JP5208532B2 - Hydrogen generator - Google Patents

Description

  The present invention relates to a hydrogen generator for continuously producing hydrogen from water.

Conventionally, as a method for generating hydrogen, (1) electrolysis of water, (2) partial oxidation method or reforming method in which hydrocarbons such as natural gas or petroleum are reacted with oxygen, air, water vapor or the like at high temperature, (
3) A method using a thermal decomposition reaction between water and carbon, and (4) a method of dissolving a metal such as zinc in an acid are known. However, the method (1) consumes a large amount of electric power and thus increases the production cost. In the methods (2) and (3), CO and the like are by-produced together with hydrogen, so high-purity hydrogen cannot be obtained. In the method of 4), since an acid is required, handling is difficult.
Thus, a new method for generating hydrogen was expected to replace them.

In recent years, a number of new hydrogen generation methods and apparatuses have been proposed to meet the above expectations.

For example, Patent Document 1 discloses a reaction vessel that contains nano-iron particles and contains a hydrogen generating agent that generates hydrogen by reaction with water or water vapor, and a water supply means that intermittently supplies water or water vapor to the reaction vessel. A hydrogen generator comprising: is disclosed.

Patent Document 2 discloses a hydrogen gas generator for generating hydrogen gas to be supplied to a fuel cell, having a shape extending in the longitudinal direction and containing a pure iron tablet, The introduction pipe for introducing water or water vapor into the first housing case, and the hydrogen gas generated by reacting the introduced water or water vapor with the pure iron tablet of the first housing case are derived. A lead-out tube, a second storage case that is disposed adjacent to the first storage case, extends in the same longitudinal direction as the first storage case, and stores a pure iron tablet, and is stored in the second storage case And an opening for introducing air to be reacted with the pure iron tablet, which is configured to transmit heat generated by the reaction of air and pure iron in the second housing case to the first housing case. It has been disclosed.

Patent Document 3 discloses a tank for storing water, a reaction container for storing a metal that generates hydrogen by a chemical reaction with water, a storage unit for storing the reaction container, and the storage unit. A heating means for heating the reaction vessel, an introduction pipe for supplying water from the tank to the reaction vessel housed in the housing portion, hydrogen generated in the reaction vessel and unreacted A return pipe for introducing water into the tank and a discharge pipe extending from the tank for discharging hydrogen and water in the tank, wherein the reaction vessel is attached to and detached from the storage section A hydrogen generator that is possible is disclosed, and as a metal that generates hydrogen by reaction with water,
Any one of iron, indium, tin, magnesium, cerium or an oxide thereof is exemplified.

In Patent Document 4, hydrogen gas is supplied by supplying pure aluminum to a liquid indium gallium alloy contained in a container through a supply pipe, supplying water from a water supply pipe, and reacting aluminum with water. A hydrogen gas generation device that generates hydrogen is disclosed.

However, the techniques disclosed in Patent Documents 1 to 4 have the following problems.

That is, in the hydrogen generating apparatus described in Patent Document 1, water or water vapor cannot be continuously supplied to react with water or water vapor to the inside of the nano iron particles. And above all, since this device is not equipped with a means for continuously supplying nano iron particles, if the nano iron particles in the reaction vessel are used up, the device is temporarily stopped and the nano iron particles are placed in the reaction vessel. The particles must be replenished.

Moreover, in the hydrogen gas generator described in Patent Document 2, when the pure iron tablet in the first housing case is used up, the device is temporarily stopped and the pure iron tablet is replenished, One containment case must be replaced. Moreover, in order to make pure iron and water react, the heating means for heating the 1st accommodation case to about 200-400 degreeC high temperature is needed.

Moreover, in the hydrogen generator described in Patent Document 3, when the metal in the reaction vessel is used up, the device must be stopped once and the reaction vessel must be replaced. Moreover, in order to make a metal and water react, the heating means for heating a reaction container to about 100-400 degreeC high temperature is needed.

In addition, in the hydrogen gas generation apparatus shown in FIG. 3 of Patent Document 4, if pure aluminum is supplied to the indium-gallium alloy contained in the container through the supply pipe and water is continuously supplied from the water supply pipe, the hydrogen gas will appear at first glance. However, this device has the following major problems in the first place. That is, the hydrogen gas generating composition itself made of indium / gallium / aluminum based on the supplied pure aluminum and indium / gallium alloy cannot be made. Therefore, in such an apparatus, it is not desired to continuously generate hydrogen gas.
JP 2006-104017 A JP 2006-69875 A JP 2004-149394 A JP 2003-12301 A

An object of the present invention is to provide a hydrogen generator that is easy to handle and can continuously generate hydrogen.

To achieve this object, the invention according to claim 1 of the present invention includes a first metal containing tin and gallium, a second metal containing silver and gallium, a third metal made of gallium, Or a gallium-based metal containing means in which at least one gallium-based metal selected from a fourth metal containing at least one selected from the group consisting of iron, copper, germanium, and antimony is contained in gallium; ,
Water storage means capable of storing water;
Water supply means for supplying the water to the water containing means;
An additive metal element supply means for supplying at least one metal element selected from the group consisting of metal elements having a standard electrode potential lower than that of gallium from the water while being separated from the water,
A composition for generating hydrogen having the gallium metal and the metal element supplied and diffused into the gallium metal by the additive metal element supply means is configured to generate hydrogen by contacting the water. It is,
The water supply means is configured to continuously supply the water to the water storage means,
The additive metal element supply means is configured to continuously supply the metal element to be added into the gallium metal,
The composition for generating hydrogen and the water are in a state where they can always be contacted, and are configured to continuously generate hydrogen,
As the gallium metal containing means, the gallium metal is housed in a lower layer, and the
As a water storage means, it consists of a first shared container capable of storing the water in the upper layer,
The additive metal element supply means includes
A foil roll made of the metal element, and a twin roll which is a side where the gallium-based metal is accommodated in the lower layer of the first shared container and is isolated from the water and sealed and rotatably supported; A roll body wound with a wire body, and the foil body or the wire body are drawn by the twin roll, and the twin roll is driven to be supplied into the gallium metal contained in the first common container. Or a motor control means for controlling the driving of the motor,
Or
A powder storage container in which powder composed of the metal element is stored, and the first container for supplying the powder from the powder storage container into the gallium metal contained in the first common container. Any one of the common container and the injector containing the gallium-based metal and attached in a sealed state isolated from the water, and an injector control means for controlling the injector It is a hydrogen generator characterized by being.

According to a second aspect of the present invention, in the first aspect of the invention, the water supply means transports the water from the water storage container to the upper layer of the first common container. a first pump, ing from the first pump control means for controlling the operation of the first pump.

The invention according to claim 3 is the invention according to claim 1 or 2, wherein the first and second shared containers, the second container, and the water provided on the convex portion side of the porous body. to accommodate a container capable of at least one of the hydrogen outlet of the hydrogen outlet provided in each of the first housing space portion that has a hydrogen sensor is attached.

The invention according to claim 4 is the invention according to any one of claims 1 to 3, wherein the first metal is made of W% tin (% means mass%, the same shall apply hereinafter), gallium. Is X%, the second metal is Y% silver and Z% gallium, and the first or second metal satisfies the following formulas (1) to (6),
The total amount of at least one metal element selected from the group consisting of metal elements whose standard electrode potential is lower than that of gallium is 0.1% or more based on the first or second metal.
0 <W ≦ 96 (1)
4 ≦ X <100 (2)
X = 100-W (3)
0 <Y ≦ 55 (4)
45 ≦ Z <100 (5)
Z = 100−Y (6)

The invention according to claim 5 is the invention according to any one of claims 1 to 3, wherein the fourth metal is at least one selected from the group consisting of gallium, iron, copper, germanium, and antimony. The total amount of at least one metal element selected from the group consisting of metal elements having a standard electrode potential lower than gallium is 0.05 to 1% based on the fourth metal standard. It is 0.1% or more .

The invention according to claim 6 is the invention according to any one of claims 1 to 5, wherein at least one metal element selected from the group consisting of metal elements whose standard electrode potential is lower than gallium is At least one of aluminum and magnesium.

According to the present invention, the hydrogen generator includes a first metal containing tin and gallium, a second metal containing silver and gallium, a third metal made of gallium, or gallium with iron, copper, germanium. And a gallium metal containing means containing at least one gallium metal selected from a fourth metal containing at least one selected from the group consisting of antimony, and a water containing means capable of containing water When,
Water supply means for supplying the water to the water containing means;
An additive metal element supply means for supplying at least one metal element selected from the group consisting of metal elements having a standard electrode potential lower than that of gallium from the water while being separated from the water,
A composition for generating hydrogen having the gallium metal and the metal element supplied and diffused into the gallium metal by the additive metal element supply means is configured to generate hydrogen by contacting the water. Therefore, it is easy to handle and can generate hydrogen continuously.

  Hereinafter, embodiments of the present invention will be described.

The hydrogen generator according to the present invention includes a first metal containing tin and gallium, a second metal containing silver and gallium, a third metal made of gallium, or gallium with iron, copper, germanium, antimony A gallium metal containing means that contains at least one gallium metal selected from a fourth metal containing at least one selected from the group consisting of: a water containing means capable of containing water;
Water supply means for supplying the water to the water containing means;
An additive metal element supply means for supplying at least one metal element selected from the group consisting of metal elements having a standard electrode potential lower than that of gallium from the water while being separated from the water,
A composition for generating hydrogen having the gallium metal and the metal element supplied and diffused into the gallium metal by the additive metal element supply means is configured to generate hydrogen by contacting the water. It is characterized by that.

The first metal is W% tin (% means mass%, the same applies hereinafter), X% gallium, and the second metal is Y% silver and Z% gallium. And the first or second metal satisfies the following formulas (1) to (6),
The total amount of at least one metal element selected from the group consisting of metal elements having a standard electrode potential lower than that of gallium is preferably 0.1% or more based on the first or second metal.
0 <W ≦ 96 (1)
4 ≦ X <100 (2)
X = 100−W (3)
0 <Y ≦ 55 (4)
45 ≦ Z <100 (5)
Z = 100−Y (6)

The fourth metal contains 0.05 to 1% of gallium with at least one selected from the group consisting of iron, copper, germanium and antimony,
The total amount of at least one metal element selected from the group consisting of metal elements whose standard electrode potential is lower than that of gallium is preferably 0.1% or more on the basis of the fourth metal.

Here, aluminum, magnesium, and zinc, which are metal elements whose standard electrode potential is lower than that of gallium, are dissolved by acid, and aluminum, zinc, and silicon are dissolved by alkali to generate hydrogen. However, these simple metal elements hardly react with neutral water. This is because the concentration of hydrogen ions contained in neutral water is low and an oxide film (or hydroxide film) is formed on the surface of each single metal element to protect the inside.

In contrast, the hydrogen generating composition used in the hydrogen generator according to the present invention generates hydrogen even with neutral water. The mechanism of this hydrogen generation is considered as follows.

That is, indium proposed as an alloy constituent element in Patent Document 4 is corroded and consumed even in ordinary weakly acidic water having a pH of about 5, but gallium is stable to acidic water up to about pH3. Almost no wear. Moreover, tin is stable to strongly acidic water having a pH of about 1 to 2, and is hardly consumed. Furthermore, since silver has a higher standard electrode potential than hydrogen, it is not consumed even by ordinary acids and alkalis.

In addition, a standard electrode potential of gallium (−0...) Is added to a metal (hereinafter referred to as a tin-gallium metal) containing tin-gallium that is stable to water in the above-described proportions.
56 V) (naturally lower than tin (−0.1375 V)), the added metal element selectively reacts with water. In addition, the oxide film (or hydroxide film) formed on the surface of the additive metal element by reaction with water is a normal dense oxide that is generated on the surface when the additive metal element is used alone. It is estimated that it becomes a sparse oxide film with many defects, not a film. Furthermore, this sparse oxide film is easily destroyed by a volume change due to the selective consumption of the additive metal element, and is peeled off by the generated hydrogen bubbles, so that the internal additive metal element and water are easily separated. Since the reaction proceeds by contact, continuously, and
It is considered that hydrogen is generated with high efficiency. Here, the reason why the tin content in the tin-gallium metal is limited to 96% by mass or less is that when the tin content exceeds 96% by mass, the hydrogen generation rate rapidly decreases. The reason why the hydrogen generation rate rapidly decreases as the tin content increases as described above is unknown at present, but it is also possible that the structure of the tin-gallium metal changes. The standard electrode potential is gallium (-0.56V)
Lower metal elements include aluminum (−1.66 V), magnesium (−2.37).
V), silicon (−0.86 V), and zinc (−0.7628 V) can be illustrated as preferable because they are relatively inexpensive and easily available. Moreover, the said additional metal element added to the said tin- gallium type metal may be added individually by 1 type, and may add 2 or more types together. In addition, the amount added is to exert the hydrogen generation effect by the above estimation mechanism,
The total amount is 0.1% by mass or more. Further, the additive metal element is not necessarily limited to a high-purity element. For example, in the case of aluminum, an industrial aluminum alloy may be used, and the hydrogen generating composition includes an industrial aluminum alloy. Inevitable impurities such as Fe and Ti may be included. Furthermore, scraps and recycled products of these metals can be used. Moreover, although the upper limit of addition amount is not specifically limited, since even if it adds excessively, the hydrogen generation | occurence | production speed | velocity tends to become slow gradually, it is more preferable to set it as 20 mass% or less, Furthermore, it is 10 mass% or less. The hydrogen generating composition having the tin-gallium metal as the first metal and the additive metal element (Japanese Patent Application No. 2007-88801, which is incorporated herein by reference) (Hereinafter referred to as a composition for generating hydrogen comprising a tin-gallium metal)) can be used as the composition for generating hydrogen constituting the hydrogen generating apparatus according to the present invention. .

As described above, the composition for hydrogen generation composed of the tin-gallium metal basically has the potential to continuously generate hydrogen. Therefore, in order to draw out this potential as a hydrogen generator thereafter. All you need to do is meet the following conditions: That is,
1) Since the tin-gallium metal is hardly consumed, replenishment is not required. there,
First, means for accommodating the tin-gallium-based metal as a basic substance (gallium-based metal accommodating means: details will be described in the examples below) is provided, and the additional metal element that decreases with the generation of hydrogen. Hydrogen is generated from the tin-gallium metal by replenishing it in the tin-gallium metal while isolating it from water so that the total amount becomes 0.1% or more based on the tin-gallium metal. Means (additional metal element supply means: details will be described later in the examples) are provided for continuing to form the composition.
2) Next, the composition for hydrogen generation composed of the tin-gallium metal contacts the water existing in a means capable of containing water (water containing means: details will be described in the examples described later), whereby the tin The additive metal element diffused in the composition for hydrogen generation made of a gallium metal is oxidized and dissolved as ions in the water in the water storage means. In exchange for this, hydrogen ions in the water are reduced and generated as hydrogen, and means for continuing to replenish the water containing means, which decreases with the generation of this hydrogen (water supply means: details) Provided in the examples below).

Thus, since the gallium metal as described above, which is liquid even at a room temperature of 25 ° C. to 30 ° C., is used as the additive metal element, the additive metal element only comes into contact with the gallium metal. Easily dissolves and diffuses into the gallium metal. As a result, it is easy to handle as a hydrogen generator (using ordinary water, without any special restrictions on the reaction, and without special heating means), and continuously with hydrogen. Can be generated. In addition, a hydrogen sensor is installed at the outlet of the generated hydrogen, and a signal from the hydrogen sensor is returned to at least the additional metal element supply means in the water supply means or the additional metal element supply means, and is controlled by feedback control. Hydrogen can be generated with the efficiency of

In addition, a standard electrode potential of gallium (-) is added to a metal (hereinafter referred to as a silver-gallium metal) containing silver and gallium, which are more stable against water than the tin-gallium metal, at a predetermined ratio. When a metal element lower than 0.56 V (of course, lower than silver (+0.8 V)) is added, the added metal element selectively reacts with water. The mechanism of hydrogen generation when this silver-gallium metal is used is the same as that when the tin-gallium metal is used. Accordingly, it is considered that hydrogen is generated continuously and highly efficiently because the reaction proceeds by the contact between the additive metal element and water. Here, the content of silver in the silver-gallium metal is limited to 55% by mass or less, as in the case of the tin-gallium metal,
This is because when the silver content exceeds 55% by mass, the hydrogen generation rate rapidly decreases. Various metal elements having a standard electrode potential lower than that of gallium can be used. From the viewpoint of the amount of hydrogen generated, and from the viewpoint of being relatively inexpensive and easy to obtain, aluminum, magnesium, aluminum And an alloy of magnesium can be exemplified as a more preferable one. In addition, as in the case of the tin-gallium metal, this additive metal element may be added alone or in combination of two or more. For example, in the case of adding an alloy of aluminum and magnesium, the hydrogen generation rate is higher than that of adding aluminum alone. Also,
The amount added is 0.1% by mass or more in total in order to exert the hydrogen generation effect by the above estimation mechanism. Further, the additive metal element is not necessarily limited to a high-purity element. For example, in the case of aluminum, an industrial aluminum alloy may be used, and the hydrogen generating composition includes an industrial aluminum alloy. Inevitable impurities such as Fe and Ti may be included. Furthermore, scraps and recycled products of these metals can be used. Moreover, although the upper limit of addition amount is not specifically limited, since even if it adds excessively, the hydrogen generation | occurence | production speed | velocity tends to become slow gradually, it is more preferable to set it as 25 mass% or less, Furthermore, it is 20 mass% or less. The composition for hydrogen generation having the silver-gallium metal as the second metal and the additive metal element (Japanese Patent Application No. 2007-, which is incorporated herein by reference)
The composition for generating hydrogen described in No. 259022 (hereinafter referred to as a composition for generating hydrogen comprising a silver-gallium metal) may be used as the composition for generating hydrogen constituting the hydrogen generator according to the present invention. it can. Note that the same effect can be obtained even when a metal substantially composed only of gallium (others are inevitable impurities) is used as the third metal.

  In addition, the standard electrode is formed on a metal containing at least one selected from the group consisting of iron, copper, germanium, and antimony in gallium at a ratio of the predetermined amount (hereinafter collectively referred to as an iron-gallium metal). The presence of a hydrogen generating composition obtained by adding a metal element having a potential lower than that of gallium selectively causes the added metal element to react with water. The mechanism of hydrogen generation when this iron-gallium metal or the like is used is the same as that when the tin-gallium metal or silver-gallium metal is used. Accordingly, it is considered that hydrogen is generated continuously and highly efficiently because the reaction proceeds by the contact between the additive metal element and water. A composition for hydrogen generation in which the addition amount of aluminum as an additive metal element with respect to the iron-gallium metal or the like as the fourth metal is 0.1% by mass or more (for example, the present specification is incorporated herein by reference) The hydrogen generating composition described in Japanese Patent Application No. 2008-11769, hereinafter referred to as a hydrogen generating composition made of iron-gallium metal, etc.) Can be used as a composition for generating hydrogen. Further, the additive metal element for the iron-gallium-based metal and the like is not limited to aluminum, and magnesium, silicon, and zinc are preferable because they are relatively inexpensive and easily available. That is, even if the total amount of at least one metal element selected from the group consisting of metal elements whose standard electrode potential is lower than that of gallium is 0.1% by mass or more based on the fourth metal reference is satisfied. do it.

  In addition, the first metal, the second metal, the third metal, or the fourth metal is not limited to being used alone, but may be combined with each other.

  As described above, the hydrogen generating composition comprising the silver-gallium metal and the iron-gallium metal is basically continuous with hydrogen in the same manner as the hydrogen generating composition comprising the tin-gallium metal. Therefore, in order to draw out this potential as a hydrogen generator, the same conditions as in the case of using the above-described composition for generating hydrogen comprising a tin-gallium metal can be prepared. That's fine. As a result, it is easy to handle as a hydrogen generator (using ordinary water, without any special restrictions on the reaction, and without special heating means), and continuously with hydrogen. Can be generated. Similarly to the case where the composition for generating hydrogen comprising the tin-gallium metal is used, a hydrogen sensor is installed at the outlet of the generated hydrogen, and the signal from the hydrogen sensor is supplied to the water supply means or the added metal. By returning to at least the added metal element supply means of the element supply means and performing feedback control, accurate hydrogen generation can be performed with a predetermined efficiency. However, this is not necessarily specified, and if only continuous hydrogen generation is to be performed, it is not always necessary to install a hydrogen sensor and perform feedback control. What is necessary is just to make a metallic element supply means function (that is, what is necessary is just to perform open loop control).

  Moreover, it is preferable that the said water supply means is set as the structure which can supply water to a water accommodating means continuously. However, the said water supply means should just be the structure which can supply water continuously, can stop supply temporarily and can also operate | move by the method of intermittent supply. As an element constituting the water supply means, for example, a pump can be used, but it is not necessarily limited to this, and a configuration in which tap water is directly supplied while adjusting the flow rate with a valve or the like may be used.

  Moreover, it is preferable that the said additional metal element supply means is the structure which can supply the metal element to add continuously in a gallium-type metal. However, the additive metal element supply means may be configured to be continuously supplied, can be temporarily stopped, and can be operated in an intermittent supply manner.

  It is preferable that the composition for generating hydrogen and water are in a state where they can always be brought into contact with each other and continuously generate hydrogen.

  In addition, as water to be brought into contact with the hydrogen generating composition comprising the tin-gallium metal, silver-gallium metal, or iron-gallium metal, pure water having a pH of 7 that is completely neutral is used. Naturally, it is naturally recommended to use normal water (inexpensive tap water). Furthermore, in order to promote the hydrogen generation reaction, the acid may be weakly acidic or weakly alkaline to such an extent that the tin-gallium metal, silver-gallium metal, iron-gallium metal, or the like does not corrode. Water need not be heated in particular, and may be at room temperature or heated to about 40 ° C.

  Moreover, as a contact method of said various hydrogen generating composition and water, various systems can be considered as shown in the below-mentioned Example.

  In addition, the hydrogen generated by the contact between the various hydrogen generating compositions and water is taken out from a predetermined outlet and collected, and by-products mainly composed of metal hydroxides generated by the reaction with water are collected. It is natural to remove. In addition, after removing this by-product, the water can be returned to the water storage means that can store the water again or the water supply means constituting the water supply means (details will be shown in the examples described later) to effectively use the water. Is possible.

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

Example 1
1A and 1B are schematic views showing a schematic configuration of a hydrogen generator according to Embodiment 1 of the present invention. FIG. 1A is a schematic plan view thereof, and FIG. 1B is a schematic cross-sectional view taken along line AA. In FIG. 1, 1 is the above-described tin-gallium-based metal as the first metal that exhibits a low-viscosity state even at room temperature, 2 is water, 3 is a gallium-based metal containing means, and initially, tin— A first common container containing gallium metal 1 and containing water 2 as an upper layer as water storage means, 4 is a water storage container storing water 2 for replenishment, and 5 is a first storage container from the water storage container 4. A first pump for transporting the water 2 to the upper layer of the shared container 3, 6 is a first pump control means for controlling the operation of the first pump 5, and 7 is sealed on the side wall 3 a of the lower layer of the first shared container 3. And a twin roll supported rotatably, 8 is a foil body of aluminum which is a metal element whose standard electrode potential is lower than that of gallium, 9 is a roll body around which the foil body 8 is wound, and 10 is a double roll body. Pulled in by the roll 7 and accommodated in the first shared container 3 A motor for driving the twin rolls 7 to be supplied into the gallium-based metal 1, 11 is a motor control means for controlling the driving of the motor 10, 12 is a water supply port provided in the first common container 3, 13 is generated hydrogen, 14 is a hydrogen outlet provided in the first shared container 3 for taking out hydrogen 13, 15 is a hydrogen sensor attached to the hydrogen outlet 14, and 16 is output from the hydrogen sensor 15. A signal 17 is an outlet for discharging the aluminum hydroxide 18 as a reaction by-product provided in the upper layer of the side wall 3a of the first common container 3 together with the water 2, and 19 stores the aluminum hydroxide 18 and the water 2. It is a tank. Moreover, the composition for hydrogen generation which consists of the above-mentioned tin-gallium-type metal is a substance which exhibited the state with low viscosity as a whole when the foil body 8 melt | dissolved and diffused in the tin-gallium-type metal 1. FIG.

  As described above, the first shared container 3 has both a function of containing the tin-gallium metal 1 as the gallium metal containing means and a function of containing the water 2 as the water containing means. The water supply means includes a water storage container 4, a first pump 5, and a first pump control means 6. The additive metal element supply means includes a twin roll 7, a roll body 9, a motor 10, and a motor control means 11.

  Next, the operation of the hydrogen generator will be described.

First, by starting the motor control means 11 and driving the motor 10, the foil body 8 wound around the roll body 9 is drawn into the first shared container 3 by the twin roll 7, and the first shared container 3 3 is supplied into the tin-gallium-based metal 1 accommodated in the lower layer 3. Thereby, the composition for hydrogen generation which showed the state with low viscosity as a whole is formed. Next, the hydrogen generating composition comes into contact with the water 2 stored in the upper layer of the first common container 3 in advance, so that the aluminum element diffused in the hydrogen generating composition is oxidized and water is added. 2 melts out as ions. In exchange for this, hydrogen ions in the water 2 are reduced to generate hydrogen 13. The hydrogen 13 is taken out from the hydrogen outlet 14 and simultaneously monitored by a hydrogen sensor 15, and an output signal 16 from the hydrogen sensor 15 is fed back to the motor control means 11 and the first pump control means 6. The motor 10 and the first pump 5 are driven so as to achieve efficiency (for example, maximum efficiency), and the foil body 8 and the water 2 are supplied to the lower layer and the upper layer in the first shared container 3, respectively. Therefore, the foil body 8 and the water 2 that are reduced with the generation of hydrogen due to the reaction are always replenished so as to satisfy the target. In the composition, the supplied aluminum naturally diffuses toward the contact interface with water due to the concentration gradient of aluminum. Further, by continuing the above reaction, the aluminum hydroxide 18 gradually accumulated in the upper layer of the first shared container 3 is discharged into the tank 19 from the discharge port 17 together with the water 2. Further, the water 2 in the tank 19 is returned again to the water storage container 4 for effective use.

In the present embodiment, the case has been described where the hydrogen sensor 15 is installed and feedback control is performed so that the hydrogen generation becomes the maximum efficiency, but this is not necessarily limited thereto. That is, if only continuous hydrogen generation is performed, it is not always necessary to install the hydrogen sensor 15 and perform feedback control. The motor control unit 11 and the first pump control unit 6 are used according to a predetermined program. It is only necessary to control the open loop and supply the foil body 8 and a predetermined amount of water 2 so that the aluminum element is 0.1% or more based on the tin-gallium metal 1 standard.

In this embodiment, an example in which aluminum is used as a metal element whose standard electrode potential is lower than that of gallium has been described. However, the present invention is not necessarily limited thereto. For example, when using magnesium, an alloy of aluminum and magnesium, silicon, zinc, titanium, lanthanum, and cerium alone, or when using three or more together such as an alloy of aluminum, magnesium, and silicon, an alloy of lanthanum and cerium ( However, since all the metal elements have a lower standard electrode potential than gallium, all these metal elements naturally react selectively with water, so the same effect as the above invention example Is clearly obtained.

Moreover, although the present Example demonstrated the example which used the foil body as a shape of the metallic element whose standard electrode potential is lower than gallium, it is not necessarily specified to this. For example, various things, such as a wire body (a solid wire, a shape in which a pipe is filled with powder), and the like can be used.

  Moreover, although the present Example demonstrated the example using the above-mentioned tin-gallium-type metal 1 as a 1st metal as a substance accommodated in the lower layer in the 1st common container 3, it was not necessarily specified by this. It is not something. For example, the above-described silver-gallium metal as the second metal, gallium as the third metal, iron-gallium metal as the fourth metal, or the like can be used. In the present embodiment, an example in which only the above-described tin-gallium metal 1 is initially stored in the lower layer in the first shared container 3 and then the aluminum foil body 8 is supplied is described. However, the present invention is not necessarily limited to this, and a form in which a composition for hydrogen generation in which an aluminum element is mixed from the beginning is accommodated and the aluminum element is sequentially replenished may be used. Further, the first shared container 3 may have a function of stirring the metal to be accommodated. The diffusion can be promoted by oscillating by ultrasonic vibration or the like. This technical idea can also be applied to Examples 2, 3, and 4 described later.

  In the present embodiment, the additive metal element supply means is composed of a twin roll 7, a roll body 9, a motor 10, and a motor control means 11, and the twin roll 7 is formed on the lower side wall 3 a of the first shared container 3. Although the example attached in the airtight state was demonstrated, it is not necessarily specified to this, The twin roll 7 is the 1st, 2nd, 3rd, or 4th of the 1st shared container 3. It is only necessary that the metal is accommodated on the side where it is isolated from water and sealed. Further, as the additive metal element supply means, for example, a powder storage container in which powder made of a metal element is stored, and first and second powders stored in the first common container 3 from the powder storage container. The side of the first shared container 3 where the first, second, third or fourth metal is housed for supply into the third or fourth metal, isolated from water Various configurations are conceivable, such as an injector mounted in a sealed state and an injector control means for controlling the injector.

(Example 2)
2A and 2B are schematic views showing a schematic configuration of a hydrogen generator according to Embodiment 2 of the present invention. FIG. 2A is a schematic plan view thereof, and FIG. 2B is a schematic cross-sectional view taken along line BB. In the present embodiment, the same constituent elements as those in the first embodiment are denoted by the same reference numerals, detailed description thereof is omitted, and only different portions will be described in detail. In FIG. 2, reference numeral 20 denotes the above-described silver-gallium metal as the second metal having a low viscosity state, and 21 denotes a first gallium metal containing means in which the silver-gallium metal 20 is first accommodated. 1 is a side wall of the first container 21, and 22 is the above-mentioned silver-gallium metal, which has a low viscosity state even when the aluminum foil 8 is dissolved and diffused in the silver-gallium metal 20. A composition for generating hydrogen comprising 23, communicated with the first container 21, a composition for generating hydrogen 22 in the lower layer, and a second container as water containing means containing water 2 in the upper layer, 23a The side wall 30 of the second container 23, 30 is provided between the side wall 21 a of the first container 21 and the lower side wall 23 a of the second container 23, from the first container 21 side to the second container 23 side. An inlet tube for supplying a composition for hydrogen generation, 1 is provided between the lower side wall 23a of the second container 23 and the side wall 21a of the first container 21, and a composition for hydrogen generation in which aluminum is reduced from the second container 23 side to the first container 21 side. A return pipe 32 for returning the product, a second pump 32 provided in the introduction pipe 30 for transporting the hydrogen generating composition supplemented with aluminum to the lower layer of the second container 23, and 33 for the second pump 32. It is the 2nd pump control means which controls a driving | operation. In the present embodiment, a first container 21 for synthesizing the hydrogen generating composition 22 and a second container 23 for generating hydrogen by bringing the hydrogen generating composition 22 into contact with the water 2 are provided. It is distinctive in that it is provided separately.

In this embodiment, the composition for hydrogen generation supplemented with aluminum is used as the second pump 32.
Therefore, the hydrogen generation composition that is forcibly transported to the lower layer of the second container 23 through the introduction pipe 30 can sufficiently supply a hydrogen generation composition that contributes to hydrogen generation, and is a reaction tank for hydrogen generation. Since it also has a function of stirring the inside of the second container 23, the reaction efficiency for generating hydrogen is improved. Further, by feeding back the output signal 16 from the hydrogen sensor 15 to the second pump control means 33, more efficient and accurate hydrogen generation can be performed.

In the present embodiment, the example in which the pump is provided only in the introduction pipe 30 has been described. However, the present invention is not necessarily limited to this, and the efficiency can be further improved by providing the pump in both the introduction pipe 30 and the return pipe 31. And accurate hydrogen generation can be performed.

In the present embodiment, an example in which only the above-described silver-gallium metal 20 is initially stored in the first container 21 and then the aluminum foil body 8 is supplied has been described.
However, the present invention is not necessarily limited to this, and the hydrogen generation composition 22 mixed with the aluminum element from the beginning may be accommodated, and the aluminum element may be replenished sequentially.
Further, in this embodiment, as in the first embodiment, the additive metal element supply means is the first, second, third, or fourth metal of the first container (however, this embodiment In the above description, the second metal has been mainly described.) A twin roll that is hermetically sealed on the side in which the second metal is accommodated and is rotatably supported, and a foil body or a wire body made of the metal element is wound. A roll body, a motor for driving the twin roll to draw the foil body or wire body by the twin roll and supply it into the second metal housed in the first container, and the motor Although the example comprised from the motor control means which controls the drive of this was demonstrated, it is not necessarily specified to this, The powder storage container in which the powder which consists of metal elements was stored, and this powder storage container Powder was stored in the first container 21 An injector mounted in a sealed state on the side of the first container 21 containing the first, second, third or fourth metal for supply into the first or second metal; An injector control means for controlling the injector, or a hopper in which at least one of a foil, a wire, and a powder made of a metal element is stored, and an outlet of the hopper Open at least one of the foil, wire, and powder from the side of the first container 21 that does not contain the first, second, third, or fourth metal. An input means (for example, a solenoid valve) for supplying the first, second, third, or fourth metal accommodated in the first container 21 is not necessarily limited thereto. ) And control of the input means for controlling the input means Or a powder storage container in which the powder is stored and the powder storage container. The first, second, and second powders contained in the first container from the side of the first container that does not contain the first, second, third, or fourth metal. Various configurations are conceivable, such as a configuration that includes an injector for feeding into the third or fourth metal, and an injector control means for controlling the injector. In the present embodiment, the example of aluminum as the metal element has been described. However, the present invention is not necessarily limited thereto, and various elements can be used as in the first embodiment.

(Example 3)
3A and 3B are schematic views showing a schematic configuration of a hydrogen generator according to Embodiment 3 of the present invention. FIG. 3A is a schematic plan view thereof, and FIG. 3B is a schematic cross-sectional view taken along the line CC. In the present embodiment, the same components as those in the first embodiment are denoted by the same reference numerals, detailed description thereof is omitted, and only different portions will be described in detail. In FIG. 3, reference numeral 40 denotes a cage-shaped ceramic porous material as a gallium metal containing means containing the above-described tin-gallium metal (not shown) as the first metal having a low viscosity state. The body 41 is provided on the convex portion side of the porous body 40 and contains water 2 and is a container as a water storage means to which the porous body 40 is attached, 41a is a side wall of the container 41, 42 is a standard electrode Aluminum powder, which is a metal element having a lower potential than gallium, 43 is a powder storage container in which the powder 42 is stored, 44 is a porous body 40 having a large number of micropores from the powder storage container 43 to the powder 42. An injector 45 for supplying the tin-gallium-based metal into the tin-gallium metal from the concave side of the injector is an injector control means for controlling the injector 44. The additive metal element supply means includes a powder 42, a powder storage container 43, an injector 44, and an injector control means 45. In the present embodiment, since the micropores on the concave side of the porous body 40 have a higher aluminum element concentration than the micropores on the convex side, the aluminum atoms naturally diffuse into the porous body 40 and generate hydrogen. It is characteristic that the composition is synthesized. Further, since the output signal 16 from the hydrogen sensor 15 is configured to be fed back to the injector control means 45, the powder is adjusted so as to have a predetermined efficiency (for example, maximum efficiency) as in the first and second embodiments. 42 can be supplied into the tin-gallium metal from the concave side of the porous body 40.

  In the present embodiment, an example in which the powder 42, the powder storage container 43, the injector 44, and the injector control means 45 are configured as the additive metal element supply means has been described. A hopper in which at least one of a foil, a wire, and a powder made of a metal element is stored, and an outlet of the hopper is opened to open the foil, the wire, and the powder. At least one of the first, second, third, or fourth metal from the concave portion side of the porous body 40 (however, in the present embodiment, the description has focused on the first metal). Supply means (for example, a solenoid valve; however, it is not necessarily limited to this) and supply means for controlling the supply means (for example, solenoid valve control means; Necessarily this Etc. constituting from not intended to be a constant.), It is considered that the different configurations. In the present embodiment, the example of aluminum as the metal element has been described. However, the present invention is not necessarily limited thereto, and various elements can be used as in the first embodiment.

Example 4
4A and 4B are schematic views showing a schematic configuration of a hydrogen generator according to Embodiment 4 of the present invention. FIG. 4A is a schematic plan view thereof, and FIG. 4B is a schematic cross-sectional view taken along line DD. In this example, Example 1,
The same constituent elements as those in FIG. 3 will be assigned the same reference numerals and detailed description thereof will be omitted, and only different parts will be described in detail. In FIG. 4, reference numeral 50 denotes a plurality of porous bodies as gallium metal containing means containing the above-mentioned silver-gallium metal (not shown) as the second metal having a low viscosity state, 51 is A plurality of first accommodating spaces serving as water accommodating means for accommodating water 2 on one side with the porous body 50 interposed therebetween, 52 is accommodated with the powder 42 on the other side with the porous body 50 interposed therebetween. A plurality of second accommodation spaces 51 a are side walls of the first accommodation space 51. The side walls 51a of the plurality of first accommodation spaces 51 are each provided with a discharge port 17 for discharging the reaction product by-product aluminum hydroxide 18 together with the water 2. Each discharge port 17 is connected to a rectangular parallelepiped tank 19. Has been inserted.

  In the present embodiment, the additive metal element supply means includes a powder 42, a powder storage container 43, an injector 44 and an injector control means 45, and the powder 42 is injected from one injector 44. The example in which the powder 42 is guided to the plurality of second accommodation spaces 52 has been described. However, the present invention is not necessarily limited thereto, and the plurality of injectors 44 are used to place the powder 42 into the plurality of second accommodation spaces. You may make it inject directly to the part 52. FIG. In this embodiment, the example in which the hydrogen sensor 15 is provided at one hydrogen outlet 14 has been described. However, when the plurality of injectors 44 are used, the hydrogen sensor 15 is provided at each hydrogen outlet 14. By configuring each output signal 16 from each hydrogen sensor 15 to be fed back to each injector control means 45, the efficiency of the entire hydrogen generator is further increased. In the present embodiment, an example in which the powder 42, the powder storage container 43, the injector 44, and the injector control means 45 are configured as the additive metal element supply means has been described. As an additional metal element supply means, a porous body in which a powder containing the metal element 42 is stored and an outlet of the hopper is opened to put the powder 42 into the plurality of second accommodation spaces 52. 50. Supply means for supplying the first, second, third, or fourth metal in 50 (however, in the present embodiment, the second metal will be mainly described) (for example, A solenoid valve; however, it is not necessarily specified to this, and a control means of the supply means for controlling the supply means (for example, a solenoid valve control means; however, it is not necessarily specified thereto). Etc. consist and may be attributed to the different configurations. In the present embodiment, the example of aluminum as the metal element has been described. However, the present invention is not necessarily limited thereto, and various elements can be used as in the first embodiment.

(Example 5)
FIG. 5 is a schematic diagram showing a schematic configuration of a hydrogen generator of Example 5 of the present invention, in which (a) is a schematic plan view thereof, and (b) is a schematic cross-sectional view taken along line EE. In the present embodiment, the same constituent elements as those in the first embodiment are denoted by the same reference numerals, detailed description thereof is omitted, and only different portions will be described in detail. In FIG. 5, 60 is a second shared container, 60a is the bottom of the second shared container 60, 61 is an aluminum block body that is a metal element having a standard electrode potential lower than gallium as an added metal element supply means, and 62 is Stainless steel mesh-like cover member as a metal that does not react with water or gallium fixed to the second common container 60, 63 is a support member that supports the block body 61, 64 is a lift mechanism for lifting the support member 63, 64a is a shaft inserted in the lift mechanism 64, and 65 is a lift mechanism control means.

  The second shared container 60 contains the block body 61 in the lower layer, the tin-gallium metal 1 applied on the surface of the block body 61 as the gallium metal containing means in the middle layer, and further through the cover member 62. In the upper layer, water 2 can be accommodated as water accommodating means. With this configuration, the block body 61 is isolated so as not to come into direct contact with the water 2. However, the tin-gallium metal 1 can contact the water 2 through the cover member 62. In the second shared container 60, a support member 63 that supports the block body 61 is installed through a hole (not shown) provided in the bottom 60a of the second shared container 60. A shaft 64 a is inserted into the support member 63.

  Next, operation | movement of this hydrogen generator is demonstrated.

  Since the block body 61 itself is an additive metal element supply means and is in direct contact with the tin-gallium metal 1, aluminum atoms are formed from the contact surface between the block body 61 and the tin-gallium metal 1. It is characteristic that the composition for generating hydrogen is synthesized by dissolving into the gallium metal 1 and spontaneously diffusing into the tin-gallium metal 1. In addition, when the hydrogen generating composition comes into contact with the water 2 that has passed through the cover member 62, the aluminum element diffused in the hydrogen generating composition is oxidized and dissolved in the water 2 as ions. . In exchange for this, hydrogen ions in the water 2 are reduced to generate hydrogen 13. This hydrogen 13 is taken out from the hydrogen outlet 14. At the same time, the hydrogen 13 is monitored by the hydrogen sensor 15, and the output signal 16 from the hydrogen sensor 15 is fed back to the lift mechanism control means 65 and the first pump control means 6.

  As the above reaction proceeds, aluminum is consumed, so that the contact surface between the block body 61 and the tin-gallium metal 1 (a composition for generating hydrogen during the reaction) gradually decreases. Since the degree of lowering of the contact surface is correlated with the amount of hydrogen 13 generated, the output signal 16 from the hydrogen sensor 15 is input to the lift mechanism control means 65 and inserted into the lift mechanism 64. The shaft 64a can be raised by a predetermined amount in accordance with the degree to which the contact surface is lowered. Thereby, the composition for hydrogen generation and the cover member 62 will be in a state which can always contact. That is, since the composition for hydrogen generation and the water 2 are always in contact, hydrogen can be generated continuously and stably. Further, the hydrogen generating composition and the cover member 62 are always in contact with each other, so that the hydrogen generating composition is rolled up together with the bubbles of hydrogen 13 generated by the contact between the hydrogen generating composition and the water 2. There is an effect to prevent.

  In the present embodiment, the cover member 62 is fixed to the second common container 60, and the support member 63 that supports the block body 61 is moved by the shaft 64a inserted in the lift mechanism 64. Although not necessarily limited to this, at least one of the block body 61 and the cover member 62 is movable so that the water 2 can come into contact with the tin-gallium metal 1 (the composition for generating hydrogen during the reaction). It suffices if it has a movable mechanism for making it.

  Further, in the present embodiment, an example using a net-like material as the form of the cover member 62 has been described. However, the embodiment is not necessarily limited to this, and the water 2 is tin-gallium metal 1 (during the reaction, It only needs to have a function capable of contacting the composition for hydrogen generation). For example, as a form of the cover member, various things such as a porous body, a foam, a nonwoven fabric, or a combination thereof can be used in addition to the net. In the present embodiment, the cover member 62 is made of stainless steel as a metal that does not react with water or gallium as a material of the cover member 62. However, the present invention is not necessarily limited to this, and ceramic, glass, Various materials such as any of the resins or composites can be used.

  In the present embodiment, the example in which the above-described tin-gallium metal 1 as the first metal is used as the gallium metal has been described. However, the present invention is not necessarily limited thereto. As in Example 1, the above-described silver-gallium metal as the second metal, gallium as the third metal, iron-gallium metal as the fourth metal, or the like can also be used.

  In the present embodiment, an example in which aluminum, which is a metal element having a standard electrode potential lower than that of gallium, is used as the block body 61 is described. However, the block body 61 is not necessarily limited to this. As in Example 1, for example, magnesium, silicon, zinc, titanium, lanthanum, and cerium are used alone, or three or more types such as an alloy of aluminum and magnesium, or an alloy of aluminum and magnesium and silicon are used together. Various materials such as lanthanum and cerium alloy (Misch metal) can be used. Further, the shape of the block body 61 is not limited to the rectangular parallelepiped described in the present embodiment, and various objects may be used as long as they have a sufficient volume to continuously generate a predetermined amount of hydrogen. can do.

  Further, as described in the present embodiment, it is preferable to provide the cover member 62 between the water 2 and the tin-gallium metal 1, but in principle, this is not always necessary.

  Although not shown in the present embodiment, the block body 61 can be replenished from the side or the lower side of the second shared container 60.

  Moreover, in the said Examples 1-5, although the example using a pump was demonstrated as an element which comprises a water supply means, it does not necessarily specify this. For example, a configuration in which tap water is directly supplied while adjusting the flow rate with a valve or the like may be used. The water supply means is preferably configured to be able to continuously supply water to the water storage means. However, the said water supply means should just be the structure which can supply water continuously, can stop supply temporarily and can also operate | move by the method of intermittent supply.

It is a schematic diagram which shows schematic structure of the hydrogen generator of Example 1 of this invention, Comprising: (a) is the schematic plan view, (b) is a schematic cross section in the AA line. It is a schematic diagram which shows schematic structure of the hydrogen generator of Example 2 of this invention, Comprising: (a) is the schematic top view, (b) is a schematic cross section in a BB line. It is a schematic diagram which shows schematic structure of the hydrogen generator of Example 3 of this invention, Comprising: (a) is the schematic plan view, (b) is a schematic cross section in CC line. It is a schematic diagram which shows schematic structure of the hydrogen generator of Example 4 of this invention, Comprising: (a) is the schematic top view, (b) is a schematic cross section in the DD line. It is a schematic diagram which shows schematic structure of the hydrogen generator of Example 5 of this invention, Comprising: (a) is the schematic plan view, (b) is a schematic cross section in the EE line | wire.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Tin-gallium-type metal 2 Water 3 1st shared container 3a, 21a, 23a, 41a, 51a Side wall 4 Water storage container 5 1st pump 6 1st pump control means 7 Double roll 8 Foil body 9 Roll body 10 Motor DESCRIPTION OF SYMBOLS 11 Motor control means 12 Water supply port 13 Hydrogen 14 Hydrogen extraction port 15 Hydrogen sensor 16 Output signal 17 Outlet 18 Aluminum hydroxide 19 Tank 20 Silver-gallium metal 21 First container 22 Hydrogen generating composition 23 2nd Container 30 introduction pipe 31 return pipe 32 second pump 33 second pump control means 40, 50 porous body 41 container 42 powder 43 powder storage container 44 injector 45 injector control means 51 first accommodating space 52 Second accommodating space 60 Second shared container 60a Bottom 61 Block body 62 Cover member 63 Support Material 64 lift mechanism 64a shaft 65 lift mechanism control means

Claims (6)

At least one selected from the group consisting of a first metal containing tin and gallium, a second metal containing silver and gallium, a third metal made of gallium, or gallium with iron, copper, germanium, and antimony A gallium-based metal containing means containing at least one gallium-based metal selected from a fourth metal containing at least a species;
Water storage means capable of storing water;
Water supply means for supplying the water to the water containing means;
An additive metal element supply means for supplying at least one metal element selected from the group consisting of metal elements having a standard electrode potential lower than that of gallium from the water while being separated from the water,
A composition for generating hydrogen having the gallium metal and the metal element supplied and diffused into the gallium metal by the additive metal element supply means is configured to generate hydrogen by contacting the water. And
The water supply means is configured to continuously supply the water to the water storage means,
The additive metal element supply means is configured to continuously supply the metal element to be added into the gallium metal,
The composition for generating hydrogen and the water are in a state where they can always be contacted, and are configured to continuously generate hydrogen,
As the gallium metal containing means, the gallium metal is contained in the lower layer, and the water containing means comprises a first shared container capable of containing the water in the upper layer,
The additive metal element supply means includes
A foil roll made of the metal element, and a twin roll which is a side where the gallium-based metal is accommodated in the lower layer of the first shared container and is isolated from the water and sealed and rotatably supported; A roll body wound with a wire body, and the foil body or the wire body are drawn by the twin roll, and the twin roll is driven to be supplied into the gallium metal contained in the first common container. Or a motor control means for controlling the driving of the motor,
Or
A powder storage container in which powder composed of the metal element is stored, and the first container for supplying the powder from the powder storage container into the gallium metal contained in the first common container. Any one of the common container and the injector containing the gallium-based metal and attached in a sealed state isolated from the water, and an injector control means for controlling the injector The hydrogen generator characterized by being.   The water supply means stores a water storage container that stores the water, a first pump that transports the water from the water storage container to an upper layer of the first common container, and a first pump that controls the operation of the first pump. The hydrogen generator according to claim 1, comprising one pump control means.   The first and second shared containers, the second container, a hydrogen outlet provided in each of the container capable of storing water and the first storage space provided on the convex side of the porous body The hydrogen generator according to claim 1 or 2, wherein a hydrogen sensor is attached to at least one of the hydrogen outlets. The first metal is W% for tin (% means mass%, the same applies hereinafter), X% for gallium, and the second metal is Y% for silver and Z% for gallium, The first or second metal satisfies the following formulas (1) to (6),
The total amount of at least one metal element selected from the group consisting of metal elements whose standard electrode potential is lower than that of gallium is 0.1% or more based on the first or second metal. The hydrogen generator as described in any one of these .
0 <W ≦ 96 (1)
4 ≦ X <100 (2)
X = 100-W (3)
0 <Y ≦ 55 (4)
45 ≦ Z <100 (5)
Z = 100−Y (6) The fourth metal contains 0.05 to 1% of at least one selected from the group consisting of iron, copper, germanium, and antimony in gallium, and the standard electrode potential is lower than that of gallium. The hydrogen generator according to any one of claims 1 to 3, wherein a total amount of at least one metal element selected from the group consisting of is 0.1% or more based on the fourth metal. Hydrogen according to at least one metal element, any one of claims 1 to 5 is at least any one of aluminum or magnesium, wherein the standard electrode potential is selected from the group consisting of lower metal elements than gallium Generator.

Images