JP6451489B2 - Method for producing reinforced electrolyte membrane - Google Patents

Description

  The present invention relates to a method for producing a reinforced electrolyte membrane.

  A reinforced electrolyte membrane reinforced by impregnating an electrolyte membrane with a porous membrane as a reinforcing membrane is known. Such a reinforced electrolyte membrane contributes to improving the durability of a fuel cell in which the reinforced electrolyte membrane is incorporated. In order to obtain a reinforced electrolyte membrane, a manufacturing method has been proposed in which a porous membrane is stretched in the width direction, bonded to an auxiliary sheet and wound into a roll, and the wound porous membrane is bonded to the electrolyte membrane. (For example, Patent Document 1).

JP 2013-114887 A

  Said manufacturing method is excellent at the point which adhere | attaches the porous membrane extended | stretched to the width direction to the adhesion area | region of an auxiliary sheet, and suppresses generation | occurrence | production of a neck-in. On the other hand, in order to improve the durability of the electrolyte membrane, it is desirable to prevent the shrinkage from occurring as much as possible in the porous membrane as the reinforcing membrane. For these reasons, there has been a demand for a method for manufacturing an electrolyte membrane that can suppress a decrease in durability through suppression of shrinkage of the porous membrane.

  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.

(1) According to one aspect of the present invention, a method for producing a reinforced electrolyte membrane in which an electrolyte membrane is reinforced with a porous membrane is provided. This manufacturing method includes a step of stretching the porous membrane in the width direction while transporting the porous membrane in a transport zone in the membrane longitudinal direction, and a porous membrane transporting device disposed at an end point of the transport zone. Bonding the electrolyte membrane to the stretched porous membrane using a transport roller.

  Since the manufacturing method of this embodiment attaches the electrolyte membrane to the porous membrane that has been stretched in the width direction at the end point of the transport area of the porous membrane, the electrolyte resin constituting the electrolyte membrane is It is allowed to enter the pores of the porous membrane before the shrinkage occurs. Therefore, there is an advantage described below.

  If the porous film stretched in the width direction is left untreated, it shrinks in the width direction over time, and this shrinkage occurs even when the porous film alone is wound into a roll. . For this reason, when the elapsed time from when the film is stretched to when it is bonded to the electrolyte membrane becomes long, the porous film is bonded and impregnated to the electrolyte membrane in a contracted state in the width direction.

  When the porous membrane is impregnated in the electrolyte membrane, the electrolyte resin (for example, electrolyte precursor) constituting the electrolyte membrane enters the pores of the porous membrane. In the impregnation with the porous membrane contracted in the width direction, there is room for expansion of the porous membrane corresponding to the amount of shrinkage of the porous membrane. When it swells, the amount of expansion of the electrolyte membrane and the porous membrane increases. Since the large expansion of the electrolyte membrane also causes wrinkles, there is a concern that the durability of the electrolyte membrane and thus the membrane electrode assembly (MEA) may be lowered.

  However, as described above, the manufacturing method of the reinforced electrolyte membrane having the above-described form allows the electrolyte resin to enter the pores of the porous membrane before the shrinkage in the width direction occurs. Regulates subsequent shrinkage of the porous membrane. As a result, according to the manufacturing method of the reinforced electrolyte membrane of this embodiment, the electrolyte can be reduced by suppressing the shrinkage of the porous membrane stretched in the width direction and by suppressing the expansion of the electrolyte membrane during the power generation operation accompanying the shrinkage suppression. A decrease in the durability of the film can be suppressed. In addition, it is possible to easily achieve the suppression of the decrease in the durability of the electrolyte membrane by bonding the electrolyte membrane at the end point of the transport area of the porous membrane.

  Note that the present invention can be realized in various modes. For example, it can be realized in the form of a manufacturing apparatus for a reinforced electrolyte membrane or a method for manufacturing a fuel cell including a reinforced electrolyte membrane.

It is explanatory drawing which shows roughly the structure of the electrolyte membrane manufacturing apparatus 100 in this embodiment. FIG. 2 is an explanatory view schematically showing the electrolyte membrane manufacturing apparatus 100 in plan view from the direction A in FIG. 1. It is a schematic sectional drawing in alignment with line 3-3 in FIG. It is explanatory drawing which shows typically schematic structure of the electrolyte membrane manufacturing apparatus 100 by a side view. 4 is a flowchart showing a manufacturing procedure of a reinforced electrolyte membrane sheet that is a manufacturing target in the electrolyte membrane manufacturing apparatus 100. It is a graph which compares and shows the dimensional change rate of embodiment goods and a comparative example goods. It is a graph which compares and shows the amount of cross leaks of an embodiment product and a comparative example product. It is explanatory drawing which shows typically schematic structure of the electrolyte membrane manufacturing apparatus 100A of a 1st modification by side view. It is explanatory drawing which shows typically schematic structure of the electrolyte membrane manufacturing apparatus 100B of a 2nd modification by side view. It is explanatory drawing which shows typically schematic structure of the electrolyte membrane manufacturing apparatus 100C of a 3rd modification by side view.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is an explanatory view schematically showing a configuration of an electrolyte membrane manufacturing apparatus 100 in the present embodiment, and FIG. 2 is an explanatory view schematically showing the electrolyte membrane manufacturing apparatus 100 in plan view from the direction A in FIG. 3 is a schematic cross-sectional view taken along line 3-3 in FIG. 1, and FIG. 4 is an explanatory view schematically showing the schematic configuration of the electrolyte membrane manufacturing apparatus 100 in a side view. As shown in the drawing, the electrolyte membrane manufacturing apparatus 100 includes a first delivery roller 110, a second delivery roller 120, a sheet conveyance roller 130, a pressure conveyance roller 132, a winding roller 140, and a winding guide roller 150. And a widening mechanism 160 and a sheet cutting edge 170.

  The first delivery roller 110 delivers the wound porous membrane sheet Ps along with the rotation of the sheet conveyance roller 130 for conveying the porous membrane and the rotation of the sheet end gripping roller in the widening mechanism 160 described later. The porous membrane sheet Ps is formed in a sheet shape as a porous membrane having a thickness of 1 to 5 μm and a porosity of about 40 to 75% using polytetrafluoroethylene (PTFE). In addition, the porous membrane sheet Ps is made of polyolefin resin such as polyethylene, polypropylene, ethylene-propylene copolymer; polysiloxane; methacrylate resin such as polymethyl methacrylate (PMMA); polystyrene, acrylonitrile-styrene copolymer ( AS resin), styrene resin such as acrylonitrile-butadiene-styrene copolymer (ABS resin); polyamide; polyimide (PI); polyetherimide (PEI); polyamideimide; polyesterimide; polycarbonate (PC); Polyarylene ethers such as ether (PPO); polyphenylene sulfide (PPS); polyarylate; polyaryl; polysulfone (polysulfone); polyethersulfone (PES) (Polyethersulfone); Polyurethanes; Polyester resins such as polyethylene terephthalate (PET); Polyetherketones such as polyetheretherketone (PEEK) and Polyetherketoneketone (PEKK); Polybutyl acrylate, Polyacrylic Polyacrylic acid esters such as ethyl acid; Polyvinyl esters such as polybutoxymethylene; Polysiloxanes; Polysulfides; Polyphosphazenes; Polytriazines; Polycarboranes; Polynorbornene; Epoxy resin; Polyvinyl pyrrolidone; polydienes such as polyisoprene and polybutadiene; polyalkenes such as polyisobutylene; vinylidene fluoride resin, hexafluoropropylene resin, hexafluoro Either it may be porous film using a resin such as acetone resin (such as a thermoplastic resin).

  A widening mechanism 160, which will be described later, is disposed between the first delivery roller 110 and the sheet conveyance roller 130, and the conveyance / extension section extends from the first delivery roller 110 to the sheet conveyance roller 130. The sheet conveyance roller 130 is disposed at the end point of the conveyance area in the conveyance / extension section. The widening mechanism 160 is disposed at both ends in the width direction of the porous membrane sheet Ps delivered from the first delivery roller 110, and constitutes a wire-type widening mechanism. The widening mechanism 160 includes an upstream sheet end gripping roller 161, a downstream sheet end gripping roller 162, and an endless gripping wire 163. As shown in FIG. 2, the upstream sheet end gripping roller 161 and the downstream sheet end gripping roller 162 are disposed to be inclined with respect to the transport direction which is the film longitudinal direction of the porous film sheet Ps. As shown, the gripping wire 163 rotates while gripping the sheet end Pse of the porous membrane sheet Ps. A plurality of small-diameter gripping rollers (not shown) that grip the sheet end Pse of the porous membrane sheet Ps together with the gripping wire 163 are disposed between the both end rollers. The widening mechanism 160 having such a configuration is located facing both ends in the width direction of the porous membrane sheet Ps, and holds the sheet end Pse across the conveyance area, and the upstream sheet end gripping roller 161 and the downstream sheet end gripping roller. The porous membrane sheet Ps is transported in the transport area between the upstream sheet end gripping roller 161 and the downstream sheet end gripping roller 162 in the transporting / stretching section by the rotation of the gripping roller between 162 and both end rollers. The widening mechanism 160 adjusts the degree of inclination of the upstream sheet end gripping roller 161 and the downstream sheet end gripping roller 162 with respect to the transport direction to change the porous film sheet Ps to a film width whose film width is a predetermined magnification. It extends | stretches in the width direction, conveying so that it may become. In the present embodiment, the widening ratio obtained by dividing the winding width Psh0 (see FIG. 2) of the porous membrane sheet Ps by the stretching width Psh1 at the end point of the transport area is a widening ratio within a range of 110 to 150%. The porous film sheet Ps is stretched in the width direction by the widening mechanism 160. Hereinafter, such stretching in the width direction of the porous membrane sheet Ps is referred to as widening stretching for convenience.

  The second delivery roller 120 sends the wound electrolyte membrane sheet Ms with the rotation of the pressure conveying roller 132 and the rotation of the winding roller 140. The electrolyte membrane sheet Ms is a sheet body of an electrolyte precursor that is a sulfonic acid-based electrolyte resin that exhibits hydrogen ion conductivity through a predetermined treatment such as hydrolysis. In the present embodiment, the electrolyte membrane sheet Ms has a thickness of 4 to 20 μm. A sheet body of an electrolyte precursor such as a Nafion membrane (Nafion is a registered trademark) was used. The electrolyte membrane sheet Ms is wound around the second delivery roller 120 in a form superimposed on the back sheet Bs, the back sheet Bs is on the roll surface side of the pressure conveying roller 132, and the electrolyte membrane sheet Ms is porous. It is sent to the pressure conveying roller 132 so as to face the film sheet Ps. The back sheet Bs is a sheet made of a fluorine-based resin sheet having releasability with respect to the electrolyte membrane sheet Ms, for example, Teflon (Teflon is a registered trademark) or a hydrocarbon-based resin.

  The pressure conveyance roller 132 forms a bonded section together with the sheet conveyance roller 130, and pressurizes the electrolyte membrane sheet Ms delivered from the second delivery roller 120 to the porous membrane sheet Ps on the roller surface of the sheet conveyance roller 130. And paste them together. Since the pressure conveyance roller 132 is disposed to face the sheet conveyance roller 130 at the end point of the conveyance area of the porous film sheet Ps, the object to be bonded to the electrolyte membrane sheet Ms by the pressure conveyance roller 132 is: The porous film sheet Ps has been stretched to a predetermined widening ratio by the widening mechanism 160. That is, the electrolyte membrane sheet Ms is bonded to the porous membrane sheet Ps that has been stretched to a predetermined widening ratio by using the sheet conveyance roller 130 and the pressure conveyance roller 132. The electrolyte membrane sheet Ms can be softened by adopting a configuration in which the pressure conveying roller 132 can be heated at the time of such sheet bonding. In this way, the softened electrolyte membrane sheet Ms can be bonded to the porous membrane sheet Ps that has been stretched to a predetermined widening ratio. Note that the pressure applied during sheet bonding is defined by a nip pressure that is adjusted by the distance between the roller surfaces of the sheet conveying roller 130 and the pressure conveying roller 132.

  The winding roller 140 feeds the porous membrane sheet Ps from the first delivery roller 110, delivers the electrolyte membrane sheet Ms from the second delivery roller 120, and the electrolyte membrane by the sheet transport roller 130 and the pressure transport roller 132. The electrolyte membrane sheet Ms rotates in synchronization with the rotation of the rollers for laminating the sheet Ms, and is wound in a state where the electrolyte membrane sheet Ms is adhered to the porous membrane sheet Ps that has been stretched to a predetermined width-enlarging rate. The winding guide roller 150 guides the electrolyte membrane sheet Ms to the winding roller 140 with tension. The sheet cutting edge 170 is disposed downstream of the bonding position of the electrolyte membrane sheet Ms according to the width of the electrolyte membrane sheet Ms, and cuts the excess sheet portion Pso on the sheet end side of the porous membrane sheet Ps. Therefore, as schematically shown in FIG. 1, the winding roller 140 is a state in which the porous film sheet Ps having the same width as the electrolyte film sheet Ms, which has been stretched to a predetermined width-expanding rate, is bonded to the electrolyte film sheet Ms. Thus, the electrolyte membrane sheet Ms is wound together with the back sheet Bs. The electrolyte membrane sheet Ms wound up in this way is treated as a semi-finished electrolyte membrane sheet CEs bonded to the porous membrane sheet Ps. The surplus sheet portion Pso cut by the sheet cutting blade 170 is taken up by a collecting roller (not shown) with a long cut portion Psh therebetween.

  The electrolyte membrane sheet Ms (semi-finished electrolyte membrane sheet CEs) wound around the winding roller 140 is sequentially fed to an impregnation section and a hydrolysis treatment section (not shown). By heating in the impregnation section, the porous membrane sheet Ps impregnates the electrolyte membrane sheet Ms (specifically, an electrolyte precursor) and undergoes hydrolysis in the hydrolysis treatment section, so that the electrolyte membrane sheet Ms becomes hydrogen ion conductive. It is used as a reinforced electrolyte membrane having The electrolyte membrane sheet Ms can be directly conveyed to the impregnation section or the hydrolysis treatment section in a state of being bonded to the porous membrane sheet Ps that has been stretched to a predetermined widening rate. The winding roller 140 is not necessary. Further, as described above, it is possible to cause the impregnation of the porous membrane sheet Ps by bonding the electrolyte membrane sheet Ms to the porous membrane sheet Ps while being heated by the pressure conveying roller 132.

  FIG. 5 is a flowchart showing a manufacturing procedure of a reinforced electrolyte membrane sheet which is a manufacturing target in the electrolyte membrane manufacturing apparatus 100.

  As shown in the drawing, in manufacturing the reinforced electrolyte membrane sheet with the electrolyte membrane manufacturing apparatus 100, the porous membrane sheet Ps from the first delivery roller 110 is delivered and transported by the widening mechanism 160 as described above. The widening stretching (step S100) and the delivery conveyance (step S110) of the electrolyte membrane sheet Ms from the second delivery roller 120 are executed in synchronization. As a result, at the end point of the transport area in the transport / stretch section (see FIG. 2), the porous membrane sheet Ps is stretched in the width direction at the predetermined widening rate described above, and this stretched porous membrane sheet The electrolyte membrane sheet Ms is pressed and bonded to Ps by the sheet conveying roller 130 and the pressure conveying roller 132 (step S120). Thereafter, the surplus sheet portion Pso of the portion extending from the electrolyte membrane sheet Ms is cut by the sheet cutting blade 170 disposed downstream of the bonding location of the electrolyte membrane sheet Ms (step S130). Then, the semi-finished electrolyte membrane sheet CEs in which the porous membrane sheet Ps having the same width as the electrolyte membrane sheet Ms and having been stretched to a predetermined widening rate is bonded to the electrolyte membrane sheet Ms is taken up by the take-up roller 140 (step S140). The surplus sheet portion Pso (see FIGS. 1 and 4) cut by the sheet cutting blade 170 is wound and collected by the collection roller (step S150), and the above-described steps are repeated. The semi-finished electrolyte membrane sheet CEs obtained in step S140 is transported to the next process such as an impregnation section and a hydrolysis treatment section.

  Next, performance evaluation will be described. The performance evaluation was performed for the dimensional change rate and the cross leak amount. In performing the performance evaluation of the dimensional change rate, first, the electrolyte membrane sheet Ms (semi-finished electrolyte membrane sheet CEs) of the example product obtained by the electrolyte membrane manufacturing apparatus 100 and the porous membrane sheet not subjected to widening stretching The electrolyte membrane sheet Ms of the comparative example in which the electrolyte membrane sheet Ms is bonded to Ps is impregnated into the electrolyte resin (electrolyte precursor) and hydrolyzed with the porous membrane sheet Ps using a heating roller. A reinforced electrolyte membrane as a product was obtained. Next, the obtained reinforced electrolyte membrane (embodiment product / comparative example product) was cut into a 10 cm square sample piece shape shown in FIG. 1 or FIG. 2, and the cut sample product (embodiment product / comparative example product). ) Was measured for the dimensional change rate (swelling) of the transport direction dimension MD and the width direction dimension TD after being immersed in warm water of 80 ° C. for 20 minutes. FIG. 6 is a graph showing the dimensional change rates of the embodiment product and the comparative product in comparison.

  As is apparent from FIG. 6, the embodiment product in which the electrolyte membrane sheet Ms is bonded to the porous membrane sheet Ps that has been widened and stretched is 3 in both the transport direction dimension MD and the width direction dimension TD. Only about ˜4% causes a dimensional change (swelling), and the dimensional change in the conveyance direction and the width direction is balanced. On the other hand, the comparative product in which the electrolyte membrane sheet Ms is bonded to the porous membrane sheet Ps that is not subjected to widening stretching has a slight change in the dimension MD in the transport direction, but the width dimension TD exceeds 20%. A dimensional change (swelling) occurred, and an unbalance occurred in the dimensional change in the conveyance direction and the width direction. When the dimensional change of the electrolyte membrane is small, mechanical stress on the electrolyte membrane is reduced due to a change in wet and dry conditions during the power generation operation of the fuel cell in which the electrolyte membrane is incorporated. In particular, when the power generation operation of the fuel cell causes the electrolyte membrane to wet, the electrolyte membrane easily swells. Therefore, if the dimensional change of the electrolyte membrane is large, wrinkles occur in the electrolyte membrane, resulting in a decrease in durability. Invite. In light of the result of the dimensional comparison in FIG. 6, it can be determined that the embodiment product is an electrolyte membrane having high durability.

  In evaluating the performance of the cross leak amount, first, both anode and cathode electrode catalysts are formed on both membrane surfaces of the reinforced electrolyte membrane (the embodiment product and the comparative example product) as a finished product obtained as described above. A fuel cell (formation product / comparative example product) is formed by forming a layer, and hydrogen gas / oxygen-containing gas (air) is supplied to the fuel cell to continuously generate power. Carried out. In this dry / wet cycle, the drying process of generating power without drawing current from both electrodes of the fuel cell is continued for a predetermined time, and then the wet process of generating power by drawing current while humidifying is continued for a predetermined time. And the amount of cross leak was calculated | required, counting a dry process and a wet process as 1 cycle. FIG. 7 is a graph showing the cross leak amount of the embodiment product and the comparative product in comparison, the horizontal axis represents the cycle number of the wet and dry cycle, and the vertical axis represents the cross leak amount.

  As is clear from FIG. 7, the embodiment product in which the electrolyte membrane sheet Ms is bonded to the porous membrane sheet Ps that has been widened and stretched is a fuel cell, even if the number of dry and wet cycles reaches 10,000 cycles. As a result, the cross leak occurred only about 1/4 to 1/3 of the allowable leak amount. On the other hand, in the comparative product in which the electrolyte membrane sheet Ms is bonded to the porous membrane sheet Ps that is not subjected to widening stretching, when the number of dry and wet cycles reaches about 4,000 cycles, the cross leak rapidly increases and the allowable leak amount is increased. A large cross leak occurred. Therefore, the reinforced electrolyte membrane of the embodiment product is a highly durable electrolyte membrane as a result of reducing the mechanical stress of the electrolyte membrane due to repeated swelling and subsequent shrinkage because the swelling is small. It can be determined that there is.

  As described above, the manufacturing method of the reinforced electrolyte membrane of the present embodiment using the electrolyte membrane manufacturing apparatus 100 is in the state of being widened and stretched at the end point of the transport area of the porous membrane sheet Ps in the transport / stretch section. Since the electrolyte membrane sheet Ms is bonded to the porous membrane sheet Ps as it is, the electrolyte resin constituting the electrolyte membrane sheet Ms enters the pores of the porous membrane sheet Ps before contraction in the width direction. The electrolyte resin that has entered the pores in this way regulates subsequent shrinkage of the porous membrane sheet Ps. As a result, according to the manufacturing method of the reinforced electrolyte membrane of the present embodiment using the electrolyte membrane manufacturing apparatus 100, the shrinkage of the expanded porous membrane sheet Ps and the electrolyte during the power generation operation accompanying the shrinkage suppression are as follows. By suppressing the expansion of the membrane, a decrease in the durability of the electrolyte membrane can be suppressed. In addition, since it is possible to easily suppress the decrease in the durability of the electrolyte membrane by bonding the electrolyte membrane sheet Ms at the end point of the conveyance area of the porous membrane sheet Ps, it is simple.

  Widening stretching by the widening mechanism 160 and superposition of the porous membrane sheet Ps and the electrolyte membrane sheet Ms using the sheet conveying roller 130 and the pressure conveying roller 132 can be easily achieved with existing equipment. The apparatus for producing a reinforced electrolyte membrane can be easily modified so that a reinforced electrolyte membrane having excellent durability can be produced.

  Next, a modified example will be described. FIG. 8 is an explanatory view schematically showing a schematic configuration of the electrolyte membrane manufacturing apparatus 100A of the first modification as viewed from the side. As shown in the figure, the electrolyte membrane manufacturing apparatus 100A sends out another electrolyte membrane sheet Ms to the sheet conveying roller 130, and bonds the electrolyte membrane sheet Ms to both sheet surfaces of the widened and stretched porous membrane sheet Ps. There is a feature. That is, the electrolyte membrane manufacturing apparatus 100 </ b> A includes a third delivery roller 180, and the third delivery roller 180 rotates another electrolyte membrane sheet Ms that has been wound up to the rotation of the sheet conveyance roller 130 and the pressure conveyance roller 132. , The winding roller 140, and the second delivery roller 120, the other electrolyte membrane sheet Ms is fed to the sheet conveying roller 130 in a state of being superimposed on the back sheet Bs. In this case, the electrolyte membrane sheet Ms is fed into the sheet conveyance roller 130 such that the back sheet Bs is on the roll surface side of the sheet conveyance roller 130 and the electrolyte membrane sheet Ms faces the porous membrane sheet Ps.

  The electrolyte membrane manufacturing apparatus 100A performs widening stretching while transporting the porous membrane sheet Ps in the transport zone in the transport / stretch section, and the end points of the transport zone are formed on both sheet surfaces of the wide stretched porous membrane sheet Ps. The electrolyte membrane sheet Ms is bonded to each other using the sheet conveyance roller 130 and the pressure conveyance roller 132. Therefore, also by the manufacturing method of the reinforced electrolyte membrane using this electrolyte membrane manufacturing apparatus 100A, the fall of durability of a reinforced electrolyte membrane can be suppressed easily.

  FIG. 9 is an explanatory view schematically showing a schematic configuration of the electrolyte membrane manufacturing apparatus 100B of the second modification as viewed from the side. As shown in the figure, the electrolyte membrane manufacturing apparatus 100B transfers the electrolyte membrane sheet Ms to the back sheet Bs before the electrolyte membrane sheet Ms is bonded to the widened and stretched porous membrane sheet Ps in the transport area in the transport / stretch section. It is characterized in that it is formed. That is, the electrolyte membrane manufacturing apparatus 100 </ b> B includes the fourth delivery roller 200, the back sheet conveyance roller 210, the electrolyte resin discharge nozzle 220, and the drying furnace 230 on the upstream side of the sheet conveyance roller 130.

  The fourth delivery roller 200 winds the back sheet Bs alone, and the back sheet conveyance roller 210 conveys the back sheet Bs in a tensioned state. The fourth delivery roller 200 and the back sheet conveyance roller 210 are accompanied by rotation of the sheet conveyance roller 130, rotation of the pressure conveyance roller 132, rotation of the take-up roller 140, and rotation of the second delivery roller 120. Then, the back sheet Bs is sent to the sheet conveying roller 130.

  The discharge nozzle 220 is disposed to face the roller surface of the back sheet conveying roller 210, and directs a solution in which an electrolyte resin for forming the electrolyte membrane sheet Ms is dissolved at a predetermined concentration toward the back sheet Bs on the roller surface. Discharge. By discharging the solution, an electrolyte membrane sheet Ms is formed on the back sheet Bs, and the formed electrolyte membrane sheet Ms is sent to the sheet transport roller 130 in a state of being overlapped with the back sheet Bs, and is a sheet at the end of the transport area. It is bonded to the porous film sheet Ps that has been widened and stretched by the transport roller 130. At this time, since the electrolyte membrane sheet Ms is immediately after being formed on the back sheet Bs through discharge of the electrolyte resin solution, the electrolyte membrane sheet Ms is in a paste form capable of maintaining the sheet form. Therefore, at the time of bonding with the sheet conveying roller 130, the electrolyte resin of the electrolyte membrane sheet Ms is impregnated by capillary action into the pores of the porous membrane sheet Ps, and the electrolyte membrane sheet Ms is porous downstream of the sheet conveying roller 130. The semi-finished electrolyte membrane sheet CEs is impregnated with the conductive membrane sheet Ps.

  The drying furnace 230 heats the semi-finished electrolyte membrane sheet CEs, evaporates the solution component of the electrolyte resin solution from the electrolyte membrane sheet Ms, and makes the electrolyte membrane sheet Ms solid. Therefore, the winding roller 140 winds up the semi-finished electrolyte membrane sheet CEs obtained by impregnating the electrolyte resin of the electrolyte membrane sheet Ms with the porous membrane sheet Ps.

  Even in this electrolyte membrane manufacturing apparatus 100B, the porous membrane sheet Ps is widened while being conveyed in the conveyance area in the conveyance / extension section, and the sheet at the end of the conveyance area is expanded into the porous film sheet Ps that has been widened and elongated. The electrolyte membrane sheet Ms is bonded together by the transport roller 130. Therefore, also by the manufacturing method of the reinforcement type electrolyte membrane using this electrolyte membrane manufacturing apparatus 100B, the fall of durability of a reinforcement type electrolyte membrane can be suppressed easily. In addition to this, the electrolyte membrane manufacturing apparatus 100B bonds the paste-like electrolyte membrane sheet Ms formed by discharging the electrolyte resin solution onto the back sheet Bs to the porous membrane sheet Ps, so that the semi-finished electrolyte membrane sheet CEs. Is an electrolyte membrane sheet in which the porous membrane sheet Ps is impregnated with the electrolyte resin of the electrolyte membrane sheet Ms. Therefore, according to the method for manufacturing a reinforced electrolyte membrane using the electrolyte membrane manufacturing apparatus 100B, it is not necessary to impregnate in the subsequent process, and the process can be simplified.

  FIG. 10 is an explanatory view schematically showing a schematic configuration of an electrolyte membrane manufacturing apparatus 100C according to a third modification as viewed from the side. As shown in the figure, the electrolyte membrane manufacturing apparatus 100C is formed by forming the electrolyte membrane sheet Ms on the back sheet Bs before bonding the electrolyte membrane sheet Ms to the porous membrane sheet Ps, and then expanding and stretching the porous membrane. It is characterized in that the electrolyte membrane sheet Ms is bonded to both sheet surfaces of the membrane sheet Ps. That is, the electrolyte membrane manufacturing apparatus 100C includes a first intermediate guide roller 241, a second intermediate guide roller 242, a third intermediate guide roller 243, a fourth intermediate guide roller 244, and an electrolyte on the downstream side of the drying furnace 230. A resin discharge nozzle 221 and a drying furnace 231 are provided.

  Each guide roller of the first intermediate guide roller 241 to the fourth intermediate guide roller 244 conveys the electrolyte membrane sheet Ms (semi-finished electrolyte membrane sheet CEs) dried in the drying furnace 230 to the drying furnace 231 while applying tension. To do. The semi-finished electrolyte membrane sheet CEs is cooled while being conveyed by these guide rollers, and receives the discharge of the electrolyte resin solution from the discharge nozzle 221 on the roller surface of the fourth intermediate guide roller 244. The discharge nozzle 221 discharges a new electrolyte resin solution to the surface of the cooled semi-finished electrolyte membrane sheet CEs, that is, the surface of the porous membrane sheet Ps impregnated in the electrolyte membrane sheet Ms. The sheet Ms is formed so as to overlap the electrolyte membrane sheet Ms impregnated with the porous membrane sheet Ps.

  The semi-finished electrolyte membrane sheet CEs on which the new electrolyte membrane sheet Ms is formed is heated while passing through the drying furnace 231, and the newly formed electrolyte membrane sheet Ms evaporates the solution components of the electrolyte resin solution. It becomes a solid state. Therefore, the winding roller 140 is formed by impregnating the electrolyte resin of the electrolyte membrane sheet Ms formed earlier with the porous membrane sheet Ps and laminating the electrolyte membrane sheet Ms formed later on the electrolyte membrane sheet Ms formed first. The semi-finished electrolyte membrane sheet CEs having the above shape is wound up. By the way, the porous membrane sheet Ps is thinner than the electrolyte membrane sheet Ms. Therefore, the porous membrane sheet Ps and the previously formed electrolyte membrane sheet Ms are impregnated with the previously formed electrolyte membrane sheet Ms. It intervenes at the boundary of lamination with the electrolyte membrane sheet Ms formed.

  Also with this electrolyte membrane manufacturing apparatus 100C, the same effects as the electrolyte membrane manufacturing apparatus 100B described above can be achieved.

  The present invention is not limited to the above-described embodiments, examples, and modifications, and can be realized with various configurations without departing from the spirit thereof. For example, the technical features in the embodiments, examples, and modifications corresponding to the technical features in each embodiment described in the summary section of the invention are to solve some or all of the above-described problems, or In order to achieve part or all of the above-described effects, replacement or combination can be performed as appropriate. Further, if the technical feature is not described as essential in the present specification, it can be deleted as appropriate.

  In the embodiment described above, the electrolyte membrane sheet Ms is bonded to the porous membrane sheet Ps with a pressure type roller configuration using a nip pressure. However, an existing bonding mechanism is used. Also good. For example, at the end point of the transport area, the pressure transport roller 132 is disposed downstream of the sheet transport roller 130 in the transport direction, and the lap is bonded so that tension is applied to the electrolyte membrane sheet Ms on the roller surface of the pressure transport roller 132. A type of bonding mechanism may be provided. Further, a suction type bonding mechanism in which the pressure conveying roller 132 is replaced with a suction roller capable of suction from the roller surface may be provided.

  In the above-described embodiment, the widening mechanism 160 has a wire-type widening mechanism using the gripping wire 163. However, the sheet ends Pse at both ends in the width direction of the porous membrane sheet Ps are gripped across the transport area. Any mechanism that can widen the film while conveying the porous membrane sheet Ps may be used. Therefore, a tenter-type or clip-type widening mechanism that grips the sheet end Pse from above and below may be used.

DESCRIPTION OF SYMBOLS 100, 100A-100C ... Electrolyte membrane manufacturing apparatus 110 ... 1st sending roller 120 ... 2nd sending roller 130 ... Sheet conveyance roller 132 ... Pressure conveyance roller 140 ... Winding roller 150 ... Winding guide roller 160 ... Widening mechanism 161 ... Upstream sheet end gripping roller 162... Downstream side sheet end gripping roller 163... Gripping wire 170... Sheet cutting blade 180. ... drying furnace 231 ... drying furnace 241 ... first intermediate guide roller 242 ... second intermediate guide roller 243 ... third intermediate guide roller 244 ... fourth intermediate guide roller Bs ... back sheet CEs ... semi-finished electrolyte membrane sheet Ms ... electrolyte membrane Sheet Ps ... porous membrane sheet Pse ... sheet end Psh ... cut section Psh0 ... winding width PSH1 ... stretched width Pso ... surplus seat MD ... conveying direction dimension TD ... widthwise dimension

Claims (1)

A method for producing a reinforced electrolyte membrane in which an electrolyte membrane is reinforced with a porous membrane,
Stretching the porous membrane in the width direction while transporting the porous membrane in the transport zone in the longitudinal direction of the membrane;
With the transport roller for endpoint porous membrane transport disposed stretching ku region of porous membrane is stretched in the width direction, in Rukoto bonded to the electrolyte membrane to stretch already said porous membrane And a step of allowing the electrolyte resin constituting the electrolyte membrane to enter the pores of the porous membrane in a state of being stretched in the width direction .

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