JP2003346861A - Fuel cell system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To supply hydrogen to a fuel cell in an easily-handled and simple system. <P>SOLUTION: This fuel cell system is provided with the fuel cell 1 and a hydrogen supply device A supplying hydrogen to the fuel cell 1. This system is also provided with a generation part 10 allowing reactant to contact the liquid and generating hydrogen as the hydrogen supply device A. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fuel cell system, and more particularly, to a fuel cell system including a fuel cell and a hydrogen supply device for supplying hydrogen to the fuel cell.

[0002]

2. Description of the Related Art In recent years, the development of fuel cells has been actively carried out. For the supply of hydrogen fuel, a hydrocarbon-based fuel is simply converted to a hydrogen-rich reformed gas using a fuel reformer or the like. Reforming technology (hereinafter referred to as first prior art)
Also, a technique using a hydrogen gas cylinder (hereinafter referred to as a second conventional technique) and a technique using a hydrogen storage alloy (hereinafter referred to as a third conventional technique) have been proposed.

[0003]

However, in the case of the first prior art, the fuel reformer operates at about 700 ° C. and takes a long time to raise its temperature. Is bad,
In the case of the second prior art, there is a problem that the volume efficiency is low because a hydrogen cylinder is used, and in the case of the third prior art, heating of the hydrogen storage alloy is necessary to release hydrogen, and hydrogen is absorbed. However, there is a problem that the efficiency is low, such as the necessity of cooling the hydrogen storage alloy, and the emergence of a new hydrogen fuel supply technology is desired.

The present invention has been made in view of the above circumstances, and has as its object to propose a new hydrogen fuel supply technique in a fuel cell system, and to provide a fuel supply system that is easy to handle and has a simple system. The point is that hydrogen can be supplied to the battery.

[0005]

According to a first aspect of the present invention, there is provided a fuel cell system including a fuel cell and a hydrogen supply device for supplying hydrogen to the fuel cell. And a generator capable of generating hydrogen by bringing a reactant and a liquid into contact with each other.

According to the present structure, the reactant and the liquid react with each other when the reactant and the liquid come into contact with each other at the generating section, and for example, the chemical formulas 1 to 11, 1
Reactions 3 to 17 occur, and hydrogen gas is generated, and the hydrogen gas is supplied from the generating section to the fuel cell. Therefore, handling is easy and a simple system is used to supply hydrogen to the fuel cell. Will be able to supply.

According to a second aspect of the present invention, in addition to the first aspect, the reactant is a solid reactant, and a combination of the solid reactant and the liquid in the generating section is different. At least one combination selected from the group consisting of a metal and an acidic solution, an alkali metal and water, an amphoteric metal and an aqueous alkali solution, and a metal hydride and water, which have a higher ionization tendency than hydrogen.

[Effects and Effects] The reactant is a solid reactant, and the combination of the solid reactant and the liquid may be a metal having an ionization tendency greater than that of hydrogen, an acidic liquid, an alkali metal and water, an amphoteric metal. Any combination of at least one selected from the group consisting of an alkaline aqueous solution, a metal hydride, and water may be used.
Reaction occurs, hydrogen gas is preferably generated,
The above-mentioned action and effect can be expected, and moreover, a metal and an acidic liquid having a greater ionization tendency than hydrogen (for example,
Chemical formulas 1 and 2), an alkali metal and water (for example, chemical formula 3), an amphoteric metal and an aqueous alkali solution (for example, chemical formulas 4 to 5)
6), metal hydride and water (for example, chemical formulas 7 to 11),
In any combination, hydrogen gas with extremely high purity of hydrogen can be obtained, which is advantageous.

[0009]

Embedded image mM + nH ₂ SO ₄ → M _m (SO ₄ ) _n + nH ₂ ↑ (where M: metal (Li, Be, K, Ca, Na, M
g, Al, Zn, Fe, Ni, Co), m, n: Coefficient (molar number))

[0010]

## STR2 ## _{mM + nHCl → M m Cl n} + n / 2H 2 ↑ ( However, M: metal (Li, Be, K, Ca , Na, M
g, Al, Zn, Fe, Ni, Sn, Co), m, n:
Coefficient (mol)

[0011]

Embedded image 2M + 2H ₂ O → 2MOH + H ₂ ↑ (where M: alkali metal (Li, Na, K, Rb,
Cs etc.)

[0012]

Embedded image Zn + 2NaOH + 2H ₂ O → Na ₂ [Zn
(OH) ₄ ] + H ₂ ↑

[0013]

Embedded image 2Al + 2NaOH + 6H ₂ O → 2Na [A
l (OH) ₄ ] + 3H ₂ ↑

[0014]

Embedded image Sn + 2NaOH + 4H ₂ O → Na ₂ [Sn
(OH) ₄ (OH ₂ ) ₂ ] + H ₂ ↑

[0015]

Embedded image CaH ₂ + 2H ₂ O → Ca (OH) ₂ + 2H ₂ ↑

[0016]

Embedded image LiH + H ₂ O → LiOH + H ₂ ↑

[0017]

Embedded image LiAlH ₄ + 4H ₂ O → LiOH + Al
(OH) ₃ + 4H ₂ ↑

[0018]

Embedded image NaH + H ₂ O → NaOH + H ₂ ↑

[0019]

Embedded image SiH ₄ + 2H ₂ O → SiO ₂ + 4H ₂ ↑

Further, the following actions and effects can be expected for each combination of a solid reactant and a liquid as described above.

In the case of a combination of a metal having a higher ionization tendency than hydrogen exemplified in Chemical Formulas 1 and 2 (hereinafter abbreviated as a base metal) and an acidic solution, a predetermined amount of hydrogen gas is generated stably for a long time. You can expect. By the way, at this time, when a metal ion of a metal having a small ionization tendency is added as compared with the base metal to be brought into contact with the acid solution, the reaction between the base metal and the acid solution is promoted, and a large amount of hydrogen gas may be obtained. it can.

In the case of a combination of an alkali metal and water as exemplified in Chemical Formula 3, the liquid may be water, so that it is easily available, and a large amount of hydrogen gas is generated instantaneously.
It is advantageous to use at startup.

In the case of a combination of an amphoteric metal and an alkali aqueous solution exemplified in Chemical Formulas 4 to 6, a desired alkali aqueous solution can be obtained by mixing a solid alkali such as sodium hydroxide or potassium hydroxide with water when necessary. Storage, transportation and handling are convenient.

In the case of a combination of a metal hydride exemplified in Chemical Formulas 7 to 11, and water, the metal hydride is a solid,
Because water is readily available, it is convenient to store, transport, and handle them.

According to a third aspect of the present invention, in addition to the second aspect, the generating section stores the liquid while leaving a space above the storage section, and the storage chamber. Separately, comprises a reaction chamber in which the liquid is stored leaving a space above and the solid reactant is provided so as to be able to contact the liquid, and a liquid stored in the storage chamber;
A liquid communication portion is provided for communicating and connecting the liquid stored in the reaction chamber, and hydrogen is supplied from the reaction chamber to the fuel cell side.

[Function and Effect] According to this configuration, the liquid stored in the storage chamber and the liquid stored in the reaction chamber are connected by the liquid communication section, so that the liquid in the storage chamber is connected. The liquid can be transferred between the storage chamber and the reaction chamber based on the pressure difference between the upper space and the upper space of the liquid in the reaction chamber. Then, when the solid reactant and the liquid come into contact with each other in the reaction chamber, and hydrogen gas is generated and supplied to the fuel cell side, when the generation of hydrogen gas becomes excessive in the reaction chamber, the pressure on the reaction chamber side becomes the storage chamber. If it is superior to the side, the liquid stored in the reaction chamber is transferred to the storage chamber via the liquid communication part, and the liquid level falls, thereby suppressing the generation of hydrogen gas, and conversely, If the generation of hydrogen gas in the reaction chamber is reduced, the liquid stored in the storage chamber is transferred to the reaction chamber via the liquid communication part and stored in the reaction chamber if the pressure on the storage chamber side is made to exceed the reaction chamber side. As the level of the liquid to be raised rises, it can be expected that the generation of hydrogen gas will be improved, so that the amount of generated hydrogen gas can be adjusted while using a simple system. And is preferred.

According to a fourth aspect of the present invention, in addition to the third aspect, the generating section includes at least two reaction chambers, and the liquid communication section is provided for each of the reaction chambers. , Wherein each of the reaction chambers is configured to be able to supply hydrogen to the fuel cell side, and each of the reaction chambers is configured to be switchable.

[Operation and Effect] The generating section has at least two reaction chambers, the liquid communication section is provided for each reaction chamber, and hydrogen gas can be supplied from each reaction chamber to the fuel cell side. Since each of the reaction chambers is configured so as to be switchable, in addition to the operation and effect according to the third aspect of the present invention, by switching and using each reaction chamber, hydrogen gas is generated to generate a fuel cell. This is preferable because maintenance such as replacement of a solid reactant can be performed for each reaction chamber while supplying to the reaction side.

According to a fifth aspect of the present invention, in addition to the third or fourth aspect, a liquid level detecting means capable of detecting the liquid level of the stored liquid in the reaction chamber is provided. A liquid addition mechanism that can newly supply the liquid when the liquid level of the liquid detected by the liquid level detection means is equal to or higher than a set position.

[Operation and Effect] As described above, when the amount of hydrogen gas generated in the reaction chamber decreases, the liquid is transferred from the storage chamber to the reaction chamber via the liquid communication part, and the liquid level of the liquid stored in the reaction chamber is reduced. With this configuration, when the liquid level rises above the set value, the liquid is additionally supplied by the liquid addition mechanism, so that the generation of hydrogen gas in the reaction chamber is further promoted. Can be expected. The liquid additionally newly supplied may be supplied directly to the reaction chamber, or may be supplied to the storage chamber.

According to a sixth aspect of the present invention, in addition to the second aspect of the present invention, a liquid storage chamber for storing the liquid is provided for providing the generating section, and a first liquid supply means is provided. By providing an overflow chamber containing the solid reactant while storing the liquid supplied from the liquid storage chamber while overflowing, and providing a collection chamber for collecting the liquid overflowed from the overflow chamber by the second supply means. There is a place.

According to the present configuration, as long as a new liquid is provided in the liquid chamber, the solid reactant is always brought into contact with the new liquid supplied from the liquid chamber in the overflow chamber. It can be expected that a predetermined amount of hydrogen gas will be generated continuously, and it is also possible to improve the economic efficiency by reusing the recovered liquid in the recovery chamber It is suitable.

According to a seventh aspect of the present invention, there is provided the above-described sixth aspect.
In addition to the features of the above, by reacting with the liquid overflowed from the overflow chamber in the recovery chamber,
It has a second reactant capable of generating hydrogen.

[Operation and Effect] According to this configuration, the second reactant of the recovery chamber reacts with the liquid overflowed from the overflow chamber to generate hydrogen, so that not only the overflow chamber but also the second reactant is generated. Also, hydrogen gas can be obtained in the recovery chamber, which is preferable.

According to the eighth aspect of the present invention, there is provided the above-described sixth aspect.
In addition to the features of the above, by reacting with the liquid overflowed from the overflow chamber in the recovery chamber,
The overflow chamber has a second reactant capable of precipitating a substance containing a component of the solid reactant.

[Operation and Effect] According to this configuration, the second reactant in the recovery chamber reacts with the liquid overflowed from the overflow chamber, thereby containing the component of the solid reactant in the overflow chamber. Since the substance can be precipitated, the solid reactant can be easily reused by collecting such a substance, which is preferable.

According to a ninth aspect of the present invention, in addition to the seventh or eighth aspect, the combination of the solid reactant and the liquid is magnesium metal and sulfuric acid;
Wherein the second reactant is sodium metal.

[Action and Effect] If the combination of the solid reactant and the liquid is magnesium metal and the liquid, and the recovery chamber is provided with sodium metal as the second reactant, the method according to claim 7 And 8 can be enjoyed, which is advantageous. That is, chemical formula 1
The reaction shown in 2 occurs in the recovery chamber, and hydrogen gas can be obtained while easily recovering and reusing the magnesium component. In addition, since the recovery chamber is provided with sodium metal, a larger amount of hydrogen gas can be obtained, which is advantageous. In other words, the liquid that overflows from the overflow chamber including magnesium metal and sulfuric acid and is collected in the recovery chamber comes into contact with sodium metal in the recovery chamber, but since the liquid contains a large amount of water, Hydrogen gas is generated by the reaction between water and sodium metal, and a larger amount of hydrogen gas can be obtained by recovering the hydrogen gas. It is sufficient that the reaction represented by Chemical Formula 1 or Chemical Formula 12 occurs. The magnesium metal means not only a mere magnesium metal but also an alloy having a magnesium component, and the sodium metal is not only a mere sodium metal, An alloy having a sodium component is also meant.

[0039]

Embedded image MgSO ₄ + 2Na + 2H ₂ O → Mg (OH) ₂
+ Na ₂ SO ₄ + H ₂ ↑

A feature of the invention according to claim 10 is that the reaction chamber according to any of claims 3 to 5 or the overflow chamber according to any of claims 6 to 9 includes There is a heat insulation structure that is insulated from the outside.

[Operation and Effect] Since the reaction chamber or the overflow chamber is insulated from the outside by the heat insulating structure, the liquid temperature rises due to the heat of the reaction, and high-temperature hydrogen gas is generated.
Therefore, since high-temperature hydrogen gas is supplied to the fuel cell, it is particularly suitable for a fuel cell operating at high temperature.
Further, since hydrogen gas having a high dew point is supplied, in particular,
This is advantageous when the fuel cell is a polymer electrolyte fuel cell.

A feature of the invention according to claim 11 is that, in addition to the features according to any one of claims 2 to 10, at least a part of hydrogen atoms of the acidic liquid is deuterium atoms.

[Operation and Effect] According to this configuration, the reaction between the base metal and the acidic liquid is promoted by the deuterium atom, and more hydrogen gas can be generated in a short time. The startup time can be reduced.

According to a twelfth aspect of the present invention, in addition to any one of the second to eleventh aspects, the solid reactant is formed into a structure in which the liquid can enter. The feature of the invention according to claim 13 is that the solid reactant is tubular or briquette in addition to the feature of claim 12, and the feature of the invention according to claim 14. The structure is such that, in addition to the characteristic structure of any of claims 2 to 11, the solid reactant is in the form of powder or granules or scale.

[Operation and Effect] If the solid reactant is formed in a structure such as a tube or a briquette into which a liquid can enter, the contact interface between the liquid and the solid reactant can be increased while increasing the contact interface. Can get a lot of hydrogen gas, and
If the solid reactant is in the form of particles or scales, the contact interface between the liquid and the solid reactant increases, and the amount of the solid reactant supplied to the liquid can be finely adjusted, which is advantageous.

According to a fifteenth aspect of the present invention, in addition to any one of the second to fourteenth aspects, the solid reactant comprises two or more metals having a greater ionization tendency than hydrogen. , The inner side is formed to have a metal having a greater ionization tendency.

[Operation and Effect] Since the solid reactant is formed to have a metal having a higher ionization tendency toward the inner side, for example, the hydrogen gas is generated by the reaction with the acidic liquid. This is preferable because the metal having higher reactivity is exposed and comes into contact with the acidic liquid, and the possibility that the amount of generated hydrogen gas is reduced can be reduced.

According to a sixteenth aspect of the present invention, in addition to the fifteenth aspect, the solid reactant includes an alkali metal inside and a metal other than the alkali metal outside. There is a place.

[Action and Effect] For example, as hydrogen gas is generated by the reaction with the acidic liquid, the alkali metal on the inner side is exposed and the reaction by the contact between the alkali metal and water occurs, and the hydrogen gas is generated. The possibility that the amount of generated gas is reduced can be reduced, which is not only preferable, but also the storage and handling before the reaction can be performed safely because the outside of the alkali metal is covered with a metal other than the alkali metal.

According to a seventeenth aspect of the present invention, in addition to any one of the first to sixteenth aspects, a hydrocarbon-based fuel is reformed into a hydrogen-rich reformed gas, and the reformed gas is reformed. A reformed gas supply device for supplying gas to the fuel cell is provided, and the characteristic configuration of the invention according to claim 18 is, in addition to the characteristic configuration according to claim 17, when starting up the fuel cell. Mainly supplying hydrogen to the fuel cell from the hydrogen supply device, during the steady operation of the fuel cell,
A supply switching means for mainly supplying a reformed gas from the reformed gas supply device to the fuel cell is provided, and the characteristic configuration of the invention according to claim 19 is the characteristic according to claim 17 or 18. In addition to the configuration, when the load of the fuel cell is increased, the reforming gas supply device supplies a reformed gas to the fuel cell, and the hydrogen supply device supplies a load corresponding supply unit that supplies hydrogen to the fuel cell. It is located.

According to the seventeenth aspect of the present invention, not only the functions and effects of the hydrogen gas supply device described above, but also the hydrocarbon-based fuel is reformed into a hydrogen-rich reformed gas. The effect that the running cost by the reformed gas supply device for supplying the fuel cell can be reduced can be expected, which is preferable.

According to the invention, hydrogen is mainly supplied from the hydrogen supply device to the fuel cell when the fuel cell is started by the supply switching means. In addition, during the steady operation of the fuel cell, the reformed gas is mainly supplied to the fuel cell from the reformed gas supply device, so that the running operation can be performed more stably with less running cost. Is preferable.

According to the nineteenth aspect,
By the load corresponding supply means, during the steady operation of the fuel cell, when the demand for hydrogen fuel on the fuel cell side increases, if the supply from the reformed gas supply device is not enough, the hydrogen supply device supplies hydrogen. Since the system can be covered, a minimum necessary compact system can be provided, which is preferable.

According to a twentieth aspect of the present invention, in addition to any one of the first to nineteenth aspects, the fuel cell is a polymer electrolyte fuel cell.

[Operation and Effect] The polymer electrolyte fuel cell has a solid polymer membrane as an electrolyte, and the conductivity of the solid polymer membrane changes in accordance with the wet state, and the conductivity in the dry state. Has the property of decreasing
Although appropriate water management is required, according to the present invention, from the hydrogen supply device to the polymer electrolyte fuel cell side, when the polymer electrolyte fuel cell is operated, the wet Since hydrogen gas in a state is naturally supplied, the start-up of the polymer electrolyte fuel cell at the time of start-up is quick, and the water content of the polymer electrolyte fuel cell is simple. It is preferable because excessive or shortage hardly occurs, the operation is relatively stable, and the output voltage is relatively stable.

[0056]

Embodiments of the present invention will be described below with reference to the drawings.

[First Embodiment] As shown in the schematic diagram of the fuel cell system according to the present invention shown in FIG. 1, the fuel cell system according to the present invention comprises a polymer electrolyte fuel cell (an example of a fuel cell; PEFC) and the PEFC
And a hydrogen supply device A for supplying hydrogen to the fuel cell 1.

As the PEFC 1, any fuel cell may be used as long as it uses a solid polymer membrane such as fluororesin sulfonic acid as the electrolyte interposed between the anode and the cathode. Good. Needless to say, the PEFC 1 may have a single cell structure composed of one cell, or may have a stacked structure in which a plurality of cells are stacked.

As shown in FIGS. 1, 2, and 3, a hydrogen supply device A for supplying a wet hydrogen gas (hereinafter, abbreviated as a wet hydrogen gas) to the PEFC 1 is provided with an acidic aqueous solution (an example of an acidic liquid). a, and a metal M having a higher ionization tendency than hydrogen (hereinafter, abbreviated as a base metal) M is provided. A generator 10 capable of generating hydrogen is provided, and hydrogen is generated from the generator 10 to the PEFC side. A supply path 20 for supplying is provided and configured.

In the present embodiment, the generating section 10 is provided as shown in FIG.
As shown in FIGS. 3 to 3, the outer cylinder 11 capable of storing an acidic aqueous solution
And an inner cylinder 12 that can be accommodated in the outer cylinder 11.

As shown in FIGS. 2 and 3, the outer cylinder 11 is formed in a substantially cylindrical shape having an opening at the top and having a bottom, in which an acidic aqueous solution a can be stored. The outer cylindrical body 11 is formed by forming a stepped portion 13 on the side and fitting the enlarged head 16 of the inner cylindrical body 12 described later through the elastic sealing material S to the stepped portion 13. The inner cylindrical body 12 can be accommodated inside. Further, a tubular injection section 14 having an opening / closing valve V1 is provided in an airtight manner above the outer cylinder 11 so that compressed air can be injected into the interior of the outer cylinder 11 from a compressor or the like. Is provided in an airtight manner so that an acidic aqueous solution can be injected into the outer cylinder 11.

As shown in FIGS. 2 and 3, the inner cylinder 12 is formed in a substantially cylindrical shape, and at the upper end thereof, an expanded portion which fits inside the stepped portion 13 of the outer cylinder 11. A radial head 16 is provided, and can be accommodated in the outer cylinder 11 in a posture in which the axial direction is along the axial direction of the outer cylinder 11. And
The inner cylindrical body 12 is housed in the outer cylindrical body 11 by fitting the enlarged diameter head 16 to the stepped part 13 via the elastic sealing material S, and has a lower end near the bottom of the outer cylindrical body 11. And the acidic aqueous solution a stored in the outer cylinder 11
Is configured to be able to flow into the inner cylindrical body 12 from the lower end side. The upper end surface of the inner cylindrical body 12 is also housed in the outer cylindrical body 11 so that the outer cylindrical body 11 and the inner cylindrical body 12 can be hermetically sealed by using a lid 18 described later. 11 is formed substantially flush with the upper end face.

In this embodiment, as shown in FIG.
As an example, a bottom portion 17 having a through hole h is provided at a lower portion on the inner peripheral side of the inner cylinder 12, and a lower metal M is placed on the bottom 17, so that the inner cylinder 12 has the lower metal M therein. It is possible to make it. By the way, the base metal M is formed in a long body such as a rectangular parallelepiped or a columnar body, and is disposed so that the longitudinal direction thereof is substantially in a vertical direction.
As will be described later, the acidic aqueous solution automatically enters the inner cylindrical body 12 in accordance with the amount of the acidic aqueous solution entering the inner cylindrical body 12 (that is, the level of the acidic aqueous solution entering the inner cylindrical body 12 moves up and down). Can be controlled. As the base metal M, for example, zinc, magnesium, aluminum, etc., any other metal having a higher ionization tendency than hydrogen may be used, and any metal having a higher ionization tendency than hydrogen may be used. A metal alloy may be used.

Then, the disk-shaped lid 18 is attached to the outer cylinder 11.
And, by mounting and fixing on the upper end surface of the inner cylindrical body 12, the inner space of the outer cylindrical body 11 and the inner cylindrical body 12 can be sealed,
In the present embodiment, as shown in FIG.
An elastic seal material S is interposed between the upper end of the outer cylindrical body 11 and the upper end of the outer cylindrical body 11 with bolts or the like. The lid 18 has a tubular supply unit 19.
Are provided in an airtight manner so that the wet hydrogen gas generated in the inner cylinder 12 can be supplied to the PEFC side. The supply section 19 is connected to the supply path 20 via an opening / closing valve V3.

The generator 10 in the present embodiment is configured as described above, and a portion surrounded by the inner side of the outer cylinder 11 and the outer side of the inner cylinder 12 corresponds to the storage chamber R1.
A portion surrounded by the inside of the lid 18 and the inside of the lid 18 corresponds to the reaction chamber R2, and the through hole h of the bottom 17 corresponds to the liquid communication section 3. As will be described in detail later, the storage chamber R1 and the reaction chamber The acidic aqueous solution can be transported based on the pressure difference in the space above the acidic aqueous solution stored between R2.

Incidentally, although not shown, the reaction chamber R2 may be provided with a heat insulating structure that is insulated from the outside. In this case, the reaction chamber R2 is insulated from the outside, so that the reaction heat As a result, the liquid temperature rises, and high-temperature hydrogen gas is generated. Then, hydrogen gas with high temperature and high dew point becomes P
It is suitable because it is supplied to EFC1.

Next, an example of a process of generating wet hydrogen gas in the hydrogen supply device A configured as described above will be described.

First, a predetermined amount of an acidic aqueous solution is injected from the injection part 15, and the first valve V1 and the second valve V2 are closed. Then, the injected acidic aqueous solution is stored in the storage chamber R.
The liquid is stored at 1 and enters the reaction chamber R2 side from below through a through hole h as a liquid communication part 3. And the reaction chamber R
When the base metal M provided in 2 is immersed in the acidic aqueous solution that has penetrated into the reaction chamber R2, a reaction occurs in which the base metal M dissolves in the acidic aqueous solution. When hydrogen bubbles come out of the liquid, hydrogen naturally comes out together with water vapor, and wet hydrogen, that is, wet hydrogen gas, is supplied to the PEFC 1 through the supply unit 19 and the supply path 20.

When the supply amount of the wet hydrogen gas supplied from the supply path 20 becomes excessive with respect to the consumption amount on the PEFC 1 side, or when the opening / closing valve V3 is closed, the wet hydrogen gas is supplied into the reaction chamber R2. The reaction chamber R2 is filled with hydrogen gas.
The pressure in the space above the acidic aqueous solution a rises. As a result, the acidic aqueous solution that has entered the reaction chamber R2 is returned to the storage chamber R1 until the pressures in the spaces above the acidic aqueous solutions a in the storage chamber R1 and the reaction chamber R2 become equal. Then, since the amount of the acidic aqueous solution in the reaction chamber R2 is reduced, by arranging the arrangement of the base metal M, the portion of the base metal M immersed in the acid aqueous solution is reduced, and the base metal M is reduced. Suppress the reaction between the metal M and the acidic aqueous solution,
It is also possible to automatically suppress the generation amount of the wet hydrogen gas.

In the present embodiment, the pressure in the space above the acidic aqueous solution a on the storage chamber R1 side can be increased by injecting the compressed air from the injection section 14 into the storage chamber R1. The pressure in the upper space in the initial state is adjusted, the pressure of the hydrogen gas supplied to the PEFC 1 is adjusted, and more acidic aqueous solution is introduced into the reaction chamber R2 to reduce the base metal M It is possible to increase the amount of hydrogen gas generated by activating the reaction with hydrogen and control the increase in the amount of supplied hydrogen.

In the present embodiment, the liquid injection unit 15
By newly supplying the acidic aqueous solution a, it is possible to activate the reaction with the base metal M, increase the amount of generated hydrogen gas, and control the increase in the amount of supplied hydrogen. 1 to 3 show an example in which the liquid injection unit 15 is provided in the storage chamber R1 as an example. However, the liquid injection unit 15 is not limited to such an example, and although not illustrated, the liquid injection unit 15 is It may be provided in the reaction chamber R2. Incidentally, although not shown, the reaction chamber
A liquid level detecting means capable of detecting the liquid level of the stored acidic aqueous solution is provided, and when the liquid level of the liquid detected by the liquid level detecting means exceeds a set position, a liquid capable of newly supplying the liquid is provided. An additional mechanism may be provided. In this case, when the liquid level of the acidic aqueous solution becomes equal to or higher than the set value, the acidic additional aqueous solution is newly supplied by the liquid adding mechanism, and the generation of hydrogen gas in the reaction chamber is further increased. Can be expected to be promoted.

The wet hydrogen gas generated from the generator 10 as described above is pure hydrogen having a very high hydrogen concentration, and has no possibility of containing carbon dioxide or carbon monoxide. Therefore, for example, even if the PEFC 1 includes a catalyst such as platinum, there is no possibility that the catalyst is poisoned by carbon dioxide or carbon monoxide, and the PEFC can be operated at room temperature.

Examples of the acidic aqueous solution a include inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, and citric acid, glycine, cinnamic acid, succinic acid, salicylic acid, formic acid, glutamic acid, and the like.
An acidic aqueous solution of an organic acid such as ascorbic acid / oxalic acid / tartaric acid / lactic acid / acetic acid may be used. Further, two or more kinds of inorganic acids and organic acids may be used, or a combination of an inorganic acid and an organic acid may be used. Incidentally, the acidic aqueous solution, if it is a deuterated acidic aqueous solution in which at least some of the hydrogen atoms contained therein are replaced with deuterium atoms, the following actions and effects can be expected, and it is more preferable. is there. In other words, the deuteration component contained in the deuterated acidic aqueous solution promotes the dissolution reaction of the base metal immersed in the deuterated acidic aqueous solution, and generates a large amount of wet hydrogen gas in a short time. It is possible to further shorten the startup time of the PEFC. Also, since a large amount of hydrogen is generated in a short time, when hydrogen gas bubbles come out of the liquid and out of the liquid, moderately bubbling the deuterated acidic aqueous solution, from the initial stage of supply, more reliably, For the operation of PEFC, wet hydrogen gas with an appropriate amount of water vapor
To the side. Incidentally, the deuterated sulfuric acid aqueous solution may be, for example, a hydrogen sulfate atom replaced with a deuterium atom by appropriately adopting other various methods such as adding heavy water, deuterium sulfate, deuterium sulfide, or the like to the sulfuric acid aqueous solution. . Needless to say, the substitution amount is more than that contained in the natural hydrogen compound.

The PEFC 1 may be supplied with oxygen gas necessary for its operation as appropriate. For example, as shown in FIG. 1, a compressed air supply device such as an air compressor is used as the oxygen gas supply device 30. In this case, compressed air having an increased oxygen concentration may be supplied from the oxygen gas supply device 30 to the PEFC 1 side.

The electric power obtained from the PEFC 1 by the fuel cell system according to the present invention may be used for loads according to various uses. For example, as shown in FIG. And the charging and discharging of the secondary battery may be performed in parallel. In the present invention, the output voltage of the power obtained from the PEFC is very stable, and
Since the start-up of the EFC at the time of start-up is fast, it is possible to stably and efficiently use desired power and power.

It is to be noted that the liquid injection section 15 is not necessarily provided, and an acidic aqueous solution may be stored in advance.
The injection section 14 may be provided or not provided. In the present embodiment, the example in which the storage chamber R1 and the reaction chamber R2 are configured as closed chambers as described above has been described. The storage chamber R1 and the reaction chamber R2 may be configured to be pressurized by other pressurizing means without being limited to air. Although not shown, a discharging means for discharging the acidic aqueous solution from the reaction chamber may be provided.

[Second Embodiment] As shown in the conceptual illustration of the system configuration in FIG. 4, the generator 10 includes two or more reaction chambers R2, and each of the reaction chambers R2 has a storage chamber R1 and a storage chamber R1. And the supply passage 20 may be capable of supplying wet hydrogen gas from each of the reaction chambers R2 to the fuel cell side. In this case, although not shown, pumps and valves are optionally provided. By switching and using each reaction chamber R2, maintenance such as replacement of the solid reactant M in each reaction chamber R2 can be performed while generating and supplying the wet hydrogen gas to the fuel cell side, It is suitable.
Others are the same as the first embodiment.

[Third Embodiment] As shown in the conceptual diagram of the system configuration in FIG. 5, the generating unit 10 is provided with a liquid storage chamber R11 storing the liquid a and a liquid storage chamber R11. An overflow chamber R12 provided with a solid reactant M while storing the liquid a supplied from the storage chamber R11 while overflowing, and an overflow chamber R provided by the second supply means.
A recovery chamber R13 for recovering the liquid a overflowed from the liquid storage chamber 12 may be provided. In this case, in the overflow chamber R12, the solid reactant M and the new liquid a supplied from the liquid storage chamber R11 are constantly or for a fixed time. Each time it is contacted, it can be expected that a predetermined amount of hydrogen gas is continuously and stably generated, and it is also possible to improve the economic efficiency by reusing the recovered liquid in the recovery chamber R13. It is suitable.

In the example shown in FIG. 5, a first connecting portion 6 is provided for communicating the liquid a stored in the liquid storage chamber R11 with the liquid a stored in the overflow chamber R12. a is supplied, and the liquid a overflowed in the overflow chamber R12 is supplied to the recovery chamber R13 via the second connection portion 7 and collected. In the example shown in FIG. 5, a third connection portion 8 that connects the first connection portion 6 and the recovery chamber R13 is provided, and the liquid a in the overflow chamber R12 is entirely recovered through the third connection portion 8. It can be collected in R13.

In this embodiment, as shown in FIG. 5, the liquid storage chamber R11, the overflow chamber R12, and the recovery chamber R
In addition to adjusting the liquid level and the bottom surface of the liquid stored in the order of 13 to an appropriate height position so as to be lower, the liquid storage chamber R11
A first space communication part J1 that communicates the space above the liquid level of the overflow chamber R12 with the space above the liquid level of the overflow chamber R12, and the space above the liquid level of the overflow chamber R12 and the recovery chamber R1.
The second space communication part J2 which communicates with the space above the liquid surface of No. 3
By itself, the liquid a naturally passes through the first connecting portion 6.
Is supplied from the liquid storage chamber R11 to the overflow chamber R12, and the liquid a is recovered from the overflow chamber R12 to the recovery chamber R13 via the second connection portion 7. Supply means,
Simple and economical. Although not shown, the first supply unit and the second supply unit may be configured using a pump or the like. Also, as shown in FIG.
May be provided so as to supply the liquid a or to make the connection portions 6 and 8 freely openable and closable.

Incidentally, for example, when the combination of the solid reactant and the liquid is magnesium (Mg) metal and sulfuric acid, if the recovery chamber R13 is provided with sodium metal, the reaction of the above-mentioned chemical formula 12 is recovered. This is preferable because it occurs in the chamber R13, and the hydrogen gas can be obtained while easily collecting and reusing the magnesium component. It should be noted that the present invention is not limited to such a configuration, and may be configured as follows. For example, if the recovery chamber is configured to have a second reactant capable of generating hydrogen by reacting with the liquid overflowed from the overflow chamber, hydrogen gas is generated not only in the overflow chamber but also in the recovery chamber. Can be obtained. Incidentally, such a second reactant may be a solid,
It may be a liquid or a gas. In the collection chamber,
By reacting with the liquid overflowed from the overflow chamber, if it is configured to have a second reactant capable of precipitating a substance containing a component of the solid reactant in the overflow chamber, the solid is easily solid. The reactants can be reused. The second reactant may be a solid, a liquid, or a gas.

The overflow chamber may be provided with a heat insulating structure that is insulated from the outside. In this case, hydrogen gas having a high temperature and a high dew point
1 is preferred.

The other points are the same as in the first embodiment.

[Another Embodiment] Another embodiment will be described below. <1> The hydrogen generator A is not limited to the form described in the above embodiments, but is provided with a generator 10 capable of generating hydrogen by bringing a solid reactant into contact with a liquid. As long as the supply path 20 for supplying hydrogen to the battery 1 is provided, any one may be used.
The modification will be described with reference to the conceptual explanatory diagram shown in FIG.

<2> As illustrated in FIG. 6, a generator 10 capable of storing an acidic aqueous solution (an example of a liquid) a is provided, and a base metal (an example of a solid reactant) M is provided in the generator 10. A liquid supply unit 31 capable of supplying an acidic aqueous solution a is provided in the generation unit 10 so that the acidic aqueous solution a supplied from the liquid supply unit 31 into the generation unit 10 can contact the base metal M. You may have. In the configuration shown in FIG.
A predetermined amount of the acidic aqueous solution a stored in the storage tower 31a is supplied into the generator 10 via the liquid supply path 31b according to the pressure of the compressed air (an example of a pressurizing unit). Then, the acidic aqueous solution supplied into the generating unit 10 is allowed to flow on the base metal M, or is stored in the generation unit 10 and the base metal M is immersed, or For example, the base metal M and the acidic aqueous solution a come into contact with each other to generate wet hydrogen gas. In this case, the amount of generated wet hydrogen gas can be controlled by adjusting the pressure of the compressed air with a simple structure, which is convenient.

<3> As an example, as shown in FIG. 6, a collecting unit 32 capable of collecting a waste liquid generated by contacting and reacting an acidic aqueous solution with a base metal to a hydrogen supply device A. May be provided. In this case, by collecting the waste liquid, the risk that the reaction of dissolving the base metal in contact with the acidic aqueous solution and dissolving it can be reduced, and the reliability of the generation of wet hydrogen gas can be prevented from being reduced. You can also.

<4> Then, as exemplified in FIG. 7A, a cylindrical body 34 having a cylindrical storage tank 33 formed around the cylindrical generating section 10 is provided. And a storage tank 33 capable of communicating with the storage tank 33, and a moving body 36 slidable up and down along the inner periphery of the generating unit 10 and capable of sealing the communication hole 35, An operation rod 37 capable of operating the moving body 36 up and down by an operation from outside the body 34 is attached to the moving body 36. Then, the cylindrical body 34 is temporarily fixed to the moving body 36 at a position where the communication hole 35 seals the communication hole 35, the acidic aqueous solution (an example of a liquid) a is stored in the storage tank 33, and If the base is provided with a base metal (an example of a solid reactant) M, a simple operation of pushing the operation rod 37 into the generator 10 is performed, and the communication is performed as shown in FIG. The acidic aqueous solution a can be infiltrated into the generator 10 through the hole 35 to generate a wet hydrogen gas, which is convenient. In addition, because of such a configuration, particularly, the size of the hydrogen supply device A can be reduced. When the generated wet hydrogen gas is sent from the generation unit 10 to the supply path 20, the transport pipe 3 to the supply path 20 is provided in the operation rod 37 as illustrated in FIG.
8 and the other end of the transport pipe 38 is connected to the supply path 20.
And a communication hole 39 communicating with one end of the transport pipe 39 from the outside thereof may be formed in the operation rod 37. Further, as shown in the figure, a pressurizing means that can pressurize the liquid surface of the acidic aqueous solution a in the storage tank 33 using compressed air or the like may be provided.

<5> As illustrated in FIG.
0 is provided in a box shape, and an acidic aqueous solution (an example of a liquid) is placed on it.
a storage box 40 capable of storing a is placed, and a communication pipe 41 communicating with the storage body 40 and the generating unit 10 is provided so that compressed air can be supplied into the storage body 40. If there is (an example of a pressurizing unit), the acidic aqueous solution a stored in the storage body 40 will enter the generating unit 10 via the communication pipe 41 in accordance with the pressure of the supplied compressed air. , Can be brought into contact with a base metal (an example of a solid reactant) M provided in the generator 10. Therefore, with a simple structure, the generation amount of the wet hydrogen gas can be controlled by adjusting the pressure of the compressed air. In addition, by stacking the generation unit 10 and the storage body 40 in this manner, the size of the device can be reduced. Can also be planned. When the wet hydrogen gas is sent from the generator 10 to the supply path 20, for example, as shown in FIG. 8, one end of the transport pipe 42 airtightly inserted into the storage body 40 is airtightly sealed in the generator 10. And the other end may be connected to the supply path 2.

<6> Further, as described in the above embodiment, the base metal (an example of a solid reactant) M is not limited to the form in which the generating unit 10 is provided in advance. As shown in FIG.
May be configured to be supplied, and may be configured to be capable of contacting with an acidic aqueous solution (an example of a liquid) a provided in the generation unit 10. In the example of FIG. 9, one end of the metal supply pipe 46 is inserted into the acidic aqueous solution a so that the base metal M can be supplied into the acidic aqueous solution a stored in the generating unit 10. From the other end of the tube 46, a predetermined amount of the base metal M can be supplied freely. In this case, it is possible to control the generation amount of the wet hydrogen gas by the supply amount of the base metal M. still,
As shown in FIG. 9, when the base metal M is supplied in the form of granules, powder, fine powder, or scale, the supply amount can be finely adjusted and the contact with the acidic aqueous solution can be performed. The area is increased, and the generation efficiency of the wet hydrogen gas can be improved.

Further, as illustrated in FIG.
Outer storage 47 capable of storing the acidic aqueous solution a around 0
And a circulating mechanism 48 capable of transporting the acidic aqueous solution a stored in the external storage body 47 into the generating unit 10 via the tank T, and configuring the generating unit 10 as an overflow tank for overflowing the acidic aqueous solution, If the tank T is configured as a waste liquid treatment tank capable of treating a waste liquid generated by contacting and reacting with an acidic aqueous solution and a base metal, the reaction of dissolving the base metal by contact with the acidic aqueous solution is suppressed. It is also possible to maintain a difficult state for a relatively long time and to stably supply wet hydrogen gas.

<7> The hydrogen supply apparatus A may be configured as shown in FIG. In the configuration illustrated in FIG. 10, a cylindrical or square box 50 is provided, and the lower part of the inner space of the box 50 is made of a base metal (an example of a solid reactant) M.
A generator 51 (equivalent to the generator 10) capable of accommodating an aqueous solution (an example of a liquid) a is provided in the box 50 with a storage 52 capable of storing an acidic aqueous solution (an example of a liquid) a and a partition plate 53 for vertically separating the storage. The partition plate 53 is provided with a rod-shaped body 55 which can be moved up and down in the box body 50, and a valve seat 57 into which a valve body 56 provided on the distal end side of the rod-shaped body 55 can be fitted and fixed. Then, for example, as shown in FIG.
The shape of 6 is formed in the shape of a cone whose outer diameter narrows toward the top,
If the valve seat 57 is formed so as to correspond to the shape of the valve body 56, the valve body 56 shown by a chain line
From the state where it is fitted and fixed to the rod 53 as shown by the solid line.
Is moved downward, a gap is formed between the valve body 56 and the valve seat 57, and the acidic aqueous solution a
Is supplied, and the acidic aqueous solution a is brought into contact with the base metal M accommodated in the generator 51 to generate a wet hydrogen gas. With such a structure, the hydrogen supply device A can be reduced in size. In addition, in the configuration illustrated in FIG. 10, the valve body 56 is moved upward and downward by the rod-shaped body 55 from the shape of the valve body 56 described above. The size of the gap formed between the valve seats 57 is adjusted, and the supply amount of the acidic aqueous solution a to the generation unit 51 can be adjusted, which is convenient. Further, as shown in FIG. 10, if compressed air can be supplied into the storage unit 52 (an example of a pressurizing unit), the supply of the acidic aqueous solution a to the generation unit 51 by the supply of the compressed air is performed. The amount can also be adjusted. In supplying the wet hydrogen gas generated in the generator 51 to the supply path 20, for example, the rod-like body 55 is formed in a cylindrical shape, and one end of the rod 55 is formed in the generator 51.
And the other end may be connected to the supply path 20.

<8> The solid reactant M may be a tube (not shown) or a briquette having a plurality of through holes 60 formed therein as shown in FIG. If an example of a structure that can enter) is used, the surface area is relatively large, the contact area with the acidic aqueous solution is increased, and the wet hydrogen gas can be generated efficiently.

<9> In the embodiments described above, one type of
The combination of a solid reactant and a liquid has been exemplified, but two or more
Of course, the combination of the above solid reactant and liquid can be used.
No. For example, although not shown, the ionization tendency is higher than that of hydrogen.
It has two or more kinds of large metals, and the inner side, the more ions
If it is formed on a metal having a large tendency to
Hydrogen gas is generated by the reaction with the neutral aqueous solution.
The more reactive base metal is exposed,
And the amount of hydrogen gas generated decreases.
This can be reduced, which is preferable. Also, solid reactants and liquids
Combination of base metal M and acidic liquid
Although the explanation has been given by way of an example,
The solid reactant and the liquid
The combination is with a metal that has a greater ionization tendency than hydrogen
Acid solution, alkali metal and water, amphoteric metal and alkali aqueous solution
Liquid, metal hydride and water
At least one combination may be used. And these
Of course, a plurality of combinations may be employed.
As shown in Fig. 2, a base metal different from an alkali metal
Is an alkali metal (in the figure, N is shown).
a) is reacted with sulfuric acid,
(H _TwoSO_Four) Soak in acidic aqueous solution such as aqueous solution
Then, in the initial stage, the outer base metal and the acidic aqueous solution
Reaction produces moist hydrogen gas, which is then
Alkali metal exposed by dissolving the noble metal of
Reaction is expected to generate wet hydrogen gas
Wear. Also, the contact between the solid reactant and the liquid
Is not limited to the form described above,
Flow over an object or immerse a solid reactant in a liquid
Or by spraying a liquid onto a solid reactant
The state may be adopted arbitrarily. And the fuel cell 1
Not limited to the polymer electrolyte fuel cell described in the embodiment,
Any fuel cell can be used.
Oxide fuel cells, molten carbonate fuel cells, phosphoric acid fuel cells
A fuel cell or an aqueous alkaline fuel cell may be used.

<10> In the embodiments described above, the form in which the solid reactant is brought into contact with the liquid has been described.
The generating unit may be any unit that can generate hydrogen by contacting a reactant with a liquid, and any combination of the reactant and the liquid may be used as long as it can generate hydrogen.
Examples thereof are as follows: a combination of an alkaline earth metal and water represented by chemical formula 13, a combination of monosilane and an aqueous alkali solution represented by chemical formula 14, a combination of an alkali metal and alcohol represented by chemical formula 15, a chemical formula Hydrogen can be obtained by a combination of an alkali metal and a carboxylic acid shown in 16 or a combination of an alkali metal and a mercaptan shown in Chemical Formula 17. The reactant is not limited to a solid but may be a liquid.

[0095]

M + 2H ₂ O → M (OH) ₂ + H ₂ ↑ (where M is an alkaline earth metal (Be, Mg, Ca,
Sr, Ba, etc.)

[0096]

Embedded image SiH ₄ + 2NaOH + H ₂ O → Na ₂ S
iO ₃ + 4H ₂ ↑

[0097]

ROH + M → ROM + 1 / 2H ₂ (where M: Na, K, etc., R: C _n H _{2n + 1} , n: 1,
2,3. . . )

[0098]

Embedded image RCOOH + M → RCOOOM + ／ H ₂ (where M: Na, K, etc., R: C _n H _{2n + 1} , n: 1,
2,3. . . )

[0099]

RSH + M → RSM + ／ H ₂ (where M: Na, K, etc., R: C _n H _{2n + 1} , n: 1,
2,3. . . )

<11> In the embodiments described above, the configuration example in which only the hydrogen supply device A is provided has been described. However, as shown in the system configuration diagram of FIG. A reformed gas supply device B for supplying the reformed gas to the fuel cell 1 by converting the reformed gas into a hydrogen-rich reformed gas is provided by a control unit (an example of a supply switching unit) C. Hydrogen supply device A
To supply the wet hydrogen gas to the fuel cell 1 from
During the steady operation of the fuel cell 1, the reformed gas supply device B may be configured to supply the reformed gas to the fuel cell 1 mainly. In this case, the operation at the time of starting the fuel cell is performed well. However, continuous operation can be performed more stably with less running cost. Further, in this case, the control unit (load corresponding supply means) C controls the fuel cell 1
When the load on the fuel cell 1 increases, the fuel cell 1
In addition to supplying the reformed gas to the fuel cell 1, the wet hydrogen gas may be supplied from the hydrogen supply device A to the fuel cell 1, and in that case, the required compact system can be obtained.

[Brief description of the drawings]

FIG. 1 is a system configuration diagram schematically showing a fuel cell system according to the present invention.

FIG. 2 is a cutaway perspective view showing a first embodiment of the hydrogen supply device.

FIG. 3 is a sectional view showing a first embodiment of the hydrogen supply device.

FIG. 4 is a conceptual explanatory view showing a second embodiment of the hydrogen supply device.

FIG. 5 is a conceptual explanatory view showing a third embodiment of the hydrogen supply device.

FIG. 6 is a conceptual explanatory view showing another embodiment of the hydrogen supply device.

FIG. 7 is a conceptual explanatory view showing another embodiment of the hydrogen supply device.

FIG. 8 is a conceptual explanatory view showing another embodiment of the hydrogen supply device.

FIG. 9 is a conceptual explanatory view showing another embodiment of the hydrogen supply device.

FIG. 10 is a conceptual explanatory view showing another embodiment of the hydrogen supply device.

FIG. 11 is a perspective view showing another embodiment of a solid reactant.

FIG. 12 is a conceptual explanatory view showing another embodiment of the hydrogen supply device.

FIG. 13 is a system configuration diagram showing another embodiment of the fuel cell system according to the present invention.

[Explanation of symbols]

A hydrogen supply device B reformed gas supply device a liquid M solid reactant R1 storage room R2 reaction chamber R11 Liquid chamber R12 overflow room R13 collection room 1 fuel cell 3 Liquid communication part 4 Liquid level detection means 5 Liquid supply means 10 generator 20 Supply channel

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Yasuo Miyake             2-5-5 Keihanhondori, Moriguchi-shi, Osaka 3             Yo Electric Co., Ltd. F term (reference) 5H026 AA06                 5H027 AA06 KK00

Claims (20)

[Claims] 1. A fuel cell system comprising: a fuel cell; and a hydrogen supply device that supplies hydrogen to the fuel cell, wherein the hydrogen supply device is capable of generating hydrogen by contacting a reactant with a liquid. A fuel cell system provided with a generator. 2. The method according to claim 1, wherein the reactant is a solid reactant, and the combination of the solid reactant and the liquid in the generating unit is a metal and an acidic liquid having a higher ionization tendency than hydrogen, an alkali metal and water, and an amphoteric metal. The fuel cell system according to claim 1, wherein the fuel cell system is at least one combination selected from the group consisting of aluminum, an aqueous alkali solution, and a metal hydride and water. 3. A storage chamber in which the generating section stores the liquid while leaving a space above, and separately from the storage chamber, wherein the liquid stores the liquid while leaving a space above and the liquid. A reaction chamber in which the solid reactant is provided so as to be capable of contacting the liquid reaction chamber, and a liquid communication part is provided for communicating and connecting the liquid stored in the storage chamber and the liquid stored in the reaction chamber. The fuel cell system according to claim 2, wherein hydrogen is supplied from the reaction chamber to the fuel cell side. 4. The generator includes at least two reaction chambers, the liquid communication unit is provided for each reaction chamber, and hydrogen can be supplied from each of the reaction chambers to the fuel cell side. 4. The reaction chamber according to claim 3, wherein each of said reaction chambers is switchable.
The fuel cell system as described. 5. A liquid level detecting means for detecting a liquid level of the stored liquid in the reaction chamber, wherein when the liquid level detected by the liquid level detecting means is equal to or higher than a set position, 5. The fuel cell system according to claim 3, further comprising a liquid addition mechanism capable of additionally supplying the liquid. 6. A liquid storage chamber for storing the liquid is provided for providing the generating section, and the liquid supplied from the liquid storage chamber by the first liquid supply means is stored while overflowing and the solid is stored. 3. The fuel cell system according to claim 2, further comprising an overflow chamber provided with a reactant, and a collection chamber for collecting a liquid overflowed from the overflow chamber by the second supply means. 7. The fuel cell system according to claim 6, wherein the recovery chamber has a second reactant capable of generating hydrogen by reacting with a liquid overflowed from the overflow chamber. 8. The recovery chamber has a second reactant capable of precipitating a substance containing a component of a solid reactant in the overflow chamber by reacting with a liquid overflowed from the overflow chamber. Item 7. The fuel cell system according to Item 6. 9. The fuel cell system according to claim 7, wherein the combination of the solid reactant and the liquid is magnesium metal and sulfuric acid, and the second reactant is sodium metal. 10. The heat insulation in which the reaction chamber according to any one of claims 3 to 5 or the overflow chamber according to any one of claims 6 to 9 is insulated from the outside. A fuel cell system having a structure. 11. The fuel cell system according to claim 2, wherein at least a part of the hydrogen atoms of the acidic liquid is a deuterium atom. 12. The fuel cell system according to claim 2, wherein the solid reactant is formed in a structure into which the liquid can enter. 13. The fuel cell system according to claim 12, wherein the solid reactant has a tubular or briquette shape. 14. The fuel cell system according to claim 2, wherein the solid reactant is in the form of particles or scales. 15. The solid reactant according to claim 2, wherein the solid reactant comprises two or more metals having a higher ionization tendency than hydrogen, and a metal having a higher ionization tendency toward the inner side. The fuel cell system according to claim 1. 16. The fuel cell system according to claim 15, wherein the solid reactant has an alkali metal inside and a metal other than the alkali metal outside. 17. The fuel cell according to claim 1, further comprising a reformed gas supply device for reforming the hydrocarbon-based fuel into a hydrogen-rich reformed gas and supplying the reformed gas to the fuel cell. 2. The fuel cell system according to claim 1. 18. When the fuel cell is started, hydrogen is mainly supplied from the hydrogen supply device to the fuel cell. During a steady operation of the fuel cell, the reformed gas is mainly supplied from the reformed gas supply device to the fuel cell. 18. The fuel cell system according to claim 17, further comprising: a supply switching unit that allows supply of the fuel cell. 19. When the load of the fuel cell is increased, a load corresponding supply unit that supplies reformed gas from the reformed gas supply device to the fuel cell and supplies hydrogen from the hydrogen supply device to the fuel cell is provided. The fuel cell system according to claim 17, wherein the fuel cell system is provided. 20. The fuel cell system according to claim 1, wherein the fuel cell is a polymer electrolyte fuel cell.