WO2006103959A1 - 水素発生材料およびその製造方法、並びに水素の製造方法 - Google Patents
水素発生材料およびその製造方法、並びに水素の製造方法 Download PDFInfo
- Publication number
- WO2006103959A1 WO2006103959A1 PCT/JP2006/305404 JP2006305404W WO2006103959A1 WO 2006103959 A1 WO2006103959 A1 WO 2006103959A1 JP 2006305404 W JP2006305404 W JP 2006305404W WO 2006103959 A1 WO2006103959 A1 WO 2006103959A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen
- aluminum
- generating material
- hydrogen generating
- water
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J7/00—Apparatus for generating gases
- B01J7/02—Apparatus for generating gases by wet methods
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/061—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of metal oxides with water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/30—Fuel cells in portable systems, e.g. mobile phone, laptop
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02B90/10—Applications of fuel cells in buildings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- Hydrogen generating material method for producing the same, and method for producing hydrogen
- the present invention relates to a hydrogen generating material capable of generating hydrogen by reaction with water and a method for producing the same.
- a solid polymer fuel cell is an example of a battery that can meet the above-mentioned demand.
- Solid polymer fuel cells that use a solid polymer electrolyte as the electrolyte, oxygen in the air as the positive electrode active material, and fuel (hydrogen, methanol, etc.) as the negative electrode active material can be expected to have higher energy density than lithium ion batteries. It is attracting attention as a battery.
- Fuel cells can be used continuously as long as fuel and oxygen are supplied. As for fuel cells, there are several candidates for the fuel to be used. Each of them has various problems, and the final decision has yet to be made!
- a fuel cell using hydrogen as a fuel for example, a method of supplying hydrogen stored in a high-pressure tank or a hydrogen storage alloy tank is partly put into practical use.
- fuel cells using such tanks are not suitable for portable power applications because their volume and weight increase and energy density decreases.
- Patent Documents 1 to 5 there is also known a method in which hydrogen generated by a chemical reaction at a low temperature of 100 ° C or lower is used as fuel for a fuel cell. These methods use, for example, a metal that generates hydrogen by reacting with water, such as aluminum, magnesium, silicon, or zinc.
- Patent Document 1 US Pat. No. 6,506,360
- Patent Document 2 Japanese Patent No. 2566248
- Patent Document 3 JP 2004-231466 A
- Patent Document 4 Japanese Patent Laid-Open No. 2001-31401
- Patent Document 5 US Pat. No. 6,582,676
- Patent Documents 1 to 3 disclose the ability to react aluminum with an alkali or an acid. According to these techniques, although hydrogen is easily generated chemically, an equivalent amount to aluminum is equivalent. It is necessary to add an alkali or an acid, and there arises a problem of a decrease in energy density due to a high ratio of materials other than the hydrogen source. In addition, the reaction product, acid or hydroxide, forms a film on the surface of the aluminum, making it impossible for the water inside the film to come into contact with water, and the acid reaction occurs on the surface of the aluminum. If you just stop, it can easily cause problems! /.
- Patent Document 4 which attempts to avoid this problem by mechanically removing the surface film, when the apparatus becomes large, such as requiring mechanical equipment for removing the surface film, There is a problem.
- alumina or the like is added as a catalyst for forming the hydroxide oxide film to generate hydrogen at a low temperature.
- metal such as aluminum does not generate hydrogen, and there is a problem that the amount of hydrogen generated decreases due to a decrease in the content of metal such as aluminum as a hydrogen source because a catalyst is added. Disclosure of the invention
- the hydrogen generating material of the present invention is a hydrogen generating material containing at least one metal material selected from aluminum and an aluminum alloy, and the metal material is a metal phase containing aluminum in a metallic state. And a surface film including an inert phase containing an oxide or hydroxide of aluminum.
- the method for producing a hydrogen generating material of the present invention comprises at least one kind of force selected from aluminum and an aluminum alloy, and a metal phase containing aluminum in a metal state, and an aluminum oxide or hydroxide
- a method for producing a hydrogen generating material including a metal material having a surface film including an inert phase containing an inert material, wherein aluminum or an aluminum alloy is pulverized in a liquid containing water and an organic solvent. Including a process.
- the method for producing hydrogen of the present invention is characterized by including a step of generating hydrogen by reacting the hydrogen generating material of the present invention with water.
- the present invention it is possible to provide a hydrogen generating material capable of generating hydrogen easily and efficiently, a method for producing the same, and a method for producing hydrogen using the hydrogen generating material as a hydrogen source.
- a hydrogen generating material of the present invention as a hydrogen source, it is possible to reduce the size of the hydrogen generator and the fuel cell.
- FIG. 1 is a diagram showing an observation result of an ordinary aluminum powder cross section used in Example 1 by an electron microscope.
- FIG. 2 is a diagram showing an observation result of a cross section of a metal material used in the hydrogen generating material of the present invention produced in Example 1 by an electron microscope.
- FIG. 3 is a graph showing the particle size distribution of the metal materials of Examples 1, 2, and 5.
- FIG. 4 is a cross-sectional view schematically showing the structure of the surface coating of the metal material of Examples 2 to 6.
- FIG. 5 is a cross-sectional view schematically showing the structure of a hydrogen generator.
- the hydrogen generating material of the present invention is selected from aluminum and aluminum alloys. It contains at least one metal material.
- the metal material is mainly composed of particles made of aluminum metal or aluminum alloy and a surface film covering the particles. This surface film includes a metal phase containing aluminum in a metallic state and an inert phase containing aluminum oxide or aluminum hydroxide.
- the aluminum in the metallic state of the present invention includes an aluminum metal or an aluminum alloy.
- the metal material also has aluminum (pure aluminum) or aluminum alloy strength.
- the composition of the alloy is not particularly limited as long as aluminum is the main constituent element.
- the alloy element include silicon, iron, copper, manganese, magnesium, zinc, nickel, titanium, lead, tin, and chromium. From the viewpoint of increasing the amount of hydrogen generation by increasing the aluminum content ratio in the metal material, the aluminum content in the aluminum alloy is preferably 80% by mass or more.
- aluminum has a surface film (acid-soluble) composed of a dense, poorly water-soluble inert phase composed of aluminum oxide or aluminum hydroxide on the surface of particles inside aluminum metal. A film is formed.
- hydrogen is generated when water penetrates the surface coating and reaches the aluminum metal inside the particles. For this reason, with a normal hydrogen generating material that uses aluminum as a hydrogen generation source, a certain period of time is required before hydrogen generation starts.
- the form of the metal phase and the inert phase in the surface film is not particularly limited. Force At least a part of the metal phase and at least a part of the inert phase are respectively formed in layers.
- the surface film is configured to include a laminated portion in which the layer made of the metal phase and the layer made of the inert phase are laminated, the reaction between the metal phase and water occurs continuously. The reactivity becomes higher. Further, the metal phase having a fine particle size may be dispersed in the inert phase.
- the metal material contained in the hydrogen generating material of the present invention is a metal material composed of a conventional aluminum or aluminum alloy, that is, a dense oxide film on the surface, depending on the structure of the surface film. Compared to a metal material formed only with hydrogen, the time until hydrogen is generated and the time until the hydrogen generation rate is maximized are shortened, and hydrogen can be produced easily and efficiently.
- the surface film of the metal material preferably has pores. This is a force that facilitates water penetration into the aluminum metal phase of the surface film and the aluminum metal inside the particles. For example, in the case where there are pores in the laminated portion of the surface film or in the interface between the laminated portion and the inside of the particles, water easily penetrates into the laminated portion and the inside of the particles, It is preferable because the metal phase contained in the laminated part or the metal inside the particles and water easily react.
- FIGS. 1A to 1C show the observation results of the cross section of the normal aluminum powder used in Example 1 described later, using an electron microscope.
- 2A to 2C show the observation results of the cross section of the metal material used in the hydrogen generating material of the present invention produced in Example 1 with an electron microscope.
- 1A and 2A show images of the above-mentioned section with a scanning electron microscope (SEM)
- FIGS. 1B and 2B show images of the above-mentioned section with a scanning transmission electron microscope (STEM).
- FIG. 1C and FIG. C is the energy dispersive X-ray microaperture in the field of view of Figures 1B and 2B, respectively. Elemental mapping by Nalizer (EDX) is shown.
- FIG. 1A in a normal aluminum powder, a dense surface film having a thickness of about 5 nm is present on the outer surface inside the particles.
- a dense surface film having a thickness of about 5 nm is present on the outer surface inside the particles.
- oxygen is distributed almost only on the surface of the aluminum powder, so the surface film is considered to be an aluminum oxide or hydroxide.
- the inside is thought to be composed of aluminum metal.
- the "protective film” shown in FIGS. 1A and 1B and FIGS. 2A and 2B is an analysis film attached to the particle surface for the purpose of protecting the particles during electron microscope observation. What exists on the outermost surface of the aluminum powder is the portion indicated by “surface coating”.
- a surface film having a thickness of about 1 ⁇ m or less is formed on the outer surface of the inside of the particle considered to be composed of aluminum metal.
- a layer in which oxygen is mainly distributed from the outermost surface side (inside the protective film) ie, contains aluminum oxide or aluminum hydroxide.
- Layer composed of an inert phase) and a layer in which aluminum is mainly distributed are alternately stacked to form a laminated portion. It can be seen that there are two or more layers in the stack (see Fig. 2B). It can also be seen from FIG. 2A that pores are formed in the surface film.
- the surface film in the hydrogen generating material may have the laminated part as a whole as long as it has the laminated part in at least a part thereof.
- the surface film may be formed on a part of the surface film.
- the laminated part may be formed, and the other part may be composed only of an inert phase.
- the ratio of the laminated portion in the surface film can be, for example, 25 to: LOO area% in the total surface area of the hydrogen generating material.
- the laminated portion of the surface film may have a structure in which a layer composed of a metal phase and a layer composed of an inert phase are laminated one by one.
- a layer composed of a metal phase and a layer composed of an inert phase are laminated one by one.
- Each of the metal phase layer and the inert phase layer may have a structure in which two or more layers are laminated to each other.
- the upper limit of the number of layers in the stacked portion is not particularly limited. Each can have 4 to 5 layers.
- the thickness of the laminated portion in the surface film is preferably 2 ⁇ m or less, for example. If the laminate is too thick, aluminum oxide and aluminum that do not participate in the hydrogen generation reaction
- the percentage of humic hydroxide is increased, the hydrogen generation efficiency may decrease.
- the lower limit of the thickness of the laminated portion can be, for example, lOnm.
- the metal material preferably contains 60% by mass or more of aluminum in a metal state.
- the hydrogen generation amount may be lowered.
- the reaction with water does not proceed in the so-called Balta state such as plate-like, block-like or lmm or larger particles, and the amount of hydrogen generated at room temperature is
- the metal material used for the hydrogen generating material of the present invention preferably has a specific force of 80% by volume or more for particles having a particle size of 60 ⁇ m or less, more preferably 90% by volume or more. That's right.
- the average particle size of the metal material is preferably 30 ⁇ m or less, more preferably 20 or less.
- the form of the metal material is not limited to the particulate form, but may be a form like a metal foil.
- the average particle diameter of the metal material in the hydrogen generating material is preferably 0.1 m or more.
- the average particle diameter of the metal material in the present specification means a value of 50% diameter in the volume-based integrated fraction.
- the particle size distribution and average particle size of the metal material referred to in this specification are values measured by a laser diffraction / scattering method.
- this method is a particle size distribution measurement method using a scattering intensity distribution detected by irradiating a measurement target substance dispersed in a liquid phase such as water with laser light.
- a laser diffraction 'scattering method for example, “Microtrac HRA” manufactured by Nikkiso Co., Ltd. can be used.
- the metal material having a surface film including the laminated portion is obtained by pulverizing aluminum or an aluminum alloy in a liquid containing water and an organic solvent, and performing surface modification of the metal material, and then the liquid. Can be obtained by removing.
- Aluminum or aluminum alloy used as a hydrogen generation source is ground to increase its surface area and improve the hydrogen generation rate.
- aluminum is pulverized by a general mechanical pulverization method such as stamp mill method, ball mill method, vibration mill method, etc.
- a general mechanical pulverization method such as stamp mill method, ball mill method, vibration mill method, etc.
- aluminum is a metal with high malleability, it expands into a foil shape and has a metallic luster. It becomes a scale-like powder.
- the surface of the metal material contains a metal phase containing aluminum in a metallic state and aluminum oxide or aluminum hydroxide. This is thought to be due to the formation of a surface film containing an inert phase.
- At least a part of the metal phase and at least a part of the inert layer are respectively formed in layers, and the surface coating is The layer made of the metal phase and the layer made of the inert phase have a laminated portion laminated together. Furthermore, by adopting the above production method, pores are formed in the surface film formed on the particle surface.
- the hydrogen generating material of the present invention can be obtained by using a metal material formed by pulverizing aluminum or an aluminum alloy in a liquid containing water and an organic solvent. If the liquid used for pulverization does not contain water and is composed of only an organic solvent, part or all of the metal material after pulverization becomes scale-like particles with metallic luster, and hydrogen generation efficiency is improved. In addition, since the pulverized material adheres to the inner wall surface of the pulverization pot of the pulverizer, the target metal material cannot be produced efficiently.
- the liquid used for pulverizing aluminum or aluminum alloy does not contain an organic solvent and is composed only of water, the surface of the metal material is oxidized or hydroxylated by pulverization. Proceeds excessively. As a result, when a large amount of oxide or hydroxide is formed, the content of metal aluminum in the metal material is lowered, and the amount of hydrogen generation is reduced. That is, by adding an organic solvent to the liquid, it is possible to control the oxidation reaction or the hydroxylation reaction during the pulverization of aluminum or aluminum alloy, and to adjust the thickness of the laminated portion in the surface film. . The thickness of the laminated portion can also be adjusted by controlling the pulverization time.
- the water content is 0. 1 part by mass of aluminum or aluminum alloy to be pulverized in order to form the surface film structure described above. It is desirable that the content be 02 parts by mass or more. 0.1 It is more desirable that the content be 1 part by mass or more. On the other hand, the water content is preferably 2 parts by mass or less, more preferably 1 part by mass or less in order to suppress the progress of acidification during the grinding of aluminum or aluminum alloy. The most desirable is 4 parts by mass or less.
- the amount of water in the liquid is too small, the surface modification of the metal material becomes insufficient, and it becomes easy to obtain a scale-like powder having a metallic luster, and the hydrogen generation efficiency of the metal material may be lowered. is there.
- the content of water in the liquid is too large, the content of metal aluminum in the metal material is decreased, which may cause a decrease in the amount of hydrogen generated.
- the organic solvent for constituting the liquid reacts with aluminum or an aluminum alloy.
- the solvent is not particularly limited as long as it is a difficult solvent, and may be a solvent that does not mix with water. Specific examples include aromatic hydrocarbons such as toluene, aliphatic hydrocarbons such as hexane and cyclohexane, ketones such as acetone, ethers, N, N-dimethylformamide, and the like.
- aromatic hydrocarbons such as toluene
- aliphatic hydrocarbons such as hexane and cyclohexane
- ketones such as acetone
- ethers such as ethers
- N-dimethylformamide and the like.
- the organic solvents those that become an azeotrope with water, such as toluene and cyclohexane, are more preferably used because the liquid can be easily removed from the pulverized product.
- the organic solvent only one kind may be used, or two or more kinds may be
- Alcohols can also be used, and alcohols with a low molecular weight (for example, 10 or less carbon atoms) such as methanol and ethanol are more highly reactive with aluminum than the organic solvents exemplified above. May react with aluminum to generate an alkoxide S, and in comparison with water, its reactivity is considerably low. Therefore, instead of the organic solvent exemplified above, or the organic solvent exemplified above It is possible to use with.
- a low molecular weight for example, 10 or less carbon atoms
- methanol and ethanol are more highly reactive with aluminum than the organic solvents exemplified above. May react with aluminum to generate an alkoxide S, and in comparison with water, its reactivity is considerably low. Therefore, instead of the organic solvent exemplified above, or the organic solvent exemplified above It is possible to use with.
- the ratio of water and organic solvent used is not necessarily limited, but for example, the oxidation of the metal material with respect to 1 part by mass of water.
- the amount of the organic solvent is preferably 5 parts by mass or more, while in order to enhance the effect of surface modification, the amount of the organic solvent is 300 parts by mass or less. Is preferable.
- the method for pulverizing aluminum or an aluminum alloy in a liquid containing water and an organic solvent is not particularly limited.
- a mechanical pulverization method using a ball mill, a sand mill, a vibration mill, a jet mill or the like can be employed.
- the metal material used for the hydrogen generating material of the present invention since hydrogen is generated during pulverization, it is desirable to provide a mechanism for escaping powerful hydrogen in the pulverizing apparatus as described above. .
- the hydrogen generating material of the present invention is produced using a metal material obtained through such a process.
- the metal material may contain 60% by mass or more of aluminum in a metal state. It is more preferable to contain 70% by mass or more. If the content of metallic aluminum in the metal material decreases, the amount of hydrogen generated may decrease.
- the powder By adding an organic solvent to the liquid used for crushing and limiting the content of water in the liquid, the amount of acid in the aluminum or aluminum alloy during crushing can be controlled.
- a hydrogen generating material can be formed using a metal material that contains a large amount of aluminum in a metallic state and can efficiently generate hydrogen.
- the content of metallic aluminum (aluminum metal or aluminum alloy) in the metal material in the present specification is measured as follows. When metal materials are analyzed with an X-ray diffractometer, aluminum metal and aluminum hydroxide are observed. Therefore, the content of aluminum element and oxygen element in the metal material is measured by fluorescent X-ray analysis (XRF), the content of oxygen element is determined, and the content of hydroxide and aluminum is determined.
- XRF fluorescent X-ray analysis
- the hydrogen generating material of the present invention can be constituted by mixing the above metal material with a heat generating material, an additive or the like to be described later.
- the metal material has good reactivity with water, hydrogen can be generated easily and efficiently even if the content of the heat generating material and additives is reduced or omitted, and the energy density is reduced. Can be improved
- the form of the hydrogen generating material is not particularly limited.
- the metal material may be in the form of powder (particulate), but may be formed into pellets or granules. It is more preferable.
- a powdered hydrogen generating material is compression-molded into pellets, the packing density is increased and the volume is reduced, so that the energy density is improved.
- the hydrogen generation rate can be increased by granulating the hydrogen generating material into, for example, millimeter-sized granules.
- the hydrogen generating material of the present invention can be used to generate a heat generating material that generates heat by reacting with water in addition to external heating that is preferably heated when reacting with water.
- the heat generated by the reaction of this exothermic material with water can also be used. Therefore, the hydrogen generating material is a heat generating material that generates heat by reacting with water. It is also preferable to contain a material. Examples of such exothermic materials include alkali metals that generate heat by reacting with water or hydration, such as calcium carbonate, magnesium oxide, calcium chloride, magnesium chloride, and calcium sulfate. Or heat generating materials, such as an alkaline-earth metal oxide, can be illustrated. Further, metal powder that generates heat by reacting with oxygen, such as iron powder, can also be used as a heat generating material.
- the content of the heat generating material is, for example, 1 point to the total mass of the hydrogen generating material. It is more preferable to be 3% by mass or more. Also, from the viewpoint of the amount of hydrogen generation, for example, 15% by mass or less is preferable. More preferably.
- the heat generating material is contained in the hydrogen generating material, it is preferable to form the heat generating material including the heat generating material into pellets or granules.
- the hydrogen generating material of the present invention can contain various additives according to various purposes.
- Examples of the additive include hydrophilic oxide (alumina, silica, magnesia, zinc oxide, etc.), carbon, water-absorbing polymer (carboxymethylcellulose, polyvinyl alcohol, polyethylene glycol, etc.), etc.
- hydrophilic oxide alumina, silica, magnesia, zinc oxide, etc.
- carbon alumina, silica, magnesia, zinc oxide, etc.
- water-absorbing polymer carboxymethylcellulose, polyvinyl alcohol, polyethylene glycol, etc.
- the content of the additive is preferably 1% by mass or more with respect to the total mass of the hydrogen generating material, for example, from the viewpoint of hydrogen generation efficiency. 10 mass% or more is more preferable. From the viewpoint of the amount of hydrogen generation, for example, it is preferably 30 mass% or less with respect to the total mass of the hydrogen generating material. 20 mass% The following is more preferable.
- the hydrogen generating material of the present invention and the production method thereof are as described above. Next, a hydrogen production method and a hydrogen production apparatus using the hydrogen generating material of the present invention will be described.
- the hydrogen generating material of the present invention promotes the reaction by heating from the outside in order to improve the force reactivity to generate hydrogen by contacting with water and to obtain a hydrogen generation rate above a certain level.
- the heating temperature should be 40 ° C or higher, and it is desirable to keep the temperature below 95 ° C to prevent evaporation of water.
- the heating method is not particularly limited as long as it is a method that can keep the hydrogen generating material and water within the above temperature range. For example, electric heating by applying current to the resistor, chemical heating, and the like.
- a chemical heating method using an exothermic reaction can be used to heat the container containing the hydrogen generating material and water from outside.
- the heat source used for the chemical heating for example, various compounds exemplified as the heat generating material that generates heat by reacting with water described above can be used.
- the exothermic material reacts with water to generate heat, and the heat can heat the reaction vessel containing the hydrogen generating material.
- the exothermic material is stored in the reaction vessel together with the hydrogen generating material, and the heat is generated in the reaction vessel. It is possible to heat the hydrogen generating material directly.
- the amount of the heat generating material used is approximately the same as the above-described preferable content when the heat generating material is previously contained in the hydrogen generating material. That is, the amount of the heat generating material used is preferably 1% by mass or more and preferably 30% by mass or less with respect to the total mass of the hydrogen generating material and the heat generating material.
- the amount of hydrogen generation can be controlled by controlling the supply of water to be reacted with the hydrogen generating material.
- the hydrogen generating material of the present invention includes a container for storing the hydrogen generating material and water, and has a mechanism for reacting the hydrogen generating material and water therein to take out the generated hydrogen.
- the container in the hydrogen generator has the above heating means for heating the external force hydrogen generating material and water. It is also possible to promote hydrogen generation as needed. In this case, the amount of generated hydrogen can be controlled by controlling the heating temperature.
- the form and shape of the container in the hydrogen generator is not particularly limited, but includes a water supply port and a hydrogen discharge port, and the inside can be sealed so that water and hydrogen do not leak to the outside. It is desirable to do so.
- the material used for the container is not particularly limited as long as it does not permeate water and hydrogen and does not break even when heated to about 100 ° C.
- heat resistant glass, metals such as titanium and nickel, and resin such as polyethylene and polypropylene can be used.
- FIG. 5 is a cross-sectional view schematically showing an example of the hydrogen generator.
- the hydrogen generator 1 is composed of a container body 2 and a lid 3.
- the lid 3 has a supply port 4 for supplying water and a discharge port 5 for discharging hydrogen.
- the supply port 4 and the tube pump 6 are connected by a supply pipe 7.
- a discharge pipe 8 is connected to the discharge outlet 5.
- a hydrogen generating material 9 is accommodated in the container body 2.
- the pump 6 can be configured using a sealed container made of a resin sheet.
- a filter is preferably installed at the hydrogen outlet 5 of the hydrogen generator so that the contents of the container body 2 do not leak outside.
- This filter is not particularly limited as long as it has a structure that allows gas to pass through but does not allow liquid and solids to pass through.
- V is a porous polytetrafluoroethylene gas-liquid separation membrane that can be used for fuel cells. Use it. It is also possible to use a polypropylene porous film or the like used as a battery separator.
- the supply of water to the inside of the container body 2 is generated by controlling the supply of water as described above, as it is desirable to be able to control the flow rate.
- the amount of hydrogen can be controlled.
- Hydrogen generated using the hydrogen generating material of the present invention does not include CO and CO, which are problematic in hydrogen obtained by reforming hydrocarbon-based fuels. Therefore, below 100 ° C
- the obtained metallic material had a blackish brown color with a loss of metallic luster on the surface, and became irregularly shaped particles having an average particle size of 12 m.
- the average particle size of the metal material was measured using “Microtrack HRA” manufactured by Nikkiso Co., Ltd.
- the content of metal aluminum in the metal material was measured by the method described above, and was 80% by mass. Further, when the content of metallic aluminum in the aluminum powder produced by the atomizing method used as the raw material was measured in the same manner, it was 99% by mass or more.
- FIGS. 1A to 1C show the observation results of the cross section of the aluminum powder produced by the atomization method used as the raw material when producing the metal material of Example 1 using an electron microscope.
- 2A to 2C show the observation results of the cross section of the metal material produced in Example 1 with an electron microscope.
- FIG. 1A and FIG. 2A show images of the above-mentioned section with a scanning electron microscope (SEM)
- FIG. 1B and FIG. 2B show images of the above-mentioned section with a scanning transmission electron microscope (STEM).
- FIG. 2C show elemental mapping with an energy dispersive X-ray microanalyzer (EDX) in the field of view of FIGS. 1B and 2B, respectively.
- SEM scanning electron microscope
- STEM scanning transmission electron microscope
- EDX energy dispersive X-ray microanalyzer
- Example 1 on the outer surface inside the particle in which aluminum is mainly distributed (that is, inside the particle made of aluminum metal), Layers with predominantly oxygen distribution (ie inert phase containing aluminum oxide or aluminum hydroxide) and layers with predominantly aluminum distribution (ie containing metallic aluminum)
- the surface of the surface layer has a thickness of about 1 ⁇ m or less, including a layered portion with multiple layers of each layer.
- a hydrogen generation test was performed using the above metal material alone as a hydrogen generation material.
- the metal material lg and 10 g of water were placed in a sample bottle, and a resistor was placed outside the sample bottle. Hydrogen was generated by heating the sample bottle to 50 ° C with a resistor, and the generated hydrogen was collected by the water displacement method and the amount of hydrogen generated was measured.
- Example 1 the aluminum powder used as a raw material was directly used as a hydrogen generating material, and a hydrogen generation test was performed in the same manner as in Example 1 to measure the amount of hydrogen generation.
- Example 1 With respect to the hydrogen generating materials of Example 1 and Comparative Example 1, the amount of hydrogen collected every 2 minutes was measured, and the starting force of the hydrogen generation test was determined as the time until hydrogen began to be generated. In addition, the time-varying force of the amount of hydrogen collected was also determined for the hydrogen generation rate, and the time until the value reached the maximum value was also determined. The results are shown in Table 1.
- Example 1 the metal material of Example 1 produced by pulverizing aluminum powder in a liquid containing water and an organic solvent generates more hydrogen than the raw material powder used as the metal material in Comparative Example 1.
- the time to complete and the time to maximize the hydrogen generation rate are significantly shorter I was able to shrink.
- 2A to C considering that the cross-sectional image force of the particles shown in FIGS. 2A to 2C, a part of the surface film is composed of a laminated portion of a metal phase and an inert phase. Before water reaches the inner aluminum metal, the metal phase and water in the above-mentioned laminated part of the surface film react with each other to become the starting point of the reaction, and the reaction between the inside of the particle and water is promoted, so hydrogen is generated.
- a metal material was produced in the same manner as in Example 1 except that the amount of water used for pulverizing the aluminum powder was changed to 0.5 g (0.1 part by mass with respect to 1 part by mass of aluminum powder) to generate hydrogen. A test was conducted to measure the amount of hydrogen generation.
- a metal material was prepared in the same manner as in Example 1 except that the amount of aluminum powder used for pulverization was changed to 3 g and the amount of water was changed to 3 g (1 part by mass relative to 1 part by mass of aluminum powder). Then, a hydrogen generation test was performed and the amount of hydrogen generation was measured.
- a metal material was produced in the same manner as in Example 1 except that the amount of aluminum powder used for pulverization was changed to lg and the amount of water was changed to 3 g (3 parts by mass relative to 1 part by mass of aluminum powder). Then, a hydrogen generation test was performed and the amount of hydrogen generation was measured.
- a metal material was prepared in the same manner as in Example 1 except that the total rotation time of the crushing pot was changed to 10 minutes, and a hydrogen generation test was performed to measure the hydrogen generation amount.
- a metal material was produced in the same manner as in Example 1 except that the amount of water used for pulverizing the aluminum powder was 0.05 g (0.01 parts by mass with respect to 1 part by mass of aluminum powder), and hydrogen was generated. A test was conducted to measure the amount of hydrogen generation.
- Example 7 A hydrogen generating material was prepared by mixing 0.9 g of the metal material prepared in Example 1 and 0.1 lg of alumina having an average particle diameter of m in a mortar. Using this hydrogen generating material, a hydrogen generation test was performed in the same manner as in Example 1, and the amount of hydrogen generation was measured.
- a hydrogen generating material was prepared by mixing 0.93 g of the metal material prepared in Example 1 and 0.07 g of carbon (“Vulcan XC-72 R” manufactured by Cabot Corporation). Using this hydrogen generating material, a hydrogen generation test was performed in the same manner as in Example 1, and the amount of hydrogen generation was measured.
- a hydrogen generating material was prepared by mixing 0.96 g of the metal material prepared in Example 1 and 0.04 g of carboxymethylcellulose (manufactured by Daicel). Using this hydrogen generating material, a hydrogen generation test was performed in the same manner as in Example 1, and the amount of hydrogen generation was measured.
- a metal material was prepared in the same manner as in Example 1 except that the liquid used for pulverizing the aluminum powder was only 16 g of water, a hydrogen generation test was performed, and the amount of hydrogen generation was measured.
- a metal material was prepared in the same manner as in Example 1 except that only 15 g of toluene was used as the liquid for pulverizing the aluminum powder, a hydrogen generation test was performed, and the amount of hydrogen generation was measured.
- FIG. 3 is a graph showing the particle size distribution of the metal materials of Examples 1, 2 and 5, with the particle size m) of the metal material on the horizontal axis and the frequency (volume%) on the vertical axis. . From FIG. 3, each of the metal materials of Examples 2 and 5 has a ratio of particles having a particle size of 60 ⁇ m or less of 80% by mass or more. I understand that.
- the hydrogen generating material of Example 2 and Example 5 is more water-soluble than the hydrogen generating material of Example 1. Element generation amount and hydrogen generation rate were small. This is presumably because the particle size of the metal material of Example 2 and Example 5 was larger than the particle size of the metal material of Example 1 and the surface area was reduced, as shown in FIG. In the hydrogen generating material of Example 3, the hydrogen generation rate increased, but the hydrogen generation amount decreased. This is thought to be due to the fact that the reaction area was increased and the hydrogen generation rate was improved because the particle size of the metal material was reduced. This is thought to be due to the decrease in aluminum in the metallic state.
- Example 4 In the hydrogen generating material of Example 4, the proportion of water added during the pulverization process is larger than that in Example 3, so that the aluminum acidification proceeds further, and the amount of hydrogen generated and the rate of hydrogen generation are in Example 1. It is thought that it fell compared with the thing of. Therefore, it is considered that the content of metallic aluminum can be controlled and the amount of hydrogen generation and the rate of hydrogen generation can be controlled by changing the ratio of aluminum and water during pulverization. It was also found that the particle size of the metal material can be controlled by changing the ratio of aluminum and water during the grinding process. Also, from Example 5, it was found that the particle size can be controlled also by changing the pulverization time. By controlling these grinding conditions, it is considered that the hydrogen generation amount and the hydrogen generation rate can be controlled by controlling the particle size.
- Example 6 The metal material used in Example 6 was prepared by reducing the proportion of water in the liquid used for pulverizing the aluminum powder. Most of the metal material after pulverization was the surface of the pulverization pot. Adhered to the surface. Moreover, a part was obtained as scale-like particles having a metallic luster. When a hydrogen generation test was performed using this metal material as a hydrogen generation material, the metal material floated in water and reacted with water. Thus, the amount of hydrogen generation was lower than that in Example 1. In contrast, the metal materials used in Examples 1 to 5 and Examples 7 to 9 were submerged in water and had good compatibility with water.
- Example 7 by using a hydrogen generating material with alumina as an additive, the metal material content was reduced to 90% by mass compared to the hydrogen generating material of Example 1, Since the alumina promoted the reaction and the reaction rate of aluminum in the metal material increased, the hydrogen generation amount and hydrogen generation rate equivalent to Example 1 could be obtained. This is probably because the addition of alumina prevented the condensation of the unreacted metal material and the reaction product of the metal material. In addition, carbon was added as an additive to form a hydrogen generating material. In Example 8 and Example 9 in which carboxymethyl cellulose, which is a water-absorbing polymer, was added as an additive to form a hydrogen generating material, as in Example 7, the metal material was compared to the hydrogen generating material of Example 1. The amount of hydrogen generated and the hydrogen generation rate equal to or higher than those in Example 1 can be secured, and the carbon and water-absorbing polymer in the hydrogen generating material are also used in the alumina used in Example 7. It has a similar effect.
- Comparative Example 3 the aluminum powder was pulverized without using water and using only an organic solvent. However, the amount of pulverized material adhering to the surface of the pulverizing pot and the metallic luster were reduced. The ratio of the scale-like particles to be further increased as compared with Example 6. Even when the hydrogen generation test was performed using this pulverized product, the pulverized product floated in water, and the amount of hydrogen generation was extremely reduced. This is because the metal materials of Examples 1 to 5 are in the form of irregular particles, whereas the pulverized product of Comparative Example 3 is in the form of scales and the surface properties are different. It is thought that it affects the difference V ⁇ .
- the amount of hydrogen generation was measured in the same manner as in Example 1 except that the temperature of the sample bottle in the hydrogen generation test was changed to 45 ° C.
- the amount of hydrogen generation was measured in the same manner as in Example 1 except that the temperature of the sample bottle in the hydrogen generation test was changed to 40 ° C.
- Example 10 and 11 in which the heating temperature of the sample bottle was changed during the hydrogen generation test, hydrogen generation was observed, and if the hydrogen generating material was heated to 40 ° C or higher, hydrogen generation It was confirmed that the amount and hydrogen generation rate could be increased significantly.
- Example 1 where the sample bottle was heated to 50 ° C, the hydrogen generation rate reached its maximum at 14 minutes after the start of heating, and then the hydrogen generation rate decreased rapidly.
- Example 10 and Example 11 where the sample bottles were heated at 45 ° C and 40 ° C, the hydrogen generation rate was lower than in Example 1, but hydrogen could be generated stably over a long period of time. It was. Therefore, it is considered possible to control the hydrogen generation rate by controlling the heating temperature.
- a metal material lg produced in the same manner as in Example 1 was placed in a glass container body having an internal volume of 50 mL shown in FIG.
- the container body was sealed with a lid having a water supply port and a hydrogen discharge port.
- a resistor was disposed outside the container body as a heating means. When electricity was passed through the resistor and the container body was heated to 50 ° C, water was supplied from the water supply port at a rate of 0.02 mLZ using a tube pump. Was confirmed. It was also confirmed that hydrogen generation stopped after a few minutes when the water supply was stopped.
- Example 12 instead of stopping the water supply, heating was stopped and the container was allowed to cool, and it was confirmed that hydrogen generation stopped after a few minutes.
- Example 3 Fabrication of polymer electrolyte fuel cell> Hydrogen was generated in the same manner as in Example 1, and the generated hydrogen was supplied to a polymer electrolyte fuel cell to conduct a discharge test. As a result, a high output of 200 mWZcm 2 was obtained at room temperature, and the hydrogen generating material of the present invention was founded to be effective as a fuel source for small and portable fuel cells.
- the present invention it is possible to provide a hydrogen generating material capable of generating hydrogen easily and efficiently, a method for producing the same, and a method for producing hydrogen using the hydrogen generating material as a hydrogen source.
- a hydrogen generating material of the present invention as a hydrogen source, it is possible to reduce the size of the hydrogen generator and the fuel cell.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- General Health & Medical Sciences (AREA)
- Sustainable Energy (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Manufacturing & Machinery (AREA)
- Fuel Cell (AREA)
- Powder Metallurgy (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06729393A EP1867603A4 (en) | 2005-03-25 | 2006-03-17 | MATERIAL FOR HYDROGEN PRODUCTION, PRODUCTION METHOD AND METHOD FOR PRODUCING HYDROGEN |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005-087600 | 2005-03-25 | ||
JP2005087600 | 2005-03-25 | ||
JP2005-131370 | 2005-04-28 | ||
JP2005131370 | 2005-04-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006103959A1 true WO2006103959A1 (ja) | 2006-10-05 |
Family
ID=37053220
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2006/305404 WO2006103959A1 (ja) | 2005-03-25 | 2006-03-17 | 水素発生材料およびその製造方法、並びに水素の製造方法 |
Country Status (4)
Country | Link |
---|---|
US (1) | US7695709B2 (ja) |
EP (1) | EP1867603A4 (ja) |
KR (1) | KR100870723B1 (ja) |
WO (1) | WO2006103959A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007238383A (ja) * | 2006-03-09 | 2007-09-20 | Nitto Denko Corp | 水素発生装置及び水素発生方法 |
WO2024024743A1 (ja) * | 2022-07-27 | 2024-02-01 | 東洋アルミニウム株式会社 | 水素発生体 |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090267023A1 (en) * | 2005-07-20 | 2009-10-29 | Takeshi Miki | Hydrogen Generating Material and Method for Producing the Same |
US7976684B2 (en) * | 2008-08-09 | 2011-07-12 | Francisco Rivera Ferrer | Jacketed ultrasound system |
WO2010026945A1 (ja) * | 2008-09-02 | 2010-03-11 | 日立マクセル株式会社 | 水素発生装置、およびそれを備えた燃料電池システム |
IT1391452B1 (it) * | 2008-09-26 | 2011-12-23 | Univ Degli Studi Modena E Reggio Emilia | Impianto cogenerativo a combustibile metallico |
US8821834B2 (en) | 2008-12-23 | 2014-09-02 | Societe Bic | Hydrogen generator with aerogel catalyst |
US8441361B2 (en) | 2010-02-13 | 2013-05-14 | Mcallister Technologies, Llc | Methods and apparatuses for detection of properties of fluid conveyance systems |
US8083816B1 (en) | 2009-09-26 | 2011-12-27 | Robert L Hirsch | Production of hydrogen by means of a mechanical scraper on aluminum in an aqueous medium |
WO2011040942A1 (en) * | 2009-09-29 | 2011-04-07 | Alumifuel Power, Inc. | Methods and apparatus for controlled production of hydrogen using aluminum-based water-split reactions |
MX2014000915A (es) | 2011-07-25 | 2014-11-21 | H2 Catalyst Llc | Metodos y sistemas para producir hidrogeno. |
US9302681B2 (en) | 2011-08-12 | 2016-04-05 | Mcalister Technologies, Llc | Mobile transport platforms for producing hydrogen and structural materials, and associated systems and methods |
WO2013089669A1 (en) * | 2011-12-12 | 2013-06-20 | Robert Hirsch | Production of hydrogen by means of a mechanical brush on aluminum in an aqueous medium |
WO2014104219A1 (ja) | 2012-12-28 | 2014-07-03 | 東洋アルミニウム株式会社 | アルミニウムフレークペーストの製造方法 |
US8926719B2 (en) * | 2013-03-14 | 2015-01-06 | Mcalister Technologies, Llc | Method and apparatus for generating hydrogen from metal |
CN104549521A (zh) * | 2015-01-14 | 2015-04-29 | 彭军 | 一种制氢催化剂及其制备方法 |
CN109734050B (zh) * | 2019-03-04 | 2022-11-08 | 武汉理工大学 | 一种基于聚合物复合改性的铝水解制氢方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002014213A2 (en) | 2000-08-14 | 2002-02-21 | The University Of British Columbia | Hydrogen generation from water split reaction |
JP2004123517A (ja) * | 2002-09-11 | 2004-04-22 | Masao Watanabe | 摩擦腐食反応を利用した水素ガス製造方法 |
JP2004231466A (ja) * | 2003-01-30 | 2004-08-19 | Uchiya Thermostat Kk | 水素発生材料、水素発生方法及び水素発生装置 |
JP2005162552A (ja) * | 2003-12-04 | 2005-06-23 | National Institute For Materials Science | 水素発生用複合材とその製造方法 |
JP2006045004A (ja) * | 2004-08-05 | 2006-02-16 | Muroran Institute Of Technology | 活性化処理されたアルミニウム微粒子を使用した水素ガス発生方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3890166A (en) * | 1972-11-17 | 1975-06-17 | Aluminum Co Of America | Activation of particulate aluminum |
JP2566248B2 (ja) | 1987-08-18 | 1996-12-25 | 健治 木本 | 水素ガスの製造方法 |
JP2001031401A (ja) | 1999-07-21 | 2001-02-06 | Kiriu Mach Mfg Co Ltd | 水素ガスの製造方法 |
US6506360B1 (en) | 1999-07-28 | 2003-01-14 | Erling Reidar Andersen | Method for producing hydrogen |
US6440385B1 (en) | 2000-08-14 | 2002-08-27 | The University Of British Columbia | Hydrogen generation from water split reaction |
JP4073703B2 (ja) | 2002-04-23 | 2008-04-09 | 本田技研工業株式会社 | 高圧容器への水素充填方法 |
-
2006
- 2006-03-17 WO PCT/JP2006/305404 patent/WO2006103959A1/ja active Application Filing
- 2006-03-17 EP EP06729393A patent/EP1867603A4/en not_active Withdrawn
- 2006-03-17 US US11/665,022 patent/US7695709B2/en not_active Expired - Fee Related
- 2006-03-17 KR KR1020077008987A patent/KR100870723B1/ko not_active IP Right Cessation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002014213A2 (en) | 2000-08-14 | 2002-02-21 | The University Of British Columbia | Hydrogen generation from water split reaction |
JP2004505879A (ja) * | 2000-08-14 | 2004-02-26 | ザ ユニバーシティ オブ ブリティッシュ コロンビア | 水分解反応による水素の発生 |
JP2004123517A (ja) * | 2002-09-11 | 2004-04-22 | Masao Watanabe | 摩擦腐食反応を利用した水素ガス製造方法 |
US20040208820A1 (en) | 2002-09-11 | 2004-10-21 | Dynax Corporation | Method for producing hydrogen gas utilizing mechano-corrosive reaction |
JP2004231466A (ja) * | 2003-01-30 | 2004-08-19 | Uchiya Thermostat Kk | 水素発生材料、水素発生方法及び水素発生装置 |
JP2005162552A (ja) * | 2003-12-04 | 2005-06-23 | National Institute For Materials Science | 水素発生用複合材とその製造方法 |
JP2006045004A (ja) * | 2004-08-05 | 2006-02-16 | Muroran Institute Of Technology | 活性化処理されたアルミニウム微粒子を使用した水素ガス発生方法 |
Non-Patent Citations (2)
Title |
---|
DENG Z.-Y. ET AL.: "Modification of Al Particle Surfaces by gamma-Al2O3 and Its Effect on the Corrosion Behavior of Al", JOURNAL OF THE AMERICAN CERAMIC SOCIETY, vol. 88, no. 4, April 2005 (2005-04-01), pages 977 - 979, XP003001209 * |
See also references of EP1867603A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007238383A (ja) * | 2006-03-09 | 2007-09-20 | Nitto Denko Corp | 水素発生装置及び水素発生方法 |
WO2024024743A1 (ja) * | 2022-07-27 | 2024-02-01 | 東洋アルミニウム株式会社 | 水素発生体 |
Also Published As
Publication number | Publication date |
---|---|
US7695709B2 (en) | 2010-04-13 |
KR100870723B1 (ko) | 2008-11-27 |
EP1867603A1 (en) | 2007-12-19 |
EP1867603A4 (en) | 2008-10-08 |
KR20070064645A (ko) | 2007-06-21 |
US20090041657A1 (en) | 2009-02-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2006103959A1 (ja) | 水素発生材料およびその製造方法、並びに水素の製造方法 | |
KR100934740B1 (ko) | 수소발생재료 및 수소발생재료의 제조방법 | |
KR100837291B1 (ko) | 수소발생재료, 수소의 제조장치 및 연료전지 | |
JP4104016B2 (ja) | 水素発生材料、水素製造用カートリッジ、水素製造装置、水素の製造方法および燃料電池システム | |
JP4947718B2 (ja) | 水素発生材料及び水素発生装置 | |
Zhou et al. | Double shelled hollow SnO 2/polymer microsphere as a high-capacity anode material for superior reversible lithium ion storage | |
US20140004422A1 (en) | Positive electrode active material for magnesium secondary battery, magnesium secondary battery, method for manufacturing positive electrode active material for magnesium secondary battery, and method for manufacturing magnesium secondary battery | |
KR20090060996A (ko) | 발전장치 | |
US20100209338A1 (en) | Hydrogen-generating material composition, hydrogen-generating material formed body, and method for producing hydrogen | |
JP2007326742A (ja) | 水素製造方法 | |
JP4537337B2 (ja) | 水素発生材料、水素発生材料の製造方法、水素の製造方法、水素の製造装置および燃料電池 | |
JP2011121826A (ja) | 水素の製造方法及び水素の製造装置、並びに燃料電池システム | |
JP2008273758A (ja) | 水素発生材料組成物および水素発生装置 | |
JP2006273609A (ja) | 水素発生装置およびそれを用いた燃料電池 | |
JP2007290888A (ja) | 水素の製造方法 | |
CN101175689A (zh) | 氢产生材料及氢产生材料的制造方法 | |
CN100590065C (zh) | 氢发生材料及其制造方法以及氢的制造方法 | |
WO2021141013A1 (ja) | 粒子の製造方法 | |
JP6981854B2 (ja) | 蓄電デバイス用炭素材料、蓄電デバイス用電極、蓄電デバイス、および蓄電デバイス用炭素材料の製造方法 | |
WO2005077572A1 (ja) | バルブ金属粉末または低級酸化物粉末の製造方法 | |
JP2012046379A (ja) | 水素発生材料組成物及び水素発生装置 | |
JP2006012533A (ja) | アルカリ電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 11665022 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2006729393 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200680001060.9 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020077008987 Country of ref document: KR |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
NENP | Non-entry into the national phase |
Ref country code: RU |
|
WWP | Wipo information: published in national office |
Ref document number: 2006729393 Country of ref document: EP |