JP2007134188A - Tube type fuel cell module and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tube type fuel cell module capable of improving reliability of seals, and its manufacturing method. <P>SOLUTION: This is the tube type fuel cell module which is equipped with hollow MEAs 2, and a heat medium tube 1 in which a heating medium making the MEAs 2 cooled or heated flows interior. The heat medium tube 1 is provided with first straight line parts 11 and second straight line parts 12, bending parts 13 in which the first straight line parts 11 and the second straight line parts 12 are connected. At surroundings of the first straight line parts 11 and the second straight line parts 12, the MEAs 2 are formed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a tube type fuel cell module and a method for manufacturing the same, and more particularly to a tube type fuel cell module capable of improving the reliability of a seal and a method for manufacturing the same.

  In recent years, research on tube-type fuel cells (hereinafter sometimes referred to as “tube-type PEFC”) has been promoted for the purpose of improving the power density per unit area to a certain level or more. A unit cell of a tube type PEFC (hereinafter sometimes referred to as a “tube type cell”) generally includes a hollow electrolyte layer and catalyst layers disposed inside and outside the electrolyte layer. MEA. For example, an electrochemical reaction is caused by supplying a hydrogen-containing gas inside the MEA and an oxygen-containing gas outside the MEA, and the electric energy generated by the electrochemical reaction is disposed inside and outside the MEA. Is taken out through a current collector. That is, in the tube type PEFC, one reaction gas (for example, hydrogen-containing gas) is supplied to the inside of the MEA provided in each unit cell, and the other reaction gas (for example, oxygen-containing gas) is supplied to the outside, thereby generating power. Therefore, the reaction gas supplied to the outer surface of two adjacent unit cells can be made the same. Therefore, according to the tube type PEFC, the separator that has the gas shielding performance in the conventional flat plate type PEFC is not required, and the unit cell can be effectively downsized.

As a technique related to such a tube-type PEFC, for example, Patent Document 1 discloses a technique related to a fuel cell in which all the components of a microcell are processed into a single fiber assembly. According to this technology, it is possible to produce a high-density energy output and minimize the volume of the electrochemical cell device (tube type fuel cell).
JP-T-2004-505417

  By the way, the electrolyte membrane provided in the tube-type cell exhibits proton conduction performance in a predetermined temperature range (for example, a range of about 80 ° C. or the like). Therefore, when the tube type PEFC is operated, it is required to maintain the temperature of the electrolyte membrane within the above temperature range. Therefore, in a tube type PEFC module having a tube type cell, a heat medium pipe is arranged inside and / or outside the tube type cell for the purpose of setting the temperature of the electrolyte membrane to an appropriate range, and the like. The tube-type cell is heated or cooled using a heat medium flowing through the.

  Thus, in the tube type PEFC, since a heat medium is used in addition to the hydrogen-containing gas and the oxygen-containing gas, the tube type PEFC module has an essential structure for sealing each of these fluids. It is provided at the end of the MEA. And in the conventional tube type PEFC module as disclosed in Patent Document 1, for example, a seal part for isolating two kinds of reaction gas, a seal part for isolating the reaction gas and the heat medium, And the seal | sticker part for isolating a heat carrier and air | atmosphere is arrange | positioned.

  However, when the temperature of each component represented by the tube type cell, the heat medium pipe, and the like rises by operating the tube type PEFC having the form disclosed in Patent Document 1, the tube type cell and the heat medium The tube expands. Therefore, the tube-type PEFC having a complicated seal structure having a large number of seal portions has a problem that the reliability of the seal is likely to be lowered, and it is difficult to solve this problem with the technique disclosed in Patent Document 1. there were.

  Therefore, an object of the present invention is to provide a tubular fuel cell module capable of improving the reliability of a seal and a method for manufacturing the same.

In order to solve the above problems, the present invention takes the following means. That is,
The invention according to claim 1 includes a hollow MEA and a heat medium pipe through which a heat medium for cooling or heating the MEA flows. The heat medium pipe includes the first straight portion and the second heat medium pipe. A tube type comprising: a straight portion; and a bent portion connecting the first straight portion and the second straight portion; and MEA is formed around the first straight portion and the second straight portion. The fuel cell module solves the above problem.

In the present invention and the invention shown below, “hollow MEA” means at least a hollow inner catalyst layer, an outer catalyst layer disposed outside the inner catalyst layer, an inner catalyst layer, and an outer catalyst. Meaning MEA including an electrolyte membrane sandwiched between layers. Furthermore, specific examples of the heat medium include water, ethylene glycol, and a mixture thereof. In addition, as long as the heat medium pipe is made of a material having corrosion resistance that can withstand the operating environment of the tube type PEFC, the constituent material is not particularly limited. However, from the viewpoint of facilitating the downsizing of the tube type fuel cell module by having the heat medium tube also function as an internal current collector, it has good electrical conductivity in addition to the above corrosion resistance. It is preferable that it is made of a material. Specific examples of the material having the corrosion resistance and good electric conductivity include Au and Pt, as well as a Cu surface coated with Ti (for example, a Cu-Ti clad material). In addition, the axial direction of the first linear portion and the axial direction of the second linear portion provided in the heat medium pipe from the viewpoint of effectively improving the output density of the tubular fuel cell module according to the present invention. Are preferably parallel to each other.
Furthermore, “the MEA is formed around the first straight part and the second straight part” means that when the heat medium pipe also functions as an internal current collector, the heat medium pipe is provided. This means that the MEA is formed on the outer surfaces of the first straight portion and the second straight portion. On the other hand, when an internal current collector is disposed between the heat medium tube and the MEA, the internal current collector disposed on the outer surfaces of the first straight portion and the second straight portion of the heat medium tube. It means that MEA is formed on the outer surface of the body.

  According to a second aspect of the present invention, in the tube-type fuel cell module according to the first aspect, the first straight portion, the second straight portion, and the bent portion are formed by bending one heat medium tube. It is characterized by.

  Here, “formed by bending one heat medium pipe” means that at least a part of the heat medium pipe is formed in a U shape by bending one heat medium pipe. It means that the U-shape is composed of a first straight part, a bent part, and a second straight part.

  According to a third aspect of the present invention, in the tubular fuel cell module according to the first or second aspect, the inlet and the outlet of the heat medium pipe are located on the same side with respect to the axial center of the MEA. Features.

  The invention according to claim 4 is a method for manufacturing a tubular fuel cell module, comprising: a hollow MEA; and a heat medium pipe through which a heat medium for cooling or heating the MEA flows. An MEA forming step of forming an MEA around the tubular member, and after the MEA forming step, the straight tubular member is bent to form a first straight portion and a second straight portion, and a first straight portion and a second straight line. And a bending step of obtaining a bent body in which the MEA is formed around the heating medium tube. In the MEA forming step, at least a length corresponding to the bending portion. The MEA is sequentially formed with a gap between the steps, or after the bending step, further includes a removing step of removing the MEA formed at least around the bent portion. To the manufacturing method Ri, to solve the above-mentioned problems.

Here, the “straight tube-shaped member” means a heat transfer medium tube before being bent to form a bent portion. Furthermore, the “form MEA on the outside of the straight pipe-shaped member” is described as a heat medium pipe formed by bending the straight pipe-shaped member (hereinafter simply referred to as “heat medium pipe”). ) Can also be divided into a case having the function of the internal current collector and a case having no function of the internal current collector. As a specific example when the heat medium pipe also has the function of an internal current collector, first, a form in which the MEA is formed so that the outer surface of the heat medium pipe and the inner catalyst layer of the MEA are in contact with each other is given. it can. Further, in order to easily remove MEA formed in the vicinity of the bent portion and in the vicinity of the inlet and outlet (hereinafter, also referred to as “MEA removal place”), is the water repellent treatment applied to the MEA removal place in advance? Or after arranging a masking member etc., the form etc. which form MEA on the outer surface of a heat-medium pipe | tube at locations other than a MEA removal location, MEA removal location on the said water-repellent treatment or a masking member, etc. are mentioned. it can. On the other hand, when the heat medium pipe does not have the function of the internal current collector, it is necessary to dispose the internal current collector between the MEA and the heat medium pipe. The form etc. which form MEA in the outer surface of the internal electrical power collector arrange | positioned so that it may contact can be mentioned.
Furthermore, as a specific example of the method of “sequentially forming MEAs with a gap of a length corresponding to the bent portion”, there is a form in which a melted or dissolved catalyst layer component or electrolyte membrane component is intermittently applied. it can. In addition, specific examples of the method of “removing the MEA formed around the bent portion” include a form in which the MEA is melted and removed by applying a laser beam to the MEA removal location and heating, or the MEA removal location. In addition to the mode of removing the mask by immersing it in a solvent, the masking member and the mode of removing the MEA formed on the surface of the masking member by removing the masking member previously disposed at the MEA removal location are listed. be able to.

  According to the first aspect of the present invention, since the adjacent first straight line portion and the second straight line portion can be connected by the bent portion, it has n straight portions and n−1 bent portions. It can be set as the form provided with the heat-medium pipe | tube of the meandering shape. Thus, if the heat medium pipe is formed in a meandering shape, the inlet and outlet of the heat medium can be limited, and the structure of the seal portion formed between the reaction gas and the heat medium is simplified. It becomes possible. In addition, since the cooling pipe is in contact with the inside of the tube-type fuel cell, the inside of the tube-type fuel cell that is particularly susceptible to heat can be efficiently cooled. Therefore, according to the present invention, it is possible to provide a tube type fuel cell module capable of improving the reliability of the seal by simplifying the structure of the seal portion.

  According to the second aspect of the present invention, since the first straight portion, the second straight portion, and the bent portion are formed by bending one heat medium pipe, the first straight portion and the second straight portion are formed. The connection between the straight portion and the bent portion can be avoided, and the reliability of the seal can be further improved.

  According to the invention described in claim 3, since the inlet and outlet of the heat medium pipe are located on the same side with respect to the axial center of the MEA, only on the side where the inlet and outlet are located, A seal portion that separates the reaction gas and the heat medium can be formed, and the structure of the seal portion can be easily simplified.

  According to the fourth aspect of the present invention, the manufacturing process includes the step of making the heat medium pipe meandered and the step of forming the MEA around the heat medium pipe. By limiting the above, a tubular fuel cell module that can simplify the seal structure is manufactured. According to such a tubular fuel cell module, since the number of seals can be reduced as compared with the prior art, the reliability of the seal is improved. Therefore, according to the present invention, it is possible to provide a method for manufacturing a tube-type fuel cell module capable of improving the reliability of the seal.

  For the purpose of maintaining the tube type cell in an appropriate temperature range, etc., the tube type PEFC module is provided with a heat medium pipe through which a heat medium passes. Since the heat medium pipe provided in the conventional tube type PEFC module (hereinafter referred to as “conventional module”) has a straight pipe shape, it is formed between the reaction gas diffusion region and the heat medium diffusion region. The number of penetration points through which the heat medium pipe penetrates the seal portion (described later) is the same as the number of heat medium pipes, and the seal structure is complicated. That is, in the conventional module, since there are many through portions that penetrate the seal and the interval between them is very narrow, the seal structure is easily complicated and the reliability of the seal is easily lowered. There was a problem that the stability as "system" tends to be lowered. In order to improve the reliability of the seal, it is effective to reduce the number of through portions and / or the number of seal portions (seal portions), and the stability of the system can be improved while reducing the number of through portions and / or seal portions. If it can be ensured, the system can be downsized and the output density can be improved.

  The present invention has been made from such a viewpoint, and the gist of the present invention is that it has a configuration including a meandering heat medium pipe and an MEA formed around the heat medium pipe. It is an object of the present invention to provide a tube-type fuel cell module capable of reducing the above-described conventional module and improving the reliability of the seal, and a manufacturing method thereof.

  Hereinafter, the tube type fuel cell module and the manufacturing method thereof according to the present invention will be described in detail with reference to the drawings.

1. Tube Type Fuel Cell Module FIG. 1 is a perspective view schematically showing a part of the tube type fuel cell module of the present invention according to the first embodiment. As shown in the figure, a tube type fuel cell module 100 of the present invention (hereinafter referred to as “module of the present invention”) 100 has a heat medium pipe 1 formed in a meandering shape, and a periphery of the heat medium pipe 1. Are formed, and an external current collector (not shown) disposed so as to be in contact with each MEA 2, 2,..., And a bent portion 13 of the heat medium pipe 1 are provided. , 13,..., 13... And a current collector 3 (see FIG. 6). The heat medium pipe 1 provided in the module 100 of the present invention also has a function as an internal current collector, and bends a single straight pipe having a Cu-Ti clad material as a base material to bend portions 13, 13, Are formed by forming first straight portions 11, 11,... And second straight portions 12, 12,..., And bent portions 13, 13,. .. Are formed on the outer surface of the heat medium pipe 1 to diffuse the reaction gas to the inside of the MEA 2, and a heat medium (for example, water or the like in the following description) is formed in the hole 17. , Sometimes referred to as “water”). Moreover, in the heat medium pipe | tube 1 concerning this embodiment, both the inlet 14 and the exit 15 are located in the near side.

  As described above, according to the module 100 according to the present embodiment, since the inlet 14 and the outlet 15 of the heat medium pipe 1 are both located on the near side, the reaction with the heat medium flowing through the holes 17 of the heat medium pipe 1 is achieved. It is sufficient to form a seal portion for sealing with gas only at the end portion on the near side of the MEAs 2, 2,..., And the seal structure can be simplified by reducing the number of seal portions. Furthermore, since the inlet and outlet of the heat medium pipe 1 are limited to the inlet 14 and outlet 15 only, only the inlet 14 and outlet 15 are formed between the heat medium diffusion region and the reaction gas diffusion region. By setting it as the form which penetrates a part (after-mentioned), a penetration location can be reduced and a seal structure can be simplified further.

  FIG. 2 is a cross-sectional view schematically showing a part of the heat medium pipe and the MEA shown in FIG. 1, and the direction perpendicular to the paper surface is the axial direction of the MEA. In FIG. 2, the reference numerals used in FIG. 1 are used, and the description of each part / member is omitted as appropriate. Hereinafter, the module of the present invention will be described with reference to FIGS. 1 and 2.

  As shown in FIG. 2, the MEA 2 formed on the outer surface of the heat medium pipe 1 includes an inner catalyst layer 21, an electrolyte membrane 22 formed on the outer side, an outer catalyst layer 23 formed on the outer side, The inner surface of the inner catalyst layer 21 and the outer surface of the heat medium pipe 1 are in contact with each other. And the heat medium pipe | tube 1 which also has a function as an internal electrical power collector is provided with the hole 17 as a heat medium flow path, and the reaction gas flow paths 16, 16,. As described above, in the module 100 of the present invention, the reaction gas (hydrogen-containing gas or oxygen-containing gas) is supplied to the inner catalyst layer 21 through the reaction gas passages 16, 16,... Formed in the heat medium pipe 1. The electricity generated by the MEA 2 is collected in the axial direction of the MEA 2 by the heat medium pipe 1. Further, since the heat medium pipe 1 is in contact with the inner catalyst layer 21, the MEA 2 can be cooled or heated by flowing cold water or hot water through the holes 17.

  FIG. 3 is a cross-sectional view schematically showing a configuration example of the seal portion provided in the module of the present invention, and FIG. 4 is a cross-sectional view schematically showing a configuration example of the seal portion provided in the conventional module. The vertical direction is the axial direction of the MEA. FIG. 3 shows only a part of the heat medium pipe, the MEA, and the seal portion provided in the module of the present invention. In addition, in FIG. 3, although the heat medium pipe | tube of the form which has three bending parts was shown, the form of the heat medium pipe | tube with which the module of this invention is equipped is not limited to the form of illustration. On the other hand, FIG. 4 shows the configuration of a conventional module provided with the same number of straight heat medium pipes as the straight part of the heat medium pipe shown in FIG. 3 and 4, components having the same configuration as the components of the module shown in FIG. 1 are denoted by the same reference numerals as those used in FIG. 1, and description thereof is omitted as appropriate. Moreover, in FIG.3 and FIG.4, description of the inlet_port | entrance of hydrogen, air, and water, and an exhaust port is abbreviate | omitted, The hydrogen-containing gas diffusion area | region and oxygen-containing gas diffusion area | region as a reactive gas diffusion area | region And the seal portion disposed between the hydrogen-containing gas diffusion region and the heat medium diffusion region are highlighted. In addition, the straight arrow of FIG.3 and FIG.4 has shown the flow direction of the water which flows through the inside of a heat-medium pipe | tube.

  As shown in FIG. 3, the module 100 ′ according to the present embodiment includes the heat medium pipe 1 and MEAs 2, 2,... Disposed on the outer surface of the heat medium pipe 1. The heat medium pipe 1 is produced by bending one straight pipe having a Cu—Ti clad material as a base material to form bent portions 13, 13,..., , Second straight portions 12, 12 and bent portions 13, 13,... In the illustrated module 100 ′, the central portion is referred to as an oxygen-containing gas diffusion region (hereinafter referred to as “oxygen diffusion region”) 7, and both sides of the oxygen diffusion region 7 are referred to as hydrogen-containing gas diffusion regions (hereinafter referred to as “hydrogen diffusion regions”). ) 6 and 6, and seal portions 5 a and 5 a are provided between the oxygen diffusion region 7 and the hydrogen diffusion regions 6 and 6, and are referred to as a hydrogen diffusion region 6 and a heat medium diffusion region (hereinafter referred to as “water diffusion region”). ) 8 are formed with seal portions 5b. As described above, according to the module 100 ′ of the present invention, since only the inlet 14 and the outlet 15 of the heat medium pipe 1 penetrate the seal portion 5 b, the structure of the seal portion can be simplified.

  On the other hand, the conventional module 900 shown in FIG. 4 has the straight heat transfer pipes 10, 10,... And the MEAs 2, 2,. … And. The module 900 shown in FIG. 3 also has an oxygen diffusion region 7 at the center and hydrogen diffusion regions 6 and 6 on both sides of the oxygen diffusion region 7 in the same manner as the module 100 ′ shown in FIG. Seal portions 5 a and 5 a are formed between the regions 6 and 6, and seal portions 95 b and 95 b are formed between the hydrogen diffusion regions 6 and 6 and the water diffusion regions 8 and 8, respectively. When the number of the heat medium pipes 10, 10,... Is “t”, in the conventional module 900, since the number of through portions penetrating each seal portion 95b is “t”, the seal structure is complicated and the seal is made. There was a problem that the reliability of the system was likely to be lowered.

  As shown in FIGS. 3 and 4, according to the module 100 ′ of the present invention, the heat medium pipe 1 has a meandering shape, so that the interval between the penetrating portions penetrating the seal portion 5 b is increased and the number of penetrating portions is increased. Can be reduced, thereby improving the reliability of the seal. Furthermore, according to the module 100 ′ of the present invention, since it is not necessary to provide a heat medium diffusion region on both ends of the module, it is possible to easily reduce the size by reducing the sealing portion, and the output density of the module 100 ′. Can be improved.

  In the above description, the form in which the inlet and outlet of the heat medium pipe are located on the same side with respect to the axial center of the MEA is exemplified, but the form of the heat medium pipe provided in the module of the present invention is in this form. The present invention is not limited, and the inlet and outlet of the heat medium pipe may be located on the opposite side with respect to the axial center of the MEA. However, from the standpoint of facilitating downsizing of the module, it is preferable that the inlet and outlet of the heat medium pipe are located on the same side with respect to the axial center of the MEA.

  Moreover, although the module 100,100 'provided with the heat-medium pipe | tube 1 of the form which can mount the 1st linear part 11 and the 2nd linear part 12 on a horizontal surface until now was illustrated, it is provided in the module of this invention. The form of the heat transfer tube is not limited to this. FIG. 5 shows another form example that the heat medium pipe provided in the module of the present invention can take.

  FIG. 5 is a perspective view schematically showing a part of the module of the present invention according to the second embodiment. 5, components having the same configuration as the components of the module shown in FIG. 1 are denoted by the same reference numerals as those used in FIG. 1, and description thereof will be omitted as appropriate.

  As shown in FIG. 5, the module 200 of the present invention according to the second embodiment includes a heat medium pipe 1a and MEAs 2, 2,... Formed on the outside of the heat medium pipe 1a. , An external current collector disposed so as to be in contact with each MEA 2, 2,..., And a current collector (not shown) disposed so as to be in contact with the bent portions 13a, 13a,. It is equipped with. As shown in the figure, the heat medium pipe 1a according to the second embodiment includes first straight portions 11, 11,..., Second straight portions 12, 12,... And bent portions 13a, 13a,. It is formed to have a substantially cylindrical shape, and the inlet 14 and the outlet 15 of the heat medium pipe 1a are adjacent to each other. In the present embodiment, the heat medium pipe 1a also has a function as an internal current collector, and bends one straight pipe having a Cu-Ti clad material as a base material to bend the bent portions 13a, 13a,. It is produced by forming. .. Are formed on the outer surface of the heat medium pipe 1 a to diffuse the reaction gas to the inside of the MEA 2, and a heat medium such as water flows through the holes 17.

  Thus, according to the module 200 concerning 2nd Embodiment, since the inlet 14 and the exit 15 of the heat-medium pipe | tube 1a are adjacent, a seal structure can be simplified.

  Moreover, according to the module 200 concerning 2nd Embodiment, since the heat-medium pipe | tube 1a is formed in the substantially cylindrical shape, it becomes possible to improve the intensity | strength as the whole module, and improves the handleability of a module. Can be made. On the other hand, in the modules 100 and 100 ′ according to the first embodiment, since the heat medium pipe 1 can be placed on a horizontal plane, a gap between the MEAs 2, 2,. In addition to being easy, since it does not have a central space formed in the case of a substantially cylindrical shape, it is easy to improve the output density. Therefore, from the viewpoint of improving the output density, it is preferable to use the modules 100 and 100 ′ of the first embodiment, and from the viewpoint of improving the ease of handling of the module, the module of the second embodiment. The module 200 is preferable.

  In order to easily understand the configuration of the module of the present invention, in FIG. 1 to FIG. 5, the description of the current collector disposed so as to be in contact with the bent portion is omitted. From the viewpoint of improving the current collection efficiency in the intersecting direction, the module of the present invention is provided with the current collector. Therefore, FIG. 6 schematically shows a module having a current collector disposed so as to be in contact with the bent portion.

FIG. 6 is a perspective view schematically showing a form example of the module of the present invention according to the first embodiment. As shown in the figure, the module 100 of the present invention has a current collector 3 in such a form that it contacts the bent portions 13, 13,... On the side where the inlet 14 and the outlet 15 of the heat medium pipe 1 are not located. Is provided. Thus, in the module of the present invention, the current collection efficiency in the direction intersecting with the axial direction of the MEA is improved by providing the current collector in contact with the bent portion of the heat medium pipe.
In addition, although FIG. 6 illustrated the form with which the collector 3 arrange | positioned so that it might contact with the bending parts 13, 13, ... of the side in which the inlet_port | entrance 14 and the exit 15 of the heat-medium pipe | tube 1 are not located was provided. The present invention is not limited to this form. In addition to the form shown in FIG. 6, the current collector is arranged so as to be in contact with the bent part on the side where the inlet and the outlet of the heat medium pipe are located, and the bent part on both sides are in contact with each other. It is also possible to adopt a form in which the first current collector and the second current collector arranged in the are provided. Among these forms, from the viewpoint of further improving the current collection efficiency, it is preferable that the first current collector and the second current collector are provided.

  In the above description, a mode in which hydrogen is supplied to the inside of the MEA and air is supplied to the outside is illustrated, but the present invention is not limited to this mode, and air is supplied to the inside of the MEA and hydrogen is supplied to the outside. It can also be in the form.

2. Method for Manufacturing Tube Type Fuel Cell Module FIG. 7 shows a simplified example of the method for manufacturing the tube type fuel cell module according to the present invention. In the module of the present invention, a heat medium pipe having only a function of heating or cooling the MEA may be provided, but from the viewpoint of facilitating downsizing of the module by reducing the number of components. As described above, it is preferable that the heat medium pipe also has a function as an internal current collector. Therefore, in the following description, an example of a module manufacturing process in which a heat medium pipe having a function as an internal current collector is provided will be described. Furthermore, in the manufacturing method of the present invention, as shown in FIG. 1 and the like, the form of MEA is formed on the surface of the straight portion of the heat transfer tube by exposing the bent portion surface of the heat transfer tube. The form which forms MEA avoiding and the form which removes MEA formed in the MEA removal location after forming MEA in the outer surface of a heat-medium pipe | tube (2) are considered. As a specific form of (2), for example, (2a) a form in which a masking member is previously disposed at an MEA removal location, an MEA is formed, and the masking member is removed after the MEA is formed is considered. Therefore, in the following description, the form (2a) is described, and the outline of the other forms is described. Hereinafter, the manufacturing method of the tube type fuel cell module of the present invention will be described while appropriately using the symbols used in FIGS. When the heat medium tube also functions as an internal current collector, the surface of the heat medium tube that contacts the heat medium (for example, the inner surface) is made of an insulating material from the viewpoint of preventing leakage. It is preferable to coat.

  In order to manufacture the tube type fuel cell of the present invention, first, a straight pipe-shaped heat medium pipe having holes 17 and grooves 16, 16,... Is prepared, and MEA 2 is formed on the outer surface of the heat medium pipe. Here, examples of the constituent material of the electrolyte membrane 22 provided in the MEA 2 include a fluorine-containing ion exchange resin, and examples of the constituent materials of the inner catalyst layer 21 and the outer catalyst layer 23 include a fluorine-containing ion exchange resin. And platinum-supported carbon.

  In order to form the MEA 2 on the outer surface of the straight pipe-shaped heat transfer medium pipe, for example, the MEA removal position of the heat transfer medium pipe (the position corresponding to the bent portions 13, 13,. A masking member is disposed on the outer surface of 15) (step S1; masking step). Then, a solvent such as platinum-supported carbon is dispersed in a solution containing, for example, a fluorine-containing ion exchange resin dissolved in an organic solvent on the outer surface of the heat transfer tube partially covered with a masking member. The inner catalyst layer 21 is formed by applying and drying the catalyst ink (hereinafter simply referred to as “catalyst ink”). Next, an electrolyte membrane 22 is formed by applying a fluorine-containing ion exchange resin or the like dissolved in an organic solvent (hereinafter referred to as “electrolyte component”) to the surface of the inner catalyst layer 21 and drying. Further, the catalyst ink is applied to the surface of the electrolyte membrane 22 and dried to form the outer catalyst layer 23 to form the MEA 2 on the outer surface of the heat transfer pipe (step S2; MEA forming step).

Thus, when the MEA 2 is formed on the outer surface of the straight pipe-shaped heat transfer medium tube, the bent portion 13 is sequentially bent by bending the portions corresponding to the bent portions among the portions where the masking member is disposed in the step S1. Are formed (step S3; bent portion forming step). After the step S3, the masking member is removed, and the MEA 2 formed on the outer surface of the MEA removal portion is removed, whereby the module 100 having the form shown in FIG. 1 (hereinafter referred to as “bent body”). (Step S4; removal step). When the bent body is formed by the above process, seal portions 5a, 5a,... That separate hydrogen and air are formed, and further, seal portions 5b, 5b are formed around the inlet 14 and the outlet 15 of the heat medium pipe. (Step S5; seal portion forming step). And after process S5 is complete | finished, the module of this invention can be manufactured by passing through processes, such as putting the bending body provided with the seal part manufactured by process S1-S5 into a predetermined | prescribed housing | casing.
Since the module 100 manufactured by such a process is provided with the heat medium pipe 1 having a meandering shape, the number of seals can be reduced. Therefore, according to the present invention, it is possible to provide a method for manufacturing a tube-type fuel cell module capable of improving the reliability of the seal.

  In the description related to the manufacturing method of the present invention, the form (2a) has been described, but the manufacturing method of the present invention is not limited to this form. As a specific example of the form (above (1)) in which the MEA is formed while avoiding the MEA removal site, which can be adopted by the production method of the present invention, the catalyst ink and the electrolyte component are applied to the outer surface of the straight heat medium pipe. In this case, a form where intermittent application is performed while avoiding the MEA removal site (intermittent application form) can be exemplified. Moreover, after forming MEA in the whole outer surface of a heat-medium pipe | tube, as another specific example of the form (above (2)) which removes MEA formed in a MEA removal location, only a MEA removal location is used as a solvent. Examples include a form in which the MEA is soaked and dissolved and removed, and a form in which the MEA is melted and removed by applying a laser beam only to the MEA removed part. In addition, as another specific example of the above (2), the MEA removal location is preliminarily treated with water repellency so that it is difficult to form the MEA, and then the MEA is removed by high pressure washing or the like. Can be mentioned. Here, when using an intermittent application form, it is good also as a form which masks a member beforehand in the said location and removes the said masking member after intermittent application.

  In addition, when using a masking member in the production method of the present invention, the material and form of the masking member are particularly limited as long as the catalyst ink and the electrolyte component can be prevented from adhering to the outer surface of the heat transfer medium tube. Not. Specific examples of the masking member include polyethylene resin, polypropylene resin, and blended materials thereof.

  Moreover, although the module of the form provided with the heat-medium pipe | tube comprised with a Cu-Ti clad material was illustrated so far, the constituent material of the heat-medium pipe | tube concerning this invention is not limited to this. Specific examples of the constituent material of the heat medium pipe according to the present invention include Au and Pt in addition to the Cu-Ti clad material.

Further, in the above description, the heat medium pipe having the first straight part, the second straight part, and the bent part is formed by bending one straight pipe-shaped heat medium pipe to form a bent part. Although described, the heat transfer tube according to the present invention is not limited to this form. The heat medium pipe | tube concerning this invention may be formed by connecting a straight pipe and a U-shaped pipe, for example. Even with the heat medium pipe of this form, the number of seal portions between the hydrogen diffusion region and the heat medium can be reduced, but a process of connecting the straight pipe and the U-shaped pipe is required at the time of manufacturing. Therefore, from the viewpoint of improving workability when manufacturing the module of the present invention, it is preferable to bend the straight pipe-shaped heat medium pipe to form a bent portion.
As a specific example of the heat medium flowing in the heat medium pipe provided in the module of the present invention, when cooling the tube type cell, the tube type cell is heated with cold water, ethylene glycol, and a mixture thereof. In some cases, warm water can be used.

  In addition, a hollow inner catalyst layer, a hollow electrolyte membrane, and a hollow outer catalyst whose axial center is substantially the same as the heat medium pipe outside the heat medium pipe having holes and grooves. Although the form by which MEA provided with a layer was formed was illustrated, the module of this invention is not limited to the said form. In the module of the present invention, for example, a plurality of internal current collectors made of wire rods are arranged so as to be in contact with the outer surface of the straight portion of the heat medium pipe having a meandering shape, and outside the internal current collector, A configuration in which a plurality of wires having an inner catalyst layer formed on the surface is disposed, and a bent body in which an electrolyte membrane and an outer catalyst layer are sequentially formed outside the wire with the inner catalyst layer may be employed. Even in such a form, if the heat medium pipe has a meandering shape, it becomes possible to reduce the number of seals, so that the tubular fuel cell module that can improve the reliability of the seal, and its manufacture A method can be provided.

  In addition, as a specific example of the constituent material of the seal part provided in the module of the present invention, a thermosetting resin (for example, epoxy resin) or an adhesive (for example, a heat-resistant epoxy adhesive) that is cured by mixing two liquids And the like.

It is a perspective view which shows roughly a part of module of this invention concerning 1st Embodiment. It is sectional drawing which shows roughly the heat-medium pipe | tube concerning this invention, and a part of MEA. It is sectional drawing which shows schematically the seal part of the module of this invention. It is sectional drawing which shows schematically the seal part of the conventional type module. It is a perspective view which shows roughly a part of module of this invention concerning 2nd Embodiment. It is a perspective view which shows roughly a part of module of this invention concerning 1st Embodiment. It is the schematic which shows the manufacturing process example of the module of this invention simplified.

Explanation of symbols

1 Heat transfer tube 2 MEA
Reference Signs List 3 Current collector 5a, 5b Seal portion 6 Hydrogen diffusion region 7 Oxygen diffusion region 8 Heat medium diffusion region 11 First straight portion 12 Second straight portion 13 Bending portion 14 Inlet 15 Outlet 16 Reactive gas flow path 17 Hole 21 Inner catalyst layer 22 Electrolyte membrane 23 Outer catalyst layer 100, 100 ', 200 Tube type fuel cell module

Claims (4)

A hollow MEA, and a heat medium pipe through which a heat medium to cool or heat the MEA flows,
The heat medium pipe includes a first straight part and a second straight part, and a bent part that connects the first straight part and the second straight part,
The tube fuel cell module, wherein the MEA is formed around the first straight portion and the second straight portion. 2. The tube-type fuel cell module according to claim 1, wherein the first straight portion, the second straight portion, and the bent portion are formed by bending one heat medium tube. . 3. The tube type fuel cell module according to claim 1, wherein an inlet and an outlet of the heat medium pipe are located on the same side with respect to an axial center of the MEA. A method of manufacturing a tubular fuel cell module, comprising: a hollow MEA; and a heat medium pipe through which a heat medium to cool or heat the MEA flows.
An MEA forming step of forming the MEA around a straight pipe-shaped member;
After the MEA forming step, the straight pipe-shaped member is bent to include a first straight portion and a second straight portion, and a bent portion connecting the first straight portion and the second straight portion. And a bending step of obtaining a bent body in which the MEA is formed around the heat medium pipe,
In the MEA forming step, the MEAs are sequentially formed with a length corresponding to at least the bent portion, or after the bending step, at least the MEA formed around the bent portion. A method for producing a tube-type fuel cell module, comprising a removing step of removing the gas.

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