JP2007284705A - Electrolytic hydrogen-generating device, method for generating hydrogen gas, and fuel cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a device for efficiently and inexpensively generating hydrogen with an electrolytic method, and to provide a fuel cell which introduces generated hydrogen into a fuel electrode. <P>SOLUTION: The electrolytic hydrogen-generating device comprises: an anion-exchange membrane; an anode and a cathode arranged on both sides of the exchange membrane so as to face each other; and a supply means for supplying an electric current between the electrodes. A material containing water is supplied to a cathode side, and a material containing an alcoholic compound is supplied to an anode side. A film formed of a strongly basic anion exchange resin can be used for the anion-exchange membrane. Because of using the anion-exchange membrane, the electrolytic hydrogen-generating device does not need to use a precious metal such as platinum for an electrode catalyst, but can use preferably any of Fe, Ni, Co and Ag, or an alloy thereof for a catalyst of the cathode, and preferably any of Co, Ag and Ni, or an alloy thereof for a catalyst of the anode. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an apparatus and method for efficiently generating hydrogen by an electrolysis method, and a fuel cell in which the generated hydrogen is introduced into a fuel electrode. More specifically, the present invention relates to an apparatus and method for efficiently generating hydrogen without using an expensive noble metal such as platinum as an electrocatalyst.

  The development of solid polymer electrolyte fuel cells has progressed and some have been put into practical use, but have not yet reached commercialization. This is because there are many problems to be solved, such as manufacturing cost problems, durability problems, and fuel storage problems. In particular, hydrogen as a fuel is difficult to handle, and there are many problems with its supply means. For example, hydrogen gas has been proposed to be stored in a high-pressure vessel, but there are still problems of danger and leakage, and storage in hydrogen storage alloys, carbon nanotubes, etc. lacks practical storage capacity. For this reason, it has also been proposed to perform reforming by attaching a thermal cracking reformer adjacent to the fuel cell. For example, a fuel such as methane or methanol is reacted with water vapor at a temperature of several hundred degrees under a catalyst. This is a method for obtaining hydrogen. Not only does this require high temperatures, but CO is also mixed into the generated hydrogen and poisons the catalyst metal of the fuel cell, leading to performance degradation. On the other hand, many methods for generating hydrogen by decomposing methanol with a low theoretical decomposition voltage by an electrolytic method have been proposed (for example, Patent Documents 1 and 2). However, all of the proposed techniques use a cation exchange membrane, the electrolytic solution becomes acidic, and the electrodes used in the electrolytic cell are limited to components mainly composed of noble metals such as platinum. Therefore, cost reduction is difficult.

  A direct methanol fuel cell (DMFC), which is a type of fuel cell that directly introduces methanol instead of hydrogen as a fuel, is also being actively studied (US Pat. No. 4,390,603, US Pat. No. 5,599,638). Calligraphy). However, DMFC has a problem of crossover in which methanol passes through the electrolyte membrane and reacts on the air electrode side, and there is a drawback that the electromotive force of DMFC itself is considerably lower than that of a battery using hydrogen.

Japanese Patent Laid-Open No. 11-229167 Japanese Unexamined Patent Publication No. 2004-137582

  An object of the present invention is to provide an apparatus and a method for efficiently and inexpensively generating electrolytic hydrogen using an alcohol compound.

As a result of intensive studies, the present inventors have used an anion exchange membrane as a separation membrane between the anode electrode and the cathode electrode, supplying water to the cathode electrode side and supplying an alcohol compound to the anode electrode side. Thus, it has been found that electrolysis is possible without using noble metals such as platinum as an electrode catalyst, and hydrogen can be produced efficiently, and the present invention has been completed.
That is, the present invention relates to the following electrolytic hydrogen generator, hydrogen gas generation method, and fuel cell.

1. An anion exchange membrane, an anode electrode and a cathode electrode arranged opposite to both surfaces of the exchange membrane, and means for supplying current between the electrodes, and a material containing water is supplied to the cathode electrode side The electrolytic hydrogen generator is characterized in that a material containing an alcohol compound is supplied to the anode electrode side.
2. 2. The electrolytic hydrogen generator according to 1 above, wherein the anion exchange membrane is made of a strongly basic anion exchange resin.
3. 3. The electrolytic hydrogen generator according to 1 or 2, wherein the cathode electrode is an electrode including a catalyst mainly composed of any one of Fe, Ni, Co, Ag, or an alloy thereof.
4). 4. The electrolytic hydrogen generator according to any one of 1 to 3, wherein the cathode electrode is an electrode containing a catalyst activated by Ni dispersion plating on the Fe surface.
5). 5. The electrolytic hydrogen generator according to any one of 1 to 4, wherein the anode electrode is an electrode including a catalyst mainly composed of any one of Co, Ag, Ni, or an alloy thereof.
6). 6. The electrolytic hydrogen generator according to any one of 1 to 5, wherein the cathode electrode, the anode electrode, and the anion exchange membrane comprise a single laminate.
7). 7. The electrolytic hydrogen generator according to any one of 1 to 6, wherein the material containing the alcohol compound is methanol or an aqueous solution thereof.
8). In an electrolytic hydrogen generator comprising an anion exchange membrane, an anode electrode and a cathode electrode arranged opposite to both surfaces of the exchange membrane, and means for supplying a current between the electrodes, water is supplied to the cathode side. electrolysis to hydrogen gas and hydroxide ions (OH ^-) is generated, the anode in a hydroxide was passed through the anion exchange membrane ion (OH ^-) and hydrogen comprises reacting an alcohol compound Gas generation method.
9. 9. The method for generating hydrogen gas as described in 8 above, wherein the anion exchange membrane comprises a strongly basic anion exchange resin.
10. 10. The method for generating hydrogen gas as described in 8 or 9 above, wherein the cathode electrode is an electrode containing a catalyst mainly composed of any one of Fe, Ni, Co, Ag, or an alloy thereof.
11. 11. The method for generating hydrogen gas as described in any one of 8 to 10 above, wherein the cathode electrode is an electrode containing a catalyst activated by Ni-dispersing plating on the Fe surface.
12 12. The method for generating hydrogen gas as described in any one of 8 to 11 above, wherein the anode electrode is an electrode containing a catalyst mainly composed of any one of Co, Ag, Ni, or an alloy thereof.
13. 13. The method for generating hydrogen gas according to any one of 8 to 12, wherein the cathode electrode, the anode electrode, and the anion exchange membrane comprise a single laminate.
14 14. The method for generating hydrogen gas according to any one of 8 to 13, wherein the alcohol compound is methanol.
15. A fuel cell comprising the electrolytic hydrogen generator according to any one of 1 to 7 as a supply device for hydrogen as a raw material.

According to the electrolytic hydrogen generator of the present invention, an anion exchange membrane is used as a separation membrane between an anode and a cathode, so that it is not necessary to use expensive noble metals such as platinum as an electrode catalyst, and a cheaper metal is used. Can greatly contribute to cost reduction. Further, the structure can be made more compact by laminating a cathode electrode, an anode electrode, and an anion exchange membrane to form a membrane-electrode assembly (MEA).
The hydrogen generator of the present invention can function as a portable or stationary fuel cell when used as a hydrogen supply device of a polymer solid oxide fuel cell.

  An electrolytic hydrogen generator according to the present invention includes an anion exchange membrane, an anode electrode and a cathode electrode arranged to face both surfaces of the exchange membrane, and means for supplying a current between the electrodes. The exchange membrane and each electrode are usually installed in an electrolytic cell. Specifically, the electrolytic cell is divided into an anode chamber and a cathode chamber by an anion exchange membrane, and an anode electrode is arranged on the anode chamber side and a cathode electrode is arranged on the cathode chamber side facing the exchange membrane.

The anion exchange membrane that can be used in the present invention is not particularly limited as long as it allows hydroxide ions (OH ⁻ ) to pass therethrough, but has excellent permeability, excellent conductivity, and strong basicity having alkali resistance. An exchange membrane made of a low resistance type anion exchange material is preferred. The exchange membrane preferably has a gas separator function so that gases generated at the respective electrodes do not permeate each other. The film thickness depends on the material of the exchange membrane and cannot be generally specified, but is determined in consideration of conductivity, membrane strength, and the like. Usually, it is 20-200 micrometers.

Examples of the anion exchange membrane material include an anion exchanger in which an anion exchange group is introduced into a styrene / divinylbenzene copolymer as a base material. As the anion exchange group, those having strong basicity are preferable, and specifically, a quaternary ammonium group or a pyridinium group is preferably used. Examples of the quaternary ammonium group include a —CH ₂ —N (CH ₃ ) ₃ OH group.
Moreover, what introduce | transduced nonionic hydrophilic polymers, such as polyallylamine, to the polyvinyl alcohol as a base material can be used. The production can be performed, for example, by preparing an aqueous solution at a ratio of 90 parts by mass of polyvinyl alcohol and 10 parts by mass of polyallylamine, pouring the solution on a plate and drying at about 60 ° C. to form a film. .

In the present invention, a material containing water is supplied to the cathode electrode side, and a material containing an alcohol compound is supplied to the anode electrode side. On the cathode side, water is electrolyzed to generate hydrogen gas and hydroxide ions (OH ⁻ ). On the anode side, hydroxide ions (OH ⁻ ) that have passed through the anion exchange membrane react with alcohol compounds to form water. And carbon dioxide is generated.

  As the material containing water supplied to the cathode side, water alone or a material obtained by adding an electrolyte such as an alkali hydroxide to water can be used. Electrical conductivity can be improved by using an alkali hydroxide. Examples of the alkali hydroxide include sodium hydroxide and potassium hydroxide, and the concentration is preferably 1.0 mol / liter or less.

  Although it does not restrict | limit especially as an alcohol compound of the material containing the alcohol compound supplied to an anode side, For example, a C1-C4 alkyl alcohol with comparatively low toxicity and low decomposition voltage can be used preferably. Specifically, methanol, ethanol, propanol, etc. are mentioned, These can also be used in mixture of 2 or more types. Moreover, water can be added to these alcohol compounds and supplied to the anode as an aqueous solution.

The reaction formula when electrolysis is performed by supplying methanol to the anode side is as follows.
Cathode: 6H ₂ O + 6e ⁻ → 3H ₂ + 6OH ⁻
Anode: CH ₃ OH + 6OH ⁻ → CO ₂ + 5H ₂ O + 6e ⁻
Hydrogen generated at the cathode electrode is taken outside and supplied to the fuel of the fuel cell or for storage. The generated hydroxide ions (OH ⁻ ) pass through the anion exchange membrane and are transported to the anode side where they oxidize methanol. As shown in this reaction formula, the overall reaction is a reaction in which one molecule of methanol and water reacts, and three molecules of hydrogen and one molecule of carbon dioxide are generated, so water must be supplied to the cathode side. The anode electrode must be supplied with alcohol (in this example, methanol).

  In order to supply these liquid materials to the anode side and the cathode side, a liquid material supply port and a discharge port are provided in the anode chamber and the cathode chamber, respectively. It is preferably a circulation type, and the liquid raw material flowing out from the discharge port is circulated to the supply port after adjusting the raw material concentration. A gas-liquid separator is provided in the circulation path to separate and acquire hydrogen from the cathode side. As for carbon dioxide generated from the anode side, almost pure carbon dioxide gas has large bubbles, so that gas-liquid separation can be satisfactorily performed without providing a gas-liquid separation device. It may be provided.

  In the present invention, by using an anion exchange membrane, the liquid does not become strongly acidic like an electrolytic hydrogen generator using a cation exchange membrane, so there is no need to use a noble metal such as platinum as an electrode catalyst metal. Cost can be reduced.

  Examples of the electrode catalyst for the cathode electrode that can be used in the present invention include Fe, Ni, Co, Ag, Zn, and alloys thereof. Examples of the electrode catalyst for the anode electrode include Co, Ag, Ni, Mo, Fe, and Cr. , Mn, alloys thereof or oxides thereof. Furthermore, it is also preferable to use the same kind of metal or another kind of metal on each metal to increase the activity.

  The important factors for selecting the metal used for these electrodes are that they are stable against reaction and hardly deteriorate, and at the same time, the decomposition voltage, particularly the activation overvoltage is low, and the cost is further low. In this respect, the cathode electrode is preferably any one of Fe, Ni, Co, and Ag, or an alloy thereof, and the anode electrode is preferably any one of Co, Ag, Ni, or an alloy thereof. Further, it is also preferable to disperse Ni and S on the surface of Fe in order to activate the cathode electrode.

  These electrode catalysts can be dispersed and supported on a substrate to form an electrode. As a base material, for example, a carbon fiber fabric used for gas diffusion electrodes or the like is a material having a three-dimensional spread in which carbon powder is dispersed, and carbon powder is kneaded using a fluororesin as a binder and formed into a sheet by hot pressing Things can be used. The carbon fiber is preferably a vapor grown carbon fiber excellent in conductivity. Examples of the carbon powder include carbon black such as ketjen black. Examples of the fluororesin used as the binder include poly (tetrafluoroethylene) resin (PTFE resin). In addition, as a base material other than carbon, for example, a titanium sponge is formed into a plate shape, a foam shape, a material having a three-dimensional spread such as sintered titanium fiber, or an expanded mesh is used. Can be used. An electrode material is formed on this substrate to form an electrode. Although there is no particular designation regarding the method for producing these electrode materials, for example, in the case of cobalt, a coating solution in which cobalt chloride acid mixed in a predetermined ratio is dissolved in butyl alcohol is applied to the electrode surface of the electrode substrate, and hydrogen is added. Cobalt can be formed on the substrate surface by pyrolysis at 200 ° C. to 600 ° C. in an air stream. The amount of the electrode material supported can be adjusted by adjusting the number of times of application / thermal decomposition.

  In addition, when the substrate is weak in a high-temperature oxidizing atmosphere such as carbon, these electrode materials are coated in advance on a metal powder such as titanium sponge, and this is applied to the substrate together with carbon, fluorine resin, etc. If it is resin sintering temperature, for example, PTFE resin, it can be baked by hot pressing while applying light pressure at 200 to 300 ° C.

  In the present invention, an anion exchange membrane, an electrode carrying a cathode catalyst, and an electrode carrying an anode catalyst can be laminated to form a so-called separation membrane-electrode assembly (MEA). By using the MEA, it is possible to fit in a compact structure, and to suppress the overvoltage of electrolysis small.

  A current collector is installed outside the electrode. The current collector is not particularly limited as long as it has conductivity and corrosion resistance, and for example, a current collector made of a copper material or a carbon material can be used.

In the present invention, the means for supplying current between the electrodes is not particularly limited, and those usually used in an electrolytic reaction can be used in the same manner. In the present invention, the current density to be applied is preferably from 0.1 to 10 A / dm ^2.

  The theoretical decomposition voltage of the reaction using methanol as the alcohol is 0.05V. How to reduce the overvoltage and extract hydrogen at a voltage close to the theoretical decomposition voltage is an important factor in the hydrogen generator, so select an electrode catalyst with a small activation overvoltage as described above and use the electrode and current collector. It is important to reduce the liquid resistance.

  The fuel cell of the present invention uses the above-described electrolytic hydrogen generator as a supply device for hydrogen as a raw material. As the connection method, a conventionally known method can be used without limitation.

  In considering the present invention, the efficiency comparison with DMFC is important. A fuel cell using hydrogen as a fuel as in the present invention practically has a generated voltage of 0.7V, while a practically generated voltage of DMFC is about 0.4V. The difference of 0.3V in this difference is more advantageous than that of DMFC in the fuel cell using hydrogen as a direct fuel. Electrolysis is generated at a voltage within this range to generate hydrogen and 0.3V including its production cost. It is required to be within the added value. Since the electrolytic hydrogen generator of the present invention is excellent in hydrogen generation efficiency and can be kept low in cost, this requirement can be satisfied sufficiently.

  On the other hand, in order to store hydrogen directly, it is bulky and not realistic unless the pressure is set to about 700 atm. However, such high-pressure storage has various dangers and problems. Instead, it is safe and efficient to store in a substance with a high hydrogen content and to electrolyze it to hydrogen when necessary. Moreover, if a hydrogen generator by electrolysis and a fuel cell are systematically combined, it is very effective as a portable power source or a stationary power source.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not restrict | limited by the following examples.

Example 1
As an anion exchange membrane, a Neoceptor (registered trademark) strong basic low resistance membrane (model number: AM-1, film thickness: 110 μm, electric resistance: 1.2 Ω · cm ² ) manufactured by Astom Co., Ltd. was used.
As the cathode electrode, an iron mesh activated by plating Ni and S was used.
As an anode electrode, a 0.2 mm-thick porous body made of carbon black and baked with PTFE resin as a binder on a titanium mesh is coated with a butyl alcohol solution of cobaltous chloride on its surface. And a cobalt phase formed by thermal decomposition at 400 ° C. was used.
Place a 1 mm thick sheet made of Teflon (registered trademark) between the cathode and the ion exchange membrane and the anode and the ion exchange membrane, respectively, and further arrange the current collecting copper plates on the outside of both electrodes so that the two electrodes do not contact each other, An electrolytic cell was produced by pressing from the outside of the current collecting copper plate. A liquid inlet and outlet were respectively provided on the cathode electrode side and the anode electrode side to enable liquid circulation. Since the liquid discharged from each electrode contains a gas, a gas-liquid separator with a mist catcher is provided separately so that hydrogen can be separated and discharged mainly from the cathode side and CO ₂ from the anode side. Each liquid was circulated back to the liquid inlet of each pole. A 0.1 mol / liter aqueous KOH solution was used for the circulating solution of the cathode electrode, and a 50% aqueous methanol solution was used for the circulating solution of the anode electrode.

When electrolysis was performed at a current density of 1 A / dm ² , the voltage was stable at 0.26 V. Hydrogen was continuously released from the cathode side, and CO ₂ was continuously released from the anode side. The concentration of each solution was adjusted by supplementing the circulating fluid with methanol or purified water. When the gas component generated from the cathode was measured by gas chromatography, it was almost 100% hydrogen. When converted from the amount, the current efficiency on the cathode side was 99.5% or more.
CO ₂ was obtained from the anode side almost as theoretically, and the overall current efficiency was maintained at 90% or more. Further, when the current density was increased to 10 A / dm ² , the voltage increased to 0.34 V, but generation of hydrogen, CO _2, etc. was successfully performed at each pole.

Example 2
As an anion exchange membrane, a Neoceptor (registered trademark) strong basic low resistance membrane (model number: AFN, film thickness: 130 μm, electric resistance: 0.3 Ω · cm ² ) manufactured by Astom Co., Ltd. was used.
As the anode catalyst, a cathode in which cobalt powder is phase-formed by a reduction reaction in hydrogen and supported on the surface of a support material in which VGCF (gas phase carbon fiber) manufactured by Showa Denko and carbon black are combined with a PTFE binder is used. As a catalyst, VGCF made by Showa Denko and carbon black are combined with PTFE binder, and Fe powder is supported on the surface by colloid method, and each one side of anion exchange membrane is applied to form a sheet. Thus, a membrane-electrode assembly (MEA) was obtained. A separator-type carbon separator manufactured by Showa Denko was used to produce a laminated electrolytic cell with four single cells. Showa Denko carbon was used for the current collector plates at both ends.
A 95% aqueous methanol solution was supplied to the anode side, and purified water distilled after ion exchange was supplied to the cathode side. The methanol aqueous solution was supplied in a circulation system, and a separator for separating the generated carbon dioxide gas was provided in the external circulation path to adjust the concentration, and then circulated again to the anode electrode. Purified water was circulated while being pushed into the cathode while being pressurized. Note that the MEA was used after being wetted with water vapor. After circulation was complete, electrolysis was started by applying a direct current from the outside. The current density was carried out at 1A / dm ^2. As a result, the electrolysis voltage was 1.06 V, and hydrogen was continuously released from the cathode side. When the generated hydrogen concentration was measured by gas chromatography, it was almost 100% excluding water vapor. The current efficiency was recorded as 98%. Further, almost theoretical CO ₂ was observed from the anode side. When the current density was increased to 10 A / dm ² and electrolysis was performed, the electrolysis voltage increased to 1.41 V, but the current efficiency was 92%, which was very good.

Example 3
The anion exchange membrane is an Astom Neocepta (registered trademark) strong basic monovalent ion permselective membrane (model number: AM-3, film thickness: 200 μm, electric resistance: 2.8 Ω · cm ² ), cathode An MEA similar to that of Example 2 was prepared, except that the electrode catalyst was activated by plating the surface of Fe powder with Ni and S instead of Fe powder.
Other separators and current collector plates also constituted an electrolytic cell in the same manner as in Example 2.
A 50% ethanol aqueous solution was supplied to the anode electrode side, and purified water similar to Example 2 was supplied to the cathode electrode side. The ethanol aqueous solution was supplied in a circulation system. A separator for separating the generated carbon dioxide gas was provided in the external circulation path, the concentration was adjusted, and then it was circulated again to the anode electrode. Purified water was used by circulating the cathode. The MEA was used after being wetted. Initially, the current density was 1 A / dm ² . The electrolysis voltage was 0.98 V, and hydrogen was continuously released from the cathode side. Hydrogen was almost 100% and the current efficiency on the cathode side was 95% or more. Further, almost theoretical CO ₂ was observed from the anode side. When electrolysis was performed with the current density increased to 10 A / cm ² , the electrolysis voltage increased to 1.28 V, but the total current efficiency was maintained at 85% or more.

Example 4
The fuel cell was operated using the hydrogen gas generated from the electrolytic cell used in Example 2 for the fuel of the fuel cell provided separately. This fuel cell uses a DuPont Nafion 117, and on one side, a Pt-Ru alloy thermal decomposition product supported on a VGCF made by Showa Denko was mixed with PTFE resin as a catalyst and mixed with carbon black. A fuel electrode was formed, and on the other side, Pt powder was supported on VGCF as a catalyst and mixed with carbon black was applied to form an air electrode to obtain an MEA. The MEA was stacked in four layers using a carbon separator made by Showa Denko as a separator, a carbon current collector plate was installed at both ends, and a fuel cell was constructed by crimping it.
As for the output of this fuel cell, the actual output voltage was 0.7 V and the output density was 130 mW / cm ² . The effective use rate of methanol for the fuel was 85%.

Claims (15)

  An anion exchange membrane, an anode electrode and a cathode electrode arranged opposite to both surfaces of the exchange membrane, and means for supplying current between the electrodes, and a material containing water is supplied to the cathode electrode side The electrolytic hydrogen generator is characterized in that a material containing an alcohol compound is supplied to the anode electrode side.   The electrolytic hydrogen generator according to claim 1, wherein the anion exchange membrane is made of a strongly basic anion exchange resin.   The electrolytic hydrogen generator according to claim 1 or 2, wherein the cathode electrode is an electrode including a catalyst mainly composed of any one of Fe, Ni, Co, and Ag or an alloy thereof.   The electrolytic hydrogen generator according to any one of claims 1 to 3, wherein the cathode electrode is an electrode containing a catalyst activated by Ni-plating the Fe surface.   The electrolytic hydrogen generator according to any one of claims 1 to 4, wherein the anode electrode is an electrode containing a catalyst mainly composed of one of Co, Ag, Ni, or an alloy thereof.   The electrolytic hydrogen generator according to any one of claims 1 to 5, wherein the cathode electrode, the anode electrode, and the anion exchange membrane comprise a single laminate.   The electrolytic hydrogen generator according to any one of claims 1 to 6, wherein the material containing the alcohol compound is methanol or an aqueous solution thereof. In an electrolytic hydrogen generator comprising an anion exchange membrane, an anode electrode and a cathode electrode arranged opposite to both surfaces of the exchange membrane, and means for supplying a current between the electrodes, water is supplied to the cathode side. electrolysis to hydrogen gas and hydroxide ions (OH ^-) is generated, the anode in a hydroxide has passed through the anion exchange membrane ion (OH ^-) and hydrogen comprises reacting an alcohol compound Gas generation method.   The method for generating hydrogen gas according to claim 8, wherein the anion exchange membrane is made of a strongly basic anion exchange resin.   The method for generating hydrogen gas according to claim 8 or 9, wherein the cathode electrode is an electrode containing a catalyst mainly composed of any one of Fe, Ni, Co, Ag, or an alloy thereof.   The method for generating hydrogen gas according to any one of claims 8 to 10, wherein the cathode electrode is an electrode containing a catalyst which is activated by Ni dispersion plating on the Fe surface.   The method for generating hydrogen gas according to any one of claims 8 to 11, wherein the anode electrode is an electrode containing a catalyst mainly composed of one of Co, Ag, Ni, or an alloy thereof.   The method for generating hydrogen gas according to any one of claims 8 to 12, wherein the cathode electrode, the anode electrode, and the anion exchange membrane comprise a single laminate.   The method for generating hydrogen gas according to any one of claims 8 to 13, wherein the alcohol compound is methanol. A fuel cell comprising the electrolytic hydrogen generator according to any one of claims 1 to 7 as a supply device for hydrogen as a raw material.