JP2003280747A - Gas pressure regulator, electrochemical device, gas storage device and gas pressure regulating method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a small, long service life, and silent gas pressure regulator, an electrochemical device, a gas storage device, and a gas pressure regulating method. <P>SOLUTION: This gas pressure regulator has an electrochemical cell composed of a first pole for decomposing gas into an ion, a second pole for converting the ion generated by the first pole again into gas, and an ion conductor sandwiched between both these poles, and a high pressure vessel arranged on one side of this electrochemical cell. The gas pressure regulating method comprises a decomposing process of decomposing the gas into the ion by the first pole, a conduction process of conducting the decomposed ion to the second pole side via the ion conductor sandwiched between the first pole and the second pole, and a converting process of converting the conducted ion again into the gas by the second pole. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a gas pressure adjusting device,
The present invention relates to an electrochemical device, a gas storage device, and a gas pressure adjusting method.

[0002]

2. Description of the Related Art Conventionally, a mechanical gas regulator has been widely used as a means for converting a high-pressure gas into a low-pressure gas (see, for example, Patent Document 1 described later).

A conventional gas regulator will be described below in accordance with the contents described in Patent Document 1.

A conventional gas regulator is constructed as shown in FIG. That is, the inlet pipe 87 is attached to one end on the inlet side of the main body case 86, and the outlet port 88 is formed on the other end. A cover 89 is fixed to an opening 86a formed in the upper surface of the main body case 86, and a peripheral edge of a diaphragm 90 is fixed between the main body case 86 and the cover 89. The diaphragm 90 is airtightly divided into an atmospheric pressure chamber 91 on the cover 89 side and a decompression chamber 92 inside the case 86.

An operating pestle 93 is provided at the center of the diaphragm 90 so as to vertically penetrate therethrough. A flange portion 93a provided on the operating pestle 93 and a nut 9 screwed to the upper end of the operating pestle 93.
A diaphragm 90 is sandwiched and fixed between the diaphragm 90 and the diaphragm 4. A spring 95 is inserted between the diaphragm 90 and the cover 89 to constantly urge the diaphragm 90 downward. An operating end of an operating lever 96 is slidably cross-coupled to a lower portion of the operating punch 93. The operating lever 96 is rotatably supported by the case 86 via a support shaft 97, and its working end is engaged with a valve body 98 facing the tip nozzle portion 87 a of the inlet pipe 87 via a working pin 99. I am fit. Note that reference numeral 89a is a ventilation hole formed in the cover 89 and communicating with the atmosphere side.

In the conventional gas regulator configured as described above, when the pressure in the decompression chamber 92 rises due to a decrease in the amount of gas consumed in the combustor (not shown), the diaphragm 90 causes the spring 95 to move. The urging force is overcome and the pressure is displaced to the atmospheric pressure chamber 91 side, the operating pestle 93 is pulled up, and the operation lever 96 is rotated counterclockwise about the support shaft 97. Then, the valve body 98 is brought close to the nozzle portion 87a to reduce the inflow amount of gas and reduce the gas pressure in the decompression chamber 92. In this way, the gas pressure in the decompression chamber 92 is kept substantially constant corresponding to the biasing force of the spring 95.

Therefore, by supplying a high pressure gas (gaseous substance) from the inlet pipe 87 side, a predetermined low pressure gas can be obtained at the outlet port 88 side.

[0008]

[Patent Document 1] Japanese Unexamined Patent Publication No. 4-244506 (1st column, 36th line to 2nd column, 17th line, FIG. 8)

[0009]

However, the conventional gas regulator of the mechanical type as described above has a large structure because of its structure, and since it has a movable portion, wear and the like due to friction occur, and Life is shortened,
Furthermore, there is a problem that a sound is produced during operation.

Further, since the depressurization mechanism is exclusively used, in order to perform the pressurization, a pressurization mechanism must be provided in addition to the depressurization mechanism.

The present invention has been made in order to solve the above-mentioned problems, and an object thereof is a compact, long-life, and quiet gas pressure adjusting device, an electrochemical device, and a gas storage device. And a gas pressure adjusting method.

[0012]

That is, according to the present invention, a first pole for decomposing gas into ions, a second pole for converting the ions generated at the first pole into gas again, and between these two poles are provided. The present invention relates to a gas pressure regulator having an electrochemical cell composed of a sandwiched ionic conductor and a high-pressure container arranged on one side of the electrochemical cell.

Further, a decomposing step of decomposing gas into ions at the first pole, and the decomposed ions are separated into the first pole and the second pole.
A gas pressure adjusting method comprising: a conducting step of conducting to the side of the second pole through an ionic conductor sandwiched between the pole and the pole; and a converting step of converting the conducted ions into gas again at the second pole. It is related to.

According to the gas pressure adjusting apparatus and the gas pressure adjusting method of the present invention, the apparatus has the decomposition step, the conduction step, and the conversion step, and there is no mechanical movable part in the apparatus. Therefore, it is possible to provide a gas pressure adjusting device that is small in size, has a long life, and is quiet.

Here, when the gas pressure regulator of the present invention is driven, for example, the electrochemical cell can be made to function so as to reduce the pressure in the high pressure vessel.

It is also possible to cause the electrochemical cell to function so as to reduce or increase the pressure in the high-pressure container, and operate the gas pressure adjusting device according to the present invention as a depressurizing device.

In these cases, since there is no mechanical moving part in the gas pressure adjusting device according to the present invention, the device is small in size,
The device can have a long life and can be quiet. Further, since one device can have a pressure reducing and pressurizing mechanism, it is possible to further reduce the size of the device as compared with the conventional gas regulator described above.

In the present invention, the gas is preferably a gas that is in a gaseous state at room temperature and atmospheric pressure, specifically, hydrogen gas or oxygen gas.

Further, it is preferable that the ionic conductor is a membrane made of an electrolyte material capable of transmitting the ionized gas, and further, the first electrode and the second electrode have an ionic dissociation equilibrium of the gas. It is preferable that the electrode film supports a catalyst such as platinum that can be carried.

The electrode has heat resistance and a surface area as large as possible, and the ion conductor and the electrodes can be adhered to each other over the entire surface through the catalyst supported on the surface. It is preferable that it has a certain degree of flexibility so that it can be adhered to a conductor, and that it is an activating electrode.

Therefore, it is preferable that the first pole and the second pole are porous or mesh-like. For example, carbon fiber or porous carbon is used as a material, and these are made into a sheet shape, and are brought into close contact with the ion conductor. It can be prepared by supporting an active catalyst on the side. Further, such a sheet-shaped electrode material may be put or attached with a net-like body made by knitting a metal wire as a core material. By inserting or sticking the metal core material, the conductivity of the electrode itself is improved, and a uniform current distribution can be expected over the entire surface.

The catalyst is preferably fine particles of platinum, ruthenium oxide, iridium oxide or the like,
Further, other electrode substances such as silver may be used as long as the reaction for this purpose proceeds, and other electrode substances may be used.

The catalyst may be supported on the electrode by a conventional method. For example, the catalyst substance or its precursor is supported on the surface of carbon powder, and a treatment such as heating is applied thereto to form catalyst particles. Alternatively, it may be a method of baking it on the electrode surface together with a fluororesin, or an electrode body not carrying the catalyst substance is prepared in advance, and then a precursor of the catalyst substance, for example, a mixed aqueous solution of chloroplatinic acid and ruthenic acid chloride. , Or a butyl alcohol solution as a coating solution, which is applied to the electrode surface, and then in a reducing atmosphere containing hydrogen,
By baking at 200 to 350 ° C., an alloy of platinum and ruthenium can be formed on the electrode surface.

In the gas pressure adjusting device according to the present invention, a low-pressure container is arranged on the other side of the electrochemical cell, the electrochemical cell serves as a gas partition, and the pressure difference between both sides of the electrochemical cell is small. It is preferable to have a means for adjusting the pressure while controlling the potential between both electrodes when it occurs. Further, it is preferable that the electromotive force generated from the pressure difference is short-circuited by a relay or the like, or the pressure is adjusted by a variable resistor.

Generally, when a pressure difference is generated on both sides of the electrochemical cell, an electromotive force is generated from this pressure difference. This is known as a Nernst's equation including a pressure term represented by the following equation (1).

E = E ₀ + (RT / 2F) ln (P1 / P2) ... Equation (1) (where E ₀ is the ionization potential of the gas, R is the gas constant, (T is temperature, F is Faraday constant, P1 and P2 are gas pressures.)

Originally, when the gas pressure is the same on both sides of the electrochemical cell as the partition wall, no potential difference occurs, but when one gas pressure rises, l in the above formula (1) is increased.
An electromotive force is generated by the term of n (P1 / P2).

For example, when the gas is hydrogen gas,
On the catalyst such as platinum supported on the electrode, the following formula (2)
There is an equilibrium as shown in. H ₂ ⇔2H + 2e ^- ··· formula (2)

The electrochemical equilibrium shifts so as to relieve the stress when the pressure rises, but it is very important that the reaction equilibrium is accompanied by a change in volume. That is, as the pressure increases, the equilibrium shifts to the right so as to alleviate it. Then, many electrons flow into the electrode and the potential becomes high. At the same time, a large amount of protons (H ⁺ ) are injected into the ionic conductor on the side of the high pressure vessel, and they try to diffuse to the side of the low pressure vessel.

However, the protons that have diffused to the low-pressure container side cannot return to hydrogen gas unless they are recombined with electrons. Therefore, when an electrical short circuit is performed to make the potential difference between both electrodes constant, recombination of protons and electrons occurs on the low-pressure container side, and hydrogen gas apparently flows from the high-pressure container side to the low-pressure container side.

What is required in this process is the gas barrier property of the ionic conductor. As will be described later, for example, when hydrogen gas is used as the gas, a proton conductor based on fullerene or the like is useful as the ionic conductor.

Further, basically, only ions of a specific gas can pass through the ionic conductor, so that the electrochemical cell also has a function as a gas purification filter. Therefore, when hydrogen gas is used as the gas, it is optimal as a regulator for supplying hydrogen gas to an electrochemical device such as a fuel cell at a constant pressure.

As described above, the basis of the present invention is the pressure-dependent Nernst equation (equation (1) above). When a pressure difference occurs between both electrodes, it is possible to short-circuit the potential of both electrodes with a relay or the like, or to perform pressure adjustment while controlling the potential of both electrodes with a variable resistor.

Further, both sides of the electrochemical cell acting as a gas partition are hermetically sealed containers, and when one side is connected as a high pressure gas tank and the other side is connected to a gas consuming system, in the hermetically sealed container on the other side. A pressure sensor is installed in the fuel cell, and this pressure sensor can be linked to a relay switch connected between both electrodes of the electrochemical cell to function to supplement gas consumption.

FIG. 1 is a schematic sectional view of a gas pressure adjusting device according to the present invention. The case where hydrogen gas is used as the gas is shown.

As shown in FIG. 1, the gas pressure adjusting apparatus according to the present invention comprises a catalyst electrode 1, 2 carrying a catalyst such as platinum.
And the proton conductor 3 sandwiched between these electrodes 1 and 2.
The electrochemical cell 4 is composed of a high pressure vessel 5 and a low pressure vessel 6 installed on both sides of the electrochemical cell 4. A vacuum pump 8 was arranged in the containers 5 and 6 via a vacuum line 7, and an H ₂ reservoir 9 and a gas flow meter 10 were connected. Further, lead introducing terminals 11 and 12 were connected to the containers 5 and 6, respectively. Although not shown, a power generation device using hydrogen gas as a fuel is connected to the tip of the gas flow meter 10.

First, the valves 13, 14, 17 are closed,
The valves 15 and 16 were opened, and the inside of the containers 5 and 6 was evacuated using the vacuum pump 8. Next, the valves 15 and 16 were closed, the valves 13 and 14 were opened, and hydrogen gas of 10 atm was introduced into both the containers 5 and 6 by the H ₂ reservoir 9 to close the valves. After that, the valve 17 was opened and only the low pressure container 6 was set to 1 atm.

At this time, the voltage difference between the leads connected to both ends of the electrochemical cell 4 was measured and found to be about 100 mV.

Next, the electrodes of the electrochemical cell 4 were short-circuited, and the pressure change in the high-pressure container 5 was measured. FIG. 2 is a graph showing changes in pressure of the high-pressure container 5 over time.
According to FIG. 2, it was found that the pressure in the high-pressure container 5 decreased with the passage of time, and the short circuit by the relay was functioning.

The proton conductor 3 includes fullerene molecules and
A substance containing at least one selected from the group consisting of a cluster containing carbon as a main component and a tubular or linear carbon structure is contained as a main component, and a proton-dissociative group is present at a carbon atom constituting the substance. It is desirable to be constituted by a derivative obtained by introducing the above (the same applies to other inventions shown below).

Here, the "proton-dissociable group" means a functional group capable of releasing a proton by ionization,
Further, “proton dissociation” means that a proton is separated from a functional group by ionization.

The fullerene molecule, which is a parent substance into which the proton-dissociable group is introduced, is not particularly limited as long as it is a spherical shell cluster molecule Cm (m is a natural number that allows Cm to form a spherical shell structure). , Usually C ₃₆ , C ₆₀ , C ₇₀ , C
₇₆ , C ₇₈ , C ₈₀ , C ₈₂ , C ₈₄ , C ₈₆ , C ₈₈ , C ₉₀ ,
A single substance of a fullerene molecule selected from C ₉₂ , C ₉₄ , C _{96 and the} like, or a mixture of two or more kinds thereof is preferably used.

These fullerene molecules were discovered in 1985 in the mass spectrometric spectrum of a cluster beam produced by laser ablation of carbon (Kroto, HW; Hea).
th, JR; O'Brien, SC; Curl, RF; Smalley, RE
Nature 1985. 318, 162.). It was only five years later that the manufacturing method was actually established. In 1990, a manufacturing method of a carbon electrode by an arc discharge method was found, and since then, fullerenes have attracted attention as a carbon-based semiconductor material. It was

As shown in FIG. 3, fullereno (Fullereno) having a structure in which a plurality of hydroxyl groups are added to a fullerene molecule is added.
l) was first reported as a synthetic example by Chiang et al. in 1992 (Chiang, LY; Swirczewski, JW; Hsu,
CS; Chowdhury, SK; Cameron, S .; Creegan, K.,
J. Chem. Soc, Chem. Commun. 1992, 1791).

The present inventor has shown such a fullerenol in FIG.
An aggregate was formed as schematically shown in (A), and when the hydroxyl groups of adjacent fullerenol molecules (in the figure, ○ represents a fullerene molecule) were allowed to interact with each other, the aggregate was macroscopic. It was for the first time able to discover that the aggregate exerts high proton conduction properties (in other words, dissociation of H ⁺ from the phenolic hydroxyl group of the fullerenol molecule).

According to the gas pressure adjusting device of the present invention,
In addition to the above fullerenol, for example, an aggregate of fullerenes having a plurality of —OSO ₃ H groups can be used as the ion conductor. Figure 4 with OH groups replaced by OSO ₃ H groups.
Polyhydroxylated fullerenes as shown in (B), ie hydrogen sulfate esterified fullerenol, were also reported by Chiang et al. In 1994 (Chiang, LY; Wan
g, LY; Swirczewski, JW; Soled, S .; Cameron, S.,
J. Org. Chem. 1994, 59, 3960). Fullerene that has been converted to hydrogen sulfate has OSO ₃ H in one molecule.
Some may contain only a group, or a plurality of groups and a plurality of hydroxyl groups may be included.

When a large number of the above-mentioned fullerenol and hydrogen sulfate esterified fullerenol are aggregated, the proton conductivity exhibited as a bulk is such that a large amount of hydroxyl groups originally contained in the molecule or protons derived from the OSO ₃ H group are transferred. Since it is directly involved, it can be continuously used even in a low humidity atmosphere.

Further, fullerene, which is a base material of these molecules, has a particularly electrophilic property, which promotes ionization of hydrogen ions not only in the highly acidic OSO ₃ H group but also in the hydroxyl group. It is thought that it contributes greatly to the above, and shows excellent proton conductivity. In addition, since a large number of hydroxyl groups and OSO ₃ H groups can be introduced into one fullerene molecule, the number density of protons involved in conduction per unit volume of the conductor becomes very large. Expresses a specific conductivity.

Since most of the fullerenol and the fullerene hydrogen sulfate ester fullerenol are composed of carbon atoms of fullerenes, they are light in weight, hardly deteriorated, and contain no contaminants. The manufacturing cost of fullerenes is also rapidly decreasing. From a resource, environmental and economic standpoint, fullerenes are considered to be more ideal carbonaceous materials than any other material.

Further, the above-mentioned proton-dissociative group need not be limited to the above-mentioned hydroxyl group or OSO ₃ H group.

That is, this dissociative group is represented by the formula -XH, and X may be any atom or atomic group having a divalent bond. Furthermore, this group has the formula --OH or --YO.
It is represented by H, and Y may be any atom or atomic group having a divalent bond.

Specifically, as the proton-dissociative group, in addition to -OH and -OSO ₃ H, -COOH, -O.
_{SO 3 H, -OPO (OH)} 2, any of -C ₆ H ₄ -SO ₃ H is preferred.

In order to synthesize the above-mentioned fullerenol which can be used in the present invention, the powder of fullerene molecule is subjected to appropriate combination of known treatments such as acid treatment and hydrolysis to form carbon atoms of the fullerene molecule. A desired group can be introduced into.

The obtained fullerene derivative can be formed into a film by coating or vapor deposition and used as the proton conductor 3 of the electrochemical cell 4.

The proton conductor 3 may consist essentially of the above fullerene derivative, or may be bound by a binder.

When the proton conductor 3 substantially consists of the fullerene derivative, it can be used as a film-shaped proton conductor 3 obtained by pressure-molding the fullerene derivative. When the fullerene derivative bound by the binder is used as the proton conductor 3, the binder can form a proton conductor having sufficient strength.

As the polymer material that can be used as the binder, one or more known polymers having film-forming properties are used. The proton conductor having such a structure can also exhibit the same proton conductivity as that of the above-mentioned proton conductor made of only the fullerene derivative.

Further, unlike the case of the fullerene derivative alone, a film-forming property derived from a polymer material is imparted, and the strength is greater than that of the powder compression molded product of the fullerene derivative, and the flexibility having the gas permeation preventing ability is provided. It can be used as a simple proton conductive thin film (thickness is usually 300 μm or less) 3.

The polymer material is not particularly limited as long as it does not hinder the conductivity of protons (due to the reaction with the fullerene derivative) as much as possible and has a film forming property. Usually, those having no electron conductivity and good stability are used, and specific examples thereof include polyfluoroethylene, polyvinylidene fluoride, polyvinyl alcohol and the like, and these are also for the reason described below. , A preferred polymeric material.

First, polytetrafluoroethylene is preferable because it is possible to easily form a thin film having a higher strength with a smaller amount than other polymer materials. The compounding amount in this case is 3% by weight or less, preferably 0.5 to
A small amount of 1.5% by weight is enough, and the thickness of the thin film is usually 100.
It can be made as thin as μm to 1 μm.

Polyvinylidene fluoride and polyvinyl alcohol are preferable because a proton conductive thin film having a selected gas permeation preventing ability can be obtained.
In this case, the blending amount is preferably in the range of 5 to 15% by weight.

If the blending amount of polyfluoroethylene, polyvinylidene fluoride or polyvinyl alcohol is less than the lower limit of each of the above ranges, the film formation may be adversely affected.

Here, in order to obtain a proton conductor thin film in which each fullerene derivative is bound by a binder,
Known film forming methods such as pressure molding and extrusion molding may be used.

The gas pressure adjusting device according to the present invention is
From the viewpoints of handling and downsizing, it is preferable that the electrodes 1 and 2 and the fullerene derivative as the proton conductor 3 are in a flexible sheet shape having physically sufficient strength.

Since the electrochemical cell 4 can function well in the atmosphere, it is possible to efficiently adjust the hydrogen gas pressure such as decompression without adjusting the temperature and humidity during operation. it can.

Since a fullerene derivative obtained by introducing a proton dissociative group into a carbon atom constituting a fullerene molecule such as fullerenol is used as a constituent material of the proton conductor 3, it is an H ₃ O ⁺ ion conductor. Unlike the case where Nafion is used, it functions even in a low humidity atmosphere without a humidifier or the like.

That is, for example, hydrogen gas can be depressurized in the low-humidity atmosphere, so that it is possible to speed up the initial operation when depressurizing hydrogen without taking time until steady operation. It should be noted that, for example, a humidifier may be provided to allow the presence of water to similarly depressurize the hydrogen gas, but the present invention does not require this.

Further, when Nafion, which is an H ₃ O ⁺ ion conductor, is used, water is generated together with the compression of hydrogen, so a dehumidifying device is required, whereas the gas pressure based on the present invention is required. The adjusting device enables adjustment of gas pressure such as decompression of hydrogen gas without a dehumidifying device or the like.

Furthermore, since the electrochemical decompression action can be efficiently performed without performing the humidification treatment, the decompressed hydrogen gas has a small water content. For this,
The dehumidification process as a post process can be dispensed with.

Therefore, the electrochemical cell 4 can efficiently adjust the hydrogen gas pressure, and the device according to the present invention is a more compact and versatile device.

Further, in the present invention, the above-mentioned proton
As a conductor, instead of the fullerene derivative, for example, carbon
Class consisting of carbon powder by arc discharge method of system electrode
After obtaining a star and subjecting this carbon powder to acid treatment, etc.
Proton (H ⁺) Introducing a dissociative group
Can be used.

Here, the above-mentioned cluster is generally an aggregate formed by bonding or aggregating several to several hundred atoms, and the aggregate (aggregate) improves the proton conductivity. At the same time, the chemical strength is maintained and the film strength becomes sufficient, and the layer is easily formed. Further, this cluster is mainly composed of carbon, and is an aggregate formed by bonding several to several hundred carbon atoms regardless of the type of carbon-carbon bond. However, it is not always composed of only 100% carbon clusters, and other atoms may be mixed. Including such a case, an aggregate having a large number of carbon atoms will be referred to as a carbon cluster.

Since the main component of the above-mentioned proton conductor is a carbon cluster as a base into which a proton-dissociative group is introduced, the protons are easily dissociated even in a dry state.
In addition to the proton conductivity, the same effects as those of the above-mentioned proton conductor can be obtained. Moreover, since a wide variety of carbonaceous materials are included in the range of the carbon clusters, as will be described later, it is possible to achieve an effect that the selection range of the carbonaceous material is wide.

In this case, the use of carbon clusters in the matrix requires the introduction of a large amount of proton-dissociative groups in order to impart good proton conductivity, which is possible with carbon clusters. Because it will be. However, if so, the acidity of the solid proton conductor is significantly increased, but unlike ordinary carbonaceous materials, carbon clusters are less prone to oxidative degradation, have superior durability, and have a tight bond between constituent atoms. Since they are in close contact with each other, the bond between atoms is not broken even if the acidity is high (that is, it is difficult to chemically change), and the film structure can be maintained.

The proton conductor having such a structure can also exhibit high proton conductivity even in a dry state, and there are various kinds as shown in FIGS. 5 to 8, which are selected as raw materials for the proton conductor. Is wide.

First, FIG. 5 shows various carbon clusters having a closed surface structure similar to spheres or spheroids formed by assembling a large number of carbon atoms (however, molecular clusters Fullerene is also shown). On the other hand, various carbon clusters lacking a part of their spherical structure are shown in FIG. In this case, the structure is characterized by having an open end, and such a structure is often found as a by-product in the process of producing fullerenes by arc discharge. When most of the carbon atoms in the carbon clusters are SP3 bonded, various clusters having a diamond structure as shown in FIG. 7 are formed.

The cluster in which most of the carbon atoms are SP2-bonded has the planar structure of graphite, or the whole or part of the structure of fullerenes and nanotubes. Of these, those with a graphite structure are
Since many of the clusters have electronic conductivity, they are not preferable as the matrix of the proton conductor.

On the other hand, since the SP2 bond of fullerene or nanotube partially contains the element of SP3 bond, many of them do not have electron conductivity and are preferable as the matrix of the proton conductor.

FIG. 8 shows various cases in which clusters are bonded to each other, and such a structure can also be applied to the present invention.

In the present invention, it is necessary to introduce the above-mentioned proton dissociative group into the carbon atoms constituting the carbon cluster. As a means for introducing the proton dissociable group, the following production method is preferable.

That is, first, carbon clusters made of carbon powder are manufactured by arc discharge of a carbon-based electrode, and then the carbon clusters are subjected to acid treatment (using sulfuric acid or the like) or further treatment such as hydrolysis. Alternatively, a carbon cluster derivative as a target product can be easily obtained by appropriately performing sulfonation or phosphoric acid esterification.

This carbon cluster derivative can be directly pressure-molded into a film-like or pellet-like shape without a binder. In the present invention, the base carbon cluster has a major axis length of 100 nm or less, particularly 1
It is preferably 00 Å or less, and the number of the groups introduced therein is preferably 2 or more.

Further, as the carbon cluster, a cage structure (fullerene or the like) or a structure having an open end at least in part is preferable. The fullerene having such a defect structure has the reactivity of the fullerene, and at the same time, the defect portion, that is, the open portion has higher reactivity. Therefore, the acid (proton) dissociative substituent introduction is promoted by an acid treatment or the like, a higher substituent introduction rate is obtained, and high proton conductivity is obtained. In addition, it is possible to synthesize a large amount as compared with fullerene, and it is possible to produce at a very low cost.

On the other hand, it is preferable to use a tubular or linear carbon structure as the base material of the proton conductor of the present invention. The tubular carbon structure is preferably tubular, for example, carbon nanotube. Also,
As the linear carbon structure, a fiber-like shape,
For example, carbon fiber is preferable.

The carbon nanotubes or the carbon fibers are structurally easy to emit electrons and have a very large surface area, so that the proton propagation efficiency can be further improved.

The carbon nanotubes or carbon fibers that can be preferably used here can be produced by an arc discharge method or a chemical vapor deposition method (thermal CVD method).

In the arc discharge method, for example, FeS, Ni,
For example, the above carbon nanotubes can be obtained by synthesizing in a He atmosphere (for example, 150 Torr) by using an arc discharge chamber using a metal catalyst such as Co, and by adhering it to the inner wall of the chamber in a cloth shape by arc discharge. Here, when the catalyst is coexistent, the carbon nanotubes having a small diameter can be obtained, and when arc discharge is performed under a non-catalyst condition, the carbon nanotubes having a large diameter are obtained. You can

As described above, it can be produced, for example, by performing arc discharge under the condition of no catalyst.
The graphene structure (cylindrical structure) of the multi-walled carbon nanotube as shown in the perspective view of (A) and the partial cross-sectional view of (B) is a high-quality carbon nanotube without defects, which is an electron emission material. Is known to have extremely high performance.

As described above, a proton dissociative group can be introduced into the carbon nanotubes obtained by the arc discharge method by the same treatment as described above, and a proton conductor excellent in proton conductivity even in a dry state. Is obtained.

The chemical vapor deposition method is a method of synthesizing the above-mentioned carbon nanotubes or the above-mentioned carbon fibers by reacting the transition metal fine particles with a hydrocarbon such as acetylene, benzene, ethylene or CO. By reacting the transition metal substrate or the coated substrate with hydrocarbon or CO gas, the carbon nanotubes or the carbon fibers are deposited on the substrate.

For example, by placing a Ni substrate in an alumina tube heated at 700 ° C. and reacting it with toluene / H ₂ gas (for example, 100 sccm), a structure as shown in the perspective view of FIG. 9C is obtained. It is possible to synthesize the above carbon fiber having

Here, the carbon nanotube preferably has an aspect ratio of 1: 1000 to 1:10, and the carbon fiber has an aspect ratio of 1: 100.
It is preferably 5000 to 1:10. The diameter of the cylindrical or linear carbon structure is 0.001 to 0.5 μ.
The length is preferably 1 to 5 μm.

The apparatus according to the present invention has only one electrochemical cell that functions as a pressure partition, but a plurality of electrochemical cells are arranged side by side in the gas flow direction and have a multi-stage structure. Good. In particular, when there is a large difference in pressure in the containers arranged on both sides of the electrochemical cell, it is essential to use several electrochemical cells.

The present invention also provides a first electrode for decomposing hydrogen gas into protons, a second electrode for converting the protons generated at the first electrode into hydrogen gas again, and a proton sandwiched between these two electrodes. An electrochemical cell made of a conductor; and a high-pressure container arranged on the first electrode side of the electrochemical cell and containing a gaseous substance containing hydrogen gas. A decompression section that functions to reduce the pressure, a hydrogen gas storage section that is disposed in contact with the second electrode side of the decompression section, and a hydrogen gas storage section that is disposed in contact with the hydrogen gas storage section. A third electrode for decomposing the supplied hydrogen gas into protons, a fourth electrode for converting the protons generated at the third electrode into water, and a proton conductor sandwiched between the two electrodes. At the 4th pole, the proton is With the conversion, but according to an electrochemical device comprising it is composed of a gas-consuming unit to take out the electrochemical energy between said third pole and the fourth pole.

Here, as a method of driving the electrochemical device of the present invention, for example, when driving the decompression section,
The electrochemical cell is caused to function so as to reduce the pressure in the high-pressure container, the hydrogen gas storage section is arranged in contact with the second pole side of the decompression section, and hydrogen supplied from the hydrogen gas storage section is provided. A third electrode that decomposes gas into protons,
A fourth for converting the protons generated at the third pole into water
The gas consuming portion consisting of a pole and a proton conductor sandwiched between these electrodes is arranged in contact with the hydrogen gas storage portion, and the proton is converted into water at the fourth pole, and It is desirable to extract electrochemical energy between the third pole and the fourth pole.

According to the electrochemical device of the present invention, similarly to the gas pressure adjusting apparatus according to the present invention described above, since there is no mechanical moving part in the electrochemical device,
The device can be small, long-lived, and quiet.

FIG. 10 is a schematic sectional view of an electrochemical device according to the present invention.

As shown in FIG. 10, the decompression unit 18 has a first electrode 1 for decomposing hydrogen gas into protons and a second electrode 2 for converting the protons generated in the first electrode 1 into hydrogen gas again.
And an electrochemical cell 4 consisting of a proton conductor 3 sandwiched between these two electrodes, and a high-pressure container arranged on the first electrode 1 side of the electrochemical cell 4 and containing a gaseous substance containing hydrogen gas. 5 and the electrochemical cell 4 functions to reduce the pressure in the high pressure vessel 5.

The hydrogen gas storage section 19 is the second decompression section 18 of the second decompression section 18.
It is arranged in contact with the pole 2 side.

The gas consuming portion 20 is disposed in contact with the hydrogen gas storage portion 19 and is generated in the third pole 21 and the third pole 21 for decomposing the hydrogen gas supplied from the hydrogen gas storage portion 19 into protons. A fourth pole 22 for converting the above-mentioned protons into water
And a proton conductor 23 sandwiched between these two electrodes, which converts the proton into water at the fourth pole 22 and takes out electrochemical energy between the third pole 21 and the fourth pole 22. It can function as a fuel cell unit. In addition, the proton conductor 23 of the fourth pole 22
O ₂ or an O ₂ -containing gas is supplied to the surface side not in contact with.

Further, a pressure sensor 24 is installed in the hydrogen gas storage unit 19, and this pressure sensor 24 works in conjunction with the relay switches 11 and 12 connected between both electrodes of the electrochemical cell 4 so as to supplement gas consumption. Function.

Further, the high-pressure container 5 is the H ₂ supply tank 2
When the pressure in the high-pressure container 5 is below a predetermined value, the valve is opened and the H ₂ supply tank 2 is connected.
It is possible to supply hydrogen gas from 5. In addition, H
_{The 2} supply tank 25 may be filled with a hydrogen gas storage alloy, a hydrogen gas storage carbon material, a metal halide or the like, and as the hydrogen gas storage alloy, LaNi ₅ , CaN
i ₅ , TiCo0.5Mn0.5, TiCo0.5Fe
0.5, TiFe0.8Ni0.15V0.05, etc., the hydrogen gas storage carbon material may be a carbon-based material, carbon nanotube, carbon fiber, activated carbon, etc., and the metal halide may be NaAlH. ₄ , LiAlH ₄ or the like may be used. Further, similarly to this, the high pressure vessel 5 may be filled with a hydrogen gas storage alloy, a hydrogen gas storage carbon material, a metal halide, or the like.

However, since the gas barrier properties of the proton conductors 3 and 23 must be high, the proton conductors 3 and 2 are
No. 3 must have the property of passing the ionized gas but not the gas itself. In order to achieve this, the proton conductors 3 and 23 are selected from the group consisting of fullerene molecules, carbon-based clusters, and tubular or linear carbon structures in the same manner as described above. Further, it is desirable that the substance is composed of at least one substance as a main component and a derivative obtained by introducing a proton-dissociative group into carbon atoms constituting the substance.

Further, according to the present invention, a gas inlet / outlet portion for introducing or discharging gas, a gas storage portion for storing gas,
A first electrode disposed in the gas storage unit for decomposing the gas into ions, a second electrode for converting the ions generated at the first electrode into gas again, and ion conduction sandwiched between these two electrodes. An electrochemical cell comprising a body, and the function of the electrochemical cell allows gas to flow in and out of the gas storage section through the gas inlet / outlet section to reduce or increase the pressure in the gas storage section. The present invention relates to a gas storage device including a depressurizing unit that functions as a.

Here, as a method of driving the gas storage device of the present invention, for example, when the gas storage device is driven, a gas is supplied to the gas storage part through the gas inlet / outlet part by the function of the electrochemical cell. It may be desirable to move in and out to function to reduce or increase the pressure in the gas store.

According to the gas storage device of the present invention, similarly to the above-described gas pressure adjusting device or electrochemical device of the present invention, since there is no mechanical moving part in the device, it is compact and has a long service life. The gas storage device can have a long length.

FIG. 11 shows a gas storage device 2 according to the present invention.
It is a schematic sectional drawing of FIG.

The gas inlet / outlet portion 27 is provided with an opening for inputting / outputting the gas and a minute space sufficient to temporarily hold the gas at an equal pressure.

The inlet / outlet pressure detecting means 28 is provided for detecting the pressure in the minute space, and is, for example, a pressure sensor using a diaphragm. As an example of such a pressure sensor, for example, as shown in FIG. 12, a sensor including a diaphragm 29, a closed space 30 in which a predetermined amount of gas is sealed, and a microswitch 31 is used.

Since the pressure on one surface side of the diaphragm 29 is the same as that of the gas inlet / outlet portion 27, the pressure difference between the pressure in the closed space 30 and the gas inlet / outlet portion 27 balances the spring force of the diaphragm 29. The diaphragm 29 is moved up to, and when the inside pressure of the gas inlet / outlet portion 27 reaches a predetermined pressure, the micro switch 31 is turned off (connected state) to off.
(Intermittent state).

The pressure wall 32 has a high pressure, for example, 10 to 30.
It is a pressure resistant wall for maintaining 0 atmospheric pressure, and has a gas transfer hole, which is a large number of openings having a minute area, at the boundary with the gas inlet / outlet portion 27. The shape of the pressure wall 32 is not particularly limited, but a cylindrical shape or a spherical shape is more preferable for evenly distributing the pressure. Note that FIG. 11 shows a cross-sectional view when the pressure wall 32 has a cylindrical shape and is cut along a plane including the center of the cylinder.

The gas transfer hole holds the first electrode 1, the ion conductor 3 and the second electrode 2 against the pressure of the gas storage portion 33, and at the same time transfers the gas from the gas storage portion 33 to the gas inlet / outlet portion 27. It is possible. The electrochemical cell consisting of the first pole 1, the ionic conductor 3 and the second pole 2 is a depressurizing section that operates as an independent component, and the entire electrochemical cell is held in the gas storage section 33. Has been done.

The lead wires 34 and 35 are electric conductors whose one ends are respectively connected to the second pole 2 and the first pole 1, and the pressure wall 3
The other end is connected to the second electrode terminal 38 and the first electrode terminal 39 while maintaining insulation from 2. The connection line 36 and the connection line 37 connect the electrode terminal 38, the electrode terminal 39 and the respective contacts of the micro switch 31.

Also, a gas storage device 26 according to the present invention.
Has a gas storage auxiliary system, and this gas storage auxiliary system has a gas inlet / outlet portion 27 of the gas storage device 26.
A gas flow path for supplying the gas to the
Pressure detecting means for detecting the gas pressure, voltage detecting means for detecting the voltage generated between the first pole 1 and the second pole 2, and a calculation for calculating a control current signal based on the gas pressure and the voltage. Means, current supply means for generating the control current, and a state of supplying the control current between the first pole 1 and the second pole 2 until the voltage reaches a predetermined value.
It is desirable to have a switching means for alternately switching between the state of detecting the voltage.

FIG. 13 is a schematic sectional view of the gas storage device 26 having the gas storage auxiliary system 40. The broken line portion shows the gas storage device 26, and the solid line portion shows the gas storage auxiliary system 40.

The flow passage 41 is structured so as to be coupled to the opening portion of the gas inlet / outlet portion 27 provided in the gas storage device 26 so that the gas does not leak.

Gas is supplied from the tank 47 to the flow path 41.

The pressure detecting means 42 is means for detecting the pressure value of the gas in the flow path 41, and for example, changes the displacement of the diaphragm into a resistance value to obtain an analog pressure value P1. The pressure detection means 42 is intended to detect the pressure of the gas inlet / outlet portion 27 of the gas storage device 26, that is, the pressure applied to the second pole 2 from the gas inlet / outlet portion 27 side. Since the flow path 41 and the gas inlet / outlet portion 27 are connected to each other, the pressures are substantially the same, and this object can be achieved by providing the pressure detecting means 42 near the flow path 41.

The first terminal 48 and the second terminal 49 are designed to maintain electrical contact with the first electrode terminal 39 and the second electrode terminal 38 of the gas storage device 26.

The switching section 46 is a switching means connected to the first terminal 48 and the second terminal 49 by a conductive wire.

S0 and S1, S3 and S4 are simultaneously turned on, and by changing the switching signal C1, S0 and S2 and S3 and S5 are turned on at the same time. Switching signal C
1 is transmitted from the calculation unit 44. When the switches on the S1 and S4 sides are connected, the pressure-voltage detection unit 43 detects the voltage generated between the first pole 1 and the second pole 2. When the switches on the S2 and S5 sides are connected, the current supply unit 45 is connected to the first terminal 48 and the second terminal 49.
Is supplied with a predetermined current.

The direction and magnitude of the current are determined by the current control signal C2, and this value is calculated by the arithmetic unit 44.

The operation of the gas storage device 26 at the time of releasing the gas is performed as follows, in the same manner as described in the description of the gas pressure adjusting device according to the present invention.

A voltage corresponding to the pressure difference between the storage portion 33 and the gas inlet / outlet portion 27 is generated between the first electrode terminal 39 and the second electrode terminal 38 of the gas storage device 26, and the connection line 36,
It is led to each contact of the micro switch 31 via the connection line 37. Here, when the pressure of the gas inlet / outlet portion 27 falls below a predetermined value, the contact of the micro switch 31 is turned on.
Then, based on the generated voltage, a current flows through the second pole 2 and the first pole 1, ions flow through the ion conductor 3, and as a result, the gas in the gas storage section 33 is decompressed by the gas inlet / outlet section 27. Flow in. When the gas inlet / outlet portion 27 is sufficiently filled with gas, the contacts of the micro switch 31 are turned off, the currents of the second pole 2 and the first pole 1 are cut off, and as a result, the conduction of ions is cut off, and the gas storage portion is cut off. The flow of the gas in 33 into the gas inlet / outlet 27 is stopped.

Here, as the contact type of the microswitch 31, the hysteresis characteristic, that is, ON / O of the switch is used.
If a switch of a type in which the pressure that shifts to each state of the FF is different is used, ON / OFF of the switch can be slowly repeated within a predetermined pressure fluctuation range.
The effect of extending the life of the switch contact can be obtained.

According to this, since the gas inlet / outlet portion 27 is filled with the gas having a constant pressure, the gas having a constant pressure can be taken out from the opening. Also, in the process of this operation, since no external power is required,
It is possible to provide a highly reliable and easy-to-maintain gas storage device.

Next, the operation of the gas storage device 26 during gas storage will be described with reference to FIGS.

During the gas storage, the gas storage device 26
The gas storage can be performed by the combined operation of the gas storage auxiliary system 40 and the gas storage auxiliary system 40.

Connection line 36 and connection line 3 of the gas storage device 26
7 is once removed or one of the connection lines is cut by a switch (not shown) provided in the middle, and then the flow path 41 and the opening of the gas inlet / outlet portion 27, the first terminal 48, the second terminal 49 and the first terminal The electrode terminal 39 and the second electrode terminal 38 are connected.

The switching section C is switched to the pressure detecting operation side by the switching signal C1, and the pressure voltage detecting section 43 detects the pressure voltage. Here, since the pressure at the second pole 2 is detected as the output P1 from the pressure detecting means 42,
The gas pressure of the gas storage unit 33 is obtained as P2 by substituting it into the above equation (1).

When P2 is lower than the pressure resistance of the pressure wall 32 of the gas storage portion 33, the pressure wall 32 will not be broken even if the pressure wall 32 is further filled, so that the gas can be further filled. Further, in order to move the gas to the storage unit 33, the switching unit 46 is switched by the switching signal C1 so that the current supply operation is performed, and the predetermined current in the direction opposite to that at the time of gas release is applied to the second pole 2. It may be applied to the first pole 1.

As the intensity of the current increases, the amount of gas movement increases, so that the filling can be performed faster. However, if an excessive current is applied, the ionic conductor 3 may be destroyed. Should be current.

Here, with respect to the predetermined current, a constant current may be applied over the entire period of filling, or the amount of current may be arbitrarily controlled according to the progress of filling.

By alternately switching the switch of the switching unit 46, the filling operation and the monitoring of the pressure of the storage unit 33 are alternately performed, and the pressure of the gas in the storage unit 33 can be increased until the pressure finally reaches a predetermined pressure. it can.

According to this, it is possible to safely fill the gas while monitoring the pressure in the storage unit 33 without providing a pressure sensor in the storage unit 33, so that the mechanism of the storage unit 33 can be simplified. . Furthermore, since there is no high-pressure portion on the gas storage auxiliary system 40 side, the gas storage auxiliary system 40 itself can be reduced in price, and at the same time, it is safe for use in ordinary households.

FIG. 14 shows an example in which another electrochemical cell is provided in the gas storage device 26 of FIG. In addition,
The components denoted by the same reference numerals as those in FIG. 11 have the same function and function, and thus the description thereof will be omitted.

The third pole 21 is provided in contact with the opening of the gas inlet / outlet portion 27. The second ionic conductor 23 is arranged between the third pole 21 and the fourth pole 22. The third terminal 50 is electrically connected to the third pole 21, and the fourth terminal 51 is connected to the fourth pole 22. The arrow indicated by 52 indicates that a liquid substance or a gaseous substance is supplied to the fourth electrode 22.

The operation of the gas storage device shown in FIG. 14 will be described below.

In the gas storage device according to the present invention shown in FIG. 14, if a specific substance is supplied to the third pole 21 and the fourth pole 22, the third pole 21, the ionic conductor 23 and the fourth pole 22 are separated. By the action, the action as a fuel cell can be performed. Here, according to the substance supplied to each electrode film, the third
The pole 21 has a function as a negative electrode or a positive electrode, and the fourth pole 2
2 has a function as a positive electrode or a negative electrode. For example, when hydrogen gas is supplied to the third electrode 21 and air (oxygen-containing gas) or oxygen gas is supplied to the fourth electrode 22, the third electrode 21 becomes the negative electrode and the fourth electrode 22 becomes the positive electrode. Thus, a negative voltage can be obtained from the third terminal 50 and a positive voltage can be obtained from the fourth terminal 51.

The operation up to the point of obtaining the gas of the predetermined pressure in the gas inlet / outlet portion 27 is as described above.

A positive voltage is applied to the fourth terminal 51, and a third terminal 50 is applied.
If a negative voltage is applied to the fourth electrode 22 and pure water or water vapor is supplied to the fourth electrode 22, hydrogen gas can be obtained at the gas inlet / outlet portion 27. Here, the operation of pressurizing the hydrogen gas in the gas inlet / outlet portion 27 to store the gas in the gas storage portion 33 is as described above.

This device is compact and portable,
Since it is a device that can generate gas such as hydrogen gas by itself and generate power, it is useful as an electric power supply device for use of electric power outdoors.

FIG. 15 shows a gas storage device 26 'having a display means 53 for displaying the state of the gas storage device 26. Here, the above-mentioned state means, for example, the pressure in the gas storage unit 33, the filling state of the gas in the gas storage unit 33, the remaining amount of the gas, or a catalyst carrying ion ionization or ionic coupling of the gas. For example, whether the electrochemical cell having the pole 1 and the second pole 2 is functioning normally.

If the pressure at the gas inlet / outlet portion 27 is found from the Nernst equation represented by the above equation (1), the gas storage portion 3 can be obtained.
You can know the pressure of 3. When the gas storage device 26 is operating, the gas inlet / outlet portion 27 is kept at a predetermined pressure by the operation of the pressure detecting means 28, so that the pressure of the gas storage portion 33 can be known.

At the same time, the pressure of the gas storage unit 33 also indicates the filling state of the gas in the gas storage unit 33. That is, the decrease in the pressure of the gas storage unit 33 means that the amount of the filled gas is decreased, and thus the filling state and the remaining amount can be known.

If the electrochemical cell is operating normally in the operating state of the apparatus, the micro switch 31 provided in the pressure detecting means 28 repeats ON / OFF, so if this operation is detected. , It is possible to determine whether the operation of the electrochemical cell is normal.

The display means 53 is, for example, a voltmeter or an LED.
Etc. are light emitting elements. The connecting line 54 is connected to the second pole 2 and the connecting line 55 is connected to the first pole 1. A connection switch 56 is provided on the way, and by pushing the push button 57 only when the display means 53 is used,
A circuit may be connected and the display means 53 may be normally separated from the electrode film.

When the display means 53 is a voltmeter, the indicator needle of the voltmeter turns ON / OFF the microswitch 31.
Shake according to. When it is ON, the first pole 1 and the second pole 2 are short-circuited, so the indicator needle of the voltmeter indicates zero, and when it is OFF, the generated voltage, that is, the voltage corresponding to the pressure difference is generated.

Here, although the internal resistance of the voltmeter is high, a small amount of gas flows out of the gas storage unit 33 because a small amount of current between the electrodes continues to flow at all times. Therefore, when display is not required, It is desirable to disconnect the display means 53 from the circuit. The display means 53 may be a visible detection means such as an LED or a buzzer appealing to the hearing. The operating point is set by LED division by resistance division.
It can be set arbitrarily by adjusting the light emission starting voltage and the pressure of the gas storage unit 33 or by setting the winding specifications of the buzzer.

According to this, the state of the gas storage device 26 can be displayed without the need for external power, the standard of the refilling time, the detection of the amount of the remaining gas, and the gas storage device 26.
There is an effect that the normal operation of can be confirmed.

FIG. 16 shows an example in which a plurality of the electrochemical cells are arranged side by side in the gas storage device 26 to form a multi-stage structure.

High-pressure gas is supplied to the high-pressure side 58. The gas to be used can be taken out from the low pressure gas side 59. The electrochemical cells 60 to 65 are arranged by providing empty chambers 66 to 70 between the respective electrochemical cells. Here, in each electrochemical cell, a proton conductor (not shown) is sandwiched between two gas diffusion electrodes, and a catalyst is carried on the surface of the gas diffusion electrode in contact with the proton conductor.

The method of controlling each electrode of each electrochemical cell is the same as that of the other embodiments described above.

According to this, it is possible to reduce the pressure difference applied to the individual electrochemical cells by sequentially performing the depressurizing operation while setting the differential pressure on both sides of each electrochemical cell to a constant predetermined value. . For example, when 6 electrochemical cells are provided, assuming that the differential pressure applied to one electrochemical cell is 20 atm, when the low pressure side 59 is 1 atm, the pressure on the high pressure side 58 is Would be 121 atmospheres. Despite such a high pressure difference of 120 atm, the withstand pressure of the electrochemical cell has only to withstand 20 atm, which has the advantage of simplifying the device design.

In the device shown in FIG. 16, a vacant chamber is provided between the electrochemical cells, but when the function of detecting the pressure in the vacant chamber is not required, such a vacant chamber is not always required. Not necessary. FIG. 17 shows a schematic cross-sectional view of the apparatus when the empty chamber is not provided between each electrochemical cell.

The basic structure of the electrochemical cells 71 to 76 is the same as that shown in FIG. 16 except that the gas diffusion electrode can be shared with the gas diffusion electrode in the next stage and the number of the electrochemical cells 71 to 76 is reduced. There is no vacant room.

The operation of this apparatus will be described below.

By the action of the catalyst 78 carried on the surface of the gas diffusion electrode 77, the supplied hydrogen gas is ionized into electrons and protons. This ionized proton moves in the proton conductor by the action of the proton conductor 79,
By the action of the catalyst 81 carried on the surface of the gas diffusion electrode 80, the protons and electrons are combined to become hydrogen gas again,
The gas diffuses inside the gas diffusion electrode 80 provided with a large number of pores for passing gas.

According to the concentration distribution, the hydrogen gas passes through the gas diffusion electrode 80, and is ionized again into protons and electrons by the action of the catalyst 82 carried on the other surface of the gas diffusion electrode 80. The ionized protons move by the action of the proton conductor 83 and reach the gas diffusion electrode 84, and return to hydrogen gas in the gas diffusion electrode 84 again by the action of the catalyst 85 carried on the surface of the gas diffusion electrode 84. .

By repeating such a process, the pressure is successively reduced. Here, as described above, the voltage is detected between the gas diffusion electrode 80 and the gas diffusion electrode 84. Therefore, depending on the generated voltage, for example, both electrodes are electrically connected to each other so that the gas diffusion electrode is connected. By applying an electric current between the gas diffusion electrode 80 and the gas diffusion electrode 84, the pressure difference between the gas diffusion electrode 80 and the gas diffusion electrode 84 can be maintained at a predetermined value, and the pressure resistance of the gas diffusion electrode and the proton conductor can be increased to a certain degree. Can be

In the embodiment of the present invention, the case where hydrogen gas is used as the gas has been described as an example. However, it is also possible to use oxygen gas as the gas, and in this case, as the ion conductor. It is preferable to use zirconium oxide or the like.

[0162]

The gas pressure adjusting device, electrochemical device, gas storage device, and gas pressure adjusting method of the present invention are small in size, have a long life, and have no mechanical moving parts in the device. It can be a quiet device.

Since it can be made small and portable,
For example, there is an effect that an individual can easily carry it and can easily operate various devices driven by using gas such as hydrogen gas.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a gas pressure adjusting device according to an embodiment of the present invention.

FIG. 2 is a graph showing a pressure change on the high-pressure container side of the gas pressure adjusting device.

FIG. 3 is a structural diagram of polyhydroxylated fullerene, which is an example of a fullerene derivative usable in the present embodiment.

FIG. 4 is a schematic diagram showing an example of the same fullerene derivative.

FIG. 5 is a schematic diagram showing various examples of carbon clusters that serve as a matrix in the proton conduction band.

FIG. 6 is a schematic view showing another example of carbon clusters (partial fullerene structure).

FIG. 7 is a schematic diagram showing another example (diamond structure) of carbon clusters.

FIG. 8 is a schematic view showing still another example of carbon clusters (clusters bonded to each other).

FIG. 9 is a schematic view of a carbon nanotube and a carbon fiber, which are the parent body of the proton conductor.

FIG. 10 is a schematic cross-sectional view of an electrochemical device according to an embodiment of the present invention.

FIG. 11 is a schematic sectional view of the gas storage device.

FIG. 12 is a schematic cross-sectional view of the inlet / outlet pressure detection means connected to the gas storage device.

FIG. 13 is a schematic sectional view of the gas storage device and a gas storage auxiliary system connected thereto.

FIG. 14 is a schematic cross-sectional view of another example of the gas storage device.

FIG. 15 is a schematic cross-sectional view of another example of the gas storage device.

FIG. 16 is a schematic cross-sectional view of a gas storage device in which the electrochemical cell has a multi-stage structure.

FIG. 17 is a schematic cross-sectional view of another example of a gas storage device in which the electrochemical cell has a multi-stage structure.

FIG. 18 is a schematic sectional view of a gas regulator according to a conventional example.

[Explanation of symbols]

1 ... 1st pole, 2 ... 2nd pole, 3, 23 ... Proton conductor,
4 ... Electrochemical cell, 5 ... High-pressure container, 6 ... Low-pressure container, 7 ...
Vacuum line, 8 ... Vacuum pump, 9 ... H ₂ reservoir, 1
0 ... Gas flow meter, 11, 12 ... Lead introduction terminal, 13, 14, 15, 16, 17, ... Valve, 18 ... Decompression section, 19 ... Hydrogen gas storage section, 20 ... Gas consumption section, 21
... 3rd pole, 22 ... 4th pole, 24 ... Pressure sensor, 25 ...
H ₂ supply tank, 26 ... Gas storage device, 27 ... Gas inlet / outlet part, 28 ... Inlet / outlet pressure detection means, 29 ... Diaphragm, 30 ... Closed space, 31 ... Micro switch, 32 ... Pressure wall, 33 ... Gas storage part, 34 , 35 ... Leader line, 3
6, 37 ... Connection lines, 38, 39 ... Electrode terminals, 40 ... Gas storage auxiliary system, 41 ... Flow path, 42 ... Pressure detection means,
43 ... Pressure / voltage detection means, 44 ... Calculation means, 45 ... Current supply section, 46 ... Switching section

Continued front page    (72) Inventor Seifumi Ata             6-735 Kita-Shinagawa, Shinagawa-ku, Tokyo Soni             -Inside the corporation F term (reference) 3K068 FA02 FB00 FC02 GA02 GA07                 5H027 AA06 DD00 KK01 KK54 MM01                 5H316 BB03 DD11 DD17 EE01 JJ03                       KK01 KK02 KK04

Claims (24)

[Claims] 1. A first pole for decomposing gas into ions, and a second pole for converting the ions generated at the first pole into gas again.
A gas pressure regulator having an electrode and an electrochemical cell composed of an ion conductor sandwiched between these electrodes, and a high-pressure container arranged on one side of the electrochemical cell. 2. A means for supplying a control current to both ends of the first pole and the second pole is further provided, and a gas flowing across the electrodes is controlled by controlling a current amount of the control current. The gas pressure regulator according to claim 1, wherein the flow rate is controlled. 3. The gas pressure adjusting device according to claim 1, wherein the gas is hydrogen gas or oxygen gas. 4. The gas pressure adjusting device according to claim 1, wherein the ionic conductor is a membrane made of an electrolyte material capable of transmitting the ionized gas. 5. The gas pressure adjusting device according to claim 1, wherein the first electrode and the second electrode are electrode films carrying a catalyst that enables ion dissociation equilibrium of the gas. 6. A low-pressure vessel is disposed on the other side of the electrochemical cell, the electrochemical cell serves as a gas partition, and when a pressure difference is generated on both sides of the electrochemical cell,
The gas pressure adjusting device according to claim 1, further comprising means for adjusting pressure while controlling potential between both electrodes. 7. The gas pressure adjusting device according to claim 6, wherein the electromotive force generated from the pressure difference is short-circuited or the pressure is adjusted by a variable resistor. 8. The gas pressure regulator according to claim 1, wherein a plurality of the electrochemical cells are arranged side by side in the gas flow direction and have a multi-stage structure. 9. An electrochemical cell acting as a gas partition is provided with closed vessels on both sides, and when one side is connected as a high pressure gas tank and the other side is connected to a gas consuming system, the closed vessel is provided in the other side. A pressure sensor is installed, and this pressure sensor works in conjunction with a relay switch connected between both electrodes of the electrochemical cell to function to supplement gas consumption,
The gas pressure adjusting device according to claim 1. 10. The gas pressure regulator according to claim 1, wherein the electrochemical cell functions as a gas purification filter. 11. The ionic conductor is a proton conductor, and is selected from at least one selected from the group consisting of fullerene molecules, carbon-based clusters, and tubular or linear carbon structures. The proton conductor is composed of a substance having the following substance as a main component and a proton dissociable group introduced into a carbon atom constituting the substance, and the proton generated at the first pole via the proton conductor. Is moved to the said 2nd pole, The gas pressure adjusting apparatus of Claim 1 characterized by the above-mentioned. 12. The proton dissociative group is —XH.
The gas pressure adjusting device according to claim 11, wherein X is an arbitrary atom or atomic group having a divalent bond and H is a hydrogen atom. 13. The gas pressure adjustment according to claim 12, wherein the proton-dissociative group is —OH or —YOH (Y is an arbitrary atom or atomic group having a divalent bond). apparatus. 14. The proton dissociative group is —OH,
_{-OSO 3 H, -COOH, -SO 3} H, -OPO (O
The gas pressure adjusting device according to claim 13, which is a group selected from the group consisting of H) ₂ and —C ₆ H ₄ —SO ₃ H. 15. The gas pressure adjusting device according to claim 11, wherein the fullerene molecule is a spherical shell carbon cluster molecule Cm (m is a natural number by which Cm can form a spherical shell structure). 16. A first device for decomposing hydrogen gas into protons.
An electrochemical cell comprising a pole, a second pole for converting the protons generated at the first pole into hydrogen gas again, and a proton conductor sandwiched between these two poles, and the first pole of the electrochemical cell And a decompression unit that has a high-pressure container that accommodates a gaseous substance containing hydrogen gas, and that the electrochemical cell functions to reduce the pressure in the high-pressure container, and the first decompression unit in the decompression unit. A hydrogen gas storage part disposed in contact with the second electrode side; a third electrode disposed in contact with the hydrogen gas storage part for decomposing hydrogen gas supplied from the hydrogen gas storage part into protons; It is composed of a fourth pole for converting the proton generated at the pole into water, and a proton conductor sandwiched between these two poles, and at the same time as converting the proton into water at the fourth pole, the third pole and Electrochemical energy between the fourth pole and An electrochemical device comprising is composed of a gas-consuming unit to retrieve the Energy. 17. An oxygen gas or an oxygen-containing gas is supplied to a surface side of the fourth electrode which is not in contact with the proton conductor, and reacts with the proton passing through the proton conductor to convert the proton into water. Converting and extracting electrochemical energy between the third pole and the fourth pole,
The electrochemical device according to claim 16. 18. A gas inlet / outlet portion for introducing or discharging gas, a gas storage portion for storing gas, and a first electrode disposed in the gas storage portion for decomposing gas into ions, the first electrode. Second, to convert the ions generated at the poles into gas again
A pole, and an electrochemical cell comprising an ionic conductor sandwiched between these two electrodes, and by the function of the electrochemical cell, allowing gas to enter and exit the gas storage section through the gas inlet and outlet section, A gas storage device comprising: a depressurization unit that functions to reduce or increase the pressure in the gas storage unit. 19. A gas storage auxiliary system is provided, wherein the gas storage auxiliary system supplies a gas flow path for supplying the gas to a gas inlet / outlet portion of the gas storage device, and a gas pressure in the gas flow path. Pressure detecting means for detecting; voltage detecting means for detecting a voltage generated between the first pole and the second pole; computing means for calculating a control current signal based on the gas pressure and the voltage; A current supply means for generating a control current, a state in which the control current is supplied between the first pole and the second pole until the voltage reaches a predetermined value, and a state in which the voltage is detected. 19. The gas storage device according to claim 18, further comprising a switching unit that alternately switches between. 20. A decomposition step of decomposing gas into ions at a first pole, and the decomposed ions through the ionic conductor sandwiched between the first pole and the second pole to the second pole side. A gas pressure adjusting method comprising: a conducting step of conducting to a second electrode; and a converting step of converting the conducted ions into a gas again at the second electrode. 21. A control current is supplied to both ends of the first pole and the second pole, and a flow amount of a gas flowing across the electrodes is controlled by controlling a current amount of the control current. Item 20. The gas pressure adjusting method described in Item 20. 22. When the electrochemical cell composed of the first electrode, the second electrode and the ionic conductor serves as a gas partition wall, and a pressure difference is generated on both sides of the electrochemical cell,
The gas pressure adjusting method according to claim 20, wherein the pressure is adjusted while controlling the potential between both electrodes. 23. The gas pressure adjusting method according to claim 22, wherein the electromotive force generated from the pressure difference is short-circuited, or the pressure is adjusted by a variable resistor. 24. In the case where a high-pressure gas storage tank is arranged on one side of the electrochemical cell acting as a gas partition wall and a closed container connected to a gas consumption system is arranged on the other side, 23. The gas pressure adjusting method according to claim 22, wherein a pressure sensor is installed in the pressure sensor, and the pressure sensor functions in cooperation with a relay switch connected between both electrodes of the electrochemical cell to supplement gas consumption.