes, such as direct methanol fuel cells.

JP 2010-027227 A JP 2002-280012 A

  In view of the above-described problems, the problem to be solved by the present invention is to provide a method for manufacturing an electrolyte membrane capable of suppressing deformation such as neck-in, wrinkles, and deflection.

SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following forms or application examples.
A first aspect of the present invention is a method for producing an electrolyte membrane comprising a reinforcing material,
A first support member in which at least two first adhesive members in which a plurality of adhesive layers are bonded to each other with a first adhesive strength are arranged on the same surface at a predetermined interval; and a second adhesive member A first step of preparing at least two second support members arranged on the same surface at a predetermined interval,
Bonding a first reinforcing material between the at least two first adhesive members with a second adhesive strength greater than the first adhesive strength on the at least two first adhesive members, A second step of adhering the second reinforcing material on the at least two second adhesive members across the at least two second adhesive members;
The electrolyte membrane material precursor is bonded to the first reinforcing material on the first adhesive member and the second reinforcing material on the second adhesive member via an electrolyte membrane material precursor. The body is sandwiched between the first reinforcing member and the second reinforcing member, and further, the first supporting member to which the first adhesive member is bonded and the second adhesive member are bonded to each other. A third step of generating a first intermediate member sandwiched by the second support material;
The second support material, the at least two second adhesive members, and the second reinforcing material are separated from the first intermediate member by peeling a predetermined adhesive layer in each of the first adhesive members. And a fourth step of separating a second intermediate member having the electrolyte membrane material precursor, the first reinforcing material, and a part of the first adhesive member;
Between the at least two second adhesive members of the second intermediate member, the first reinforcing material, the electrolyte membrane material precursor, and the second reinforcing material on the at least two second adhesive members. A fifth step of cutting the material;
It is a manufacturing method provided with.

[Application Example 1] A method of manufacturing an electrolyte membrane including a reinforcing material, wherein a plurality of adhesive layers are bonded to each other in a multilayer with a first adhesive strength with a predetermined interval on the same surface. A first step of preparing at least two first support members disposed; and a second support member having at least two second adhesive members disposed on the same surface at a predetermined interval; Bonding a first reinforcing material between the at least two first adhesive members with a second adhesive strength greater than the first adhesive strength on the at least two first adhesive members, A second step of adhering a second reinforcing material across at least two second adhesive members across at least two second adhesive members; and the first reinforcement on the first adhesive member The material and the second reinforcing material on the second adhesive member are bonded together via an electrolyte membrane Thus, the electrolyte membrane is sandwiched between the first reinforcing member and the second reinforcing member, and further, the first supporting member to which the first adhesive member is bonded and the second bonding member. A third step of generating a first intermediate member sandwiched by the second support material to which the member is bonded, and peeling a predetermined adhesive layer in each of the first adhesive members, From the first intermediate member, one of the second support member, the at least two second adhesive members, the second reinforcing member, the electrolyte membrane, the first reinforcing member, and the first adhesive member. Between the at least two second adhesive members of the second intermediate member, and a fourth step of separating the second intermediate member having a portion between the at least two second adhesive members. A fifth step of cutting the reinforcing material of 1, the electrolyte membrane, and the second reinforcing material; Manufacturing method to obtain.

  With such a configuration, the first reinforcing member is bonded across at least two first adhesive members on the first support member, and at least two second members on the second support member are bonded. Since the first reinforcing material and the second reinforcing material are bonded to each other through the electrolyte membrane after the second reinforcing material is bonded across the adhesive members, it is generated when the reinforcing material or the electrolyte membrane is conveyed. Deformation can be suppressed. Further, since the first reinforcing material, the electrolyte membrane, and the second reinforcing material are cut between the second adhesive members, deformation such as neck-in, wrinkles, and deflection is suppressed, and both surfaces are reinforced with the reinforcing material. In addition, a highly strong electrolyte membrane can be obtained.

Application Example 2 In the manufacturing method according to Application Example 1, before the third step, the first reinforcing material bonded onto the first adhesive member is further removed from the surface of the first reinforcing material. A manufacturing method comprising a step of cutting up to the predetermined adhesive layer in one adhesive member. With such a manufacturing method, the second intermediate member can be easily separated from the first intermediate member at the location where the cut is made.

Application Example 3 The manufacturing method according to Application Example 1 or 2, wherein at least a part of the first intermediate member from which the second intermediate member is separated in the fourth step is used as the first step. The manufacturing method used as said 1st support material prepared by. With such a manufacturing method, the first support member from which the second intermediate member has been separated can be reused for manufacturing the electrolyte membrane, so that the cost for manufacturing the electrolyte membrane can be reduced. .

[Application Example 4] The manufacturing method according to any one of application examples from Application Example 1 to Application Example 3, wherein the first reinforcing material, the electrolyte membrane, and the second reinforcement in the fifth step. The second support member and the second adhesive member disposed on the second support member are separated from the second intermediate member after the material is cut, and the separated A manufacturing method in which a second support member and the second adhesive member disposed on the second support member are used as the second support member prepared in the first step. With such a manufacturing method, since the second support member and the second adhesive member can be reused for manufacturing the electrolyte membrane, the cost for manufacturing the electrolyte membrane can be reduced.

[Application Example 5] The manufacturing method according to any one of Application Examples 1 to 4, further comprising: the first reinforcing material cut in the fifth step; the electrolyte membrane; A manufacturing method comprising the step of impregnating the second reinforcing material with an electrolyte to impart ion conductivity. If it is such a manufacturing method, it can utilize as an electrolyte membrane of a fuel cell by impregnating the cut reinforcing material and electrolyte membrane with an electrolyte and imparting ion conductivity.

  The present invention can be realized in various forms in addition to the above-described method for manufacturing an electrolyte membrane. For example, realized in the form of an apparatus for manufacturing an electrolyte membrane, a membrane electrode assembly equipped with an electrolyte membrane, a fuel cell equipped with a membrane electrode assembly, a fuel cell system equipped with a fuel cell, a vehicle equipped with a fuel cell system, etc. You can also

It is a fragmentary sectional view which shows schematic structure of a fuel cell provided with the electrolyte membrane manufactured by the manufacturing method as one Embodiment of this invention. It is a flowchart which shows the manufacturing method of an electrolyte membrane provided with a reinforcing material. It is a schematic diagram for demonstrating the mode of the 1st support material in step S10. It is a schematic diagram for demonstrating the mode of the 2nd support material in step S10. It is a schematic diagram for demonstrating a mode that the 1st reinforcement material in step S20 is adhere | attached. It is a schematic diagram for demonstrating a mode that the 2nd reinforcement material in step S20 is adhere | attached. It is a schematic diagram for demonstrating step S40. It is a schematic diagram for demonstrating step S50. It is the figure which showed a mode that the 1st reinforcement material and the 2nd reinforcement material were bonded together via the electrolyte membrane material precursor in step S50. It is a schematic diagram for demonstrating step S60. It is a schematic diagram for demonstrating step S70. It is a schematic diagram for demonstrating step S90. It is a schematic diagram for demonstrating step S100. It is the schematic diagram which showed a mode that a support material was reused. It is the figure which showed the measurement result of the neck-in amount of an electrolyte membrane. It is the figure which showed the relationship between the cycle number of a fuel cell, and cell voltage. It is the figure which showed the manufacturing method of the electrolyte membrane when not making a notch | incision to the predetermined adhesion layer of a 1st adhesion member. It is the figure which showed the manufacturing method of the electrolyte membrane when notching from the top of the electrolyte membrane material precursor. It is the figure which showed a mode that the 1st reinforcement material, electrolyte membrane material precursor, and the 2nd reinforcement material were cut | disconnected on the 2nd adhesion member.

A. Configuration of fuel cell with electrolyte membrane:
FIG. 1 is a partial cross-sectional view showing a schematic configuration of a fuel cell 100 including an electrolyte membrane manufactured by a manufacturing method according to an embodiment of the present invention. The fuel cell 100 is a solid polymer fuel cell that generates electric power by receiving supply of a fuel gas (for example, hydrogen) and an oxidant gas (for example, oxygen) as reaction gases. The fuel cell 100 has a stack structure in which a plurality of single cells 30 are stacked.

  The unit cell 30 includes a membrane electrode assembly 20 having an electrolyte membrane 10 and an anode side electrode 31a and a cathode side electrode 31c formed on both surfaces of the electrolyte membrane 10, respectively. The membrane electrode assembly 20 includes an anode side gas diffusion layer 32a on one surface and a cathode side gas diffusion layer 32c on the other surface. The anode side gas diffusion layer 32a includes an anode side separator 33a and a cathode side gas diffusion layer 32c. The gas diffusion layer 32c is adjacent to the cathode side separator 33c. A fuel gas flow path 34a is formed between the anode side gas diffusion layer 32a and the anode side separator 33a, and an oxidant gas flow path 34c is formed between the cathode side gas diffusion layer 32c and the cathode side separator 33c. Yes.

  The electrolyte membrane 10 is a fluororesin-based ion exchange membrane that exhibits good proton conductivity in a wet state, and in the present embodiment, the first reinforcing material 12a is disposed on the anode side surface of the electrolyte membrane material 11, It has a three-layer structure in which the second reinforcing material 12c is disposed on the cathode side surface. The electrolyte membrane material 11 constituting the electrolyte membrane 10 is a polymer electrolyte membrane formed of a fluorine-based sulfonic acid polymer as a solid polymer material, and has good proton conductivity in a wet state. In the present embodiment, Nafion (manufactured by DuPont: registered trademark) is used as the electrolyte membrane material 11. The first reinforcing material 12 a and the second reinforcing material 12 c are layers having proton conductivity in which a porous film is impregnated with an electrolyte, and are members that reinforce the electrolyte membrane material 11. In the present embodiment, PTFE (polytetrafluoroethylene) formed in a thin film shape is used as the first reinforcing member 12a and the second reinforcing member 12c. Hereinafter, the first reinforcing material 12a and the second reinforcing material 12c are collectively referred to simply as the reinforcing material 12.

  The anode side electrode 31a and the cathode side electrode 31c include carbon particles carrying a catalyst such as platinum or a platinum alloy, and a solid polymer electrolyte resin exhibiting proton conductivity. The anode side gas diffusion layer 32a and the cathode side gas diffusion layer 32c are formed of a material having gas permeability and conductivity. As a material of the anode side gas diffusion layer 32a and the cathode side gas diffusion layer 32c, for example, a carbon-based porous body such as carbon paper or carbon cloth, or a metal porous body such as a metal mesh or foam metal can be used.

  The anode side separator 33a and the cathode side separator 33c are formed of members having gas barrier properties and electronic conductivity. In the present embodiment, the anode-side separator 33a and the cathode-side separator 33c are formed of dense carbon that has been made to be gas impermeable by compressing carbon. The anode side separator 33a and the cathode side separator 33c can be formed of a metal member such as press-formed stainless steel in addition to a carbon member such as dense carbon.

The fuel gas flow path 34a is formed between the anode side gas diffusion layer 32a and the anode side separator 33a, and the oxidant gas flow path 34c is formed between the cathode side gas diffusion layer 32c and the cathode side separator 33c. The fuel gas flow path 34a is a hydrogen (H ₂ ) gas flow furnace, and the oxidant gas flow path 34c is an oxygen (O ₂ ) gas flow path.

B. First embodiment:
B-1. Manufacturing method of electrolyte membrane:
FIG. 2 is a flowchart showing a method for manufacturing the electrolyte membrane 10 including the reinforcing material 12. Hereafter, each step of the manufacturing method of the electrolyte membrane shown in FIG. 2 is demonstrated using FIGS. Step S10 is the first process of the present application, step S20 is the second process of the present application, step S50 is the third process of the present application, step S60 is the fourth process of the present application, and step S70 is the fifth process of the present application. It corresponds to each.

  3 and 4 are schematic diagrams for explaining step S10. FIG. 3 shows the state of the first support member 4a, and FIG. 4 shows the state of the second support member 4c. In step S10, at least two first support members 4a (FIG. 3) in which at least two first adhesive members 3a are arranged on the same surface at a predetermined interval, and second adhesive members 3c are on the same surface. At least two second support members 4c (FIG. 4) arranged at a predetermined interval are prepared. Hereinafter, the first support member 4a and the second support member 4c are collectively referred to simply as “support member 4”. Further, the first adhesive member 3a and the second adhesive member 3c are collectively referred to simply as “adhesive member 3”.

  The support material 4 has a property of being higher in rigidity than the reinforcing material 12 included in the electrolyte membrane 10, and retains the shapes of the reinforcing material 12 and the electrolyte membrane material 11 and conveys them without deformation such as neck-in, wrinkles, and deflection. It is used as a transport material. As the support material 4, for example, a backup film such as PET (polyethylene terephthalate), PP (polypropylene), PEI (polyetherimide), PI (polyimide), or fluororesin formed in a film shape can be used.

  The adhesive member 3 is used for bonding the reinforcing material 12 and the support material 4 together. As shown in FIG. 3, the first adhesive member 3a has a multilayer structure in which four layers (3aa, 3ab, 3ac, 3ad) of adhesive layers are laminated in this embodiment. As shown in FIG. 4, the second adhesive member 3c is composed of one adhesive layer in the present embodiment. The interval at which the adhesive member 3 is disposed on the support member 4 (refers to the distance from the end of one adhesive member 3 to the end of the other adhesive member 3, "L1a" in FIG. 3, "L1c" in FIG. In the following description, “L1a” and “L1c” are also simply referred to as “L1”.) In step S70 described later, the electrolyte membrane 10 is cut from the second support material 4c. The interval is wider than the width (for example, the length indicated by “L2” in FIGS. 3 and 4). In the present embodiment, the distance “L1a” between the first adhesive members 3a disposed on the first support member 4a and the distance “L1c” between the second adhesive members 3c disposed on the second support member 4c. "Is the same, but the intervals may be different as long as the intervals are wider than the width" L2 "for cutting the electrolyte membrane 10 from the second support material 4c. As the adhesive member 3, for example, a tape having a width of several mm to 20 mm using silicone rubber as a base material can be used. As the adhesive member 3, a tape using a natural rubber, an acrylate copolymer or the like as a base material may be used.

  After preparing the support member 4 provided with the adhesive member 3 on the same surface, the reinforcing material 12 is disposed on the adhesive member 3 and bonded in step S20. 5 and 6 are schematic diagrams for explaining step S20. FIG. 5 shows a state in which the first reinforcing member 12a is disposed and bonded to the first supporting member 4a across the first bonding member 3a, and FIG. 6 shows the second bonding to the second supporting member 4c. The mode that the 2nd reinforcement material 12c is arrange | positioned ranging over between the members 3c is shown. The adhesive layer 3aa and the first reinforcing member 12a are bonded with a larger adhesive strength (strength necessary for peeling the bonded member) than the adhesive layer 3aa and the adhesive layer 3ab. The adhesive strength between the adhesive layer 3aa and the adhesive layer 3ab corresponds to the “first adhesive strength” of the present application, and the adhesive strength between the adhesive layer 3aa and the first reinforcing member 12a corresponds to the “second adhesive strength” of the present application. . As shown in FIGS. 5 and 6, the reinforcing member 12 is disposed so as to straddle between the adhesive members 3, and thus is not in close contact with the support member 4 between the adhesive members 3. Further, the reinforcing material 12 is arranged on the supporting material 4 without wrinkles or deflection via the adhesive member 3 due to the high rigidity of the supporting material 4.

  When the reinforcing material 12 is disposed across the adhesive member 3 on the support material 4, the reinforcing material 12 is conveyed to a predetermined processing position by the support material 4 (step S30). The reinforcing material 12 is conveyed in a state in which deformation such as neck-in, wrinkles, and deflection is suppressed by the high rigidity of the support material 4.

  FIG. 7 is a schematic diagram for explaining step S40. In step S40, the four layers included in the first adhesive member 3a from the surface side of the first reinforcing member 12a bonded across the first adhesive member 3a disposed on the first support member 4a. Of the adhesive layers (3aa, 3ab, 3ac, 3ad) are cut by the cutter 9 to between the adhesive layer 3aa and the adhesive layer 3ab. The cut can be made to a deeper layer (for example, between the adhesive layer 3ac and the adhesive layer 3ad) than between the adhesive layer 3aa and the adhesive layer 3ab. As shown in FIG. 7, the location where the cutter 9 cuts from the surface of the first reinforcing member 12a is on the first adhesive member 3a. Therefore, the cut first reinforcing member 12a is It remains arranged on the first support member 4a via one adhesive member 3a.

  FIG. 8 is a schematic diagram for explaining step S50. In step S50, between the 1st reinforcement material 12a arrange | positioned ranging over between the 1st adhesion members 3a with which the 1st support material 4a is provided, and the 2nd adhesion members 3c with which the 2nd support material 4c is provided. The second reinforcing material 12c disposed across the substrate is bonded together via the precursor of the electrolyte membrane material 11. The precursor of the electrolyte membrane material 11 (hereinafter also referred to as the electrolyte membrane material precursor 11f) means the electrolyte membrane material 11 before being given ion conductivity. As shown in FIG. 8, the first reinforcing material 12a, the electrolyte membrane material precursor 11f, and the second reinforcing material 12c may be bonded together at the same time through the electrolyte membrane material precursor 11f. Alternatively, the electrolyte membrane material precursor 11f may be disposed on the first reinforcing material 12a or the second reinforcing material 12c in advance by, for example, extrusion molding and then bonded.

  FIG. 9 shows a step S50 in which the first reinforcing member 12a disposed across the first adhesive member 3a provided in the first support member 4a and the second adhesive member provided in the second support member 4c are provided. It is the figure which showed a mode that the 2nd reinforcement material 12c arrange | positioned ranging over between 3c was bonded together via the electrolyte membrane material precursor 11f. Arranged across the first reinforcing member 12a disposed across the first adhesive member 3a provided in the first support member 4a and the second adhesive member 3c provided in the second support member 4c. A member obtained by bonding the second reinforcing material 12c thus bonded via the electrolyte membrane material precursor 11f is hereinafter also referred to as a “first intermediate member 50”. As shown in FIG. 9, the electrolyte membrane material precursor 11 f included in the first intermediate member 50 has a width for cutting the electrolyte membrane 10 from the second support material 4 c (the length indicated by “L2” in FIG. 9). It covers a wider width. In the first intermediate member 50, the first reinforcing member 12a is not in close contact with the first supporting member 4a between the first adhesive members 3a of the first supporting member 4a, and the second supporting member 4a Between the 2nd adhesion members 3c with which material 4c is provided, it has the structure where the 2nd reinforcement material 12c is not stuck to the 2nd support material 4c.

  FIG. 10 is a schematic diagram for explaining step S60. In step S60, between the adhesive layer 3aa and the adhesive layer 3ab, from the first intermediate member 50, the second support member 4c, the second adhesive member 3c, the second reinforcing member 12c, and the electrolyte membrane material precursor. 11f, the first reinforcing member 12a, and a part of the first adhesive member 3a are separated. The separated second support member 4c, second adhesive member 3c, second reinforcing member 12c, electrolyte membrane material precursor 11f, first reinforcing member 12a, and part of the first adhesive member 3a, It is also referred to as “second intermediate member 60”. Specifically, in the present embodiment, among the first adhesive members 3a on the first support member 4a, inside the adhesive layer 3aa that has been cut in step S40, the first intermediate member 50 The second intermediate member 60 is separated. As shown in FIG. 10, on the second support material 4c after separation, the second reinforcing material 12c straddling the second adhesive member 3c, and the electrolyte membrane material precursor 11f on the reinforcing material 12c, The first reinforcing material 12a is disposed on the electrolyte membrane material precursor 11f, and a part of the adhesive layer 3aa cut in step S40 remains at both ends of the first reinforcing material 12a. . On the other hand, a part of the adhesive layer 3aa and the adhesive layers 3ab, 3ac, 3ad are arranged on the first support material 4a, and the first reinforcing material 12a is provided on a part of the adhesive layer 3aa. A part of remains.

  FIG. 11 is a schematic diagram for explaining step S70. In step S70, the first reinforcing member 12a, the electrolyte membrane material precursor 11f, and the second adhesive member 3c included in the second intermediate member 60 separated from the first intermediate member 50 in step S60 are used. The two reinforcing members 12c are cut with a cutter 9, for example. As shown in FIG. 11, the location where the laminate composed of the first reinforcing material 12a, the electrolyte membrane material precursor 11f, and the second reinforcing material 12c is cut is between the second adhesive members 3c. This is a portion that is not in close contact with the support material 4c. Further, the width to be cut is the width indicated by “L2” in FIGS. 3, 4, and 9. Therefore, the laminated body including the cut first reinforcing material 12a, the electrolyte membrane material precursor 11f, and the second reinforcing material 12c has a first adhesive member on the first reinforcing material 12a as shown in FIG. This is a laminate in which 3a is not bonded and the second adhesive member 3c is not bonded to the second reinforcing member 12c. The laminated body including the first reinforcing material 12a, the electrolyte membrane material precursor 11f, and the second reinforcing material 12c may be separated from the second support material 4c after being cut as shown in FIG. Since the film material precursor 11f has a certain degree of adhesive strength, it is integrated to the extent that the laminated shape is maintained.

  By performing steps S10 to S70 described above, the electrolyte membrane 10 in which the first reinforcing material 12a, the electrolyte membrane material precursor 11f, and the second reinforcing material 12c are laminated can be obtained. The electrolyte membrane 10 obtained by laminating the first reinforcing material 12a, the electrolyte membrane material precursor 11f, and the second reinforcing material 12c obtained in the present embodiment is a second portion of the second supporting material 4c. In order to cut the width indicated by “L2” in FIG. 3, FIG. 4 and FIG. 9 between the adhesive members 3c at locations where they are not in close contact with the support material 4, as shown in FIG. The support material 4 is not provided.

Next, after impregnating the electrolyte into the electrolyte membrane 10 in which the reinforcing material 12 and the electrolyte membrane material precursor 11f obtained in step S70 are laminated, ion conductivity is imparted by hydrolysis (step S80). For example, the electrolyte impregnation is performed by applying a solution containing the electrolyte material to the electrolyte membrane 10 in which the first reinforcing material 12a, the electrolyte membrane material precursor 11f, and the second reinforcing material 12c are laminated, and then on the transfer roll. By applying heat. As the electrolyte, for example, a fluorine-based solid polymer electrolyte such as a fluorine-based sulfonic acid polymer can be used. Thereafter, ion conductivity is imparted to the electrolyte membrane 10 impregnated with the electrolyte. For example, the ionic conductivity is obtained by first immersing the electrolyte membrane 10 in which the first reinforcing material 12a, the electrolyte membrane material precursor 11f, and the second reinforcing material 12c impregnated with an electrolyte are laminated in an alkaline solution (NaOH solution). Then, the —SO ₂ F group of the reinforcing material 12 and the electrolyte membrane material precursor 11 f is modified to —SO ₃ Na group. Thereafter, they can be imparted by washing them with water and immersing them in an acidic solution (H ₂ SO ₄ solution and H ₂ NO ₃ solution) to modify —SO ₃ Na groups to —SO ₃ H groups.

  By performing step S80, the electrolyte membrane 10 impregnated with an electrolyte and imparted with ion conductivity can be obtained. By forming the anode side electrode 31a and the cathode side electrode 31c on both surfaces of the electrolyte membrane 10, the membrane electrode assembly 20 shown in FIG. 1 can be obtained.

B-2. Reuse of support material:
FIG. 12 is a schematic diagram for explaining step S90 shown in the flowchart of FIG. In step S90, a part of the first adhesive member 3a and a part of the first reinforcing member 12a are peeled from the first intermediate member 50 after the second intermediate member 60 is separated in step S60. Specifically, in the present embodiment, the adhesive layer 3aa remaining on the first support material 4a in step S60 and the first reinforcing material 12a on the adhesive layer 3aa (hereinafter referred to as the first support material 4a). The adhesive layer 3aa and the first reinforcing material 12a remaining on the upper surface are also collectively referred to as a “first end material”) and peeled off from the first support material 4a. When the first end material is peeled, only the adhesive layers 3ab, 3ac, and 3ad remain on the first support material 4a. Therefore, the first support material 4a from which the first end material is peeled is removed by the above step. It can be reused as the first support material 4a used in S10. In step S90, if the adhesive layer 3aa has a sufficient area to dispose the first reinforcing member 12a on the first supporting member 4a without neck-in, wrinkles, or deflection, the first reinforcing member Only the material 12a is peeled off from the first support material 4a, and the first support material 4a including a part of the adhesive layer 3aa and the adhesive layers 3ab, 3ac, and 3ad is used in the step S10. May be reused as

  FIG. 13 is a schematic diagram for explaining step S100 shown in the flowchart of FIG. In step S100, the second support member 4c and the second adhesive member 3c are separated from the second intermediate member 60 after the reinforcing material 12 and the electrolyte membrane material precursor 11f are cut. Specifically, in this embodiment, after cutting the electrolyte membrane 10 in step S70, as shown in FIG. 13, the adhesive layer 3aa remaining on the second support material 4c, the first reinforcing material 12a, and the electrolyte membrane material The precursor 11f and the second reinforcing material 12c (hereinafter, the adhesive layer 3aa remaining on the second supporting material 4c, the first reinforcing material 12a, the electrolyte membrane material precursor 11f, and the second reinforcing material 12c are collected. (Also referred to as “second end material”) is peeled off from the second adhesive member 3c. When the second end material is peeled off, only the second adhesive member 3c remains on the second support material 4c. Therefore, the second support material 4c from which the second end material is peeled is removed from the step S10. It can be reused as the second support material used in. Note that the order in which step S90 and step S100 are performed may not be the order shown in the flowchart of FIG. Step S90 may be performed after performing Step S100, or Step S90 and Step S100 may be performed simultaneously.

  FIG. 14 is a schematic diagram showing how the support material 4 is reused by performing Step S10 to Step S100. If it is the manufacturing method of the above electrolyte membrane 10, as shown in FIG. 14, the 1st support material 4a provided with the 1st adhesive member 3a in the process of manufacturing the electrolyte membrane 10, and the 2nd adhesive member 3c Since the electrolyte membrane 10 can be manufactured by circulating the second support material 4c provided with a belt conveyor or a line conveyor, the first support material 4a provided with the first adhesive member 3a and the second adhesive member It is not necessary to prepare the second support member 4c having 3c every time in step S10, and workability can be improved. In addition, since the electrolyte membrane 10 is manufactured by reusing the two support materials 4 of the first support material 4a and the second support material 4c, which are relatively expensive, the manufacturing cost of the electrolyte membrane 10 can be reduced. . Specifically, in step S90, the adhesive layers 3ab, 3ac, and 3ad are provided in which the adhesive layer 3aa remaining on the first support material 4a and the first reinforcing material 12a (first end material) are peeled off. The first support material 4a is reused as the first support material 4a used in step S10. Since the first adhesive member 3a is composed of four layers of adhesive layers 3aa, 3ab, 3ac, and 3ad, even if the first end material including the adhesive layer 3aa is peeled off in step S90 as described above, a new adhesive layer is formed. The electrolyte membrane 10 can be manufactured by using the remaining adhesive layers 3ab, 3ac, and 3ad included in the first support material 4a without disposing on the first support material 4a. When all of the first adhesive members 3a are peeled off from the first support material 4a, the first support material 4a can be reused repeatedly because it is only necessary to newly arrange the adhesive layers in multiple layers in step S10. Can do. Note that the timing of newly arranging the adhesive layer on the first support material 4a may not be after the first adhesive member 3a has been completely peeled off from the first support material 4a, and any timing may be set. Can be adopted. For example, a new adhesive layer 3aa and an adhesive layer 3ab may be disposed after the adhesive layer 3aa and the adhesive layer 3ab are peeled off.

  On the other hand, the second support material 4c can be reused as the second support material used in step S10 by peeling off the second end material on the second adhesive member 3c in step S100. Therefore, it is not necessary to prepare the second support member 4c including the second adhesive member 3c every time in step S10. If the adhesive force of the second adhesive member 3c is not sufficient to bond the second reinforcing member 12c, the adhesive force from the second support member 4c is sufficient in step S100. After the second adhesive member 3c that has disappeared is once peeled off, a new second adhesive member 3c can be arranged and circulated on the second support member 4c.

B-3. Experimental result:
FIG. 15 is a diagram showing a measurement result of the neck-in amount between the electrolyte membrane 10 produced in the present embodiment and the electrolyte membrane to be compared. The electrolyte membrane to be compared was an electrolyte membrane that was in close contact with the support material 4 and was produced as follows. First, the film-like first adhesive member 3a was bonded to the entire surface of the first support member 4a, and the first reinforcing member 12a was directly disposed thereon. Similarly, a film-like second adhesive member 3c was bonded to the entire surface of the second support member 4c, and the second reinforcing member 12c was directly disposed thereon. Next, the first reinforcing member 12a on the first supporting member 4a and the second reinforcing member 12c on the second supporting member 4c are overlapped with each other through the electrolyte membrane material precursor 11f. 3, the same width as the width “L2” shown in FIG. 4 and FIG. 9 is cut by the cutter 9, the reinforcing material 12 is provided on both surfaces of the electrolyte membrane material precursor 11 f, and the film-like adhesive member 3 is provided on both surfaces of the reinforcing material 12. However, the laminated body by which the supporting material 4 was bonded together on both surfaces of the adhesive member 3 was produced. Finally, the first adhesive member 3a, the first support member 4a, the second adhesive member 3c, and the second support member 4c are peeled from the laminate, and the first reinforcing member 12a and the electrolyte are peeled off. An electrolyte membrane in which the membrane material precursor 11f and the second reinforcing material 12c were bonded together was obtained. The electrolyte membrane thus produced was used as a comparative electrolyte membrane. The amount of necking-in of the electrolyte membrane is determined by measuring the width of the electrolyte membrane after fabrication with reference to the width (cut width) of each electrolyte membrane cut by the cutter 9, and the ratio of shrinkage with respect to the reference is as follows: Calculation was performed using equation (1).

((Cut width−width of electrolyte membrane after fabrication) / cut width) × 100 (1)

  As shown in FIG. 15, the neck-in amount of the electrolyte membrane to be compared is about 15%, whereas the neck-in amount of the electrolyte membrane 10 of this embodiment is less than 1%. From this result, it can be seen that the electrolyte membrane 10 produced in the present embodiment has a significantly reduced neck-in amount than the electrolyte membrane to be compared.

FIG. 16 illustrates the fuel cell 100 including the electrolyte membrane 10 manufactured in the present embodiment as “this embodiment product”, and the fuel cell including the comparison target electrolyte membrane as “comparison target product”. It is the figure which showed the relationship between and cell voltage. The number of cycles is the number of repetitions when the high temperature state and the low temperature state of the fuel cell are one cycle, and specifically means the number of repetitions when the start and stop of the fuel cell are one cycle. In this experimental example, the cell voltage was measured by setting the output current to 0.8 A / cm ² while repeating the cooling cycle in the temperature range from −20 ° C. to 80 ° C. As shown in FIG. 16, in the fuel cell 100 using the electrolyte membrane of the present embodiment, a decrease in cell voltage when the number of cycles is increased is suppressed as compared with a fuel cell including an electrolyte membrane to be compared. .

  When the fuel cell is repeatedly heated and cooled repeatedly, the electrolyte membrane repeatedly shrinks and swells, but the location where the electrolyte membrane is deformed due to neck-in, wrinkles, deflection, etc. is weak, so in such locations When the electrolyte membrane deteriorates and cross leak occurs, the cell voltage tends to decrease. Since the fuel cell using the electrolyte membrane 10 of the present embodiment has a smaller neck-in amount of the electrolyte membrane than the fuel cell using the electrolyte membrane to be compared, the deterioration of the electrolyte membrane even when the number of cycles increases. It is thought that the decrease in cell voltage accompanying the increase in the number of cycles was suppressed.

C. Second embodiment:
In the first embodiment, the second intermediate member 60 is separated from the first intermediate member 50 between the adhesive layer 3aa and the adhesive layer 3ab that have been cut in step S40, but no cut is made. In addition, the second intermediate member 60 can be separated.

  FIG. 17 is a view showing a method of manufacturing the electrolyte membrane 10 when notching up to a predetermined adhesive layer of the first adhesive member 3a. In such a case, as shown in FIG. 17, the first adhesive member 3a is bonded without being cut by the cutter 9 (step S50a). Then, the 1st reinforcement material 12a provided with the 1st adhesion member 3a, the electrolyte membrane material precursor 11f, and the 2nd reinforcement material 12c are arranged straddling between the 2nd adhesion members 3c. The support material 4c and the first support material 4a including the adhesive layers 3ab, 3ac, and 3ad can be separated (step S60a). This is because the adhesive strength between the adhesive layer 3aa and the first reinforcing material 12a is greater than the adhesive strength between the adhesive layer 3aa and the adhesive layer 3ab. Next, the second reinforcing member 12c, the electrolyte membrane material precursor 11f, and the first reinforcing member 12a disposed across the second adhesive member 3c on the second supporting member 4c are, for example, a cutter. If it cut | disconnects by 9, the electrolyte membrane 10 on which the reinforcing material 12 and the electrolyte membrane material precursor 11f were laminated | stacked can be obtained (step S70a). In step S60a, the second support in which the first reinforcing member 12a including the adhesive layer 3aa, the electrolyte membrane material precursor 11f, and the second reinforcing member 12c are disposed across the second adhesive member 3c. The first support material 4a separated from the material 4c includes the adhesive layers 3ab, 3ac, and 3ad, and does not have the first end material. Therefore, the first support material 4a can be reused as it is as the first support material 4a used in step S10 (step S90a). If the adhesive layer 3aa, the first reinforcing material 12a, the electrolyte membrane material precursor 11f, and the second reinforcing material 12c remaining on the second supporting material 4c are peeled from the second adhesive member 3c, the second The second support material 4c including the adhesive member 3c can be reused as the second support material 4c used in step S10 (step S100a).

D. Third embodiment:
In the first embodiment, in step S40, between the adhesive layers 3aa and 3ab from the surface side of the first reinforcing member 12a disposed across the first adhesive member 3a included in the first support member 4a. The above is cut by the cutter 9, but the electrolyte membrane material precursor 11f may be further superposed on the first reinforcing material 12a and then cut by the cutter 9.

  FIG. 18 is a view showing a method of manufacturing the electrolyte membrane 10 when a cut is made from above the electrolyte membrane material precursor 11f to between the adhesive layers 3aa and 3ab. In such a case, after the electrolyte membrane material precursor 11 f is cut by the cutter 9, the electrolyte membrane material precursor 11 f disposed on the first support material 4 a and cut by the cutter 9, and the second support The second reinforcing material 12c disposed on the material 4c is bonded (step S50b). Thereafter, a second support material in which the first reinforcing material 12a including the adhesive layer 3aa, the electrolyte membrane material precursor 11f, and the second reinforcing material 12c are disposed across the second adhesive member 3c. 4c, a first reinforcing material 12a including a part of the electrolyte membrane material precursor 11f, a part of the adhesive layer 3aa, and a first support material 4a including the adhesive layers 3ab, 3ac, and 3ad. (Step S60b). The second reinforcing member 12c, the electrolyte membrane material precursor 11f, and the first reinforcing member 12a disposed across the second adhesive member 3c on the second support member 4c are cut by, for example, the cutter 9 Then, the electrolyte membrane 10 in which the reinforcing material 12 and the electrolyte membrane material precursor 11f are laminated can be obtained (step S70b). Since the adhesive layer 3aa, the first reinforcing material 12a, and the electrolyte membrane material precursor 11f remain on the adhesive layer 3ab included in the first support material 4a, the adhesive layers 3ab, 3ac can be removed by removing them. 3a can be reused as the first support material 4a used in step S10 (step S90b). Similar to Embodiment B above, the adhesive layer 3aa, the first reinforcing material 12a, the electrolyte membrane material precursor 11f, and the second reinforcing material are formed on the second adhesive member 3c included in the second support material 4c. Since the second adhesive member 3c remains, the material 12c can be peeled off from the second adhesive member 3c and reused as the second support material used in step S10 (step S100b).

E. Summary:
As described above, according to the method for manufacturing the electrolyte membrane 10 in the various embodiments described above, the reinforcing material 12 and the electrolyte membrane material precursor 11f are transported using the support material 4, so that the neck being transported is present. The electrolyte membrane 10 in which deformation such as in, wrinkles and deflection is suppressed can be manufactured. The electrolyte membrane 10 includes a first reinforcing material 12a, an electrolyte membrane material precursor 11f, and a second reinforcing material 12c that are disposed across the second adhesive member 3c included in the separated second support material 4c. Are cut between the second adhesive members 3c. Therefore, deformations such as neck-in, wrinkles, and deflection of the electrolyte membrane 10 that occur when the support material 4 is peeled from the electrolyte membrane 10 can be suppressed. As a result, the fuel cell including the electrolyte membrane 10 of the present embodiment has high durability because the cell voltage is prevented from decreasing even when the high temperature state and the low temperature state are repeated. In addition, when the first reinforcing material 12a and the second reinforcing material 12c are bonded together via the electrolyte membrane material precursor 11f, the first reinforcing material 12a and the second reinforcing material 12c are respectively provided with the first support. Since it can be bonded together while being held by the material 4a and the second support material 4c, the time during which the reinforcement material 12 is not supported by the support material 4 can be reduced, and neck-in and wrinkles generated in the reinforcement material 12 can be reduced. Deflection can be suppressed. Therefore, in the production line of the electrolyte membrane 10, it is possible to make the location where the reinforcing material 12 is supplied into a desired location, so that the degree of freedom in designing the production line of the electrolyte membrane 10 can be increased. Furthermore, in the method for manufacturing the electrolyte membrane 10 in the various embodiments described above, it is possible to reuse the relatively expensive support material 4 for manufacturing the electrolyte membrane 10. Therefore, the manufacturing cost of the electrolyte membrane 10 can be reduced. Therefore, improvement in the quality of the electrolyte membrane, improvement in design freedom, and reduction in manufacturing cost can be achieved at the same time.

F. Variation:
As mentioned above, although various embodiment of this invention was described, this invention is not limited to these embodiment, A various structure can be taken in the range which does not deviate from the meaning. For example, the following modifications are possible.

  In the above-described method for manufacturing an electrolyte membrane, Nafion is used as the electrolyte membrane material 11. However, the electrolyte membrane material 11 is not limited to this, and other examples such as Aciplex (registered trademark), Flemion (registered trademark), and the like. A fluorine-based sulfonic acid membrane can be used. As the electrolyte membrane material 11, a fluorine-based phosphonic acid film, a fluorine-based carboxylic acid film, a fluorine-hydrocarbon graft film, a hydrocarbon-based graft film, an aromatic film, or the like may be used.

  In the above-described method for manufacturing an electrolyte membrane, a PTFE film is used as the reinforcing material 12. However, the reinforcing material 12 is not limited to this, and can be formed of an acid-resistant and alkaline material. For example, PFA (tetrafluoro (Ethylene / perfluoroalkyl vinyl ether copolymer) and PVDF (polyvinylidene fluoride). The reinforcing material 12 has a shape that partially reinforces the electrolyte membrane material 11 (for example, a lattice shape that partially reinforces the electrolyte membrane material 11 or a shape that reinforces the outer peripheral portion of the electrolyte membrane). Also good.

  In step S10 in the method for manufacturing an electrolyte membrane described above, the support member 4 including the two adhesive members 3 with a predetermined interval is prepared as illustrated in FIGS. 3 and 4. However, the adhesive member 3 included in the support material 4 is prepared. The number of is not limited to this. For example, the support material 4 provided with the four adhesive members 3 in a rectangular shape can be prepared.

  In step S10 in the above-described method for manufacturing an electrolyte membrane, the second adhesive member 3c included in the second support member 4c has only one layer. However, the second adhesive member 3c includes the first support member 4a. It may be a multilayer structure in which adhesive layers are laminated like the first adhesive member 3a provided. In step S20, the first reinforcement member 12a is provided on the first adhesive member 3a provided in the first support member 4a, and the second reinforcement member is provided on the second adhesive member 3c provided in the second support member 4c. Although the material 12c is installed, the electrolyte membrane material precursor 11f may be installed instead of the first reinforcing material 12a or the second reinforcing material 12c. By doing so, the electrolyte membrane 10 in which one side is reinforced with the reinforcing material 12 can be produced.

  In step S40 in the above-described method for manufacturing an electrolyte membrane, the cutter 9 cuts between the adhesive layer 3aa and the adhesive layer 3ab, so that the first intermediate member 50 is bonded between the adhesive layer 3aa and the adhesive layer 3ab. The second intermediate member 60 is easily separated inside the portion where the cut of the adhesive layer 3aa is cut. However, even if step S40 is omitted, it can be easily separated in the same manner. For example, in step S10, if the first adhesive member 3a on which the adhesive layer having a dotted line such as a perforation is previously laminated is disposed on the first support member 4a, the first perforation is located at the perforation. The second intermediate member 60 can be separated from the intermediate member 50. Further, for example, in step S10, the first intermediate member 50 is formed at a location where the adhesive strength differs by changing the adhesive strength of the plurality of adhesive layers stacked on the first support member 4a for each adhesive layer. The second intermediate member 60 may be separated from the second intermediate member 60. The method of varying the adhesive strength for each adhesive layer can be performed by changing the material of the adhesive layer or increasing or decreasing the adhesion area. The increase / decrease in the adhesion area can be adjusted by the size of the adhesive layer itself, but can also be adjusted by the surface roughness of the adhesive layer.

  In step S70 in the above-described method for manufacturing an electrolyte membrane, a laminate including the first reinforcing material 12a, the electrolyte membrane material precursor 11f, and the second reinforcing material 12c is placed between the second adhesive member 3c and the second adhesive member 3c. If the cut portion is from the end of one second adhesive member 3c to the end of the other second adhesive member 3c, the first portion is cut. It may be on the second adhesive member 3c. FIG. 19 is a diagram illustrating a state in which the first reinforcing member 12a, the electrolyte membrane material precursor 11f, and the second reinforcing member 12c are cut on the second adhesive member 3c. Even in such a case, the second adhesive member 3c and the second support material 4c are not attached to the entire surface of the second reinforcing member 12c as in the above-described method for manufacturing the electrolyte membrane to be compared. It is possible to suppress deformation such as neck-in, wrinkles, and deflection that occur when the second adhesive member 3c is peeled off. In this case, if the adhesive force between the second adhesive member 3c and the second support member 4c is greater than the adhesive force between the second adhesive member 3c and the second reinforcing member 12c, Since the adhesive member 3c remains on the second support member 4c, the second support member 4c including the second adhesive member 3c can be easily reused for the manufacture of the electrolyte membrane 10 as shown in FIG. .

  In step S70 in the method for manufacturing an electrolyte membrane described above, the penetration depth at the tip of the cutter 9 for cutting the laminate composed of the first reinforcing material 12a, the electrolyte membrane material precursor 11f, and the second reinforcing material 12c is as follows. The depth at which the cutter 9 does not touch the support material 4c of 2 is such that the penetration depth at the tip of the cutter 9 can maintain the rigidity of the second support material 4c. The depth which touches the 2nd support material 4c may be sufficient. Even if the laminate including the reinforcing material 12 and the electrolyte membrane material precursor 11f on the second support material 4c is cut at such a depth, the second support material 4c can be reused.

3a ... 1st adhesive member 3c ... 2nd adhesive member 3aa, 3ab, 3ac, 3ad, ... Adhesive layer 4a ... 1st support material 4c ... 2nd support material 9 ... Cutter 10 ... Electrolyte membrane 11 ... Electrolyte membrane Material 11f ... Electrolyte membrane material precursor 12a ... First reinforcing material 12c ... Second reinforcing material 20 ... Membrane electrode assembly 30 ... Single cell 31a ... Anode side electrode 31c ... Cathode side electrode 32a ... Anode side gas diffusion layer 32c ... Cathode side gas diffusion layer 33a ... Anode side separator 33c ... Cathode side separator 34a ... Fuel gas passage 34c ... Oxidant gas passage 50 ... First intermediate member 60 ... Second intermediate member 100 ... Fuel cells L1a, L1c ... spacing at which the adhesive layer is disposed on the support material L2 ... width for cutting the electrolyte membrane from the support material

Claims (5)

A method for producing an electrolyte membrane comprising a reinforcing material,
A first support member in which at least two first adhesive members in which a plurality of adhesive layers are bonded to each other with a first adhesive strength are arranged on the same surface at a predetermined interval; and a second adhesive member A first step of preparing at least two second support members arranged on the same surface at a predetermined interval,
Bonding a first reinforcing material between the at least two first adhesive members with a second adhesive strength greater than the first adhesive strength on the at least two first adhesive members, A second step of adhering the second reinforcing material on the at least two second adhesive members across the at least two second adhesive members;
The electrolyte membrane material precursor is bonded to the first reinforcing material on the first adhesive member and the second reinforcing material on the second adhesive member via an electrolyte membrane material precursor. The body is sandwiched between the first reinforcing member and the second reinforcing member, and further, the first supporting member to which the first adhesive member is bonded and the second adhesive member are bonded to each other. A third step of generating a first intermediate member sandwiched by the second support material;
The second support material, the at least two second adhesive members, and the second reinforcing material are separated from the first intermediate member by peeling a predetermined adhesive layer in each of the first adhesive members. And a fourth step of separating a second intermediate member having the electrolyte membrane material precursor , the first reinforcing material, and a part of the first adhesive member;
Between the at least two second adhesive members of the second intermediate member, the first reinforcing material, the electrolyte membrane material precursor, and the second reinforcing material on the at least two second adhesive members. A fifth step of cutting the material;
A manufacturing method comprising: The manufacturing method according to claim 1,
Prior to the third step, further comprising a step of cutting from the surface of the first reinforcing material bonded onto the first adhesive member to the predetermined adhesive layer in the first adhesive member. A manufacturing method. It is a manufacturing method of Claim 1 or 2, Comprising:
A manufacturing method in which at least a part of the first intermediate member from which the second intermediate member is separated in the fourth step is used as the first support member prepared in the first step. It is a manufacturing method as described in any one of Claim 1- Claim 3, Comprising:
From the second intermediate member after the first reinforcing material, the electrolyte membrane material precursor and the second reinforcing material are cut in the fifth step, the second supporting material and the second Separating the second adhesive member disposed on the support member, and separating the second support member and the second adhesive member disposed on the second support member, A manufacturing method used as the second support material prepared in the first step. It is a manufacturing method as described in any one of Claim 1- Claim 4, Comprising:
Furthermore, the fifth step was impregnated electrolyte and the being cut first reinforcing member before Symbol second reinforcing member in comprises a step of imparting ion conductivity method.

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