WO2007086139A1

WO2007086139A1 - Solid polymer electrolyte fuel cell

Info

Publication number: WO2007086139A1
Application number: PCT/JP2006/301419
Authority: WO
Inventors: Kiyoshi Hanafusa; Hiroichi Ishida
Original assignee: Mitsubishi Denki Kabushiki Kaisha
Priority date: 2006-01-30
Filing date: 2006-01-30
Publication date: 2007-08-02
Also published as: JPWO2007086139A1

Abstract

This invention provides a solid polymer electrolyte fuel cell that, even when a discharge chemical reaction is repeated during long-term operation, exhibits a prolonged cell service life without increasing the production cost. A compound comprising material A and material B, i.e., A1-XBX (0.2 ≤ X ≤ 0.8), is used as a catalyst for a negative electrode reaction layer (3). Material A is any metal selected from Sr, Ca, Mg and Be, and material B is a metal having d orbit. Since material A is an alkaline earth metal, aggregation by sintering does not occur even when a discharge chemical reaction is repeated during long-term operation of the solid polymer electrolyte fuel cell and the total surface area of the metal particles is not reduced. As a result, the use of this compound as a catalyst can provide a solid polymer electrolyte fuel cell that does not cause a deterioration in current-voltage characteristics and has a prolonged service life.

Description

Specification

Polymer electrolyte fuel cell

Technical field

TECHNICAL FIELD [0001] The present invention relates to a polymer electrolyte fuel cell, and more particularly to a catalyst used for a negative electrode reaction layer of a polymer electrolyte fuel cell.

Background art

[0002] The negative electrode reaction layer of a conventional polymer electrolyte fuel cell (hereinafter sometimes simply referred to as "fuel cell") is composed of carbon paper and a catalyst supported thereon.

In general, only a noble metal such as platinum (Pt), a platinum ruthenium alloy (Pt—Ru), or palladium (Pd) is used as a catalyst material.

[0004] Here, Ru of Pt_Ru is added to reduce the poisoning of carbon monoxide (C0) generated when reforming liquid fuel such as methanol (see Patent Document 1). ).

[0005] Patent Document 1: JP 2004-281211 A

[0006] As described above, since the catalyst of the negative electrode reaction layer so far is a metal particle made of a noble metal such as Pt, Pt—Ru, Pd, etc. Aggregation by sintering increases the particle size and reduces the total surface area.

For this reason, the current density is lowered, and the current-voltage characteristics are deteriorated. In other words, the output of the fuel cell decreased and the battery life was shortened.

[0008] Since noble metals are expensive, it has been difficult to increase the amount of catalyst, increase the current density, and achieve high output.

Disclosure of the invention

An object of the present invention is to solve the above-described problems and provide a fuel cell having a long battery life without increasing the manufacturing cost even if the discharge chemical reaction is repeated by long-term operation. To do.

[0010] The polymer electrolyte fuel cell according to the embodiment of the present invention includes an electrolyte membrane, a positive electrode reaction layer formed on one main surface of the electrolyte membrane, and the other main surface of the electrolyte membrane. And a negative electrode reaction layer, wherein the negative electrode reaction layer is a thin film carrier. A carrier AB and a compound AB (0.2.

1-X X

≤X≤0.8)), the material A is any metal of Sr, Ca, Mg, Be, and the material B is a metal having d orbitals It is characterized by that.

[0011] According to the polymer electrolyte fuel cell of the aspect of the present invention, the compound AB is used as a catalyst for the negative electrode reaction layer. Where material B is a metal with d orbitals, so compound A

1-X X

B has catalytic activity. And since material A is alkaline earth metal, sintering

1-X X

Aggregation of compound A B due to is suppressed.

1-X X

[0012] Therefore, even if the discharge chemical reaction is repeated in a long-term operation, the total surface area of the catalyst is almost the same as in the initial stage, so that a decrease in current density can be suppressed.

As a result, the battery life of the polymer electrolyte fuel cell can be extended as compared with the case where conventional Pt, Pt—Ru, Pd is used as the catalyst for the negative electrode reaction layer.

[0014] The objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description and the accompanying drawings.

Brief Description of Drawings

FIG. 1 is a cross-sectional view showing a configuration of a polymer electrolyte fuel cell according to a first embodiment.

FIG. 2 is a graph showing a current-voltage characteristic of the polymer electrolyte fuel cell according to the first embodiment.

FIG. 3 is a diagram showing current-voltage characteristics after 10,000 hours of operation of the polymer electrolyte fuel cell according to the first embodiment.

FIG. 4 is a cross-sectional view showing a configuration of a polymer electrolyte fuel cell according to Embodiment 3.

FIG. 5 is a circuit diagram showing a configuration in which two wound fuel cells according to Embodiment 4 are connected in series.

FIG. 6 is a circuit diagram showing a configuration in which two wound fuel cells according to Embodiment 4 are connected in parallel.

FIG. 7 is a circuit diagram showing a configuration in which a plurality of wound fuel cells according to Embodiment 4 are connected in series and parallel.

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] (Embodiment 1) <A. Technical idea of the invention>

First, before describing the configuration of the polymer electrolyte fuel cell according to Embodiment 1, the technical idea of the present invention will be described.

[0017] When the discharge chemical reaction is repeated in the long-term operation of the fuel cell, the output decreases because the metal particles of the catalyst aggregate due to sintering and the surface area is reduced.

[0018] Therefore, even if the discharge chemical reaction is repeated in the long-term operation of the fuel cell, the catalyst that promotes the chemical reaction of the negative electrode, in which the metal particles do not aggregate due to sintering and the catalytic activity is the same as the initial, did.

Here, we considered that the metal particles do not agglomerate due to sintering and that the catalytic activity is the same as that in the initial stage with different elements.

[0020] First, considering an element in which metal particles do not aggregate, since the transition metal is a metal, it aggregates by sintering although not as much as the platinum group. This is the same because the alkali metals of Group I of the periodic table are also highly metallic.

[0021] On the other hand, metals of Group III of the periodic table are stable as metals. At normal temperature, no oxide film is formed on the surface of the particles, and it dissolves not only in alkaline but also in acidic solution.

However, the polymer electrolyte membrane has a sulfone group and is acidic at that portion.

For this reason, metals belonging to Group VIII of the periodic table cannot be used because they dissolve when they come into contact with the polymer electrolyte membrane.

[0023] In view of this, attention was paid to alkaline earth metals of Group II of the periodic table that contain many elements that form an oxide film at room temperature where the metallicity is weaker than that of alkali metals and are not soluble in acidic solutions.

[0024] Here, the alkaline earth metal elements include beryllium (Be), magnesium (Mg), and calcium.

(Ca), strontium (Sr), and barium (Ba).

[0025] However, since Ba does not form an oxide film on the surface at room temperature and reacts with water vapor in the air and easily forms a hydroxide, it cannot be handled. On the other hand, Sr, Ca, Mg, and Be can be handled because an oxide film is formed on the surface at room temperature.

[0026] Then, in the hydrogen reduction atmosphere at the negative electrode in the initial discharge of the fuel cell, Sr, Ca, Mg

, Be oxide is immediately removed by reacting with hydrogen to change into water vapor. Therefore, release It exists as metal particles in the electricity.

[0027] The thickness of the oxide film is Be> Mg> Ca> Sr, and the oxide film formed on Sr is the thinnest, and it is considered that the oxide film is excluded and returned to the metal first. It is considered a promising material.

[0028] Sr, Ca, Mg, and Be are not poisoned by carbon monoxide generated by reforming liquid fuel such as methanol.

[0029] Next, elements with catalytic activity are all possible if they have metals with d orbitals, but group VIII of the periodic table is most likely next, group VI and group VII. Is expensive.

Therefore, Sr, Ca, Mg, Be and transition metal compound A B (Material A is Sr, Ca, Mg, Be l-X X

As a result of paying attention to any of these metals, material B is a transition metal of group VIII or VI or VII of the periodic table, compound AB (material A is Sr, as described in the following embodiment) C lX X

Any of a, Mg and Be, material B is a metal having d orbital, especially platinum (Pt), ruthenium (Ru), molybdenum (Mo), nickel (Ni), cobalt (Co), palladium (Pd), rhodium (Rh), iridium (Ir), osmium (Os), rhenium (Re), technetium (Tc), titanium (Ti), iron (Fe), vanadium (V), chromium (Cr), manganese Catalysts (Mn), copper (Cu), and zinc (Zn)) were discovered.

[0031] It has also been found that these catalysts improve the current-voltage characteristics at the initial stage of discharge and improve the output by simply extending the battery life of the fuel cell.

[0032] In addition, if the material B is a metal having a d orbital, the compound A B has catalytic activity by forming a bimetal with the material A even when it does not have catalytic activity.

1-X X

I got it.

[0033] <B. Configuration>

Next, the configuration of the polymer electrolyte fuel cell according to Embodiment 1 will be described. Figure

1 is a cross-sectional view showing a configuration of a polymer electrolyte fuel cell according to Embodiment 1. FIG.

A positive electrode reaction layer 2 is formed on one main surface of the electrolyte membrane 1. The negative electrode reaction layer 3 is formed on the other main surface of the electrolyte membrane 1. A positive electrode 4 is formed on the positive electrode reaction layer 2. A positive electrode separator 6 is formed on the positive electrode 4, and a positive electrode current collector plate 8 is formed on the positive electrode separator 6. A negative electrode 5 is formed on the negative electrode reaction layer 3. A negative electrode separator 7 is formed on the negative electrode 5. A negative electrode current collector plate 9 is formed on the negative electrode separator 7.

[0036] The positive electrode separator 6 is formed with a flow channel 10 for flowing an oxygen-containing gas. The negative electrode separator 7 is formed with a channel groove 11 for flowing fuel gas.

The positive electrode reaction layer 2 is composed of carbon paper as a thin film carrier and a platinum (Pt) catalyst carried thereon. The negative electrode reaction layer 3 is composed of carbon paper as a thin film carrier and a catalyst supported on carbon paper. The catalyst is Compound A B (0.2 ≤ X ≤ 0.8) consisting of Material A and Material B. The thin film carrier is

1-X X

Any material other than carbon paper may be used as long as it can carry a medium.

[0038] Here, in the first embodiment, the material A is any metal of Sr, Ca, Mg, and Be, and the material B is selected from Pt, Ru, Mo, Ni, and Co. Any metal with d orbitals.

[0039] Specifically, Sr Pt, Sr Ru, Sr Mo, Sr Ni, Sr Co, Ca Pt, Mg

l-X X 1-X X 1-X X 1-X X 1-X X 1-X X 1-

Any compound of Pt and Be Pt is used as a catalyst.

X X 1-X X

[0040] Further, since Sr is solid-solved with any of Pt, Ru, Mo, Ni, and Co, the composition ratio X is 0.

Limited to the range 2≤X≤0.

[0041] Furthermore, since any one of Ca, Mg, and Be and one of Pt, Ru, Mo, Ni, and Co are dissolved, the composition ratio X is 0.2≤X≤0.8. Limited to the range of

[0042] <C. Method for producing polymer electrolyte fuel cell>

Next, a method for manufacturing the polymer electrolyte fuel cell according to Embodiment 1 will be described.

[0043] First, the compound AB used as a catalyst for the negative electrode reaction layer 3 is produced by a production method described later.

1-X X

Manufactured.

[0044] Then, after obtaining the catalyst, the negative electrode reaction layer 3 is manufactured by supporting the carbon paper at the same volume ratio as the conventional platinum catalyst.

[0045] The fuel cell shown in FIG. 1 can be obtained by preparing each layer constituting the fuel cell, such as the electrolyte membrane 1, and stacking and joining them in a predetermined order.

[0046] <C 1. Method for Producing Compound Sr Pt> Hereinafter, a method for producing a catalyst used for the negative electrode reaction layer 3 of the polymer electrolyte fuel cell according to Embodiment 1 will be described.

[0047] First, a method for producing the compound Sr Pt will be described.

1-X X

[0048] Using a stainless steel ball mill, strontium powder and platinum powder are pulverized and mixed at a predetermined ratio (1_X: X).

[0049] Subsequently, a mixture of strontium powder and platinum powder is put into a tungsten crucible.

[0050] Then, using a vacuum substitution type high-temperature furnace manufactured by Tokai Koetsu Kogyo Co., Ltd. under an argon atmosphere.

Heat to 50 ° C to melt and alloy the mixture.

[0051] The alloyed mixture is cooled and then crushed to produce the compound Sr Pt (0.2 ≤ X ≤ 0.8).

1-X X

Build.

[0052] Here, the product name KST (purity: 99. 95%) of 堺匕学工業 Co., Ltd. was used as the strontium powder. Platinum powder used was Tanaka Kikinzoku Co., Ltd., with a purity of 5 Nup.

<0053> <C 2. Method for Producing Compound Sr Ru>

1-X X

Next, a method for producing the compound Sr Ru of the negative electrode reaction layer 3 will be described.

1-X X

[0054] First, a strontium powder and a ruthenium powder are mixed at a predetermined ratio using a stainless steel ball mill.

Mix (1 x: x).

[0055] Next, a mixture of strontium powder and ruthenium powder is placed in a tungsten crucible.

[0056] Then, using a vacuum substitution type high temperature furnace manufactured by Tokai Koetsu Kogyo Co., Ltd.

Heat to 50 ° C to melt and alloy the mixture.

[0057] The alloyed mixture is cooled and then crushed to give the compound Sr Ru (0.2≤X≤0.8).

1-X X

To manufacture.

[0058] Here, the product name KST (purity 99. 95%) of 堺匕学工業 Co., Ltd. was used as the strontium powder. The ruthenium powder used was Tanaka Kikinzoku Co., Ltd. with a purity of 5 Nup.

[0059] <C-3. Method for producing compound Sr Mo>

1-X X

Next, a method for producing the compound Sr Mo will be described.

1-X X

[0060] First, a strontium powder and a molybdenum powder are mixed at a predetermined ratio using a stainless steel ball mill.

Mix (1 x: x). [0061] Next, a mixture of strontium powder and molybdenum powder is placed in a tungsten crucible.

[0062] Then, the mixture is heated to 2650 ° C under an argon atmosphere, and the mixture is melted to be alloyed.

The alloyed mixture is cooled and then crushed to produce the compound Sr Mo (0.2 ≤ X ≤ 0.8).

1-X X

Build.

Here, the product name KST of Sakai Chemical Industry Co., Ltd. was used as the strontium powder. The product name M12 of Toshiba Material Co., Ltd. was used for the molybdenum powder.

[0064] <C-4. Method for Producing Compound Sr Ni>

1-X X

Next, a method for producing the compound Sr Ni will be described.

1-X X

[0065] First, strontium powder and Nikkenole powder are mixed in a predetermined ratio (1 x: x) with a stainless ball mill.

[0066] Next, a mixture of strontium powder and Eckenole powder is placed in a tungsten crucible.

[0067] Then, the mixture is heated to 2000 ° C under an argon atmosphere, and the mixture is melted to be alloyed.

After cooling the alloyed mixture, it is ground to produce the compound Sr Ni (0.2 ≤ X ≤ 0.8).

1-X X

Build.

[0068] Here, the product name KST of Sakai Chemical Industry Co., Ltd. was used as the strontium powder. The nickel powder used was a 45N purity product from Nippon Heavy Chemical Industry Co., Ltd.

[0069] <Method for producing C-5 compound Sr Co>

1-X X

Next, a method for producing the compound Sr Co will be described.

1-X X

[0070] First, a strontium powder and a cobalt powder were mixed at a predetermined ratio (1

_x: x)

[0071] Next, a mixture of strontium powder and cobalt powder is placed in a tungsten crucible.

[0072] Then, the mixture is heated to 2000 ° C under an argon atmosphere, and the mixture is melted to be alloyed.

The alloyed mixture is cooled and then crushed to produce the compound Sr Ni (0.2 ≤ X ≤ 0.8).

1-X X

Build.

Here, the product name KST of Sakai Chemical Industry Co., Ltd. was used as the strontium powder. Cobalt powder

, Nippon Heavy Chemical Industry Co., Ltd. Purity 4-5N products were used.

[0074] The material A was replaced with strontium, and calcium, magnesium, and beryllium were used. A compound was also produced, and a fuel cell was prepared using it as a catalyst for the negative electrode reaction layer 3. Since the manufacturing method is the same as that when strontium is used, detailed description is omitted.

[0075] <D. Effect>

<D- 1. Current-voltage characteristics of polymer electrolyte fuel cells>

FIG. 2 is a graph showing the current-voltage characteristics of the polymer electrolyte fuel cell according to the first embodiment. Figure 2 illustrates the initial characteristics of the fuel cell at 80 ° C.

[0076] Further, in FIG. 2, among the compounds A B (where A = Sr, B = Pt, Ru, Mo, Ni, Co),

l-X X

The characteristics of X = 0.4, which showed the best fuel cell characteristics in the range of 0.2≤X≤0.8, are shown. Fig. 2 shows the characteristics of the fuel cell when conventional Pt, Pt-Ru, and Pd are used as the catalyst.

[0077] Furthermore, FIG. 2 shows the most characteristic in the range of 0.2≤X≤0.8 for any material of A = Ca, Mg, Be and a compound consisting of B = Pt. The characteristics of X = 0.4, which was good, are also shown.

[0078] From FIG. 2, the catalytic power of these compounds is higher than that of conventional catalysts such as Pt, Pt-Ru, and Pd.

It can be seen that the current-voltage characteristic is good and the output is high.

[0079] The reason why the catalyst having the compound A B power has higher catalytic activity than the platinum group catalyst is

1-X X

In Pt and Ru, the surface of the group VIII, VI, and VII transition metals such as Pt (111) and Ru (0001) is the catalytically active surface, whereas in the catalyst with the compound AB, they are combined with Sr. , Ca

1-X X

This is probably because the bimetal surface of Mg and Be has become a catalytically active surface.

[0080] Although the details are not clear, the following reasons may be considered.

[0081] Pt, Pt-Ru, and Pd have surface hydrogen molecule adsorption / dissociation ability, but do not have hydrogen absorption ability, and therefore no catalytic reaction occurs inside the catalyst.

In contrast, the compound A B (A = Sr, Ca, Mg, Be, B = Pt, Ru, Mo, Ni, Co)

1-X X

Sr, Ca, Mg, and Be have not only surface hydrogen molecule adsorption / dissociation ability but also hydrogen absorption ability, so that hydrogen penetrates into the catalyst and causes catalytic reaction.

[0083] Then, the electrons released from the hydrogen by the catalytic reaction are transferred from the inside of the compound A B to the surface.

1-X X

Move to. As described above, it is considered that the current-voltage characteristic is improved as a result of the catalytic reaction inside the catalyst. [0084] <D- 2. Battery life of polymer electrolyte fuel cells>

Next, the battery life of the polymer electrolyte fuel cell according to Embodiment 1 will be described with reference to FIG. FIG. 3 is a graph showing current-voltage characteristics after the polymer electrolyte fuel cell according to Embodiment 1 has been operated for 10,000 hours.

[0085] From FIG. 3, the polymer electrolyte fuel cell using the conventional platinum group catalyst has a voltage drop of 40%, whereas the polymer electrolyte fuel cell according to Embodiment 1 is It can be seen that there is no decline at all.

[0086] This is because the catalyst used in the conventional negative electrode reaction layer 3 is sintered and agglomerated in a long-term operation, whereas the catalyst of the present invention does not sinter and agglomerate.

[0087] Also, a compound B was produced using the metal B as Pd, Rh, Ir, Os, Re, Tc, Ti, Fe, V, Cr, Mn, Cu, and Zn.

1-X X

[0088] A fuel cell was manufactured by supporting these catalysts on carbon paper at the same volume ratio as a conventional catalyst such as platinum. Then, we measured the current-voltage characteristics at the beginning and after 10,000 hours of the fuel cell. The current-voltage characteristics were worse than those of Pt, Ru, Mo, Ni, and Co, both at the beginning and after 10,000 hours.

[0089] As described above, since the polymer electrolyte fuel cell according to Embodiment 1 uses the compound AB as the catalyst of the negative electrode reaction layer 3, the conventional Pt, Pt-Ru, Pd catalyst Place

1-X X

Unlike the case, aggregation due to sintering is suppressed.

[0090] Therefore, since the total surface area of the compound serving as the catalyst is almost the same as the initial value, the current density does not decrease.

As a result, the battery life of the fuel cell can be made longer than that of the conventional catalyst made of Pt, Pt-Ru, Pd.

Here, the material B having the d orbital contains a metal having no catalytic activity. Therefore, both material A and material B may not have catalytic activity. However, even in such a case, if the material B is a metal having d orbitals, the compound A B has catalytic activity.

1-X X

I will endure that I will do it.

[0093] Further, the polymer electrolyte fuel cell according to Embodiment 1 uses Compound A B as a catalyst.

1-X X

As a solid polymer fuel cell using conventional Pt, Pt-Ru, Pd catalysts In comparison, the current-voltage characteristics are improved in the initial stage, high voltage and high current can be extracted, and the output can be further improved.

[0094] Furthermore, the solid polymer fuel cell catalyst according to the first embodiment has a lower material cost than the catalyst having Pt, Pt-Ru, Pd force, and therefore can reduce the manufacturing cost of the fuel cell. .

In the polymer electrolyte fuel cell according to Embodiment 1, the output can be increased by selecting Sr as the material A.

[0096] In the polymer electrolyte fuel cell according to the first embodiment, as the material B, Pt, Ru, Mo, Ni, Co, Pd, Ti, Fe, V, Cr, Mn, Cu, Zn Raise using any power metal.

[0097] Since these metals have catalytic activity, the output of the fuel cell can be further improved as compared with the case where the material B does not have catalytic activity.

[0098] Note that as the material A, a metal complex of any one of Sr, Ca, Mg, and Be is used, and as the material B, Pt, Ru, Mo, Ni, Co, Pd, Rh, Ir, Os, Re , Tc, Ti, Fe, V, Cr, Mn, Cu, Zn using a metal complex to form compound AB and react with it as a negative electrode

1-X X

A fuel cell used as the catalyst for layer 3 was also formed.

[0099] By using complexes as the materials A and B, the structural stability of the compound A B is improved, and the fuel

1-X X

It turned out that the output of a battery improves a little.

[0100] <E. Other production method of compound A B>

1-X X

In the polymer electrolyte fuel cell according to the first embodiment, the catalyst is formed by the melt alloying method, but may be manufactured by the thermal decomposition method described below.

[0101] In the pyrolysis method, AC1 and BC1 or BC1 or BC1 containing materials A and B are

2 2 3 4

By melting 'decomposition, materials A and B are obtained. Then it can be cooled to obtain compound A B

1-X X

The

[0102] The compound catalyst such as Sr B, for example, when B is Pt,

1-X X

It can be created by decomposing at 500 ° C in a vacuum and blowing off chlorine gas.

[0103] Compound AB can be easily formed by producing a catalyst using the thermal decomposition method or the melt alloying method described above.

1-X X

[Embodiment 2]

<A. Configuration> In the polymer electrolyte fuel cell according to Embodiment 2, the Sr particles coated with Pt are used as the compound Sr Pt that is the catalyst of the negative electrode reaction layer 3.

1-X X

[0105] Here, the surface of the Sr particle is not completely covered with Pt, but the Sr particle surface has an appropriate gap between Pt so that the fuel gas can react with the Sr particle surface through Pt. It is covered.

[0106] Other configurations are the same as those of the first embodiment, and the same configurations as those of the first embodiment are denoted by the same reference numerals, and redundant description is omitted.

[0107] <B. Manufacturing method>

Next, a method for producing a catalyst according to the second embodiment will be described. The coating of Sr particles with Pt was performed by the following method.

[0108] After adding a predetermined ratio of Sr powder to the electroless platinum plating PTM01L B solution of High Purity Chemical Industry Co., Ltd. and stirring, Pt was electrolyzed (also referred to as dispersion or mixed plating) to Sr. It was prepared by filtering and drying.

[0109] The catalyst thus obtained was supported on carbon paper at the same volume ratio as that of a conventional catalyst such as platinum to produce a fuel cell.

[0110] In general, the nitro complex or nitroammine complex of material A or B is subjected to electroless oxidation-reduction reaction with material A or B in a reducing agent hydrazine and a stabilizer hydroxy noreamine salt solution to remove the solution. By doing so, it is possible to obtain compound AB.

1-X X

[0111] <c.Effect>

In the case of direct reforming with liquid fuel such as methanol or ethanol where the fuel gas is not hydrogen gas, the liquid reacts with the Sr portion in the compound Pt catalyst.

1-X X

[0112] In order to prevent this reaction, the polymer electrolyte fuel cell according to Embodiment 2 is thinly coated with a high-density polymer film made of Pt on the Sr particle surface.

[0113] As a result, since the film has a high density, the reaction between Sr and liquid can be prevented. In addition, since the coating film is thin and there is a gap between Pt, the catalytic activity of the compound Sr Pt is not lost, and

1-X X

Since hydrogen gas molecules, which are fuel, are small in size, they can permeate this film, so the chemical reaction is not slowed down.

[0114] Note that the material A is any metal of Sr, Ca, Mg, and Be, and the material B is Ru, Mo, Compound AB, which is any metal among Ni, Co, Pd, Rh, Ir, Os, Re, Fe, V, Cr, Mn, Cu, and Zn, was also produced by electroless plating.

1-X X

[0115] And in this case as well, it was found that the reaction between the liquid and the material A can be prevented.

[0116] In the second embodiment, the surface of Sr particles as material A is coated with Pt as material B. However, the surface of Pt particles may be coated with Sr.

[0117] That is, it is sufficient that the material A and the material B are coated with one force and the other.

[0118] <D. Other production method of catalyst>

In the polymer electrolyte fuel cell according to Embodiment 2, the catalyst is formed by the electroless plating method, but may be manufactured by the manufacturing method described below.

[0119] <D— 1. Electrolytic plating method>

First, the electrolytic plating method will be described.

[0120] The Sr-coated electrode was electrolyzed at 25 ° C, pH 12 (PH12), 0.5 A / dm2 in alkaline cyanate solution with strontium tetracianoplatinate, and then Sr Pt was removed.

After reducing with hydrogen gas, pulverize. Thereafter, a complex may be formed.

[0121] <D-2. CVD method>

Next, the CVD method will be described.

[0122] The liquid raw materials bis (ethylcyclopentagenyl) strontium and ethylcyclopentagenyl (trimethyl) platinum were flown on the Si substrate at a predetermined ratio by the CVD method to deposit Sr Pt.

1-X X Then, after cooling, it is scraped from the substrate, pulverized into a fine powder, and then the compound Sr Pt

1-X X One powder can be obtained. Thereafter, a complex may be formed.

[0123] Ku D— 3. Sputtering>

Next, the sputtering method will be described.

In the 0124] sputtering, 10- ² Torr~10- ⁵ TorrAr DC method at a vacuum degree of a high-frequency method or magnetron system, evaporating the material A or material B. Then, the material A or the material B is condensed on the substrate. Then, the condensed powder is scraped off and pulverized to obtain a coating powder of Compound AB.

1-X X

[0125] <D-4. Vacuum evaporation method>

The vacuum vapor deposition method, first, a material A heating evaporation of at 10- ⁶ Τοιτ (10- ⁴ Pa) or more vacuum And condensing on a substrate made of material B.

[0126] Next, the condensed product is scraped off and pulverized to obtain a coating powder of Compound A B.

1-X X

Obtained.

[0127] <D- 5. Thermal spray method>

The coating material A is made into fine particles by melting or softening by heating. Then, the coating material A is accelerated and collided with the surface of the coating target material B to solidify and deposit the flattened particles on the substrate. Thereafter, the deposit was scraped and pulverized to obtain a coating powder of the compound A B.

1-X X

[0128] <D—6 · Ion plating method>

A plasma discharge part was placed between the evaporation source of material A and the substrate made of material B, and before material A reached the substrate, it was excited by plasma of IKeV or less lOOeV.

[0129] It is a kind of PVD (Physical Vapor Deposition), and material A was evaporated in a high vacuum, and the evaporation flow was ionized.

[0130] The ionized evaporative flow is accelerated toward a substrate made of metal B with a negative voltage applied, and collides with the substrate with a high level of kinetic energy.

[0131] At this time, the film of the compound A B produced is scraped off and powdered to form the compound A B.

1-X X 1-X X coating powder was obtained.

[0132] <D-7.

A mixture of material A or material B and material B + ions or material A + ions forms a colloidal solution of material B + ions or material A ⁺ ions, which is then immersed in a substrate made of material A or material B, and then immersed in a hydrochloric acid solution. Material A was then coated with Material B by promoting the chemical plating reaction.

[0133] Next, the coated material of compound A B is scraped off and pulverized.

1-X X powder can be obtained.

[0134] <D-8.Plasma method>

As the plasma method, the following plasma ion implantation method and plasma CVD method were performed.

[0135] <D- 8- l. Plasma ion implantation method>

Plasma ion implantation means that material A is made into positive plasma and metal B immersed in the plasma is used. A negative pulse high voltage was applied to the resulting substrate, and ions were implanted into material B and coated. Thereafter, the coated powder is scraped off and pulverized to obtain a coating powder having a compound AB force.

1-X X

[0136] <D- 8- 2. Plasma CVD method>

Next, in the plasma CVD method, the raw material gas of material A and the raw material gas of material B are discharged and decomposed together with an appropriate diluent gas to be deposited on the substrate. The compound A B can be obtained by scraping and crushing the deposited metal.

1-X X

[0137] As the plasma excitation method, any of direct current, high frequency, and ECR may be used, but in the first embodiment, high frequency is used.

[0138] <D-9. Aggregation method>

In a vacuum, the material B to be used for the heat was evaporated by heating and agglomerated on the surface of the material A. Coating powder with compound A B power by scraping off the agglomerated material and crushing

1-X X

You can get a body.

[0139] <D- 10. Laser Ablation Method>

The target of material A or material B is irradiated with a laser and sublimated. And it recrystallizes on the board | substrate of the material B or the material A arrange | positioned facing the said target.

[0140] Next, the crystallized film is scraped off and pulverized to produce a compound A B coating.

1-X X

Powder can be obtained.

[0141] By producing the catalyst by the above production method, a coating powder that is a powder of compound A B in which one of material A and material B is coated with the other can be easily formed.

1-X X

[0142] (Embodiment 3)

<A. Configuration>

FIG. 4 is a cross-sectional view showing the configuration of the polymer electrolyte fuel cell according to the third embodiment. As shown in FIG. 4, the polymer electrolyte fuel cell according to Embodiment 3 has a wound shape. The polymer electrolyte fuel cell is disposed inside the housing 14. In FIG. 4, the positive electrode side layer 12 is a collection of the positive electrode reaction layer 2 and the positive electrode 4 (see FIG. 1). That is, the positive electrode side layer 12 indicates a layer in which the inner side is the positive electrode reaction layer 2 and the outer side is the positive electrode 4. Similarly, the negative electrode side layer 13 is a layer in which the inner side is the negative electrode reaction layer 3 and the outer side is the negative electrode 5.

[0144] Also, lead wires (not shown) connected to the positive electrode 4 and the negative electrode 5, respectively, are drawn out from holes (not shown) provided in the housing 14 in order to extract the current to the outside. ing . Note that a gap generated between the hole of the housing 14 and the lead wire is sealed with resin or the like.

[0145] Other configurations are the same as those in the first embodiment, and the same components as those in the first embodiment are denoted by the same reference numerals, and redundant description is omitted.

[0146] <B. Manufacturing method>

Unlike the platinum group metals Pt, Pd, and Pt—Ru, the alkaline earth metals Sr, Ca, Mg, and Be are quite ductile. Therefore, the compound AB of the present invention is also quite ductile.

1-X X

[0147] For this reason, in the single cell structure shown in Fig. 1, the carbon paper of the negative electrode reaction layer 3 is firm and difficult to bend when a platinum group catalyst is supported, but is flexible when the catalyst of the present invention is supported. Easy to bend at.

[0148] Therefore, first, the electrolyte membrane 1, the positive electrode reaction layer 2, the negative electrode reaction layer 3, the positive electrode 4, the negative electrode 5, the positive electrode separator 6, the negative electrode separator 7, the positive electrode current collector plate 8, and the negative electrode current collector plate 9 are predetermined. Laminate and join in order.

[0149] Then, after joining the respective layers, the cell-shaped solid polymer fuel cell shown in Fig. 4 can be produced by bending it compactly.

[0150] <C. Effect>

In the conventional polymer electrolyte fuel cell, it was necessary to stack a plurality of cells in series in order to increase the output. And we had to take out and connect the electrode leads by the number of layers.

[0151] Since the polymer electrolyte fuel cell according to Embodiment 3 has a spiral shape, the structure can be simplified and the occupied volume can be reduced by simply pulling out two electrode leads.

[0152] As a result, the size of one fuel cell can be reduced.

[0153] In addition, since the electrode width is constant in the electrode manufacturing apparatus, the constant is set from the device power supply voltage. With respect to voltage, the number of stacked layers is constant in the stacked type, so the height and length of the fuel cell are determined. However, since the fuel cell according to the third embodiment is a whirling type, when it is connected in series to make a constant voltage, the number of whistling can be freely changed, so that the height and length can be freely changed. For this reason, a shape can also be changed freely.

[Embodiment 4]

<A. Configuration>

The polymer electrolyte fuel cell according to Embodiment 4 is obtained by electrically connecting a plurality of wound fuel cells 40 in series, in parallel, or in series-parallel according to the output required for the device.

[0155] Figs. 5 to 7 are circuit diagrams of the polymer electrolyte fuel cells electrically connected as described above.

[0156] FIG. 5 is a circuit diagram of a fuel cell in which two cell-shaped fuel cells 40 are connected in series. FIG. 6 is a circuit diagram of a fuel cell in which two fired fuel cells 40 are connected in parallel. FIG. 7 is a circuit diagram of a fuel cell in which a plurality of fired fuel cells 40 are connected in series and parallel.

[0157] In Fig. 7, a plurality of fired fuel cells 40 are connected in series, and a plurality of sets of fired fuel cells 40 connected in series are connected in parallel.

[0158] Then, the reference potential V is applied to the terminal 71. And from terminals 72 and 74

0

A constant voltage is output to the outside.

Further, as can be seen from FIG. 7, the voltage output from the terminal 72 is lower than the voltage output from the terminal 74. That is, the polymer electrolyte fuel cell according to Embodiment 4 is configured to output a plurality of voltages to the outside in accordance with the output required for the device.

[0160] Each individual fuel cell 40 is connected so that it can be removed from the other fuel cell 40. For example, the old fuel cell 40 can be freely replaced with a new one. It is structured so that it can be replaced.

[0161] <B. Effect>

By connecting as described above, a high voltage and large current can be extracted, that is, a high output solid polymer fuel cell can be assembled.

[0162] When the circuit shown in Fig. 7 is configured by connecting a plurality of stacked fuel cells in parallel, If the characteristics of one of the fuel cells that make up the fuel cell deteriorate, the entire stacked fuel cell becomes unusable, and the entire stacked fuel cell must be replaced.

However, the polymer electrolyte fuel cell according to Embodiment 4 is configured using a plurality of wound fuel cells 40. Therefore, even if the characteristics of a single fuel cell 40 deteriorate, only it can be replaced with a new one, so that it can be repaired easily and inexpensively.

[0164] Further, as described in the third embodiment, the size of one fuel cell can be reduced by making it so that a plurality of fuel cells 40 are connected in series. An integrated fuel cell can also be miniaturized.

Claims

The scope of the claims

[1] electrolyte membrane (1),

A positive electrode reaction layer (2) formed on one main surface of the electrolyte membrane (1);

A negative electrode reaction layer (3) formed on the other main surface of the electrolyte membrane (1);

A polymer electrolyte fuel cell comprising:

The negative electrode reaction layer (3)

A thin film carrier;

Compound A B (0.2), which is supported on the thin film carrier and made of Material A and Material B

1 -X X

A catalyst with ≤X≤0.8.8)

Have

The material A is a metal selected from the group consisting of Sr, Ca, Mg, and Be, and the material B is a metal having a d path.

[2] The polymer electrolyte fuel cell according to claim 1, wherein the material A is Sr.

[3] The material B includes Pt, Ru, Mo, Ni, Co, Pd, Rh, Ir, Os, Re, Tc, Ti, Fe, V, Cr,

3. The polymer electrolyte fuel cell according to claim 1, wherein the solid polymer fuel cell is one of Mn, Cu, and Zn.

[4] The material B is any one of Pt, Ru, Mo, Ni, Co, Pd, Ti, Fe, V, Cr, Mn, Cu, and Zn. 2. A polymer electrolyte fuel cell according to 1.

5. The polymer electrolyte fuel cell according to any one of claims 1 to 4, wherein one of the material A and the material B is coated with the other.

6. The polymer electrolyte fuel cell according to any one of claims 1 to 5, wherein the material A and the material B are a complex of the metal.

[7] The compound A B is produced by a melt alloying method or a thermal decomposition method.

1 -X X

The polymer electrolyte fuel cell according to any one of claims 1 to 4.

[8] The compound A B is formed by a plating method, a CVD method, a sputtering method, a vacuum deposition method, a thermal spraying method,

1 -X X

Manufactured by any one of a plating method, a catalyzer and an accelerator method, a plasma method, an agglomeration method, and a laser ablation method. Item 6. The polymer electrolyte fuel cell according to Item 5.

[9] The polymer electrolyte fuel cell according to claim 1, wherein the shape of the polymer electrolyte fuel cell is a wound shape.

9. The polymer electrolyte fuel cell according to any one of 8.

[10] A plurality of the polymer electrolyte fuel cells (40) according to claim 9,

A plurality of the polymer electrolyte fuel cells (40) are connected to each other in series, parallel or in series.