JP2000021418A - Solid high polymer electrolyte fuel cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce cost at mass producing, and to reduce size by providing a pair of electrodes for sandwiching a solid high polymer electrolyte film and a supply discharge means of fuel gas, constituting a conductive separator between laminated cells out of metal having an inactive metallic layer on the surface in an acidic atmosphere, and connecting the gas flowing groove to the gas supply discharge means by a gas sealing material. SOLUTION: A conductive separator is preferably consists an SUS 316 plate having the surface plate with gold and silver, and on the hydrogen side, a gas guiding phenol groove 6 up to a wavy gas flowing groove is formed of the phenol projecting part 5 from a manifold hole 4 through press working. A curved continuing gas flowing groove is arranged in an air side separator. An electrode/electrolyte jointing body having a positive/negative electrode catalyst layer jointed to both surfaces of the central part of a proton conductive high polymer electrolyte film, is sandwiched by two kinds of separators and a gasket to become a constituting unit of a fuel cell. The separator can be formed thinner than a carbon plate by obviating cutting work.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a portable power supply,
The present invention relates to a fuel cell using a solid polymer electrolyte used for an electric vehicle power supply, a home cogeneration system, and the like.

[0002]

2. Description of the Related Art A fuel cell using a solid polymer electrolyte is
Electric power and heat are simultaneously generated by electrochemically reacting a fuel gas containing hydrogen and a fuel gas containing oxygen such as air. First, its structure
On both surfaces of a polymer electrolyte membrane that selectively transports hydrogen ions, a catalyst reaction layer mainly composed of carbon powder carrying a platinum-based metal catalyst is formed. Next, a diffusion layer having both gas permeability and electronic conductivity is formed on the outer surface of the catalyst reaction layer, and the diffusion layer and the catalyst reaction layer are combined to form an electrode.

Next, a gas seal material or a gasket is arranged around the electrodes with a polymer electrolyte membrane interposed therebetween so that the supplied fuel gas does not leak outside or the two types of fuel gas do not mix with each other. This sealing material and gasket are integrated with the electrode and polymer electrolyte membrane beforehand,
This is referred to as MEA (electrode electrolyte membrane assembly). MEA
A conductive separator plate for mechanically fixing the MEA and electrically connecting adjacent MEAs in series with each other is arranged outside the. A gas flow path for supplying a reaction gas to the electrode surface and carrying away generated gas and surplus gas is formed in a portion of the separator plate that contacts the MEA. Although the gas flow path can be provided separately from the separator plate, a method of providing a gas flow path by providing a groove on the surface of the separator is general.

In order to supply the fuel gas into the groove, a pipe jig for branching the pipe for supplying the fuel gas into the number of separators to be used and connecting the branch directly to the separator-shaped groove is required. . This jig is called a manifold, and the type directly connected from the fuel gas supply pipe as described above is called an external manifold. There is a type of this manifold called an internal manifold which has a simpler structure. In the internal manifold, a through hole is provided in a separator plate in which a gas flow path is formed, an inlet / outlet of the gas flow path is passed to this hole, and fuel gas is directly supplied from this hole.

[0005] Since the fuel cell generates heat during operation, it is necessary to cool the fuel cell with cooling water or the like in order to maintain the cell in a good temperature state. Usually, a cooling unit for flowing cooling water every 1 to 3 cells is inserted between the separators. In many cases, a cooling water flow path is provided on the back surface of the separator to serve as a cooling unit. The MEA, the separator and the cooling section are alternately stacked, and after stacking 10 to 200 cells, it is common to sandwich this with an end plate via a current collector plate and an insulating plate and fix it from both ends with fastening bolts. This is the structure of a simple stacked battery.

In such a polymer electrolyte fuel cell,
The separator is required to have high conductivity, high gas tightness with respect to the fuel gas, and high corrosion resistance to the reaction when redoxing hydrogen / oxygen. For this reason, the conventional separator is usually made of a carbon material such as glassy carbon or expanded graphite, and the gas flow path is formed by cutting the surface of the separator or, in the case of expanded graphite, by molding using a mold.

However, in recent years, attempts have been made to use metals such as stainless steel in place of conventionally used carbon materials.

[0008]

In the conventional method of cutting a carbon plate, it is difficult to reduce not only the material cost of the carbon plate but also the cost of cutting the carbon plate, and the method using expanded graphite is also difficult. The cost is high, and this is considered as an obstacle for practical use.

Further, in the above-mentioned method using a metal, the metal is exposed to an oxidizing atmosphere at a high temperature. Therefore, if the metal is used for a long time, corrosion or dissolution of the metal occurs. When metal corrodes,
The electric resistance of the corroded portion increases, and the output of the battery decreases.
Further, when the metal is dissolved, the dissolved metal ions diffuse into the polymer electrolyte and are trapped at ion exchange sites of the polymer electrolyte. As a result, the ion conductivity of the polymer electrolyte itself is reduced. For these reasons, there has been a problem that when the metal is used as it is for the separator and the battery is operated for a long period of time, the power generation efficiency gradually decreases.

[0010]

To solve the above problems, a solid polymer electrolyte fuel cell according to the present invention comprises a pair of electrodes sandwiching a solid polymer electrolyte membrane, and means for supplying and discharging fuel gas to and from the electrodes. In a solid polymer electrolyte fuel cell obtained by laminating a unit cell with a conductive separator, the conductive separator is made of a metal material having an inert metal layer formed on the surface with respect to an acidic atmosphere, and The conductive separator forms a gas flow groove through which the fuel gas flows, and further connects the gas flow groove and the means for supplying and discharging the fuel gas with a material having a gas sealing property with respect to the fuel gas. And

At this time, it is effective that the inert metal layer formed on the surface of the conductive separator with respect to the acidic atmosphere is made of gold or silver.

Further, it is effective that the metal layer formed on the surface of the conductive separator has a physical flexibility with respect to the acidic atmosphere with respect to the acidic atmosphere.

Further, it is effective that the gas flow grooves formed in the conductive separator have a plurality of linear shapes parallel to each other.

It is effective that the convex portion of the gas flow groove formed on one surface of the conductive separator forms a concave portion of the gas flow groove on the back surface of the conductive separator.

The above manufacturing method comprises a cleaning step, an activation step, a nickel strike plating step,
It has a gold plating or silver plating process.

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The point of the present invention is to suppress the corrosion and dissolution of a conductive separator made of metal, thereby maintaining its chemical inertness even when exposed to an acidic atmosphere while maintaining its conductivity. I found a way to do that.

When a conductive separator made of a metal material is used in a fuel cell, the convex portion of the gas flow groove formed on one surface of the conductive separator forms a concave portion of the gas flow groove on the back surface of the conductive separator. It is useful to form.
However, when this was used to form a laminated battery, the electrical contact portion of the conductive separator became point contact, and when this was exposed to an acidic atmosphere for a long time, the contact resistance of this portion increased. In order to overcome this phenomenon, for example, a sponge-like conductive layer having physical flexibility is formed on the surface of the conductive separator to overcome the above-mentioned increase in contact resistance.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

[0019]

(Example 1) A catalyst for a reaction electrode was prepared by supporting 25% by weight of platinum particles having an average particle size of about 30 on acetylene black-based carbon powder. A dispersion solution of the perfluorocarbon sulfonic acid powder shown in Chemical Formula 1 in ethyl alcohol was mixed with a solution of this catalyst powder dispersed in isopropanol to form a paste. Using this paste as a raw material, an electrode catalyst layer was formed on one surface of a carbon nonwoven fabric having a thickness of 250 μm using a screen printing method. Amount of platinum contained in the reaction electrode after forming the 0.5 mg / cm ^2, the amount of perfluorocarbon sulfonic acid was adjusted to be 1.2 mg / cm ^2.

[0020]

Embedded image

These electrodes have the same structure for both the positive electrode and the negative electrode, and the catalyst layers printed on both sides of the central portion of the proton conductive polymer electrolyte membrane having an area slightly larger than the electrodes so that the catalyst layers are in contact with the electrolyte membrane side. The electrode / electrolyte assembly (MEA) was formed by joining by hot pressing. Here, as the proton conductive polymer electrolyte, a thin film of the perfluorocarbon sulfonic acid shown in Chemical Formula 2 with a thickness of 25 μm was used.

[0022]

Embedded image

The structure of each component of the polymer electrolyte fuel cell manufactured in this embodiment is shown in FIGS. 1, 2 and 3.

First, a method for producing a conductive separator made of metal whose surface is gold-plated will be described. As shown in FIG. 1, a SUS316 plate having a thickness of 0.3 mm was used, and a 5.6 mm pitch (groove width of about 2.8 mm) corrugated processing section 1 was press-formed in a central area of 10 cm × 9 cm. Formed by At this time, the depth of the groove 2 (the height of the mountain 3) is about 1 m
m. Next, a gold plating layer was formed on this surface to a thickness of 0.5 μm. The plating method is as follows: cleaning is performed using dipsol (trade name of Dipsol Co.) as a cleaning agent, activation treatment is performed with a hot sulfuric acid solution heated to 80 ° C., and then nickel strike plating treatment and nickel plating are performed. Treatment and gold plating. Next, as shown in FIG. 1, manifold holes 4 for supplying / discharging hydrogen gas, cooling water, and air were provided on two opposing sides, respectively.

Next, as shown in FIG. 2 (a), a gas is guided to the separator on the hydrogen side from the manifold hole to the gas flow groove formed by processing the metal plate by the convex portion 5 made of phenol resin. Groove 6 is provided. In addition, the protrusions 5 made of a phenol resin are overlapped so that the two grooves are adjacent to each other and are curved and connected.

The protrusion made of phenol resin had a thickness of about 1 mm and was equal to the height of the groove of the separator plate. The gasket 7 is formed in the same manner on the outer peripheral portion of the separator plate and around the manifold hole to correspond to the shape of the metal plate.

Further, as shown in FIG. 2B, in the separator on the air side, six adjacent grooves are formed so as to form a curved and continuous gas flow groove. The structure is changed between the air side and the hydrogen gas side because the gas flow rate differs between the air side and the hydrogen gas side by about 25 times. Conversely, in such a structure, it is possible to obtain an optimum gas flow rate and gas pressure loss by changing the shape of the resin gas flow groove in accordance with the gas flow rate.

Next, as shown in FIG. 3, the MEA 8 was sandwiched by these two types of separators and gaskets to form a structural unit of the battery. As shown in FIG. 3, the positions of the gas flow grooves 9 on the hydrogen side and the gas flow grooves 10 on the air side were configured to correspond to each other so that excessive sending force was not applied to the electrodes. A cooling unit 11 for flowing cooling water was provided for every two cells stacked. SUS316 metal mesh 12 is used for the cooling section to ensure conductivity and cooling water flow,
A gasket 7 made of phenol resin was provided on the outer peripheral portion and the gas manifold portion to form a seal portion. Grease 13 is applied thinly to portions requiring gas sealing, such as the gasket and MEA, the separator plate and the separator plate, and the gasket and the separator plate, so that the sealing properties are secured without significantly lowering the conductivity.

After stacking 50 cells of the above MEA, the MEA was fastened with a stainless steel plate and a fastening rod at a pressure of 20 kgf / cm ² via a current collector and an insulating plate. If the fastening pressure is too small, gas leaks and the contact resistance is large, so the battery performance will be reduced.On the contrary, if it is too large, the electrode will be damaged or the separator plate will be deformed. It was important to change the fastening pressure.

As the battery of the comparative example, a battery having a conductive separator formed of a SUS316 plate having no surface coating as in the batteries of the above-described examples was manufactured. In the battery of the comparative example, the configuration was the same as that of the above example except for the conductive separator.

The polymer electrolyte fuel cells of the present example and the comparative example thus prepared were maintained at 85 ° C., and hydrogen gas humidified and heated to a dew point of 83 ° C. was applied to one electrode side. Humidified and heated air was supplied to the other electrode side so as to have a dew point of 78 ° C. As a result, a battery open-circuit voltage of 50 V was obtained when there was no load in which no current was output to the outside.

The battery was subjected to a continuous power generation test under the conditions of a fuel utilization rate of 80%, an oxygen utilization rate of 40%, and a current density of 0.5 A / cm ² , and the change over time in output characteristics is shown in FIG. As a result, it was confirmed that the output of the battery of the comparative example decreased with the driving time, while the battery of the present example maintained the battery output of 1000 W (22 V-45 A) for 8000 hours or more.

In this embodiment, the case where the gas flow groove is a plurality of parallel straight lines is tried. However, as shown in FIG. 4, the gas discharge manifold hole is connected to the gas discharge manifold hole through the twice curved portion 14 from the gas supply manifold. Various structures are also possible, such as a connection structure and a structure in which a central manifold hole and an outer manifold hole are connected by a gas flow groove like a snail shell.

Although the case where the metal is in a plate shape has been tried, various shapes such as a sponge shape are also possible.

(Embodiment 2) In Embodiment 1, a conductive separator having a gold plating layer formed on a metal surface was used. In this embodiment, an example in which a silver plating layer is formed will be described. In this example, the plating method, the battery configuration, and the conditions for evaluating the characteristics of the battery were all the same as those in Example 1.

As in the first embodiment, the fuel cell was maintained at 85.degree. C., hydrogen gas humidified and heated to a dew point of 83.degree. C. was applied to one electrode, and 78 was applied to the other electrode.
Supply air humidified and heated to a dew point of ° C, fuel utilization 80%, oxygen utilization 40%, current density 0.5A
/ Cm ² shows the battery output at the initial time when the continuous power generation test was performed under the condition of / cm ² , and also when the operation time has passed 8000 hours. The results are shown in Table 1.

[0037]

[Table 1]

(Embodiment 3) In Embodiment 1, a conductive separator having a metal plating layer formed on the surface of a metal was used. In this embodiment, a gold paste layer having an organic binder component was further formed thereon. Then, an example in which a conductive layer having physical elasticity is formed on the surface portion of the conductive separator will be described. In this example, the plating method, the battery configuration, and the conditions for evaluating the characteristics of the battery were all the same as those in Example 1.

The method of forming a gold paste layer having an organic binder component is as follows: 50% by weight of gold particles having an average particle diameter of 20 μm.
With 10% by weight of a bisphenol-based epoxy monomer,
The mixture was dispersed in a mixture of 10% by weight of the curing agent and 50% by weight of ethylcellosolve as a diluent, and was applied on a gold plating layer formed on a conductive separator.
For 5 hours.

As in the first embodiment, the fuel cell was maintained at 85 ° C., and hydrogen gas humidified and heated so as to have a dew point of 83 ° C. was applied to one electrode side, and 78 g was applied to the other electrode side.
Supply air humidified and heated to a dew point of ° C, fuel utilization 80%, oxygen utilization 40%, current density 0.5A
/ Cm ² shows the battery output at the initial time when the continuous power generation test was performed under the condition of / cm ² , and also when the operation time has passed 8000 hours. The results are shown in Table 1.

(Embodiment 4) In the above embodiment, SUS3
The conductive separator made of No. 16 was plated with gold, and a flexible gold paste layer was formed thereon. However, by adjusting the components of the gold paste layer, SUS31
6 can be formed directly on the conductive separator. At this time, when the components of the gold paste layer are adjusted, if the amount of the gold component is too small, the SUS 316 is directly exposed to the external atmosphere, and the long-term corrosion resistance of the conductive separator decreases. On the other hand, if the amount of the gold component is too large, on the other hand, the binder component decreases, and the problem that flexibility is lost occurs. In addition, it is naturally necessary to optimize the particle size of the gold powder. The smaller the particle size, the lower the electrical resistance. However, if the particle size is too small, there is a problem that the handling as a paste becomes difficult.

In consideration of this point, in the above-mentioned production process, 80% by weight of gold particles having an average particle size of 5 μm were mixed with 10% by weight of a bisphenol-based epoxy monomer and 10% by weight of a curing agent thereof.
5% by weight of CMC (carboxymethylcellulose),
Dispersed in a mixture of 50% by weight of ethylcellosolve as a diluent and applied directly on a conductive separator,
What was left standing at 20 ° C. for 5 hours also showed excellent stability as described above. Other configurations are the same as those of the first embodiment.

As in the first embodiment, the fuel cell was maintained at 85 ° C., and hydrogen gas humidified and heated so as to have a dew point of 83 ° C. was applied to one electrode side, and 78% was applied to the other electrode side.
Supply air humidified and heated to a dew point of ° C, fuel utilization 80%, oxygen utilization 40%, current density 0.5A
/ Cm ² shows the battery output at the initial time when the continuous power generation test was performed under the condition of / cm ² , and also when the operation time has passed 8000 hours. The results are shown in Table 1.

[0044]

According to the present invention, as a separator plate, a metal material such as stainless steel can be used without cutting in place of the conventional carbon plate cutting method, so that the cost can be significantly reduced during mass production. Further, the thickness of the separator can be further reduced, which contributes to the compactness of the laminated battery.

[Brief description of the drawings]

FIG. 1 is a diagram showing a configuration of a conductive separator used in a fuel cell according to a first embodiment of the present invention.

FIG. 2 is a diagram showing a configuration of a hydrogen separator used in the fuel cell according to the first embodiment of the present invention.

FIG. 3 is a diagram showing a configuration of a fuel cell stack according to the first embodiment of the present invention;

FIG. 4 is a diagram showing a configuration of another conductive separator that can be used in the fuel cell according to the first embodiment of the present invention.

FIG. 5 is a diagram showing output characteristics of the fuel cell according to the first embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Corrugated processing part 2 Groove 3 Crest 4 Manifold hole 5 Phenol convex part 6 Phenol groove 7 Phenol gasket 8 MEA 9 Hydrogen side gas circulation groove 10 Air side gas circulation groove 11 Cooling part 12 Metal mesh 13 Grease 14 Bent part 15 Seam

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Hisao Gyoten 1006 Kadoma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Inventor Kazuhito Hato 1006 Odaka Kadoma Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. (72) Inventor Makoto Uchida 1006 Kadoma, Kadoma, Osaka Pref. Matsushita Electric Industrial Co., Ltd. (72) Inventor Hideo Ohara 1006 Odama, Kadoma, Kadoma, Osaka Pref. Matsushita Electric Industrial Co., Ltd. (72) Yasushi Sugawara 1006 Kazuma Kadoma, Kadoma City, Osaka Prefecture, Japan Matsushita Electric Industrial Co., Ltd. (72) Inventor Teruhito Kanbara 1006 Kadoma Kadoma, Kadoma City, Osaka Prefecture Inside the Matsushita Electric Industrial Co., Ltd. Address F-term (reference) Matsushita Electric Industrial Co., Ltd. 5H026 AA02 AA06 BB04 BB10 CC03 CC04 EE02

Claims (6)

[Claims] 1. A solid polymer electrolyte fuel in which a pair of electrodes sandwiching a solid polymer electrolyte membrane and a unit cell having means for supplying and discharging fuel gas to and from the electrodes are stacked via a conductive separator. In the battery, the conductive separator is made of a metal material having an inert metal layer formed on the surface with respect to an acidic atmosphere, and the conductive separator forms a gas flow groove through which the fuel gas flows. A solid polymer electrolyte fuel cell, wherein the gas flow groove and the means for supplying and discharging the fuel gas are connected by a material having a sealing property. 2. The solid polymer electrolyte fuel cell according to claim 1, wherein the metal layer formed on the surface of the conductive separator with respect to an acidic atmosphere is made of gold or silver. 3. The solid polymer electrolyte fuel cell according to claim 1, wherein the inert metal layer formed on the surface of the conductive separator for an acidic atmosphere has a physical flexibility. 4. The solid polymer electrolyte fuel cell according to claim 1, wherein the gas flow grooves formed in the conductive separator have a plurality of parallel linear shapes. 5. The gas separator according to claim 1, wherein the convex portion of the gas flow groove formed on one surface of the conductive separator forms a concave portion of the gas flow groove on the back surface of the conductive separator. 5. The solid polymer electrolyte fuel cell according to 3, 3 or 4. 6. The method according to claim 2, further comprising a cleaning treatment step, an activation treatment step, a nickel strike plating treatment step, and a gold plating or silver plating treatment step.
6. The method for producing a solid polymer electrolyte fuel cell according to 3, 4, or 5.